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By H. C. Horwood

INTRODUCTION THE Argosy Gold Mines, Limited, which joined the ranks of active Ontario gold producers during the summer of 1936, holds a group of 21 claims on Casummit lake, in the Patricia portion, district of Kenora, northwestern Ontario. The Company is developing and mining goldbearing quartz veins that occur in a series of greywackes and slates of probable Keewatin age. The writer made a geological examination of the property and the surrounding area for the Ontario Department of Mines during the early part of the field season of 1936. This paper is a report on the general geology, structure, and ore deposits at the mine and is based almost entirely on data compiled during the examination. HISTORY Mineralization was first discovered on the property in May, 1929, by A. F. Hewitt, who, with J. A. Borthwick, decided that the country had prospecting possibilities and commenced work in April. Mr. Hewitt staked, and with his partner, J. Ziyone, still holds the group of claims lying immediately east of the present Argosy holdings. Mr. Borthwick staked six claims, K.R.L. 9,681 to 9,686, inclusive, adjoining Hewitt's on the west and later added claims K.R.L. 9,733 to 9,740, inclusive, to his holdings. F. Fiskness, who was also prospecting in the region, discoveted No. 1 vein on Borthwick's claims, and with his two partners, L. Parth and H. Jones, staked claims K.R.L. 9,758 to 9,763, inclusive, to the northwest of Borthwick's and Hewitt's ground. In July, 1929, the Casey Mountain Operating Syndicate, which held ground to the northwest, secured an option on Borthwick's claims. The Fiskness-Parth-Jones property was added in January, 1930, to protect the west dip of the veins. During the winter of 1930-31, the veins were explored by diamond drilling, No. 2 for a length ?of 900 feet and a vertical depth of from 51 to. 375 feet? and No. 3 .t~ a slope depth of 175 feet. I~ August, 1.931, after the msrallat10n of a miming plant, the Casey Summit Gold Mmes, limited, was incorporated to take over the property from the Syndicate. The Maple leaf Mines optioned a controlling interest in the stock in August, 1933, and on September 17th, 1934, brought a 50-ton amalgamation mill into production. From early in October to December 27th, 1934, when the mill was closed down, 4,094 tons of ore were treated to yield 887.89 ounces of gold and 87 .26 ounces of silver( ! ).

Jan 1, 1937

"INTRODUCTIONGold tailings retreatment plants have been operated for many years throughout the world. Several large tailings retreatment facilities have been operated profitably in South Africa since 1976 and there are tailings retreatment operations in Canada currently in production with more in the feasibility stages.The Timmins Gold Tailings Project of ERG Resources Inc. was designed to treat 8,000,000 tonnes per annum of gold tailings for an eight month operating season, and commissioning of the operation began in July 1988. The payback period for this project is about 3 years which corresponds to an IRR of 30%.This report summarizes the metallurgical characteristics of the reclaim tailings, describes the process flowsheet which was developed to enable ERG to economically recover gold from the Timmins area tailings, and reviews commissioning activities."

Jan 1, 1989

By P. Fredriksson, S. Seetharaman

In the ladle refining process, the ?FeO?-content of the ladle slag is of great importance in the chemistry as well as the energetics of the process. An optimization of the process requires an accurate knowledge of the thermodynamic activities of ?FeO? in the ladle slags. Due to the discrepancies in the existing data, renewed attempts are being made at the Royal Institute of Technology to generate reliable data for binary, ternary and multi component slags containing ?FeO? at steelmaking temperatures. In order to measure the activities of ?FeO? in the slags, a gas equilibration technique was employed in the present work. The slags, kept in Pt-crucibles, were equilibrated with a CO-CO2-Ar gas mixture and quenched after equilibration. The chemical composition of the slag was analyszed. From a knowledge of the thermodynamics of Fe-Pt system, the ?FeO? activities in the slag could be evaluated. The results of the present studies, together with other literature values, were optimized in the slag software, THERMOSLAG® developed in the Royal Institute of Technology, Sweden. The results of the optimization are presented. Model calculations were performed with the KTH slag software, THERMOSLAG®, by using plant data from OVAKO Steel, Hofors, Sweden. It was found that oxygen estimations in the metal from the ?FeO? analyses of slags, obtained by conventional sampling and analysis methods, where less reliable. Estimation of the oxygen levels utilizing the sulphur partition between the slag and the metal were carried out using the THERMOSLAG® software. Reasonable estimations of the oxygen contents in the metal confirmed that this could be a very useful tool for the plant operator. Keywords: ladle, thermodynamics, slags, ?FeO?, experimentation, modelling, sulphur partition

