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By Oleg I. Platonov

Method of high-temperature reduction of oxygen-bearing sulfurous gas has been developed at Copper Plant (CP) of MMC ?Norilsk Nickel? Trans-Polar Division (PD) with the aim of producing elemental sulfur from Vanyukov furnace? off-gas. Non-explosive reduction technology of oxygen-bearing sulfurous gas by methane utilized at Copper Plant has been designed to separate the processes of gas heating and sulfur dioxide reduction based on different kinetic of the reactions oxygen fixing and SO2 reduction. First, natural gas promptly reacts with oxygen contained in the process gas to heat a gas mixture up to the temperature of sulfur dioxide reduction (1200C). Then isothermal reduction takes place within 1 sec. Combustion chamber (pre-chamber) design developed based on the above principles is presented. Practical experience of the two reduction reactors operation at CP since 1996 proves high efficiency of the developed reduction process. The volume efficiency rises dramatically thanks to the fact that both fuel and reducing agent are fed into the reactor volume in the form of high-speed turbulent jets providing an intensive mixing of the reacting gases. On condition of equal internal volume of the reactors, the developed process offers higher efficiency of reagent interaction resulting in sulfur conversion exceeding 90%, as compared to the equilibrium one.

Jan 1, 2006

By Zenon R. Llanos

"The disposal of spent hydroprocessing (HDP) catalysts in the petroleum refining industry has been a concern in the past due to their classification as listed hazardous wastes. However, because these catalysts have higher metal concentrations than regular ores, and the recent surge in prices for molybdenum, vanadium, nickel and cobalt what used to be considered as a liability for generators is now viewed as a valuable renewable source of strategic metals. At the same time the generation of spent catalysts has steadily risen due to new environmental regulations for low sulfur fuels and an increased appetite of gasoline consumers. This paper will examine spent catalyst market and the role played by Gulf Chemical & Metallurgical Corporation in the reclamation of metals over the last sixty years. Introduction Hydroprocessing (HDP) catalysts are used in petroleum refineries for two main applications: desulfurization and cracking. The catalyst support is alumina or mixtures of alumina and silica. Active metals include molybdenum, nickel, cobalt and tungsten. The selection of catalysts depends on the application and sometimes the cost. The life cycle of HDP catalysts is represented in Figure 1. The catalyst cycle in a reactor varies from continuous to one-two years. Catalysts used in various refining processes are deactivated by coke, sulfur, vanadium and other impurities in the refinery feedstocks and become spent. Refineries can optionally send the spent catalysts for regeneration, metals reclamation or landfilling. Catalysts used for refining heavy crudes often can not be regenerated. Catalysts used with light oils can be reused twice or three times after regeneration. When the option for regeneration is not viable, spent catalysts are send metal reclamation facilities or landfills."

Jan 1, 2008

By P. W. Godbehere

Over the past three years the Horne Smelter has successfully introduced concentrate smelting by injection in Peirce-Smith converters, allowing definitive closure of its last operating reverberatory furnace, while commissioning a large acid plant treating off gases from its Noranda reactor. Future strategies include a major revision to present converter practices to permit further significant reductions in sulphur and dust emissions. This paper gives an overview of the status of these and other technical and operating developments which will further contribute to ensuring the Horne's position as an efficient custom smelter of primary and secondary feeds.

Jan 1, 1993

By Qian Fu

Although chlorine fluxing to remove magnesium has been widely practiced in the aluminum industry for many years, there appear to have been few fundamental studies of the kinetics and transport phenomena involved. The paper describes such a study in which the rates of reaction of individual argon/chlorine bubbles with aluminum/magnesium melts were measured. The detachment of bubbles from a submerged nozzle, at variable depth in the melt, was detected by a microphone and the arrival of the bubble at the top surface by conductivity probes. Analysis of exit gases and mass balances yielded the overall progress of reaction. Experimental results are interpreted in terms of heterogeneous reaction kinetics and mass transport to the bubble-melt interface,

