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By T. A. de Almeida, M. de Paiva Bueno, M. Powell

The mining industry is one of the foundations of modern society, providing not only the raw materials needed to maintain a contemporary lifestyle, but also serving as a basis for the development of future technologies. From the most basic components of an appliance to the materials needed to design an electric car or a space rocket, each raw material has gone through a painstaking procedure of extraction and processing, and ways to make this process more efficient will be of great help to meet an ever-increasing demand for minerals. One of the biggest challenges when extracting mineral resources is to measure the variability of the mineral body prior to processing. Comminution is the most power-demanding stage, and the lack of geometallurgical testing, often for financial reasons, may result in an inefficient operation. The Geopyörä Rock Breakage test was developed with the objective of making mineral variability data more accessible by providing both standard comminution parameters and rock mechanical properties at low cost, and with a modest sample size, allowing a larger number of samples to be tested to reduce uncertainties and assure productivity. The objective of this paper is to present the results of an extensive validation of this new rock breakage method against two of the main tests currently in use, namely the SMC® and Bond ball mill work index tests. More than 100 samples have been tested and the results compared, showing that the new method can accurately estimate the parameters of the traditional tests. This confirms that the new test is a reliable tool for comminution and geometallurgical tests.

Feb 1, 2023

By Claudio Sulca, Fernando Salas

Como parte de la política de mejora continua de nuestra compañía y de nuestro proceso de gestión de activos, uno de nuestros principales objetivos es lograr que nuestros activos alcancen y superen las horas de operación y ciclo de vida estimados en nuestro plan de negocios, asegurando la confiabilidad y buscando un equilibrio con los costos de reparación y costos horarios de rendimiento. Uno de los procesos importantes para lograr este objetivo es el proceso de monitoreo de condiciones, el cual asegura la salud y confiabilidad de los activos.

Sep 30, 2022

By R van Wyk

In today’s mining environment the use of heavy mechanical devices and other high-tech electronic devices like two-way radios, cellular phones and even automated mining systems, form a vital part of the daily operations of a mining site. These human-made devices and some of the naturally occurring events, like lightning and gamma radiation, can have negative effects on electronic detonators and the associated control equipment.On larger mining operations the necessity to move the point of safety for blasting further away from the blast area, introduced remote firing via radio frequencies for electronic detonator systems. Other influences on electronic detonators can be abuse or ignorance. To ensure the safety of the end-user, an electronic detonator must be resistant to some common mistakes that users can make. One of main concerns here is resistance to static discharge or incorrect wiring. Despite the daily use of electronic detonator solutions, scepticism and concern still exists amongst those who believe the system raises the risk of a premature initiation of the blast through some form of interference trigger.This paper will help users understand how electronic detonators and the associated control equipment protects itself from external influences. Focus will be on protection schemes to counter static and over-voltage discharge and methods to ensure protection of secure wireless radio links and detonator communications. With well engineered communication systems and solid static and over-voltage protection, an electronic detonator system can be more reliable and safer than other detonator systems. The following main points will be discussed:what makes a detonator an electronic detonator,static electricity and over-voltage protection,the general influence of electromagnetic energy on the detonator,the influence of lightning on detonators,the protection of radio communication’s links as used by remote firing equipment, andthe safety protection features built into remote firing equipment.

