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By SANDEEP KUMAR JENA

This review work reports the recovery of potassiumfromdifferent rocks and mineral sources. The global demand for potassiumis rising consistently due to the growth of agricultural production. A major portion of the world potassium production is consumed in making of fertiliser; however, other uses include those in pharmaceutical, glass, ceramic, food and detergent industries. The availability of soluble potash minerals (sylvite, kainite and carnallite) in different countries like Canada, USA, Israel and Russia makes them as major potash producers, whereas agricultural-based countries like Liberia, Somalia, Central African Republic, Thailand, Indonesia and Malaysia including India meet their potassium requirement through import only. On the contrary, the availability of huge potassium-bearing rocks/minerals (like nepheline syenite, feldspar, mica, glauconitic sandstone) in these countries containing around 4–17% K2O would be a prospective for commercial production of potassium. The potassium recovery from minerals/rocks is very complicated due to the uniform distribution of potassium throughout the crystal structure. Different physico-chemical separation methods like bioleaching, chemical leaching, flotation and roast leaching have been discussed for the successful recovery of potash values from these rocks/minerals. However, the recovery of potassium from hugely available seawater using the chemical precipitation, solvent extraction,membrane separation and ionic exchangemethods is not cost-effective due to the low concentration of potassium.

Aug 31, 2020

By L. Shevenell, L. Stillings

The Acid Drainage Technology Initiative-Metal Mining Sector (ADTI-MMS) has established a Pit Lake Committee to enhance the science and understanding for the long-term management of pit lakes. Participation in this new committee is from members of federal and state agencies, industry, and academia, including numerous individuals representing 10 states. Work has begun on a pit lake literature search and review, database, classification, and sampling and monitoring procedures document. Coordination with the International Network for Acid Prevention (INAP) has been established. Future work will include preparing a prediction and assumption verification document, a report identifying variables upon which water quality is dependent, and an applied remediation technologies document, including an evaluation of the effects of backfilling.

Jan 1, 2002

By Robert F. Mehl

THE mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystalline symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by slip along atomic planes.1 This slip may be inhibited in a number of ways: by the interatomic forces of cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by lattice distortion caused by solid solution formation or by mechanical strain; by the intercrystalline boundaries where slip is restrained, probably by the non-registration of the atom planes in adjacent crystallites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.3 In pure metals, and perhaps also in solid solutions, the atom planes of easiest slip are those exhibiting the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be predicted from the analysis of the lattices. Concerning the interatomic forces, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bottone,5 correlate the hardness of the pure metals with the atomic volume,

Jan 1, 1928

By Will H. Coghill, F. D. DeVaney

"Many of the iron ore deposits on the western end of the Mesabi Range Minnesota consist of the so-called ''wash ores."" Because of their high silica content these ores must be washed or concentrated to make them merchantable. Washing plants have been in operation for 20 years, during this period large quantities of tailings have accumulated in tailings ponds. These tailings contain the aggregate millions of tons of iron oxides which, if recovered, would greatly to the available tonnages and to the revenues of the mining companies. It the purpose of this paper to outline give results of concentration tests on tailings.In order that the reader may understand more clearly the type of material under consideration, a short description of the characteristics of the wash ores of the Western Mesabi Range and a brief resume a washing methods that have been are now being employed will be given. Appleby and Newton4 In their description of the district and of the ores say:The Western Mesabi district embraces the territory west of the town of Nashwauk in Itasca County. The territory to the east of this dividing line is known as the Central and Eastern Mesabi district. This subdivision is rot wholly arbitrary. While the ore bodies in the two districts resemble each other in. shape, size, and general structure, there is a marked and very important difference in the character of the respective ores. For purposes of comparison, the western deposits have been called washable ore bodies, and the central and eastern, standard ore bodies. The latter ores are the result of natural concentration processes which have teen carried far enough to produce a large proportion of high-grade ore Wet can be marketed direct; the Western Mesabi ores present a lesser degree of natural concentration and are as a rule of too low grade to admit of marketing without preliminary treatment. In many cases the grade can be improved by washing, hence the material is called washable ore. Exceptions to thin general rule may be noted in both districts. Many of the Western Mesabi ore bodies contain quite a proportion of merchantable ore. There are also portions of central and eastern Mesabi ore deposits which are of low grade and which can be improved by washing."

