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By Sandeep Kumar Asarapalli, Sunil Kumar Bisoyi, Bhatu Kumar Pal

Spontaneous heating of coal is one of the major concerns in the coal mining industry. Hundreds of millions of tons of coal are lost each year because of spontaneous heating. If necessary arrangements are made, many fires due to spontaneous heating may be avoided. Therefore, protective measures have become essential to prevent coal from spontaneous combustion. A large amount of coal reserve can be saved by the assessment, suppression, and prediction of spontaneous heating of coal, which also helps in betterment and efficient coal production. The use of chemical retardants can act as inhibitors for the liability of coal toward spontaneous heating by increasing its ignition temperature, thereby, increasing its incubation period. The coal-chemical mixture can be used for whitewashing the exposed coal in galleries as it creates a layer between coal and oxygen in the atmosphere, delaying the oxidation process and ultimately inhibiting the spontaneous heating liability of coal. This work examines the effect of chemicals such as sodium chloride, calcium carbonate, potassium iodide, sodium nitrate, and potassium chloride on the spontaneous heating of a coal sample. Thereby, it suggests a better chemical for inhibiting the liability of coal toward spontaneous heating. The experimentation involves flammability temperature (FT), crossing point temperature (CPT), and differential thermal analysis (DTA). The ignition and oxidation temperatures were found from the above experimental methods for Lingaraj open-cast coal mine samples, with and without adding chemicals. The results are cross-checked and verified through DTA. Correlation analysis was carried out among the results obtained from CPT, DTA, and FT, and better chemical retardants that effectively inhibit coal’s tendency toward spontaneous heating were suggested.

Dec 23, 2023

By Peter Sylvén, Darwin Morales

Despite being crucial for the smelting process, furnace tapping using oxygen lances has not been considered an operation that brings value. Therefore, these important tools have not seen a significant change in over 100 years. Problems related to the use of oxygen lances include: • Inaccurate tool: causing damages shortening the life of the taphole refractories. • Safety: extended exposure to the operator in an unsafe area of the furnace. • Cost: high oxygen consumption & high lance consumption. • Time consuming and frustrating to connect one lance to another. This paper will suggest a very good solution; new concept thermal lances. We will show how these provide an outstanding performance for a more efficient, faster and cost-effective furnace tapping operation. These new lances are very accurate tools that enable the operator to perform a more controlled operation; resulting in longer taphole life, fewer repairs and less down-time.

Jan 1, 2016

By Pedro G. Salmon

The broad general distinction between primary and secondary batteries lies in the fact that in the former the current is produced by the consumption of one or both of the elements composing the cell, while in the latter the elements retain their form as such, and merely pass from one state of chemical combination to another. Much has been said in condemnation and but little in praise of storage-batteries; yet, notwithstanding the severe criticisms passed upon them, the skepticism with which electricians have viewed them, and the ignorance with which they have been handled, they continue to push their way into use. Their manufacture has now become a well-defined and established industry.

Jan 1, 1890

By Louis D. Huntoon

SHORTLY after publication of the article in the July, 1924, issue Of MINING AND METALLURGY, entitled "Canada as a Gold Producer," requests were received to determine the ownership of production. Advices have also been received that considerable discussion has taken place on the same questions both in Canada and Great Britain. The author is indebted to R. H. Coates, Dominion Statistician, and George C. Bateman, Secretary, Ontario Mining Association, for the following figures and takes this opportunity of expressing his appreciation. There have been no statistics compiled as to ownership of production. Statistics were compiled as of Dec. 31, 1921 relative to the distribution of stocks, bonds and "other securi¬ties" in industrials, agriculture excepted, throughout the Dominion, and "distribution of ownership of securities issued by mining companies incorporated and operating in Ontario" for the same year. Stock registration does not necessarily represent actual ownership' as large blocks may be endorsed and not transferred; neither does registration actually represent production. When the charts are studied individually and collectively one cannot help but be impressed with the fact .that in the mineral industry of Ontario and the Dominion at large, Canadian registration predominates, the United States registration is about half that of Canada, and Great Britain is about half that of the United States. When the nickel-copper industry is excepted the British registration falls to a very low percentage. Since Dec. 31, 1921, British capital has commenced to flow into mining enterprises in Ontario and it has been already rewarded by the discovery of valuable ore deposits.

