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By R. Adsero

"A high altitude review of the state of the mining industry provided by a study of multifactor productivity shows a continuation of lower output year on year for the capital and labor inputs applied. The story is sadly similar for both U.S. mining and the Australian mining sector. In fact, according to PwC analysts, the world’s mining equipment productivity has declined 20 percent during the past seven years (Lumley, 2014). Although the reasons for the continuing decline in mining productivity are varied, the need for improvement is clear.The world’s mining industry fleet of more than 400 large draglines moves billions of tons of overburden and ore (phosphate, limestone, etc.) annually. This discussion will review a few of the tools available for improved productivity in dragline operations.Benchmarking equipment performance exposes the possibilitiesIn the September 2013 Mining Engineering cover story Graham Lumley and R. Adsero suggested that analyzing best practice equipment performance from an industrywide database for specific equipment performance improvement goals would be beneficial (Adsero, 2013). Benchmarking equipment performance by normalizing differences and then comparing specific measures of performance will provide a road map to improvement for those following the leaders. For those already performing at best practice levels, a benchmark confirms and bolsters what has already been achieved. As described in the SME February 2014 paper by this author, best practice is the average of the top 10 percent in annual output. Filling performance gaps identified by a comparison to best practice by investigating the details of the why and taking action to change, makes all the difference. This is true for all major mining equipment. Given the large gap between average performance and best practice performance most mining operations can benefit. Best practice performance provides a view of what is possible to the 90 percent majority of mining operations that are performing below the top 10 percent.For dragline mining operations, identifying specific characteristics and practices of leading dragline performance will provide a reference for comparison."

Nov 1, 2016

By S. J. Broderick

[The term "nonmetallic minerals? as commonly used is the mining industry, refers to those minerals of industrial importance that are mined essentially for uses other than for the metals contained. The field comprises several hundred rod minerals of industrial importance, of which 70 have can adequately described in the textbook Industrial Minerals and Rocks. A few o f the more important nonmetallic products are sand and gravel, salt, phosphates, clays, refractories, limestone, and cement materials. Some of the minerals, such as bauxite and pyrolusive, have both metallic and nonmetallic applications, but in this report only the nonmetallic mineral phases are considered. In the organic field of nonmetallics only coal is considered, as, the others - petroleum, natural gas, natural bitumens, and hydrocarbons - are of no importance in water softening.]

Jan 1, 1941

By D. Majuste

This paper describes an experimental approach to evaluate the effect of organic impurities or even additives on metal electrowinning and product quality. In addition to electrowinning tests and electrochemical measurements, the approach includes organic analysis by Fourier Transform Infrared spectroscopy and gas chromatography; video monitoring of the reaction interface; and product characterization by using scanning electron microscopy, crystallographic texture and bending tests. The mechanical behavior of metal cathodes was assessed with a customized bending device that is able to bend the cathodes up to angles similar to that of the stripping machine. In this work, the effect of a potential organic impurity, lubricating oil, on the production of electrolytic zinc is taken as a case study. The findings of the investigation allowed a better understanding on the role of this organic on energy consumption and product quality and a qualitative prediction for the behavior of Zn cathodes during the stripping operation. Simple control and optimization procedures resulted in significant energy savings.

By Wenjun Ju, Xiaodong Sun, Jianwei Zheng, Bingding Yi, Zhaorui Ma, Pengfei Jiang, Lingfu Zhu, Yangfa Zheng