Jan 1, 2004

By Robert K. Jonas

"Minerals processors can improve production by using the best available control technology to control their operations. Many mines use expert systems that can provide improved results over manual or basic control, but better results can be achieved using multivariable predictive control. Over the past few years, the application of multivariable predictive control has gained acceptance in many mining processes and has recently proven to be suitable for some of the most challenging processes. This advanced control technology has been successfully applied to a wide variety of processes; alumina digestion, ball mills, CCD/thickeners, kilns/calciners/roasters, heat exchangers/evaporators, and more demanding processes like SAG mills and flash smelters.This paper discusses the needs of advance control technologies in the mining industry, including the impact of these technologies on best practices for implementation and long term sustainability. Results of the multivariable predictive control applications in mineral processing are discussed, and in particular the application to the SAG mill. In addition, an example of the benefits improvement that can be achieved with this technology is presented.INTRODUCTIONThere has been a long term perception in the mainstream mineral processing industry that best advanced control solution is an expert system. There a numerous instances of expert systems used for control of SAG mills, as well as kilns or roasters, thickeners and more recently flotation circuits. Many of theses expert systems have been installed by small, independent companies or by OEMs of processing equipment. Undoubtedly these expert systems have provided millions in benefits to the owners of mineral processing plants.It is this author’s proposition that it is a misconception to believe that expert systems are the best solution for mineral processors, and that in many cases the best solution is Multivariable Predictive Control (MPC). Better control and optimal operations can be achieved through the use of MPC. Another important consideration when considering advanced control technologies is the implementation and support effort. These types of applications have been known to deteriorate, even to disuse, when they are not kept up to date with changes to the process or equipment. The audience is invited to listen to discussion and draw their own opinion. The author has been involved in installing control systems for over 20 years, advanced solutions for over 15 years, and has had privilege to consult with many miners concerning the selection and application of advanced controls over the past 6 years."

Jan 1, 2008

By R. S. Olsen

The Bureau of Mines is engaged in research to recover aluminum from kaolinitic clay and other nonbauxitic domestic resources. As part of this work, calcined Georgia kaolin was prepared by a process that prevents slime formation and makes the leached residues fast settling and easy to filter. The leaching reaction for calcined kaolinitic clay in a 5 pct stoichiometric excess of boiling 23-to 26-pct HCI was found to be zero order. Rate constants based on the weight-fraction of aluminum in the clay were found to be between 0.095 and 0.15 min-1 depending on feed preparation and leaching parameters. The mathematical relationships between aluminum extraction and time for both batch and continuous, stirred-tank operations were derived and verified experimentally.

Jan 1, 1983

By Zetti Gavelán

Lack of skilled workforce in mining industry during the current decade has been a serious concern for most mining organization globally. At the beginning of this decade the major envisioned difficulty was related to generational breach of mining professionals. By 2003, mining industry recover from a low metal prices cycle following by a worldwide mining investment boom in 2005 that triggers a talent war among mining companies that was not only limited to professional level but skilled operators as well. Despite world?s economy collapse in October 2008, impact on mining industry was small comparing to other industries and appears to show evidence of healing. Under this context, fundamentals that have been driven lack of skilled workforce for the mining industry in previous years still valid. Starting in 2007, Minera Argentina Gold SA - Barrick Veladero, subsidiary of Barrick Gold, initiated an innovative selection and training program for candidates without exposure to mining. Following our corporate social responsibility mandates, Barrick Veladero decided to change its hiring process entirely, concentrating on selection and training of local people with no experience rather than hire experienced mining operators. This paper shares Barrick Veladero experiences on its hiring program, challenges faced, and current results.