Nov 8, 2011

By G. Clarkson, M. Hitch, R. Clarkson

"A novel reagent-free method of extracting gold from gravity middling concentrates in the Yukon placer fields is presented in this paper. This method exploits the malleability of gold by submitting concentrates to grinding in a rod mill. Brittle waste minerals are effectively reduced, whereas malleable gold particles are flattened and are then extracted by classification through sieves. Recoveries in the field using a laboratory-sized rod mill regularly exceeded 90%, whereas correlation laboratory tests indicated recovery to be most sensitive to the mill charge size. This method has broad potential, including application to the gravity circuits of large hard-rock processing circuits.RÉSUMÉ Cet article présente une nouvelle méthode sans agents réactifs d’extraction de l’or dans les concentrés gravimétriques mixtes que l’on trouve dans les districts placériens du Yukon. Cette méthode exploite la malléabilité de l’or en broyant des concentrés dans un broyeur à barres. Les déchets miniers cassants sont bien réduits, alors que les particules d’or malléables sont écrasées puis extraites par classification au travers de cribles. Si les récupérations sur le site à l’aide d’un broyeur à barres de laboratoire excèdent 90 %, les essais de concordance en laboratoire indiquent que la récupération est très sensible à la taille de la charge du broyeur. Cette méthode présente un grand potentiel, notamment une application possible aux circuits gravimétriques des grands circuits de traitement des roches dures.INTRODUCTIONExploiting the high density of gold to separate it from waste materials is the oldest known mineral processing technique. This basic technique is still widely used in gravity concentration circuits today; however, gravity processing invariably results in high-value middlings, especially in the Yukon placer gold fields. In addition to having a uniquely high density, gold is also the most malleable metal. This unique malleability can be exploited to extract gold from otherwise inaccessible gravity middlings.The Yukon placer gold industry has been continuously ongoing since the 1860s, and today produces approximately 60,000 oz t (1.87 million grams) of crude gold annually, most of which is from the Klondike region near Dawson City (Van Loon & Bond, 2014). It is important to note that Yukon placer miners do not use any chemical extraction methods; rather, gravity upgrading methods are the sole processing techniques used. Placer deposits are typically coarse, well liberated, and naturally gravity concentrated and recoverable, thus making more expensive chemical extraction unnecessary (Mitchell, Evans, & Styles, 1997). Furthermore, a strict permitting regime, environmental concerns, lack of expertise, and fear of repercussions from regulators prevent miners from attempting more advanced processing methods, such as flotation or cyanidation. Even simple chemical extractions like mercury amalgamation have not been implemented for decades, with one observer noting that, as many as 30 years ago, “the art of mercury for amalgamating appear[ed] to be dying [in the Yukon]” (Osler, 1983)."

Jan 1, 2017

By William Gleason

From Nov. 16-20, the Extraction 2025 Conference will be presented in Phoenix, AZ. The unique conference brings together the 12th International Copper Conference, the 6th International Symposium on Nickel and Cobalt as well as cross-cutting symposia. Extraction 2025 is co-organized by The Metallurgy and Materials Society (MetSoc) of the Canadian Institute of Mining, Metallurgy and Petroleum (CIM), the Society for Mining, Metallurgy & Exploration (SME) and The Minerals, Metals & Materials Society (TMS). The previous, and first Extraction meeting (Extraction 2018) was held jointly by these three societies seven years ago in Ottawa and was a huge success with more than 90 percent of respondents indicating interest in attending a future event. Kimberly Mills, senior process engineer at Samuel Engineering, is the lead for SME. “This installment of Extraction is featuring Copper 2025, Nickel-Cobalt 2025 as well as crosscutting symposia,” said Mills. “All three societies participate on the International Organizing Committee for the Copper Conference Series and are well situated to host this event together. TMS is also hosting the Ni-Co conference this year and agreed to include it as part of Extraction. There are many aspects that can be shared between these commodities to share information on processing technologies and to learn from each other.” SME is the overall conference chair and running the logistical aspects of the event, which includes managing all aspects of the venue and the registration system as well as tours and short courses, Mills said. “SME has many dedicated members serving in various capacities on organizing and programming committees, including Nick Gow serving as Technical Committee Co-Chair for Copper and Adam House assisting on the Copper IOC.” When Extraction 2025 kicks off, it will be focused on the metals needed for the global energy transition with a special focus on copper and nickel-cobalt. “With as rapidly as the industry is changing and the huge demands for these metals we have some serious challenges ahead of us,” Mills explained. “These challenges require collaboration, creative solutions and engaging experts, both inside and outside of our fields, with a push for sustainable sourcing, ethical supply chains, environmental and social responsibility.” The International Copper Conference was started in 1987 as a collaboration between the Institute of Mining Engineers of Chile (IIMCH) and MetSoc of the CIM. The event is typically held every four years and has always been held as a standalone or headlining event at a society annual meeting, said Mills. “Over the years, this conference series alone has brought together members of IIMCH, MetSoc, TMS, SME, the Society for Metallurgists and Miners from Germany (GDMB), the Mining and Materials Processing Institute of Japan (MMIJ), the South African Institute of Mining and Metallurgy (SAIMM) and the Nonferrous Metals Society of China (NFSOC),” she added. “Being a part of Extraction allows for even more sharing of ideas and expansion of networking. This conference has not been held in the United