The presence of hard roof poses a significant threat to the safety of underground coal mining. In this study, a mechanical model is established for underground stopes to analyze the overburden structure with the advancing of the mining face. It is indicated that the load-bearing arch structure (LBAS) is formed above the stope for roofs with regular hardness, whereas the reversed-basin bearing structure (RBBS) is formed for hard roofs. Compared with the LBAS, the RBBS can induce an additional pressure at the foot of the bearing structure, and this effect becomes less as the distance between the hard roof and stope increases. The ultra-deep borehole hydro-fracturing technique (UHT) is proposed to weaken the hard roof for pressure release, and the associated equipment and procedures are also presented. The UHT is based on horizontal drilling along the axial direction of the roadway in the roof, and then the receding segmented hydraulic fracturing technique is used to achieve the purpose of fracturing (weakening) of the surrounding rocks. Field tests are carried out in 3022 roadway of Daliangwan coal mine in Yulin to assess the developed technique, equipment, and fracturing procedures. To evaluate the fracturing effect, deep borehole stress-meters are installed at different depths of the fractured and un-fractured zones of the roadway, along with hydraulic support pressure sensors placed at the mining face. The results show that compared with the un-fractured zone, the pressure on the wall and pillar sides is lower than that in the fractured zone, and the associated weighting duration and weighting area ratio of the fractured are reduced by 53.23% and 33.59%, respectively. This indicates that the presented UHT can provide a new solution for the prevention and control of mining disasters induced by hard roof failures in underground coal mining.

Nov 2, 2020

By Louis A. Panek

Tests of mine-roof models in a centrifuge show that the suspension effect due to bolting a horizontally bedded mine roof with frictionless surfaces of contact between beds depends principally on the number of bolted beds and their relative flexural rigidities, provided that sufficient bolt tension is exerted to prevent strata separations at the bolt locations. Strata separations tend to occur in the unbolted roof mainly because the beds have unequal thicknesses. "Suspension effect" refers to the transfer of part of the weight of weaker or thinner beds to the flexurally more rigid beds by roof bolts or by any other means. The factors investigated were number of beds in the bolted unit, bed thickness, modulus of elasticity of beds, length of bolts, spacing of bolts across and along the opening, bolt load, and intensity of roof load. The general principles of behavior of the bolted roof beds are explained by an approximate theory. Model test data are used to validate the theory and to obtain an expression for the "suspension efficiency". As the suspension effect actually observed in the models is smaller than that predicted by the approximate theory, the suspension efficiency in general is less than unity. Mathematical expressions are obtained for (1) the change in roof bending stress due to the suspension effect, which is needed for design of a roof-bolting system, (2) the change of roof deflection due to the suspension effect, which may be useful for evaluating the effectiveness of a roof-bolting system, and (3) the bolt load or pre-load that is required to achieve the desired reinforcing effect.

Jan 1, 1962

By Evandro Tolentino

As fibras vêm sendo empregadas nos materiais de construção civil desde o início da humanidade. No começo da década de 50 houve o início da utilização de fibras de aço no reforço de matrizes de cimento. Com isso foram notadas alterações no comportamento do material, sendo detectado o aumento da tenacidade pós-fissuração. Esta é uma pesquisa experimental que teve como objetivo a definição de parâmetros de ensaios para a produção de argamassas de cimento Portland, que utilizem fibras de sisal nas suas composições, tratadas quimicamente por acetilização com intuito de reduzir a absorção de água. O sisal (Agave Sisalana) apresenta boas propriedades físicas e mecânicas. As fibras foram cortadas manualmente nos comprimentos de 20 mm. As diferentes composições de argamassas foram produzidas com 0,2% e 0,4% de fibra de sisal, em relação ao volume total da argamassa. Estudou-se o comportamento mecânico dos compósitos com ensaios de resistência à tração na flexão. Os resultados mostraram uma melhoria na resistência à tração na flexão para argamassas com fibras tratadas quimicamente por acetilização.

Oct 30, 2017

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By Alberto Pool

El azufre es un elemento no metálico que proviene de yacimientos que lo contienen al estado nativo. En ese sentido, el presente texto revisa los diferentes yacimientos nacionales de azufre, tipos y composiciones. Dichos yacimientos se dividen en volcánicos (tipo solfatárico) y sedimentarios (tipo yeso). Los primeros se encuentran asociados a cráteres, laderas y fumarolas de volcanes, y los segundos, se encuentran asociados a yeso, caliza y calcita, sin conexión con procesos volcánicos.