Jan 1, 1996

By Alim Ullah

Process, quality and management control are necessary in order to produce DRI of required quality and at minimum cost. Although the characteristics of the two (2) principal inputs, that is, iron oxide feed and natural gas (for gas-based DRI plants) can affect the operation of a DRI plant significantly, they are outside the control of plant operators, at least in the short run. The quantity of reduction gas, its composition and reduction gas temperature are some of the key process variables. Statistical Process Control (SPC) can be used in a DRI plant to minimize the production of off-grade material and costs, as well as to improve the overall operation of the plant. One of the key quality variables to be measured and controlled is percent metallization, defined as FeM/FeT*100 where, FeM and FeT respectively are metallic iron and total iron in DRI. Control charts are used to monitor the quality of DRI produced and, when necessary, corrective actions are taken to bring the product back within the control limits. Management control can consist of essentially following how well the plant performs against some pre-established standards of parameters like daily production, downtime, consumption of material and energy, etc. In this respect, it is suggested that yield, defined as theoretical consumption/actual consumption of iron oxide feed, be used to monitor the consumption of feed material. Similarly, instead of using natural gas per ton of DRI produced, a better criterion would be efficiency, defined as theoretical natural gas consumption/actual natural gas consumption.

Jan 1, 2006

By Roberto Parra, Roberto Parada

"A novel process for minor elements control in copper pyrometallurgical production is proposed based on a theoretical analysis and the results of an experimental program. Its application can solves operational problems related to volatile elements that determine pollutants gas emissions and the final quality of anodes. The process considers a calcination of mixtures of the dust with sulfidizing agents such as dirty copper concentrate or elemental sulfur at temperature under 800 °C. The product are a clean calcine that recovers all the Cu content on the dust and a gas stream that collect the minor elements as sulfides species. The calcine can be returned to the smelter avoiding the As increasing in the circuit and so on, the capacity for the treatment of dirty concentrates for the smelter can be higher. The possibility to apply vacuum in the calcinations step can decrease the operation temperature. The solid condensed from the gas has different options for its stabilization, with the advantage that this stream represents few mass with high As content.IntroductionThe control of undesired minor elements (IVIES) in conventional pyrometallurgical copper production is especially relevant for ore deposits associated to Andes region. The concentrates that are being produced present every time higher levels of volatiles and harmful elements: group Va (As, Sb and Bi), Pb, Zn, and Sn."

Jan 1, 2008

By Beatriz Amarai Campos, Jorge Alberto Soares Tenorio1, Denise Crocce Romano Espinosa, Adriana Johanny Murcia Santanilla

"The aim of the present work is to investigate the recovery of nickel from obsolete cell phones printed circuit boards. The printed circuit boards were firstly submitted to a grinding process and then leached in sulfuric acid. Nickel was extracted from aqueous solution using Cyanex 272. Aqueous/organic ratio was 1/1. The effect of both pH and modifier addition on selectivity of extraction was investigated.IntroductionCurrently, electric and electronic equipments (EEE) have become a necessity to the modern life. Associated with this necessity comes the continuous and increasing replacement of those equipments by new ones. The accelerated technology advances are responsible for the generation of electric and electronic waste. This waste can be dangerous not only to human health but also to the environment. Waste of electric and electronic equipments (WEEE) has a variety of components and metals in its composition becoming a potential pollutant to the environment when not properly discarded. Its wrong disposal causes a loss of materials that could be recovered and reused. Therefore WEEE treatment is an important matter because it can assist the reduction of waste generated and the recovery of valuable metals.Printed circuit board (PCBs) is an essential component of EEE and is typically very complex from a chemical point of view. Several metals may be present in its composition, such as cooper, nickel, iron, zinc, lead, tin and silver1''. This characteristic hinders the development of a simple treatment, making it necessary the application of chemical and mechanical processing for their recycling'4'. The UN estimates that approximately 20 to 50 million of tonnes of WEEE are generated worldwide each year."

Jan 1, 2011

By Baoxiang Zhang, Jing Zhang

"As extruded Mg-9Zn-0.6Zr-2Er magnesium alloys were hot-rolled at 400°C, followed by solution treatment at 400 °c for 1. 5h and artificial aging at 200°C for 10h. Microstructures and tensile mechanical properties of the alloys after hot rolling, solution and aging treatment were examined respectively. Optical micrographs of the as-rolled and as-solution alloys showed fine grain structures, due to the formation of Er-and Zn-bearing compounds at grain boundaries which obviously improved the thermal stability of the alloy. Yield strength as high as about 335 MPa was obtained for the as-rolled alloy, showing that the mechanical properties of the alloy was greatly benefit from the grain refinement and dynamic precipitation of fine MgZn2 during hot rolling. Due to solution heat treatment, vast majority of the Mg-Zn phases dissolved into the matrix, and precipitated out again as fine dispersoid during the subsequent aging, resulting in an enhanced aging-hardening effect.IntroductionWith high specific strength and low density, magnesium alloy has stimulated significant interest for the applications in microelectronics, aerospace and automobile industries. Due to its HCP structure, magnesium alloys exhibit relatively poor strength and ductility. Great efforts have been made to improve the properties of magnesium alloys.Thermo-mechanical processing which combined with subsequent heat treatment can strengthen magnesium alloys due to the strain-hardening mechanism, homogeneous distribution of second particles and grain refinement [1, 2]. However, commercial wrought magnesium alloys have high tendency of grain growth at high temperature due to lack of effective solutions to stabilize the microstructure [3, 4, and 6]. But Magnesium-RE alloys containing high rare earth were reported to have remarkable thermal-stability, Rare earth (RE), such as Y, Nd, Yb, Gd, Ce, were known to form second-phase particles that have higher thermal stability combining with Zn and matrix in Mg[12-17]."