Jan 1, 1925

This paper describes major technical developments in rod mill design and operating practice since its introduction into the North American minerals industry over fifty years ago. The basic operating characteristics of the wet, overflow rod mill are described, and significant operating variables are reviewed in terms of their effects on mill power draw, power efficiency, and practical aspects of circuit operation. Key factors for improving the economic performance of rod milling circuits are identified.

Jan 1, 1986

By R. R. Johnson

The Hama Mining Company owns and operates The Groveland Mine near Iron Mountain, in the Upper Peninsula of Michigan. The orebody is part of the Menominee Range of the Lake Superior District. The ore (generally known as Jasper taconite) contains an average of 35% iron ranging from 28% to 39% with an overall split of 60% magnetite and 40% hematite. The variations encountered throughout the orebody require a certain amount of blending to reduce feed changes to the mill. One of the variables which affects the crushers, as well as the mill, is the range of hardness which has a low of 7.9 and a high of 24.6 as measured by the Bond Twin pendulum impact and crushing technique. Reference is made to hardness only to point out its effect on crushing and wear rate variations. Over a period of time, these variables do, of course, average out. Mining of the low grade ore started in 1959 and has operated continuously to date. Preparation of the feed for conventional rod and ball mill grinding is accomplished by three stages of crushing. Reduction of crude ore is first passed through a 54 inch gyratory crusher; then through a secondary crusher; followed by two or three tertiary crushers in closed circuit with screens as production quotas require (Figure 1). Current demand to the crushers is about 5,200,000 tons of crude ore per year.

Jan 1, 1976

By H. R. Hanley, Charles Y. Clayton

ONE of the most important contributions to the art of electrolytic zinc production has been the aluminum cathode. This has been used in all major production since its commercial development in 1916. The literature is replete with important contributions, some of which may have been replaced by better ones, but thus far there appears no other metal to take the place of aluminum as cathode material. Credit for this innovation goes to Sherard Cowper Coles, of England. When experi¬menting on the extraction of zinc from Broken Hill ore at Hayle, Cornwall, in 1893, he introduced the aluminum cathode, and in 1895 obtained British Patent No. 20073. The reason for this dominant position of aluminum as cathode material in zinc sulphate electrolytes is its unique surface, to which electrodeposited metals usually do not tightly adhere. The metal must be of high purity for best results. It is possible to develop a starting-sheet method by which thin electrodeposited sheets of cathode zinc are made and stripped from a smooth aluminum plate. Such thin sheets of cathode zinc may be used as are the copper sheets in standard electrolytic copper-refinery practice. However, complications arise because of extreme warping of the zinc starting sheet after a few hours of deposition, and thus special arrangements must be made to compensate for this abnormality. Reasons advanced for the ease with which deposits may be stripped from the aluminum surface are: (1) presence of a permanent oxide coating on the metal, (2) failure of aluminum to alloy with the deposit, (3) differences in coefficient of expansion, (4) high position of aluminum in the electromotive series of metals. Of these reasons for nonadherence, which may have some application in general deposition, probably the oxide coating has the greatest bearing on the subject of zinc deposition. Adherence of zinc deposits has occasionally had serious effect oil tonnage and production costs. Opinions have differed as to the specific

Jan 1, 1938

By B G. Lottermoser

Phosphate induced stabilisation has been used to create passive iron phosphate coatings on pyrite and pyrrhotite. The formation of solid phosphate coatings on sulfide grains thereby inhibits sulfide oxidation. The aims of the study were to determine whether phosphate induced stabilisation could control sulfide oxidation and metal mobility in partly oxidised, polymineralic, sulfidic mine wastes. Waste materials were obtained from the acid mine drainage generating, abandoned Montalbion silver mine site, far north Queensland, Australia. The waste consists of quartz, kaolinite/illite, sulfide minerals (galena, chalcopyrite, tetrahedrite, sphalerite, pyrite, arsenopyrite), and pre- and post-mining oxidation products (hydrated Fe, Cu, Pb and alkali mineral salts). SEM observations of waste material treated with potassium orthophosphate showed that metal, metal-alkali and alkali phosphate coatings developed on all sulfides (with the exception of tetrahedrite). The abundance of phosphate phases was dependant on the availability of cations in solution for complexation with the phosphate anion. In turn, the release of cations was dependent on sulfide oxidation or the dissolution of efflorescent mineral salts. Experiments aiming to dissolve these phosphate coatings û using a strongly oxidising solution û showed that the phosphate coatings remained stable, preventing acid generation and metal release. The results of this study demonstrate that liquid phosphate stabilisers can suppress sulfide oxidation and immobilise metals in partly oxidised, polymineralic mine wastes.

