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"The pyrometallurgical method of recycling car batteries suffers from a potential for air pollution violations, which prompts the desire for a viable hydrometallurgicaJ alternative. Several Processes have been proposed, including leach-electrowinning routes using HBF4 and/or HzSiF6 based electrolytes, along with anodes of PbO2 on inert substrates.A study has been carried out to evaluate the proposed systems, with the intention of demonstrating a six month life of an electrolyte-anode combination. The work, which focused on the use of HzSiF6, has indicated that there was no acceptable anode, and has lead to the development of a technique to produce smooth, glassy, adherent coatings on graphite, and to the development of an anode composed of a series of copper cored graphite rods.The paper will present results on leaching and electrowinning experiments, as well as the description of a flowsheet for a pilot plant that will be used to produce one tone per day of refined lead from spent battery paste."

Jan 1, 1997

By Zhucheng Huang, Ronghai ZHONG, Liangming Wen, Tao Jiang

The reduction roasting-magnetic separation and its strengthening of high silicon coal-containing mini-pellets by sodium additives were researched. The results show that the carbon gasification reaction and reduction of fine hematite in high silicon coal-containing mini-pellets with 3% sodium additives were enhanced. Comparing with no sodium additives, the gasification rate of carbon with 3% sodium additives reacting with CO2 for 40 minutes at 950 and the metallization rate of reduced pellets with 3% sodium additives after roasting for 35 minutes at 960 increased from 35.15% and 58.72% to 86.98% and 86.15%, respectively. The analysis of SEM equipped with EDS demonstrates that the inner pore of reduced pellets with 3% sodium additives was more developed and the iron grains size significantly enlarged, meanwhile, the iron grade of concentrate increased from 60.45% to 80.23% and the iron recovery rate decreased from 84.67% to 80.78% after grinding-magnetic separation.

Jan 1, 2016

By Brian Patrick, Norman Bell, Mark Schoenfield, Thomas Weber, Dietrich Gross

"The reduction of carbon dioxide emissions and the resultant greenhouse gas affect is hampered by the fact that all fossil fuels contain copious quantities of carbon. Process tweaking can keep the amount of carbon dioxide to a minimum but cannot significantly reduce the amount of carbon dioxide generated. The very nature of utilizing fuels requires that they be burned to release the heat required for the various processes. Reduction of metal oxides to manufacture or modify pure metals, generation of power, transportation and many other forms of fuel usage result in much of the generation of man made carbon dioxide. Oxyfuel is a unique contributor to carbon dioxide emissions. While creating higher concentrations of carbon dioxide the total volume of carbon dioxide generated is reduced. This paper will examine the unique characteristics and potential of oxyfuel that make the generation of lower volumes of carbon dioxide possible.Nearly ten years ago a commercial application of oxy-fuel was installed at Jupiter Aluminum Company in Hammond, Indiana. This process was funded and developed by Dietrich Gross CEO. This aluminum remelt facility now runs completely on oxy-fuel and has continuously for over ten years. This has reduced the melt rates to as low as 750 BTU per pound in continuous melting periods."

Jan 1, 2009

By Pavol Loderer

Mineral froth pumping utilising centrifugal slurry pumps is a major engineering challenge for the end users and pump manufacturers due to the undesirable outcome of unstable pump performance. Most of these challenges occur due to incorrect pump selection and suction tank design. The traditional approach is to oversize the pump for pumping mineral froth. New horizontal slurry froth pump designs offer opportunities to improve the mineral froth with challenging (high) Froth Volume Factor while maintaining high efficiency, long wear life and stable pumping performance. This paper examines the flotation process in detail and how froth pumps are designed to handle this arduous process.

By H. Kohno

The Onahama No.3 tankhouse started commercial operation in early 1973, with the capacity of 8,500 metric tons per month. When the No.3 tankhouse was constructed, the starter sheet stripping section was rebuilt at the No.2 tankhouse and electrolyte purification section was expanded. The previous AIME paper in 1976 described the design principles of the No.3 tankhouse and its layout, This paper describes the starter sheet stripping machine in the No.2 tankhouse and the electrodes handling system in the No.3 tankhouse and all these equipments were developed for the operation of the No.3 tankhouse. A Hazelette continuous casting machine was also introduced in order to cast thin anodes with accurate shape. Owing to the adoption of thin anodes, gold, silver and copper inventory is reduced by 40%. Jumbo tanks and newly developed mechanical equipments were adopted and no work on cells during pulling up operation was achieved. Using thin anodes with accurate shape, inspection work was completely abolished while maintaining high current efficiency and high cathode quality. Labor cost was reduced by 70% and only six operaters can produce? 8,500 metric tons of cathodes per month. The same new electrolysis process is appreciated and has been used as a newly built independent tankhouse by Kidd Creek Mines Ltd., in Canada in 1981 with excellent results