Jan 1, 2012

By Zbigniew Smieszek, Ryszard Chamer, Ryszard Prajsnar, Zygmunt Kurek

"Lead-containing wastes processed at the IMN’s Division in Legnica originate mainly from dry and wet dedusting installations of the technological lines for copper production. These are lead dusts and lead-zinc dusts characterised by the specific properties resulting from the chemical composition of the Polish copper concentrates. Besides lead, they contain many accompanying metals and impurities such as zinc, copper, sulfur, chlorine, potassium, sodium, and also bituminous substances. Processing of lead-containing dusts is conducted in the installations of rotary-rocking furnaces heated with gas-oxygen burners fitted with auxiliary systems for cleaning process gases and refining re-circulating dusts. The processing technology utilizes innovative process and technical solutions enabling disposal of lead-containing wastes from copper metallurgy and from non-ferrous metals industry according to the BAT recommendations and to the guidelines specified in integrated permission. In this paper, the main technological aspects of processing lead-containing dusts at the IMN’s Division in Legnica have been presented.IntroductionCrude lead is obtained in Polish lead metallurgy from various primary and secondary materials, such as Zn-Pb concentrates, lead-bearing dusts of copper metallurgy and battery scrap. In zinc smelter Miasteczko Slaskie S.A. crude lead is produced from sulfide and oxide Pb-Zn concentrates in ISP process. Orzel Bialy S.A. and Baterpol Ltd. produce crude lead in short rotary furnaces in the process of smelting products of mechanical battery scrap separation– desulfurised or not desulfurised paste and metallic fraction. KGHM Polska Miedz S.A. and IMN Divison in Legnica produce crude lead in rotary furnaces in the process of smelting of polymetallic dusts and slimes from copper production processes."

Jan 1, 2008

By Fernanda Margarido

Recovery of metals contained in the electrode materials of batteries was studied considering an integrated recycling process constituted by physical and chemical operations. The physical treatment included the shredding of the spent batteries, followed by a wet sieving operation of the fragmented material. The physical behavior of Ni-Cd and Zn-Mn based (alkaline and saline) system batteries was studied and compared. In that sense, shredding operation was performed and the sieving of shredded fractions was accomplished to evaluate the efficiency of the separation of electrodes and scrap. For Ni-Cd batteries the loss of electrode material with the supra fraction (scrap) after the shredding operation was lesser than the Zn-Mn batteries. Especially for saline-type batteries, the electrode attached to the scrap was substantial leading to important losses. This difference can be explained by the composition of the case materials and the internal physical constitution of the electrodes. The wet sieving studies carried out allowed optimizing the separation of the electrode fine fractions from the scrap materials through the analysis of selectivity Cd/Fe or Zn/Fe. For Ni-Cd batteries, maximum selectivity was achieved for the granulometry of 1.4 mm, while for alkaline and saline systems best selectivity were obtained at 2.8 mm and 5.6 mm, respectively. This process allowed the recovery of about 70% of electrodes for Ni-Cd and alkaline systems, and 50% for saline batteries, with less than 5% of scrap as contaminant. This physical step can be considered as a pre-treatment of this type of waste material envisaging its valorization by chemical treatment, as improves the concentration of the elements of interest and decreases the iron content.

Jan 1, 2006

By Suk J. Im, I. S. Min, Daesoo Kim

UFP are defined by atoms or their clusters having diameter in the range of l0Å-0.l.um. Due to a ratio of very large surface area to volume, they have peculiar properties such as extra high surface energy. Recently UFP deposition technique may find its new applications to various areas such as conductive/resistive film formation. In this method, gas flow with UFP jet through the nozzle which is considered to be a free molecular flow is maintained at a very high speed (~100m/s). Using this technique, mixture film of Fe and Ni, and Ag/ Ag-Alloy etc. were obtained, and their mechanical and electro-magnetic properties were determined. The experimental results are pending. The test results and discussion will be presented in the main paper.