May 1, 2010

By Tjaar A. Louw, Albert P. Van Niekerk, Johannes J. Louw, Attie J. Goosen

Unlike molecular high explosives, commercial explosives based on ammonium nitrate do not detonate ideally according to the theoretical model for steady state, one-dimensional detonation. One of the reasons for this deviation from ideal detonation is the slower chemical reaction, due to less intimate contact between the oxidiser and fuel components. It is well known that the inclusion of gas pockets, such as microballoons, in the formulation of ammonium nitrate based emulsions and watergels enhances the performance of these explosives. Various different interpretations of the “hot spot” theory have been proposed to explain this phenomenon.

Jan 1, 1997

By James A. Finch, Stéphanie Somot

"The self-heating facility developed at the Noranda Technology Centre [Rosenblum and coworkers, 2001; 1995] has now been established in the Department of Mining, Metals and Materials Engineering at McGill University. A research program into mechanisms has been initiated (with support now from four industrial partners under Camiro). The first investigation is into the role of pyrrhotite (Po), the most commonly suspected mineral to trigger self-heating. Following a standard experimental protocol, self-heating was assessed on samples of Po mixed with sand as an inert material. With increasing Po content, self heating progressively increased but, interestingly, the samples visually appeared less and less oxidized. A high Po content, it was hypothesized, may give a more reducing environment favouring formation of H2S. The presence of this gas could be significant as it has a high exothermic heat of reaction with oxygen. The system was modified to test the hypothesis by including copper pieces and copper sulphate to react with (and therefore reveal) the gas as copper sulphide. Evidence is presented in support of H2S production, which to our knowledge has not been shown before and introduces a potentially important avenue of investigation into self-heating mechanisms.INTRODUCTIONSelf-heating of sulphide minerals poses potential environmental and safety hazards in mining of ores, and storage and transport of concentrates. While some conditions are known to be critical, the reactions remain poorly understood making self-heating difficult to predict and control.A major advance in measurement was introduced by Rosenblum and co-workers [Rosenblum et al., 2001; Rosenblum and Spira 1995]. A self-heating assessment method was developed and applied to various sulphide-bearing materials The method is based upon automated calorimetric cells with data acquisition, now available to McGill researchers and which have been used for the study reported here."

Jan 1, 2006

By O. I. Ostrovski, D. K. Belashchenko

The aim of this paper is the construction of models of systems with ionic and ionic-covalent bonds (molten salts) using experimental diffraction data and the calculation of their structure and thermodynamic and transport properties. Modelling was performed using algorithm BELION, in which the non-coulomb part of interaction potential between ions in the model was determined by the method of iterative simulation which targeted agreement between calculated and experimental partial pair correlation functions (PPCFs). The ionic charges in salts, which can be fractional, were determined by minimization of internal energy. In this paper, the algorithm BELION is applied for chlorides of alkaline-earth metals. Pair potentials, PPCFs, atomization energies, self-diffusion coefficients and electric conductivity are calculated. The charge of alkaline-earth metals was in the range of 2.0-2.1, slightly increasing from Mg to Ba. Partial pair correlation functions and atomization energies of models agree well with experimental data for MgCl2, SrCl2and BaCl2. Keywords: molten salt, molecular dynamics, partial pair correlation function, ionic charge, atomization energy, diffusion.

Jan 1, 2004

By T. Tamura

It is known that the CaO-FetO-P2O5slag system has a wide liquid miscibility gap at steelmaking temperatures and this two-liquid slag phase has many advantages such as high activities of both FetO and CaO and high amount of P2O5. The phosphorus distribution ratio between the two-liquid slag and molten steel was confirmed to be higher than that between CaOsat.-FetO-P2O5slag and molten steel. The two-liquid slag may be useful for dephosphorization of molten steel and reduction of slag volume. Furthermore, the phase equilibrium of two-liquid CaO-FetO-P2O5slagsaturated with MgO was measured to determine the applicability of the two-liquid slag to dephosphorization in steelmaking process. Keywords: slag, refractories, solid solution, two-liquid phase, dephosphorization, steelmaking, phase equilibrium.