Jan 1, 1977

By Elmer Ccahuana, Filiberto Mamani

La determinación del tajo óptimo involucra varios aspectos como la metalurgia, costos operativos, precios de metales, etc. para dimensionar la geometría del tajo. No obstante, la metodología tradicional no incluye el blending3 como parámetro de optimización del tajo a pesar de que existen muchas minas a tajo abierto, en especial auríferas, que emplean la mezcla de materiales para el procesamiento de los mismos. Pysight4 es un algoritmo que permite determinar el tajo óptimo por aproximación a través de generación de tajos para los escenarios en base a la combinación de las leyes de corte por materiales.

Sep 29, 2023

By S. M. Woodring

Research objectives included 1) determine relationships if any between spectral response of soil and soil textural groups, Unified Soil Classification subgroups and selected landforms and 2) develop computer assisted techniques for engineering soils mapping of remotely sensed data. The sire in northeastern Kansas, 1.6 Km by 43 Km (1.0 mi by 27 mi), contained glacial and alluvial soils. Multispectral scanner data (0.40 to 1.80 pm) collected at 915 meters altitude (3,000 feet) were analyzed using two distinct computer techniques: the nonsupervised approach involving delineation of soil training areas directly by computer and the supervised approach entailing training area selection manually by the researcher. Computer classification of surface materials follows both methods. Non supervised analysis results failed to show a consistant relation- ship between landform type and soil spectral class. Landforms correlating well displayed either unusually bright or unusually dark spectral signatures. Supervised analysis results showed a strong relationship between soil texture and soil spectral class. A moderately strong tie was shown between engineering soils groups (ML, CL, CH and OH) and their respective spectral classes, and a weak association between landform type and soil spectral class. An analysis procedure for engineering soils mapping by computer of remotely sensed data was developed. 1. Locate cultural features by visual examination of imagery. 2. Produce generalized bare soil-vegetation- water map using nonsupervised technique. 3. Outline significant soil fields for computer training using supervised approach. 4. Computer-classify entire area based on these soil fields.

Jan 1, 1974

By Jose Carlos D'Abreu, Edelink Efrain Tinoco Falero, Mauricio Marcos Otaviano

The production and consumption of Direct Reduced Iron (DRI) are continuously increasing, as a consequence of the impact of shale gas extraction technology on the Natural Gas (NG) market. Considering this context, DRI may improve the Blast Furnace (BF), Electric arc Furnace (EAF) and LD converter ’s productivities and consequently their competitiveness. In this work the results of a cooperative research conducted by PUC-Rio University and a Brazilian mining company are presented. Laboratory-scale simulation tests, using DR commercial pellets and typical industrial operational parameters of a benchmarked DR shaft furnace, were conducted and planned using statistical and factorial analysis. In the simulated experiments, the following three regions of the DR shaft furnace were considered: Reduction Zone (RZ), Transition Zone (TZ) and Cooling Zone (CZ). Three stages were considered in the research development: (i) the reactions and equations concerning pellet metallization and Carbon precipitation were analyzed; (ii) experiments focused on the de finition of the carburization kinetic equations occurring in the Transition and Cooling zones, and finally, (iii) aimed to develop the “METCARB” model, a computational program conceived to simulate mathe- matically the metallization and carbonization reactions along the height of the furnace. In conclusion, a comparison is made with industrial results in order to validate the resulting “METCARB” model.