Oct 1, 2025

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999

By Michael Moats, Weston Hartzell

The stable domestic supply of gallium, indium, and germanium has been identified as a critical need for the USA. Electric arc furnace dusts processed to recover zinc produce a process residue that could be a potential source of these critical materials. An industrial zinc leach residue was characterized to determine the predominant mineral phases and leached with common mineral acids. Atmospheric agitated leaching using sulfuric acid and hydrochloric acid were examined to determine the extractions of gallium, indium, and germanium as a function of concentration, temperature, and time. Extractions of gallium were found to be similar to iron in all experiments. The maximum percentage of Ga, Ge, and In leached into solution were 82%, ~100%, and 89%, respectively.

Aug 8, 2023

By M. S. Moats, W. C. Hartzell

The stable domestic supply of gallium, indium, and germanium has been identified as a critical need for the United States. Electric arc furnace dusts, processed to recover zinc, produce a residue that could be a potential source of these critical materials. An industrial zinc leach residue was characterized to determine its particle size, chemical composition, and predominant mineral phases. Heated, atmospheric, agitated leaching using sulfuric acid and hydrochloric acid was examined to determine the extractions of gallium, indium, and germanium as a function of concentration and temperature. Extractions of gallium were found to be similar to iron in all experiments. The maximum percentage of Ga, Ge, and In leached into solution were 71%, 63%, and 48%, respectively.

Feb 1, 2023

By Peng Lv, Shiqian Liu, Bin Xu, Qian Li, Yongbin Yang, Tao Jiang

The treatment process of a low-grade refractory gold ore containing sulfide minerals and carbonaceous matters was studied in this work. The gold extraction of this ore by all-sliming cyanidation was only 11.75%. Hence, a pretreatment was necessary. In this paper, a flotation-preoxidation-cyanide leaching process was developed. The concentrate from the flotation procedure was processed using different preoxidation methods. A concentrate containing 34.08g/t of gold with the gold recovery ratio of 81.20% was obtained by flotation. After roasting, microwave heating or alkaline pressure oxidation, the gold cyanidation ratio reached 82.37%, 81.26% and 71.09% respectively. Roasting was an effective, reliable and mature technique to oxidize sulfide minerals and carbonaceous matters. Roasting and microwave heating both produced dangerous environmental pollutants while alkaline pressure oxidation was eco-friendly.

Jan 1, 2015

By M. J. Steffens

ESPLIM is a novel separation technique that combines the advantages of solvent extraction and electrostatic dispersion but its application in the extraction of nickel by the direct solvent extraction route and the effect of high electrostatic field on the stability of organics have not been explored. These were investigated in this study and it was found that the technique allows 97% extraction of the nickel in a single stage compared with 3 stages by the conventional solvent extraction. Also, three months of exposure to 5.0 kV under simulated operational conditions had no adverse effect on the stability of organics.