Jan 1, 1988

By Eiki Ono, Atsushi Yamatodani, Shigeru Sunagawa, Yasushi Takasaki, Atsushi Shibayama, Yasunori Higuchi

"During metallurgical processing of non-ferrous metals, smelting residue (inc. smelter slag, flue gas and so on) is inevitably generated as secondary product.In this research, some experimental feasibilities were investigated to recover/remove Cu and As from the residue. Primarily, the removal of As and volatilized materials from the residue was examined by pyrometallurgical treatment (dry-process). In the second stage after treating the residue with a dry-process, leaching and solvent extraction as hydrometallurgical treatments (wet-process) were also investigated by using H2SO4 solution as a two stage leaching treatment, to dissolve various metals from the leach residue. Then, solvent extraction was examined by using LIX-84I as an extractant to recover and separate Cu from impurities from the final (2nd) leached solution. For the leaching stages, the removal of 90 % As and the leaching rate of 85 % Cu could be achieved by 0.25 mol/l and 1.0 mol/l H2SO4 solution, respectively. On the other hand, the extraction of over 90 % Cu and stripping was carried out by solvent extraction. 1. IntroductionIn metallurgical process for non-ferrous metals, smelting residue (inc. smelter slag, flue gas and so on) is inevitably generated as secondary product, i.e., flue dust, slug and so on. The smelting residue includes some useful metals and undesired toxic materials; Cu, Pb, Ca and As, etc.In Japan there is one undisclosed place stockpiled with 10,000 ton of smelting residue from abandoned smelters about 25 years ago. Therefore it is necessary to reduce the residual amount for space and environmental protection including water treatment by separating and removing toxic materials."

Jan 1, 2008

By Nan Zhang, Lei Zhang, Gai-feng Xue, Lina Wang, Pu Liu

"A novel ß-diketone modified silica gel was synthesized by a simple reaction. The prepared material was characterized by diffuse reflectance FTIR spectroscopy and it was used for the adsorption of heave metal ions in the industrial waste water. The main parameters affecting the sorption of heavy metal ions, including pH, water flow rate, and elution, have been investigated in detail. Under the optimized operating conditions, most of the targeted heavy metal ions could be removed. The material could be simply regenerated by hydrochloric acid solution. The method is rapid, selective, economic and applicable to the removal of heavy metal ions from industrial waste water.IntroductionToxic organic pollutants and heavy metals ions mainly from industrial activities such as plating, metallurgy and dyeing industries, are a threat to human health and the surrounding environment, because of their toxicity and persistence after being released into the natural environment [1]. These pollutants must be removed or degraded to an acceptable level, before being discharged to the receiving waters. Therefore, detection and determination of heavy metal ions in industrial waste water is very important.Inductively coupled plasma optical emission spectrometry (ICP-OES) is the most used technique for the determination of heavy metal ions because of its capability for rapid multi-element detection over a wide concentration range and with relatively low detection limits. Compared to other techniques such as neutron activation analysis (NAA), X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES has the above advantages. Some constituents in industrial waters, such as organic compounds and inorganic salts, may cause matrix effects. In order to achieve accurate and reliable results, an efficient preconcentration of heavy metal ions and their separation from the matrix are usually required."

Jan 1, 2012

By David Dreisinger

The pressure oxidation of pyrite is an important hydrometallurgical technology, especially in the total oxidation of refractory gold ores and concentrates (gold is locked in the pyrite structure preventing direct cyanide recovery). It has been noticed in some commercial applications and benchscale studies that the leaching of pyrite may be slow and apparently can be inhibited by the presence of molten elemental sulfur in the leach pulp. The purpose of this study was to determine whether Ortho-Phenylene-Diamine (OPD) could be used as a surfactant or dispersant for sulfur in the pressure oxidation of pyrite. OPD has previously been shown to be useful for pressure leaching of zinc and copper sulfides at 150 C.In this work, the interfacial chemistry of sulfur was studied at temperatures of up to 190 C in the presence and absence of OPD and other surfactants. The contact angle between molten sulfur and pyrite was also measured. Finally, the impact of OPD on the kinetics of pyrite oxidation was measured in bench-scale pressure oxidation experiments. The essential finding of this study was that OPD lowers the interfacial tension between molten sulfur and acid solutions and increases the contact angle (reduces wetting) between molten sulfur and pyrite. The work of adhesion between sulfur and pyrite was reduced by more than an order of magnitude in the presence of OPD. In bench scale tests, addition of OPD was found to significantly accelerate the rate of oxidation of pyrite. Conveniently, it was found that OPD was also fully degraded during high temperature oxidation processes. No residual OPD was detected in solution or solid samples from the leach testing. OPD is recommended as a sulfur dispersant in the pressure oxidation of pyrite and/or elemental sulfur containing feeds.