Mar 1, 2018

By P Collier

From 1972 until 1989 when operations were suspended Bougainville Copper Limited (BCL, owned 53.58 per cent by Rio Tinto Limited) operated a large open pit mine and processing facility at Panguna on Bougainville Island, Papua New Guinea producing copper concentrate containing significant quantities of gold and silver.BCL has a stated vision of recommencing operations at Panguna. In 2008, Rio Tinto, on behalf of BCL, conducted a multi-disciplinary study to assess the technical and financial viability of redeveloping the Panguna operation. One of the key outputs of the study was a Joint Ore Reserves Committee (JORC) Code compliant mineral resource statement based on the existing block model and fundamental data, archived since mine closure. Historical data (including the resource block model and drill hole data) was recovered from computer archives by a former Panguna mine employee familiar with the various obsolete data formats, thus maintaining an unbroken chain of custody of the data by Rio Tinto since operations were suspended. No additional data were collected as part of this study.The extensive data and documentation archive facilitated a sufficiently detailed evaluation of the fundamental data and model to support an updated resource statement. Table 1 of the JORC Code was used to guide the model validation process.Reconciliation of blasthole and metallurgical plant data with the reserve model, indicated that the copper and gold drill hole composite database was significantly biased towards underestimation in several key domains due to a combination of the following: mineralisation loss during core loss, core loss (minor), vertical drill holes failing to intersect sufficient subvertical mineralised fractures and veins, drill hole spacing too wide, and variable diamond drill hole core size. The resource model evaluation was based on three material types (all previously mined at Panguna), that were defined based on cut-off grade and rock type parameters: direct feed ore – material for delivery directly to the plant, preconcentration and screening ore – subeconomic material beneficiated to produce fines of economic grade, and waste. Three pit shells and designs were generated based on three separate sets of economic parameters. These economic parameters were also used to assign material types to the block model. The three resulting models were then evaluated against the corresponding pit shells.Classification of the resource was approached conservatively due to the inherent bias in the drill hole data. Consequently only Indicated and Inferred resources were tabulated.The study highlighted the importance of maintaining detailed documentation pertaining to resource estimates and operational history, particularly reconciliation, and the value that can be added by a simple, low-cost data compilation exercise.

Aug 22, 2011

By R. Rocca, M. B. Bever

THE adiabatic elastic deformation of a body is accompanied by a change in temperature. This phenomenon is known as the thermoelastic effect. Under adiabatic conditions the temperature of a metal bar is decreased by an elastic elongation and is increased by an elastic compression. All materials which elongate on heating behave in this manner. The sign of the thermoelastic temperature change is reversed for the few materials which have a negative coefficient of thermal expansion. The following equation for the thermoelastic effect can be derived from fundamental thermody-namic theorems, as shown in the Appendix: dT8 =-a1/cs T dss [1] Cs In this equation, T is the absolute temperature, S is the entropy, a, is the coefficient of linear thermal expansion, cs' is the heat capacity per unit volume at constant stress and s is the stress (positive in tension). Eq 1 can be applied to small, but finite changes in stress in the following form: ?Ts =- a1/cs T?ss [2] The sign of the temperature change AT is opposite to that of the change in stress s for materials which have a positive coefficient of thermal expansion. Eq 2 has been verified for many different materials and stresses at room temperature. No previous publication appears to have been devoted to an in- vestigation of the thermoelastic effect over a range of temperatures. Review of Literature Lord Kelvin (W. Thomson) presented a general theory of the thermoelastic effect in 1851' and later applied it to a solid, subject to an arbitrary system of stresses'. His analysis was based on a cycle of isothermal and constant-strain transformations and led to Eq 2 above. Even today, one of the clearest expositions of the thermoelastic effect is found in Lord Kelvin's article on elasticity in the Ninth Edition of the Encyclopedia Britannica (1878). R. ROCCA, Junior Member, and M. B. BEVER, Member AIME, are Research Assistant in Metallurgy and Associate Professor of Metallurgy, respectiuely, Massachusetts Institute of Technology, Cambridge, Mass. AIME New York Meeting, Feb. 1950. TP 2760 E. Discussion (2 copies) may be sent to Transactions AIME before APT. 1, 1950, and is scheduled for publication Nov. 1950. Manuscript received Oct. 15, 1949.

Jan 1, 1951

By George W. Bain

Methods of mining building stone of any sort are planned to produce as few fractures as possible, and present a strong contrast to methods of mining metallic ores, which must be crushed eventually and have fractures produced in as great profusion as possible. Shocks transmitted to a stone invariably make it more porous and more permeable and reduce its effective life, therefore methods of mining building stone involve as This building illustrates the fine detail of workmanship, unprotected sharp corners and thin edges, and tall narrow columns characteristic of marble structures. These features require exceedingly coherent stone, and preservation of these features for decades or centuries demands many special quarrying precautions to keep absorption to 0.14 per cent or less, a detail not essential to stone for coarser architectural types. few shocks as possible. This is singularly true for marble because marble structures are intended to have long life, greater delicacy of line, more gracefulness and fineness of sculpture than those made from any other structural material (Fig. 1). So that delicate lines may remain in almost perfect preservation for decades, or even centuries, it is important