Jan 1, 1987

By Toshiaki Tsuru, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition behavior of Zn-Cr alloys from the methanol baths was investigated. In the methanol baths of low Cr3+ concentration, Cr (III) compound was incorporated in the deposits and no lusfrous Zn-Cr alloys was deposited. However, Cr was existed as metallic state in the deposits obtained from the baths of higher Cr3+ concentration. With an increase in water content in the baths, the chemical state of Cr in the deposits changed from metallic to trivalent state. Under the condition that metallic Cr can be electrodeposited, Zn deposition was significantly polarized to the potential of Cr deposition.INTRODUCTIONAn attention has been paid to Zn-Cr alloy plated steel sheet because of its excellent properties for body panels of automobile and electrical appliances [1]-[4]. This plating process can be operated using the sulfate solutions containing Cr3+ ion [1] - [6].In decorative single Cr plating, on the other hand, many attempts have been made to electroplate Cr from trivalent electrolytes, which is motived by environmental deficiencies of the presently used hexavalent process [7]. [8]. However, it has been reported that in the aqueous solutions the behavior of the electroreduction of 0 3+ is atypical due to the complicated nature of the chemistry and electrochemistry of cr3+ species [9]-[11]. Even in Zn-Cr alloy plating, it is difficult to codeposit metallic Cr with Zn in simple sulfate electrolytes [l]-[4], [12]. Therefore, it can be expected that the electrodeposition behaviors of Zn-Cr alloys as well as Cr are significantly changed when the electrodeposition is conducted in non-aqueous plating solutions.In this study, the electrodeposition of Zn-Cr alloy was conducted from methanol solutions to clarify the electroreduction mechanism of Cr3·-Cr0 in the alloy deposition process."

Jan 1, 2000

By Yang Xianwan, Zhu Xiaoyun, Guo Zhongcheng, Zheng Yanping, Zhai Dacheng

"Corrosion resistance of RE-Ni-W-P-SiC composite coating and 3 l6L stainless steel in corrosion media of H2SO4, HCl, H3PO4 and FeC13 solutions at different concentrations by means of immersion methods and anodic polarization curves obtained by DHZ-1 electrochemical synthetic tester and HDV-7 transistor constant potentiometer. Immersion experiment results show that corrosion rate of RE-Ni-W-P-SiC composite coating as-deposited in HCl solutions increases with the rise of HCl concentrations, on the contrary, the corrosion rate of the composite coating after heat treatment decreases with increasing the HCl concentrations the corrosion rates of the coatings as-deposited and after heat treatment in H2SO4 and H3PO4 solutions respectively decrease with the rise.of H2SO4 and H3PO4 concentrations the corrosion rate of the deposit as-deposited in FeC13 solutions decreases with increasing FeC13 concentrations, while the rate of the composite coating after heat treatment increases .with the rise of FeC13 concentrations.In addition, the corrosion rate of 3 l 6L stainless steel in the corrosion media of H2SO4, HCl, H3PO4 and FeC13 solutions at different concentrations increases with rising of concentrations. Furthermore, the corrosion rate of 316L stainless steel in the corrosion media of H2SO4, HCl, H3PO4 and FeC13 solutions respectively is much greater than that of the RE-Ni-W-P-SiC composite coating as-deposited and after heat treatment in the same corrosion media.1. IntroductionAll the materials and their products, when processed, stored and used, it is inevitable that the corrosion, wear, fatigue and crack occur owing to the actions of surroundings. Those early failure and abrasion, through all kinds of departments and profession that corrosion consumes one percent of tens of the steel products of the whole world; and two or four percent of the GDP is lost because of the corrosion."

Jan 1, 2000

By D. R. Parker

"This paper canvasses emerging trends in public policy and law, which may influence the zinc industry's interest in recycling. There are forces at work beyond direct economic benefits that will drive recycling of zinc, including:• corporate determination to pursue sustainable practices and product stewardship.• public perceptions and pressure,• customer and investor demand,• workforce recruitment, and• protection and expansion of marketsIn this paper, these ""indirect"" forces are examined with particular focus on the zinc industry: It is concluded that, in today's world with an emerging precautionary approach to policy and law making, public perception concerning the environmental implications of metal products, and the need to conserve resources for future generation, a strong industry response is required."