Jan 1, 2004

By F. E. du Plessis, P. De Waal

Through the development of innovative in-line mineral quantification sensors, the possibility has arisen to apply modern control theory to implement automatic process control for electrostatic high tension (“HT”) roll separators. A pilot-scale set-up was constructed to enable continuous tests to be carried out. A typical dry mill feed was continuously pre-heated and separated with a modern lab scale HT roll machine. The mineralogy as well as mass-flow of the non-conductor stream was quantified in-line, and the combined streams were re-circulated in an endless loop by a combination of vibration feeders and a bucket elevator. A fractional factorial experiment was executed to determine the most significant control parameters of the HT roll separator. Then a multi-input, multi-output dynamic model of the HT electrostatic separator was extracted by the application of standard system identification techniques for automatic control. The most important control variable to ensure a stable product grade could be identified. This allowed a robust single-input, single-output controller to be implemented. The process variable and set-point was mineral grade and the control variable was electrode voltage. Roll speed was manually adjusted while the mineral grade was kept on set-point by the control system. The roll speed, where maximum mass flow and therefore maximum yield was produced on-grade, could therefore be rapidly determined. Atmosphere humidity and ore temperature served as disturbances. Some other adjustable parameters were kept constant during the experiments, namely feed mineralogy, splitter settings and feed rate. Delivery of maximum yield, with a controlled grade, can improve production while reducing the burden of complex manual tuning. Manual tuning previously involved coping with multiple parameters with uncertain cross coupling influences on the end result. Even the end result was typically only known after completion of mineral assays. Automatic grade stabilisation and yield optimisation for a HT roll separator bank requires in-line measurement of mineralogy and mass flow, as well as the implementation of a robust process control system.

Jan 1, 2005

By S C. Dominy

This contribution examines the effect of feedstock sampling before the sorting stage of polyethylene terephtalate (PET) bottle recycling. Batches of waste PET bottles may contain non-PET bottles which need to be removed by sorting. Any residual presence of PVC is detrimental for the quality of products manufactured from recycled PET. The maximum tolerated concentration of PVC in cleaned PET is extremely low, which places high demands on the recovery of PVC achieved by sorting. To be confident of attaining the desired PET quality after sorting, acceptance sampling of truckloads of PET bottles may take place prior to sorting. It is shown that accounting for sampling uncertainty requires that the sorting process achieves a consistently high recovery of PVC bottles.CITATION:Glass, H J and Dominy, S C, 2017. Plastics recycling and sampling, in Proceedings Eighth World Conference on Sampling and Blending , pp 129–134 (The Australasian Institute of Mining and Metallurgy: Melbourne).

May 9, 2017

By Paul Grady, Martin Froehling, Curtis Mohns, Eliab Roman

"Since the idea of processing rock to unlock the valuable minerals inside was put into practice, efforts to improve production began. Methods have been learned that allow for operation in environments and under circumstances where it would not have been possible until now. All existing operations have experienced at least some form of productivity improvement measures. The objective is simple: generate more product of better quality in less time and at lower unit cost. Since the year 2000, various modifications have been made at the Kemess Concentrator in efforts to improve productivity. The following is a discussion of these modifications and their contributions to the success of the operation.INTRODUCTIONThe Kemess South Mine, a major producer of gold and copper, is located in north-central British Columbia. Kemess was brought into production in May 1998 by Royal Oak Mines with a modern mill controlled by a fully integrated Foxboro IA DCS system and employing 134 people. On February 11, 2000 Northgate Exploration Limited (now Northgate Minerals Corporation) acquired Kemess Mine from receivership. Since acquisition in 2000, Kemess has seen many accomplishments, including the reduction of costs by 40% site wide.The mill has a nameplate capacity of approximately 56,000 tonnes per day which is processed through a Metso (Svedala) 60” x 89” Primary Gyratory Crusher and then conveyed by a 60” conveyor to a stockpile with 48 hours of total storage capacity. The nominal minus 6” rock from the stockpile is fed to two parallel grinding circuits (A & B). Each section consists of a 10.4 m F x 4.7 m SAG mill with dual drive motors (4,480 kW apiece) discharging onto a 2.4 m x 7.3 m Metso (Svedala) single deck vibrating screen to remove the coarse material for recycle to the SAG mill by a Continental 45º high angle sandwich conveyor. Screen undersize is pumped along with ball mill discharge to a cyclopac consisting of twelve Krebs 66 cm F cyclones to classify flotation feed to a size of approximately 65% minus 200 mesh. Cyclone underflow feeds a Metso (Svedala) 6.8 m F x 11.0 m ball mill, also with dual drive motors (4,480 kW apiece). The primary grinding circuit has 35,840 kW available for grinding."