Jan 1, 1938

By George W. Bain

Methods of mining building stone of any sort are planned to produce as few fractures as possible, and present a strong contrast to methods of mining metallic ores, which must be crushed eventually and have fractures produced in as great profusion as possible. Shocks transmitted to a stone invariably make it more porous and more permeable and reduce its effective life, therefore methods of mining building stone involve as This building illustrates the fine detail of workmanship, unprotected sharp corners and thin edges, and tall narrow columns characteristic of marble structures. These features require exceedingly coherent stone, and preservation of these features for decades or centuries demands many special quarrying precautions to keep absorption to 0.14 per cent or less, a detail not essential to stone for coarser architectural types. few shocks as possible. This is singularly true for marble because marble structures are intended to have long life, greater delicacy of line, more gracefulness and fineness of sculpture than those made from any other structural material (Fig. 1). So that delicate lines may remain in almost perfect preservation for decades, or even centuries, it is important

Jan 1, 1938

By M. Mohammadi Zahrani

The morphological modification of primary and eutectic Mg2Si phases by bismuth (Bi) addition in Mg-5wt.% Si in-situ composite was investigated. It was found that with addition of 0.5wt.% Bi, the morphology of primary Mg2Si precipitates was altered from coarse dendritic to polygonal shape, and their mean size was significantly decreased from more than 20 µm to about 8 µm. Moreover, the rod-like eutectic Mg2Si in Bi modified Mg-Si alloy solidified much finer than that of the base alloy. Such improved microstructure of the modified alloy resulted in 10% tensile strength and 20% elongation improvement. The isotropic growth manner of primary Mg2Si particles in modified alloy was attributed to the poisoning of growth in preferred directions by dissolving Bi atoms in Mg2Si lattice. The reduction in size of eutectic Mg2Si was found to be the result of Mg3Bi2 compound formation around eutectic Mg2Si rods.

Oct 1, 2011

By O. Norman Lotter

The formulation and use of mixed collector suites in sulphide flotation can be traced back as far as 1957 with the work of Glembottskii and his co-workers in Moscow. The subject was reviewed by Lotter and Bradshaw in 2010, and proposed a synergy between ideally-selected different reagent types to deliver improved performance, in particular the in situ catalysis of a xanthate to dixanthogen by a dithiocarbamate. Correctly formulated for a particular application, an optimally arranged mixed collector suite delivers the following improvements to the flotation process: • An increase in the flotation kinetics • Improvement in coarse, or middling, particle recovery • Reduction in total dosage requirement • Best results are found from testing the ratios of the collectors. This is of critical importance. In all an optimally formulated mixed collector system usually delivers an increase in paymetals recovery of 1–4% absolute, with a gain in concentrate grade in the range 10–20% relative. In recent years, the addition of semi-conductor theory and associated electrochemistry has contributed significantly to this toolbox by way of identifying optimum domains of Eh and pH for the flotation of individual minerals. In the case of mixtures of minerals, this is where the mixed collector system delivers significant value by way of presenting a mixed set of collector radicals and dimers in a common Eh and pH domain for overall performance. This calls on a fundamental understanding of organic chemistry, mineralogy, semiconductor theory, and electrochemistry. Whereas the selection of grinding media type effectively influences the Eh, the pH can be easily controlled by pH modifiers. The theory of this system, and some industrial case studies, are discussed.

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By George W. Heunisch

The properties of Neutra-Fix® and Neutra-Ment® , two new lime substitutes for the treatment of acid mine drainage (Arm), have been compared with lime and Alkament®, two products presently in use for AMD treatment. The two new products are basically dolomitic byproducts and produce sludges that are more compact than those from lime. Sludge settling rates are faster than lime with iron concentrations after 24 hours that comply with EPA regulations. Material utilization and optimum pit are reported.

Jan 1, 1984

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969