Jan 1, 2005

By Hsing Kuang Lin

Extraction of zinc from chloride solution with dibutyl butylphosphonate (DBBP) in Escaid 110 has been investigated. The distribution coefficient of zinc was found to be independent of equilibrium pH. This independence indicates that the mechanism of the extraction may be solvation. Slope analysis for the system of dilute zinc chloride solution reveals that two moles of DBBP react with one mole of zinc. A series of tests were conducted to bring DBBP to its full loading capacity and the analysis of the results confirms this stoichiometric factor of 2. Extraction isotherms were established by varying either the AIO ratio or the concentration of zinc in the aqueous feed. Both curves were found to be identical.

Jan 1, 1990

By Ho-Sung Yoon, Jyothi Rajesh Kumar, Jin-Young Lee

"Global population is a key factor in future energy requirements, especially considering the important elements of global energy resources, electricity production, the accessibility/non-accessibility of electricity, greenhouse gas emissions and the states of nuclear reactors. Everyday human requirements depend on industrial products, and industries need a considerable amount of electricity to run. Nuclear fuel is inexpensive and bolsters industrial growth. As uranium reserves are being consumed rapidly, an alternative source of energy in the nuclear industry is thorium. Here, primary energy supplies by various sources from 1993 to 2011 as well as estimates of future needs to 2020 are discussed. This study finds that primary energy sources are mainly fossil fuels, renewables sources, and nuclear and hydro energy. In addition, growth depends on increases mainly in renewable sources.Recovery of thorium from its ores by using hydrometallurgical routes were described and discussed. The final part of this paper was presented a case study of the thorium extraction from Korean monazite ore leach liquors by using Prieme JM-T diluted in A150 diluent as an extractant system. And possible separation of the thorium from rare earths (REs) and base metals were calculated by measuring of separation factors and finally, the recovery of thorium from loaded organic of Prieme JM-T was established.THORIUM IS FUTURE NUCLEAR FUEL?Global energy consumption is increasing everyday with the high population growth, high industrialization of numerous countries and the higher level of good and services consumption that follows it. If we look at specific sectors of the economy, oil consumption grew by 0.8 million barrels per day, globally, whereas the increase was 0.4 % for natural gas and coal 1.8 % for nuclear power and just under 2.0 % for hydroelectric power (Asheley 2009). Use of renewable sources of energy for power generation and transportation increased by 3% in 2014 (BP 2015)). Thus alternative source of energy must be identified and developed to meet this increasing demand. Thorium is a potential one for the nuclear industry."

Jan 1, 2016

As the title indicates the central themes discussed in this contribution are sustainable development, information systems, and extractive industry. More specifically, the objective is to present a prototype for the systematic generation of extractive industry (henceforth: EI) û specific sustainability information. The paper begins with the authorÆs viewpoints on the core notions of sustainability, and development, as well as their relationship to information. These set the stage for the introduction of the information system (IS), as well as the follow-up sustainability information system (SIS) extractive industry sustainability information system (EISIS) concepts and related discussions. The paper continues with a second part, in which, efforts to research and develop an EISIS prototype are described. First, the team is presented. Second, the systemÆs aim and target groups are briefly discussed. After, an articulated overarching EISIS conceptual model emphasising capital accumulation, and service flow concepts û is presented. This is followed by a detailed description of the assembled prototype with a focus on data and information generation. The formulation of data generation, storage and transmission processes, as well as its use in sustainability interpretation rules and their embedment in the conceptual model is made with respect to monetised stock and flow parameters, measured in the appropriate dimensions. In the third part, the author presents and discusses the results of a first round of prototype experimental development in three major EI firms. First, the system observation, and data analysis protocols are described. Second, a review of protocol implementation, and respective results, is made. Finally, the overall performance of the proposed prototype, and development process issues are discussed, before suggesting areas for improvement and future research. The paper ends with a conclusion in which the author provides a retrospective balance of the æknowledge creation projectÆ, as well as a prospective outlook for research in this field; before acknowledgements are made and references provided.

Jan 1, 2009

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar&apos; have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF&apos;-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".&apos; The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley&apos;s publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1&apos; for ?H°, and the entropy function.

Jan 1, 1952

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton&apos; reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler&apos; stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952