Jan 1, 2000

By Hiroshi Ono

"By newly developed ICP method, trace amounts of As(III), As(V) .,Sb(III) and Sb(V) were precisely determined within accuracy of sub ng/ml. As(III) and Sb(III) were separated from As(V) and Sb(V) by extracting into ·xylene as diethyldithiocarbamate complexes using diethylammonium diethyldithiocarbamate (DDDC), and then back-extracted into nitric acid for a quantitative determiruition by ICP-AES equipped with hydridegeneration system The recoveries of As(III) and Sb(III) were satisfactory throughout the extraction with 0.04mol/l DDDC in xylene from lmol/l hydrochloric acid solution and the back-extraction with 7 mol/l nitric acid. As(V) and Sb(V) were reduced to As(III) and Sb(III) by ascorbic acid and potassium iodide, and their quantities were determined as mentioned above. The detection limits were found to be 0.58ng/ml for As(III), 0.63ng/ml for Sb(III) using 50ml of a sample. The proposed method was applied to analysis of the real sample.Introduction In drain, arsenic(AS) concentration is prescribed below 0.lmg/l, so As must be removed. As is existed at .the form of As(III) or As(V) in solution. For t1Jeir difference of chemic;µ property, it is not easy to remove As in solution. So it is an urgent necessity to develop for determining concentration of As(III) and As(V). Antimony( Sb) has resemblance .chemical property to As. So Sb was experimented the same as As.The separation and determination of As(III) and As(V) have been carried out using several methods, such as ICP after copreclpitating separation, HPLC, direct hydride generation atomic absorption. However these methods have some problems. One of main problems is that HPLC and direct hydride generation atomic absorption methods are influenced by coexisting elements."

Jan 1, 2000

By Shun Fujieda, Shigeru Suzuki, Kozo Shinoda, Tetsuo Fujita

"Dowa Metals & Mining Co. Ltd. has developed and plant-practiced a unique scorodite synthesis technology (DMSP®) for arsenic immobilization by oxidizing Fe(ll) ions in the presence of As(V) ions. Dowa has improved the DMSP® technology and has developed the process extensively for other applications. This paper focuses on the applicability of the DMSP® for various cases of copper smelting, and introduces other technologies for fixing arsenic and recycling gallium from GaAs, simultaneously processing (fixing) arsenic and thallium, and fixing and recovering arsenic from dilute arsenic solutions. The DMSP® was found to be applicable not only for various processes in nonferrous smelting, but also for other applications with a high potential for reducing environmental problems.IntroductionDowa Metals & Mining Co. Ltd. developed a method for synthesizing scorodite at ambient pressure [1], The scorodite is precipitated by oxidizing Fe(II) ion in a high-concentration As(V) solution. The scorodite produced in this way does not readily release arsenic because of its high crystallinity. Dowa built a demonstration plant for this technology at the Kosaka Smelter and established the production of scorodite at 30 t As/month by treating intermediate products from copper smelting as the starting material. The DMSP® was demonstrated to be favorably applicable to copper smelting [2]. We are engaged in further increasing the amount of arsenic fixation by the use of this process. Further improvements in productivity, cost reduction and applicability in various processes have been devised. Dowa has been endeavoring to resolve other problems as well as to improve productivity. We have gained extensive knowledge on arsenic treatment in our endeavors, enabling us to solve problems and improve productivity. This paper introduces the investigations and developments related to DMSP®."

Jan 1, 2012

By Katsunori Okaya, Gjergj Dodbiba, Hiroyuki Ono, Toyohisa Fujita, Seiji Matsuo

"In an attempt to raise the copper grade of Printed Circuit board (PCB) by removing other components, carbonization treatment was investigated. The crushed PCB without surface-mounted parts was carbonized under nitrogen atmosphere. After screening, the char was classified by size into oversized pieces, undersized pieces and powder. The copper foil and glass fiber pieces were liberated and collected in undersized fraction. The liberation of copper foil from the oversized pieces was also investigated. The copper foil was liberated easily from glass fiber by stamping treatment. Liberation rate of copper foil was high at high carbonized temperature. The experimental results indicated that 90% of oversized char was liberated and the copper foil recovery from PCB carbonized at 1073K was 110kg/t. The copper recovery from char powder by flotation was also investigated. 15% of the copper grade and 80 % of the copper recovery were obtained, whereas the removal rate of silicon was 55%.IntroductionWaste Electrical and Electronic Equipments (WEEEs) should be recycled because they have many kinds of valuable materials and most WEEEs include Printed Circuit Boards (PCBs). In Japan, about 30 km2 per year of Printed Circuit board (PCB) has been produced [1], PCBs are normally separated from WEEEs and picked up by hand and sold to non-ferrous metal market because PCBs include high grade of copper and other precious metal such as gold, silver and palladium [2]. However, PCB also has impurities such as silicon, aluminum and calcium which are slag materials in non-ferrous smelting process, and other harmful elements such as lead, bromine and antimony. Low grade PCBs are sold after removal of invaluable parts or sometimes land filled without any treatment"