Jan 1, 2003

By J. H. Jansky, P. W. Jeran, G. L. Hassett, M. C. Irani

This Bureau of Mines report tabulates methane emissions from U.S. bituminous coal mines with daily emission rates of at least 100,000 cfd according to States, counties, and coalbeds. Most of the methane emitted is from mines in the Appalachian States. Total daily emissionin 1975 was 216.3 MMcfd, compared with 227.0 MMcfd in 1971 and 214.5 MMcfd in 1973. Thirty counties in nine States had daily methane emissions of 1 MMcfd or more, These emitted 93 percent of the total methane. The highest emissions were from Monongalia County, W. Va,, which accounted for 18.9 percent of the total. This was followed by Marion County, W. Va., 9.6 percent; Buchanan County, Va., 8.5 percent; Jefferson County, Ala., 6.1 percent; and Washington County, Pa., 5.9 percent. The Pittsburgh coalbed emitted 45.7 percent of the total methane, followed by the Pocahontas No. 3 coalbed with 12.9 percent. The report lists 196 mines, of which 60 had daily methane emissions of 1 MMcfd or more. Included in this compilation are the identification and thickness of the coalbed, methane emission, coal production and ventilation rates, number of drifts, shafts, and slopes used for ventilation purposes, shaft depth, age of mine, and gas-to-coal ratio.

Jan 1, 1975

By Kristine Bruce Wanderley, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenorio

Magnesium is present in nickels leach liquor and it is often disposed in waste barriers. However, new technologies with the aim of recuperating magnesium and other metals in the liquor have proven that it is possible to reduce the amount of metal lost during nickel ore processing. In this context, high temperature crystallization removes magnesium, with a concentration of 8 g/L, as MgSO4 H2O from the leach liquor. Kinetic studies of this process are needed to evaluate the thermodynamics of the growth of crystals. Thus, this work aims to study the crystallization kinetics of MgSO4 H2O. Temperatures of 230, 210 and 200 °C were investigated in a batch crystallization system in solutions with pH2. Aliquots were taken at each hour up to 5 h of time residence and analysed by ion chromatography for magnesium concentration. The reaction mechanism as well as rate constant and activation energy for each reaction temperature were obtained

Mar 1, 2018

By Brian Langdon

The DRIVEN GROUT PILE was developed in 1989 by DeWitt Construction, Incorporated. This piling essentially consists of a cost-in-place concrete piling that reacts on a steel boot that is driven to bearing. This report will describe the driven grout pile, its background and its installation. The advantages and disadvantages of this system are also discussed. Finally, the results of actual field installations are presented and discussed. BACKGROUND The DRIVEN GROUT PILE was developed out of a need for a low-cost high capacity piling (100 ton) that could be installed with ordinary pile driving equipment. This search was motivated by attempting to incorporate the material economy of an auger-cast piling with the "empirical load test" of a driven pile. Typically, the least cost material for piling in the 100 ton range is concrete (grout). A grout shaft with minimal reinforcement can withstand a compressive load of 100 tons for a material cost in the range of $6.00 to $8.00 per lineal foot. A pipe piling with a capacity of 100 tons has a unit material cost ranging to $13.00 per lineal foot. The marriage of these two advantages resulted in the DRIVEN GROUT PILE. A pile that utilizes the economy of a reinforced grout shaft and has the loading confidence of a driven pile.