Jan 1, 2003

By Ken-ichi Miyazawa

A Center of Excellence (COE) titled the Creation of Nature-Guided Materials Processing, called Nature COE, has been established at Nagoya University. In the Nature COE, a new field of material research is being developed through learning the laws of nature, namely, methods of attaining ?appearance of the maximum function under the minimum substance and energy consumption?, which the nature and living organisms have acquired through their evolution in long period. As one of the specific features, an ?Open Cluster Program? was originated for promoting the researches conducted by young researchers and Ph.D. students with those in and out of the university and also for fostering them, together with such educational programs for Ph.D. students as the research incentive, the oversea training and the international lodging seminar programs. The Open Cluster Program has been found to be effective for fostering of young researchers and students, for promoting their researches, for gathering researchers and knowledge from the world and for propagating the research fruits. Through conducting these programs, world-highest intelligent fruits and a gathering of young minds to lead the new field are expected. In this COE, the researches are conducted on (1) materials used for living bodies, (2) mimicking structures which nature or living bodies are forming and (3) materials processing by mimicking processes to form the structures observed in the nature or the living bodies. These researches are conducted by four groups to extend the processes observed in the natural world to a new type of processing that is thoroughly rationalized by plunging a scalpel of engineering, and to establish a new academic field of materials science and engineering.

Jan 1, 2006

By Goren Lindkvist

Elkem has a small industrial scale. Muti-Purpose furnace at the MEFOS Metallurgical Research Facility in Lulea, Sweden. The furnace is 2 meters in diameter with installed power of 4.8 MVA, equipped with oil coiled freeze lining, gas tight electrode seals and feed chutes and a slag flow control for continuous tapping. During tests in June, 1991, the furnace was continuously operated on a high silica slag at loads from 1.5 to 4,0 MW. The slag was then charges to a low silica, high iron and lime composition. Steel plant dust was added, smelted and reduced. The slag was made more ceramic by adding alumobrick and alumina. Data from the start-up and initial operating phase of the, Elkem EAF dust plant at Laclede Steel will also reviewed.

Jan 1, 1992

By Anestis Vlyssides, Elli Maria Barampouti, Sofia Mai, ?postolos Vlyssides

"A new anaerobic reactor variation, the UASB/CO2-stripper reactor was conceived. It consisted of a conventional UASB reactor that recirculated the biogas produced. The sludge characteristics of this system were examined when treating high strength wastewater. From the data collected, it was obvious that the UASB/CO2-stripper system can satisfactorily operate at higher loading rates (25 g COD·L-1·d-1). A pronounced effect on the quality of the granular sludge was observed. The VSS/TSS ratio decreased sharply. A considerable decrease in the mean granule diameter was observed, while the specific gravity of the granules increased. The sludge bed porosity increased significantly leading to a considerable expansion of the sludge bed. These changes in the sludge properties led to a gradual shift of the system towards a fluidized bed process as far as its hydraulic characteristics were concerned.IntroductionIn recent years energy considerations and environmental concerns have increased the interest in direct anaerobic treatment of industrial wastes. The anaerobic method of waste treatment offers, under the present circumstances, a number of significant advantages with trivial or more serious drawbacks over other treatment methods. The major obstacle to the application of the process for this specific purpose is perhaps the difficulty of extending it to a stable and simple operational form. A number of reactor configurations has been developed leading to high biomass concentrations, e.g. the contact process, the filter reactor, the UASB reactor, and the fluidized bed systems, but the process stability problem still remains [1].A prime objective in the operation of anaerobic waste treatment process is the maintenance of a proper pH range. Thus, a possible solution to the process stability problem could be obtained by increasing alkalinity in the anaerobic systems. Therefore, the main objective of this paper is to present and evaluate the results of a system (UASB/ CO2-stripper) with increased alkalinity concentrations."