Jan 1, 2005

By C. E. Julihn, Lowell B. Moon

"INTRODUCTION To increase the supply of ore needed to produce steel the Bureau of Mines has explored 187 mineral deposits containing chromium, iron, manganese, cobalt, nickel, fluorspar, tungsten, vanadium, or coal during the fiscal years. 1940-44, the deposits thus explored were selected from several thousand that were first examined to appraise their possibilities. The objective of the exploration was to determine the tonnage and grade of ores upon which mining, operations might be based, and the metallurgical processing that was most suitable for their utilization.Most of these deposits were sub-marginal by pre-war standards; hence there had been no incentive for their exploration, yet many such deposits were known to exist that probably contained ore sufficient in grade and amount to be utilized as war reserves.Some of the Bureau's exploration projects have disclosed substantial or even very large amounts of ore, much of which is fairly high in grade. In a few of them bodies of high-grade ore have been found, though in others the tonnage has proved to be too small or too low-grade for utilization."

Mar 1, 1945

Analysis of rock discontinuities, collected using a scanline method, has been undertaken at the Iron Duke open cut mine, on the southern margin of the Middleback Range in the Gawler Craton, South Australia. The iron mineralisation, which is a product of supergene enrichment of carbonate sediments, is located on the W (western) limb of a gently N plunging D2 macrosyncline. Mesofolds plunge shallowly to the NE or steeply to SE, suggesting two shortening events, of which the second produced significant macrofolds. Discontinuities include:faults and shears which display variable orientations, mainly striking WNW dipping steeply N; mesofractures or joints maintaining a well constrained orientation, dipping steeply S, subvertical striking E-W; and bedding surfaces which are folded about a gently N plunging axis. Through this example of the regional control exerted on local discontinuities, it is clear that discontinuities are not randomly distributed as often assumed in purely statistical approaches. Commonly for rocks of any age there is a distinct discontinuity pattern, reflecting the geological deformation history. If the controls exerted on local rock discontinuities can be determined and assigned a number related to their significance, the way forward is available to develop a site specifc knowledge base that can make realistic predictions for any position in a given rock mass. Such a procedure would involve assessment of the regional geology, linked to scanned discontinuities either via manual or automatic means. Recent advances in automatic scanning rock faces (eg by the I-SiTE Laser Radar) to determine discontinuities distributions, enable the rapid calculation of rock characteristics. This is a significant advance in rock engineering, providing a method of safe and quick collection of data. However it creates problems in the presence of an increase in the geotechnical data available, which should be assessed in the context of the regional geology. Although techniques are underway to analyse post-blast discontinuities, the next signifant potential advance in this area could be the integration of a knowledge based system to assess discontinuities ahead of mining, incorporating regional assessment and human intuition.

Jan 1, 2000

By T. Johnson

Mining activity in a number of metal ores has been running quite high over the last few years. In particular, those metals that employ acid functional extraction processes such as copper, nickel, cobalt and uranium have been particularly active. The world?s largest nickel mine ? the massive $4.76 billion Ambatovy nickel mine on the African island nation of Madagascar is nearing completion. When it reaches its full production capacity in 2013, the mine will produce 60,000 MT/yr of nickel and 5600 MT/yr of cobalt. Coming on the heels of the Ambatovy project is the Long Harbour Processing Plant in Newfoundland, Canada which will process the ore from Vale?s Voisey Bay mine in Labrador. Voisey?s Bay is expected to generate more than 50,000 MT/yr of nickel ore when it starts up in 2013. Next up will be the Boleo project in Mexico on the Baja peninsula. When commissioned in 2013, the $1.4 Billion Boleo project is expected to produce 60,000 MT/yr copper, 3100 MT/yr cobalt, 36,000 MT/yr zinc and 100,000 ? 250,000 MT/yr manganese carbonate.