Jan 1, 1990

Sanes are utilized to make molds for metal castings in the foundry industry. Approximately a half ton of sand is disposed of for each ton of metal cast in this country. The purpose of this investigation was to study and develop a process to separate chromite sand and silica sand from reclaimed sands for a steel foundry. Physical separations were utilized to yield silica and chromite sands with desirable molding properties. Several different separation methods, including electrostatic, magnetic, and various gravitational approaches were examined. Experimental results are presented. A method was developed to separate chromite sand from silica sand after mechanical or thermal reclamation. The reclaimed sands are passed through a rare earth magnetic separator to separate chromite sand and magnetic impurities from non-magnetic silica sand. Chromite sand can be recovered from magnetic silica sand or magnetic impurities very effectively using a wet concentrating table. The applicabilities of the separation methods are discussed.

Jan 1, 1995

Henry D. Hibbard, Plainfield, N J. (communication to the Secretary*):—This very interesting history is a valuable addition to our knowledge of the basic process and its introduction to this country. In addition to the attempts noted in the paper which were made here to establish the basic Bessemer process, and the experiment with the Siemens-Martin process at the Otis works, there were others made with the latter-named process at about the same date, all of which failed or, at least, were discontinued. The first attempt which survived was that of Carnegie,

Jan 1, 1911

By D. W. Mitchell

INE operators have a choice of several classi- fications of mechanical loaders. Within each classification there are many types and makes available. Table I lists loaders on which manufacturing data as to operating characteristics are available. This paper discusses the conditions met in a mine as they affect these characteristics. It is assumed that management will provide satisfactory engineering, supervision, power, maintenance, loader service within a concentration of workings, and a balanced working cycle served by balanced production equipment. These are factors which affect the optimum operational efficiency of a loader. The conditions which determine loader choice are: Height of Vein—The main limitation to the use of a loading machine is the height to which the vein is mined; i.e. a loader cannot be higher than the place in which it is to work unless rock is taken. Since there are several low vein loaders being developed and successfully applied, this does not appear to be a requisite of an efficient mining operation. The maximum useable height of a loader should be equal to the working seam thickness less a working clearance for travel and operation. A—Working seam thickness = B—Artificial roof support thickness = C—Safe headroom below support = (generally about 6 in.) D—Height of roadway = E—Total of B + C f D =_______________________ A—E = maximum loader height F—Distance from top of roadway to bottom of roof support = G—-Height of loader's coal or ore line (see Table I) = H—Difference between F and G = Size of largest broken particle + a safety factor of 2 to 3 in. H is a loadability factor and is important because the clearance over the top of the conveyor chain to the roof or roof support must be greater than the largest broken particle or else the particle and/or the conveyor chain may be broken. From this standpoint it might be desirable to use a lower height machine even though it may have a smaller capacity, though this is warranted only when increased lump realization offsets lower man-day and machine pro- duction rates. Ivan Given has stated, "Loading should not be handicapped by securing lump only to grind it in the breaker." Width of Working Place—The width of a working place is the greatest width a place may be safely driven. The working place includes not only the face but the roads the loader must tram when mucking out more than one face. The width is limited by the system of placing props with sufficient room between them for the machine runner (about 2 ft). Maximum width of place in which the loader will operate at maximum efficiency is determined by the type of mounting. With track-mounted loaders, maximum width of place is determined by maximum angular swing of the loading head and proximity of track to the face. The use of double track leads to added expense and operational complexities. Several mines that have used double-track systems have found that a substantial saving is made by the use of machines that load out wider places. Trackless loaders may work in rooms of any maximum width. Minimum width of place in which a loader will operate is determined by width of the loader plus a safe movement area for the operator. Often a barodynamic study of the mine will show that either an increase in room width and/or a change in the system of propping may be made by using roof bolting, full or part-width room timbers, removable aluminum I-beams at the face, etc. Increasing the width of a working place will, in general, increase loader operating efficiency by providing more material per fall and by decreasing the preparation and moving time per ton. A change in the system of propping that would increase the minimum width might permit the use of a higher capacity loader with safer working conditions. Proper face tirnbering is necessary to insure safety from roof falls and because the speed of preparation and loading generally increases since the men work with greater assurance and there is less chance of kicking out posts. Maximum Room Length—With the exception of the scraper and the duckbill, the limit to room