Jan 1, 2011

By Ilija Ilic

Recovery of tin from tinplate and production of good-quality detinned-plate for further processing in ironworks has been the subject of interest for many years. Tinplates are mostly used for production of tin containers for food industry and consumer goods. The research carried out so far included determination of the parameters of dissolution of tin from tinplates by alkaline solution of NaOH and electrochemical recovery of tin from the alkaline solutions. During leaching, NaNO3 and methanitrobenzoic acid (MNBA) as oxidants were studied. By leaching the waste tinplate which contains 0.31 % of tin with a solution of 1.12 mol/dm3 NaOH, 0.26 mol/dm3 Na2CO3 and 0.09 mol/dm3 MNBA at temperature of 70°C for 60 mm, a degree of tin leaching of 97 % was attained. MNBA facilitates oxidation of Sn2+ into Sn4+ suitable for obtaining compact, and not spongy, Sn cathode deposit, as it was the ease earlier. Recovery of tin by electrolysis from solutions obtained by leaching was studied to determine the effect of electrolyte composition on the quality of cathode deposit and the degree of electric current efficiency. Experimental results obtained at a laboratory level were checked on an enlarged laboratory set up where continuos leaching of tin from waste tinplate and its electrolytic recovery from the solution obtained were carried out. The experimental set-up -operated under semi-industrial conditions, and about 500 kg of waste tinplate was processed yielding about 1.160 kg of tin (99 % Sn).

Jan 1, 2000

By Junji Shibata

The waste acid mixture whose main component is phosphoric acid, is discharged from the etching process in the liquid crystal production industry. In order to separate impurity acids from the phosphoric acid, trioctyl phosphate (TOP) is used as an extractant. TOP can extract acetic and nitric acids selectivity. The extraction and stripping operations are carried out for the acid mixture by beaker-scale experiments and countercurrent multistage operations with mixer-settler equipment. TOP selectively extracts the acetic and nitric acids in the acid mixture. From the results of the McCabe-Thiele analysis obtained by beaker-scale tests, the extraction for acetic and nitric acids are approximately 100%, respectively, by 6-stage extraction with a phase ratio (A/O) of 0.4. On the other hand, almost all of acetic and nitric acids are stripped with water from the organic phase by 4-stage stripping with a phase ratio (A/O) of 1.0. About 95% of acetic and 98% of nitric acids can be removed from the acid mixture without extracting phosphoric acid in case of the mixer-settler equipment operation. There are several steps such as slicing, lapping, chemical etching and mechanical polishing in the silicon wafer production process. The chemical etching step is necessary to remove any damaged layer caused in the slicing and lapping steps. The typical etching liquor is the acid mixture comprising nitric acid, acetic acid and hydrofluoric acid. The waste acid is treated by a neutralization method with a high alkali cost and balky solid residue. A solvent extraction method is applicable to separate and recover each acid. Acetic acid is first separated from the waste liquor using 2-ethlyhexyl alcohols as an extractant. Then, nitric acid is recovered using TBP (Tri-butyl phosphate). Finally hydrofluoric acid is separated with TBP solvent extraction. The expected recovered acids in this process are 2mol/L acetic acid, 6mol/L nitric acid and 6mol/L hydrofluoric acid. The yields of this process are almost 100% for acetic acid and nitric acid. On the other hand, it is important to recover and reuse the metal values contained in various industrial wastes from a viewpoint of environmental preservation. Most industrial products are made through processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane separation, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. Some examples of the application of solvent extraction to the treatment of wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse solution, etching solution and pickling solution are introduced.