Feb 27, 2013

By Yu. E. Emelyanov, A. V. Bogorodsky, R. N. Nabiulin, S. V. Balikov

"The paper describes the results of the study of gold-copper flotation concentrate atmospheric oxidation at different sizes of material, varying oxidation time, with air or oxygen blow. The study showed the low rate of sulphide oxidation during oxidation of flotation concentrate at a feed size (P98 -74 µm). The coppery recovery into solution was 48%; the recovery of gold by subsequent cyanidation reached 86%. Preliminary flotation concentrate grinding to P98 -20 µm provided oxidation of 90% of copper minerals, 80% of arsenopyrite and 15% of pyrite. The gold recovery by atmospheric oxidation of a fine-ground flotation concentrate increased by 59%, from 36% to 95%, the NaCN consumption reduced by 21 kg/t, from 30 to 9 kg/t. INTRODUCTION Processing of sulphide gold-copper ores and concentrates using conventional cyanidation technology results in higher reagent consumption and lower gold recovery. Destruction of sulphide minerals and extraction of copper from a processed product prior to cyanidation is essential for improving efficiency of precious metals recovery and reducing main reagents consumption. Atmospheric oxidation (AO) is one of the most promising hydrometallurgical methods of refractory gold-copper concentrates processing, along with biooxidation and pressure oxidation. The nature of this approach lies in oxidation of sulphides at 90-95°C, in acidic or alkaline conditions, with bubbling of oxygen or air, after preliminary ultrafine grinding (1-4). The following reactions of sulphide oxidation occur during atmospheric oxidation of a gold-copper flotation concentrate. Pyrite is oxidized with the formation of ferric sulphate (1) and elemental sulphur at low temperatures (2), whereas some portion of elemental sulphur reacts to form sulphuric acid: FeS2+3,75O2+0,5H2O=0,5Fe2(SO4)3+0,5H2SO4; ?G=-1144,02 kJ/mol (1)"

Jan 1, 2018

By Graham Davey

"Low speed stirred milling has been employed for many years in the metalliferous and industrial minerals industries. High speed stirred milling is a relatively new method of grinding in the metalliferous process industries. However it has been it has been in wide spread use in the industrial mineral field for over 30 years for various minerals. Many existing metallurgical operations are looking to maximize economic return from existing deposits, requiring new thinking and technologies. By combining low speed and high-speed milling fine and ultrafine grinding efficiency and operating costs can be improved.The correct selection of different fine grinding technologies is covered, when each mill is applicable and when a combination of the VERTIMILL® Grinding Mill and SMD provides the best economic solution.INTRODUCTIONUltra-fine grinding of minerals has been in wide spread use in the industrial mineral field for over 30 years. Within the last 10 years the metalliferous industry has shown interest in the ability to produce ultrafine particles, as chemical, physio-chemical and physical separation processes have advanced to be able to treat ultrafine metalliferous particles. Also as the primary mineral deposits, around the world are depleted, new more difficult deposits must be mined. Existing operations are also looking to maximize economic return from existing deposits, requiring new thinking and technologies.The traditional approach for gold containing refractory material has been to liberate the locked gold by chemically destroying the pyrite through oxidation. Roasting, pressure oxidation, and bacterial oxidation all employ various degrees of temperature, pressure and catalysis to react the pyrite with oxygen to produce iron oxide and sulfur by-products. However all of these methods are economically impacted due to specific operational added requirements and emissions controls. Pressure and bacterial oxidation have very high capital and operating costs."

Jan 1, 2006

By H. Y. Sohn, R. D. Hagni, M. K. Kojo

Reflected light microscopy was used to study the mineralogy and textures of experimental reactions of a nickel concentrate with a slag. Such an interaction is an important step in the bath smelting of nickel sulfide concentrate. Concentrate particles in the central portions of the pellets are rounded and develop vermicular SO2 gas porosity. In the outer portions of the pellets, the original minerals of the concentrate, pyrrhotite, pentlandite, pyrite, chalcopyrite, and violarite have agglomerated and reacted to form two intergrown phases: 1) pyrrhotite solid solution (Fe0.75Ni0.18Cu0.01S) and pentlandite solid solution (Fe0.58Ni0.51Cu0.03S). Magnetite formed euhedral crystals, skeletal crystals, and dendrites at the margins of the matte. Prismatic ferrohypersthene and octahedral Mg-Al-Fe spinel crystals and dendrites are present in the glassy slag.

Jan 1, 2001

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965