Jan 1, 1952

By Carlos Andrade

An engineering endeavor involves the creation of an expansive, environmentally conscious reinforced sloped MSE wall system. The objective is to enlarge a flat mining work area. Situated in southern Arizona, this mine is dedicated to extracting essential resources such as Manganese, zinc, silver, and lead, crucial for advancing clean and renewable energy initiatives. The project necessitates the implementation of a Mechanically Stabilized Earth retention system. This system aims to both expand the mine’s working area and facilitate access to underground tunnels. The expansion pad must be robust enough to endure the substantial loads exerted by heavy mining machinery. The wall’s reinforcement components are strategically designed to counteract the challenges posed by aggressive soil conditions with low resistivity. Furthermore, they must be resilient against potential damage during installation. The system’s ease of transportation is crucial due to challenging access conditions, and its design must allow for efficient drainage. A significant consideration is the integration of a face system that fosters vegetation growth and seamlessly merges with the existing flora of the area. In addition, plans include the construction of an access road downslope from the wall. The chosen solution involves a reinforced sloped system with a 70-degree incline. The wall’s surface is adorned with an erosion control mat, intended to promote the proliferation of vegetation. For added durability, the wire basket units are equipped with galvanized wire featuring a polymer coating. High tensile strip bonded geogrids, featuring a robust polyester core, provide essential reinforcement. The completed wall is an impressive feat, spanning 1500 feet in length and soaring to a height of 45 feet. It stands as a testament to innovative engineering in harmony with environmental and functional considerations.

Feb 1, 2024

By O. Mejia, J. Drozdiak

"This paper summarizes a comprehensive energy and cost study comparing an existing SAG mill based circuit at Huckleberry Mine with two proposed circuits involving comminution technologies which are associated with energy efficiency: high pressure grinding rolls (HPGR) and high speed stirred mills. The specific energy requirements expressed as kWh/t for the proposed circuits were determined from pilotscale HPGR and stirred mill testing conducted at the University of British Columbia. Samples and operating data were collected from Huckleberry’s copper-molybdenum concentrator to evaluate current mill performance for comparison. To support the base case, the SABC circuit was modeled using JK SimMet® software. The main comparison focused on the complete energy requirements for each circuit, including materials handling equipment such as conveyors, screens, feeders and pumps. This paper also provides capital and operating cost estimates for each of the comminution circuits. The results showed that the HPGR - ball mill circuit achieved a 21% reduction in energy consumption over the existing SAG - ball mill circuit at the same P80 grind size of 160 µm. At a grind of 80% passing 75 µm, the HPGR - stirred mill circuit showed a 34% reduction in energy compared to the base case. It was concluded that the energy reduction for the new flowsheets significantly improved the economics of the Huckleberry comminution duty.INTRODUCTIONUp until now, tumbling mills such as AG/SAG mills and ball mills have had a dominant bearing on the design and economics of comminution circuits. However, it is commonly agreed that the majority of employed comminution processes are energy intensive and energy inefficient, accounting for up to 80% of overall process plant energy consumption and having an efficiency of as low as 1% (Abouzeid and Fuerstenau, 2009; Fuerstenau and Abouzeid, 2002). The U.S. department of energy reported that there is a potential to reduce energy consumption in the metals industry by up to 61% from current practice to bestestimated practical minimum energy consumption; suggestions included the implementation of best practices and the adoption of energy efficient mining and mineral processing technologies such as advanced blasting techniques, high pressure grinding rolls (HPGR) and stirred mills (U.S. DOE, 2007)."