Jan 1, 2008

By Stella Agatzini

Column leach tests were conducted to evaluate the amenability of poor Greece nickel laterites to heap leaching with dilute sulfuric acid at ambient temperature. The ore tested was a limonitic laterite with less than 1 % nickel and it was subjected to a suitable pretreatment with water prior to it being loaded into the columns, following findings of preliminary research work. The acid solution was recycled after suitable pH adjustment. Factorial designs were used to determine the effects and interactions of the following factors: sulfuric acid concentration, ore column height, ore grain size and ratio of leach solution volume to the ore quantity. The response which were investigated included nickel and cobalt recoveries, codissolution of iron, calcium, magnesium, aluminum, chromium and silica and also sulfuric acid consumption. Experimental error was also detennined. The tests showed that a nickel recovery of 88% could be achieved in 60 days.

Jan 1, 1993

By M. Frades, C. Frías, G. Díaz, A. B. Mejías

"In recent years, zinc recovery from flue dusts and other industrial wastes has been increased, offering to the market a large tonnage of secondary zinc oxides, which can not be processed directly to render high quality zinc because of the hazardous impurities and halogens content.The ZINCEXTM Technology has been commercially applied for more than thirty years and represents the most suitable solution to deal with secondary or crude zinc oxides due to its flexibility, simplicity, and cost-efficiency, allowing production of SHG electrolytic zinc and pure zinc sulfate salts thanks to the flexibility and selectivity of the zinc solvent extraction unit regarding to get rid of impurities.A dual plant able to produce electrolytic zinc and crystallized zinc sulfate has been engineered to provide a flexible and profitable solution to zinc market. A description of the study and the relevant achievements is presented in this paper.IntroductionZinc is a valuable commodity in the marketplace and can be recycled again and again and still maintain its physical and chemical properties. Zinc recycling offers both environmental and economic benefits such as reducing volumes of material that end up in landfills, saving energy by reducing the need for mining and smelting, and relieving environmental impact on the land and water, and conserving zinc ore [1].The supply of zinc able to be re-processed will be increasing from year to year according to secondary materials enter the recycling stream, and as a result, more recycled zinc will become available in the market. Thus, some existing zinc refineries are implementing an annexed treatment line to process secondary oxides in conjunction with primary zinc concentrates [2].The galvanized steel scrap is normally recycled in electric arc furnaces or in basic oxygen furnaces, which generates a large tonnage of zinc-bearing flue dusts (EAFD). Around one million ton EAFD is yearly produced at the USA and the EU, respectively. The flue dusts are treated commercially by pyrometallurgical ways such as waelz kilns, electrothermic furnaces, etc, to yield secondary zinc oxides that can not be processed directly to render high quality zinc because of the hazardous impurities and halogens content [3]."

Jan 1, 2008

By Dhanesh Chandra

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD application applies to deposition of high-purity metallic/alloy coatings. Vapor pressures of solid Os3(CO)12,Rh6(CO)16, Ru3(CO)12, Ir4(CO)12, Re2(CO)10, Co2(CO)8, Cr(CO)12,, and W(CO)6carbonyls have been measured using gravimetric-torsion effusion system. The vapor pressure data is used for many low and high temperature CVD applications. Interesting decomposition/disproportionation vaporization behavior has been notedfor Rh6(CO)16, Ru3(CO)12 and Co2(CO)8. The vaporization studies of Rh6(CO)16 showed virtually complete decomposition to Rh metal and the measured molecular weight of the effusing gas from the solid Rh6(CO)16 was 27.75 g/mol, close to that of carbon monoxide as compared to 1065.56 g/mol for the value of solid Rh6(CO)16. Electron microscopic characterization, X-ray line broadening results for Rh carbonyl has been performed on the vaporization product. However, Ru3(CO)12, Co2(CO)8 showed very complex behavior. The molecular weights of the vaporizing species have been estimated and the numbers of vaporizing species are proposed. For example, there was partial decomposition of Ru3(CO)12to(approx. 52%) metallic Ru and CO gas during vaporization, as suggested by the difference in the molecular weight of the vaporizing species of 107.58 g/mol compared to the actual value of 639.33 g/mol. The dimer Co2(CO)8 partially disproportionates to tetramer Co4(CO)12, monomer Co(CO)4, and CO gas. Whereas, the Os3(CO)12, Cr(CO)12,, and W(CO)6have shown virtually no disproportionation. The total vapor pressures of all the above-motioned carbonyls, partial pressures of various species, average molecular weights of the effusing gases, equilibrium constants for the vaporization reactions, their enthalpies, entropies, and Gibbs energies will be presented.

Jan 1, 2006