Jan 1, 2003

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the furnace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By A. Vahed

The Goro Nickel Project is situated in the Southern Province of New Caledonia. Inco Limited and Goro Nickel S.A. have developed a process that features the use of pyrohydrolysis to produce nickel oxide. The process treats a blend of laterites by Pressure Acid Leaching followed by solvent extraction of nickel and cobalt using Cyanex 301®. Purified nickel chloride solution is converted to high purity NiO product and 6M hydrochloric acid, which is recycled back to the SX circuit. In co-operation with Andritz AG, spray roaster and fluid-bed pyrohydrolysis technologies were examined for this purpose. Tests were conducted at the Andritz AG pilot plant in Vienna, Austria, and at Goro in larger scale installations. The latter served to establish process engineering design parameters for scale-up. Several process variables were investigated in both technologies and the off-gas characteristics were established. Fluid-bed pyrohydrolysis was selected for the Goro commercial plant, primarily because it produced a granular nickel oxide. The main focus of this paper is to outline the results obtained in pilot plant studies of liquid fueled fluid bed pyrohydrolysis for the Goro Project. Keywords: lnco Goro Nickel, Fluid Bed Pyrohydrolysis, Pilot Plant Tests

Jan 1, 2004

By Seshadri Seetharaman, Nurni N. Viswanathan, Haijuan Wang

"In order to make the stainless steel making process efficient and environment friendly, it is essential to minimize the loss of chromium to the slag phase. With a view to investigate the advantages of using CO2 to attain moderate oxygen partial pressures in the oxidant gas during the decarburizations of stainless steel, the present experiments were carried out to understand the oxidation kinetics of Fe-Cr alloys and Fe-V alloy with gas mixtures containing CO2. In the present work, the oxidation behavior of Fe-Cr and Fe-V was examined by thermogravimetric analysis (TGA). Various mixtures of O2 and CO2 were used as the oxidant gas and the oxidation rate was followed by the weight changes as a function of time.The experiments demonstrated that the oxidation rate is independent of temperature at present experimental situation, but has strongly related to the Cr-content of the alloy as well as the oxygen partial pressure in the oxidant gas mixture. The wetting of alumina by the iron drop and the change of the drop shape during the course of the oxidation were investigated by X-ray radiography."

Jan 1, 2010

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the fum ace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By Gaifeng Xue, Jingxuan Zhou, Shangchao Liu

"Both COD and TOC can characterize organic pollution of coking wastewater. In theory, there is a linear correlation between these two indicators. After continuous monitoring TOC and COD of coking waste water, linear regression relationship between of these to indicators was studied with the use of mathematical statistics. And conversion equation between these two indicators was established, and using t-test method for significance testing. The results showed that the linear relationship of COD and TOC was significant. Also interval estimation of equation slope and intercept were given in the condition of 95% confidence level. A linear regression equation established can be used to indirectly convert TOC to COD with high precision and accuracy.IntroductionBoth chemical oxygen demand (COD) and total organic carbon (TOC) are measure of the degree of characterization for organic pollution of water bodies. The current COD standard analytical methods is Potassium dichromate titration method [1] . there are some disadvantages in this method, such as only part of organic matter in the water bodies being oxidated, the refluxed steps, a long time needed for each measurement, high cost. It is the most important that sulfuric acid silver and mercury sulfate reagents used in the measurement may easily lead to secondary pollution. In contrast, the measurement of TOC is by the method of combustion or Photocatalytic Oxidation. The result could be easily got from the instrument. There are some advantages in this way, such as easy operation, short time and little expenses for each measurement and no secondary pollution 121• In addition, the measurement of TOC has higher degree of precision and accuracy than the measurement of COD both in the determination of calibration standards and actual samples. The meaning and contrast of TOC and COD are listed in the table 1."

Jan 1, 2013

By K. Abe

Onahama Smelter has two green-charge reverberatory furnaces and the annual smelting capacity is 600 thousand tons copper concentrate. In addition to the concentrate, various kind of industrial wastes has been processed and utilized. First, the brick waste from converter is ground and used as raw material of castable for repairing the copper melt launders. Second, the slag containing calcium-sulfide from other foundry is fed to the reverberatory furnaces. Calcium sulfide is oxidized to CaO. The melting rate of concentrate is accelenlled and the slag loss is decreased. Third, the tip tire made of waste car tire is charged into the reverberatory furnaces as fuel. The steam of waste heat boiler for turbine generators has been increased so as to decrease the electricity cost. Fourth, the sulfur accretion from other chemical plant is blended into the copper concentrate and the sulfur is recovered as the gypsum for sale. Fifth, the processed waste oil has been utilized in the copper concentrate dryer by which the smelting capacity was increased effectively. Consequently, Onahama smelter contributes to the society by processing the wastes to the harmless slag and utilizing them as fuel through the copper smelting.

Jan 1, 1996

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