Jan 1, 2013

By SAHENDRA SINGH, SANJIT KUMAR PAL, DHARMITA HORO

The North Singhbhum Mobile Belt (NSMB) lies between two crustal-scale shear zones, the South Purulia Shear Zone (SPSZ) at the north, and the Singhbhum Shear Zone (SSZ) at the south. The Babaikundi-Birgaon Axis (BBA) is an east-west trending secondary shear zone in the NSMB lying south of SPSZ, which is known for the occurrence of gold along with other sulfide minerals within the quartz reefs. The present study has been carried out at north of Ichadih village, which lies on the BBA. The present study attempts combined electrical resistivity tomography (ERT) and self-potential methods along a profile of 470-m length in the Ichadih area to map the potential mineralized zones. Initially, ERT sections generated by Wenner, Wenner- Schlumberger, dipole-dipole, and joint inversion of the combined array have been analyzed, and results are validated through the analysis of model resolution. A prominent low resistivity (10–100 Ωm) associated with quartz reef/limonitic quartz reef at a depth of approximately 30–85 m, encircled by a high resistive (more than 10,000 Ωm) formation associated with metasedimentary rock, has been delineated using joint inversion of the combined array. Further, analysis of self-potential (SP) anomaly using particle swarm optimization inversion also confirms the prominent low SP anomaly at a depth of 77.3 m, which is analogous to the low resistivity anomaly identified in the joint inversion of the combined geo-electric array. Subsequent analysis of a complex synthetic geo-electrical model analogous to the present field situation proves the efficacy of the joint inversion of combined arrays. As a whole, joint inversion of multi-array data is established as an efficient technique for better subsurface imaging in case of the complex subsurface structure. In-depth analyses confirm the possibility of sulfide mineral-rich deposit (quartz reef/limonitic quartz reef) which requires further geological drilling and lithogeochemical sample analysis, for possible future exploration.

Oct 26, 2020

By E. W. Parker

PROBABLY everyone is well aware that from April 1 to September 11, 1922, anthracite production was completely suspended; during those 163 days not one ton of coal was produced in the anthracite region. The production loss was about 30 million tons, and although production is now at its peak, there is no possible way by. which, within any short space of time, that deficiency can be made up. During that time the miners sacrificed in wages something over 100 million dollars. The anthracite companies paid out in cash, keeping their mines in condition to operate when mining should be resumed, something like 30 million dollars without taking in one cent of revenue. The tonnage of domestic sizes included in that lost output was about 21 million tons. The anthracite operators figured that between September 11, 1922, and March 31, 1923, they would possibly be able to produce about 60 per cent. of the tonnage that was mined the preceding year, that is, from April 1, 1921, to March 31, 1922. The problem then arose as to how that tonnage could be distributed equitably throughout the United States and Canada. We had in our records in Phila-delphia the distribution by communities, about 20,000 of them, to which anthracite had been shipped during the last five years, so that we were well posted as to what each community should be entitled to receive. We allotted to each of those 20,000 communities 60 per cent. of the tonnage that it had received during the preceding coal year, and we have endeavored to see that whatever tonnage we have been able to produce should be equitably distributed on that basis. It was a matter simply of voluntary cooperation by the anthra-cite operators who placed the distribution of their tonnage practically in the hands of the Pennsylvania Fuel Commission; the anthracite companies have almost without exception acceded to every request that we have made of them. When communities were reported entirely out of coal, a telegram or letter to the directors obligated to that community has resulted in some anthracite being shipped there, so that we have thus far kept the distribution on a fairly equitable basis. Prior to the suspension of mining operations, pre-liminary negotiations were carried on for the renewal of the wage scale, the operators thinking that it could be adjusted satisfactorily, and that the same method of procedure would be followed as during the 20 years succeeding the strike of 1902. At every termination of the wage agreement since that date, until last year, an agreement had been reached early in the season that mining operations should be continued, with the under-standing that any new agreement should be retroactive to April 1. At the meeting of the committees of anthra-cite operators and miners, on March 21, 1922, the opera-tors were presented with an ultimatum by the miners to the effect that unless an agreement were reached within ten days, mining operations would cease. That was protested against by the committee of operators as being unfair, not only to the operators and the public but to the men themselves. In spite of this protest the suspension occurred and, as you know, continued until September 11.

Jan 4, 1923

By Donald MacFadgen

Since 1950, a total of 164 miles of levels and rooms have been roof-bolted in the collieries of the Dominion Coal Company. Roof bolting is an efficient and economic method of sup-port where heavy timber sets or steel booms are necessary for temporary roof support, or where conventional methods of support interfere with the passage of mechanical mining equipment. This paper discusses present roof bolting practices and special bolting applications. THE practice of roof bolting in be collieries of the Dominion Coal Company dates from 1950, when preliminary studies and experiments were carried out in a mechanized room and pillar section of Dominion No. 20 Colliery. These studies were made in close liaison with members of the United States Bureau of Mines who were conducting similar studies. Following the successful application of roof bolting in No. 20 Colliery, this method of roof support was introduced into other collieries

Jan 1, 1963

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970