Nov 1, 1930

By A. C. Fieldner, S. H. Katz

"Introduction.Recent experiments (Fieldner, A.C., Katz, S.H., Kinney, S.P., and Longfellow, E.S., Poisonous gas from carbon tetrachloride fire extinguishers, Jour. Franklin Institute, October, 1920, pp. 543-565), by the Bureau of Mines have shown that carbon tetrachloride extinguisher liquids when applied to fires produce small quantities of irritating and poisonous gases which may be dangerous in very closely confined spaces where conditions are such that the user can not escape without breathing the fumes. The results of the experiments have been confirmed in an independent investigation by the Underwriters Laboratories (Nuckalls, A.H., Corrosive action and products formed when carbon tetrachloride extinguisher liquids are applied to fires, Nat. Fire Protection Assoc. Quarterly, vol. 14, January, 1921, pp. 221-236) who conducted similar experiments for the purpose of determining the corrosive action of these fumes on metals. Both investigations showed that carbon tetrachloride vapor, hydrochloric acid gas, and phosgene were produced in addition to the ordinary products of combustion, such as smoke, carbon monoxide and carbon dioxide. The Bureau of Mines' tests were made by applying a one-quart extinguisher to a wood fire of excelsior in a gas-tight room of 1000 cubic foot capacity. The glass and metal construction of this chamber limited the experimental fire to very small dimensions. It was, therefore, deemed desirable to make a test on a larger scale in the entry of the Bureau's experimental mine in order to similate more nearly the practical use of carbon tetrachloride and other types of extinguishers in mines.Description of extinguishers.Two series of tests were made under identical conditions on different days. Commercial carbon tetrachloride extinguishers were used in the first series of tests and ""foamite firefoam"" extinguishers in the second series of tests."

Jun 1, 1921

In terms of throughput, product size and power draw, grindcurves provide a measure of the response of the mill performance to changes in mill operating parameters ? usually mill filling. Since presenting the principle in 2006, grindcurves have been applied to a wide variety of AG and SAG mills. Mill response has been carefully measured for variations in: mill fillings from 15% to 40%; throughput by a factor of two; power by 50%; feed blends; liner profile; and mill speed from 65% to 80%. The outcomes of this extensive program of work are presented as the measured grindcurves. How they have enhanced our understanding of mill operation and how they may be applied to practical daily mill control is discussed. It is proposed that this technique provides a viable and valuable mill control tool that may find extensive application in the industry.

Jan 1, 2012

At a large meeting of the members of the American Fund for French Wounded it which Mr. Franklin D. Roosevelt presided and at which Mrs. B. Girault Lathrop, President of the Paris Administration A. F.F. W., gave a most interesting address, special rows of seats were reserved for the members of the W. A. A. I. M. E. Those who were unable to be present will be glad to hear that Mrs. Lathrop complimented our organization on having supplied the largest dispensary operated by the A. F. F. W. and the Red Cross in northern France. The A. F. F. W. is going to erect an American Memorial Hospital at Rheims and it is hoped that the one hundred beds in the hospital will be endowed in memory of the men who gave their lives for the liberty of the world. It will be possible not only to endow beds, for which sums of $6000 each are needed, but also to give, as. memorials, sun- parlors at a cost of $10,000 each, two roof gardens at $5000 each, a laundry at $10,000 and a garage at $10,000. The New York Section has undertaken to endow a heel in memory of members of the A. I. M. E. who gave their lives in the Great War. Perhaps other Sections or groups of Sections may wish to do the same thing, or if no other Section cares to assume so much responsibility possibly individuals may like to join the fund already growing in New York, in which case they should send their contributions to Mrs. W. Y. Westervelt, 1 Lexington Ave., New York, N. Y.

Jan 6, 1919

By Lindsay D. Norman

Computer models for simulating the construction and for calculating the properties of particulate solids in two- and three-dimensional systems (coverings of circles and packings of spheres, respectively) were developed. By simulating the physical process of constructing circle coverings and sphere packings, in which the circles or spheres were randomly selected from many different distributions of sizes, physically realizable loose random assemblies were simulated whose physical and geometrical properties were predictable with the computer. Many of these properties, such as the number of contacts, are extremely-difficult to measure accurately, or considerable ingenuity is required in their determination. All of these properties were easily and accurately calculated by the computer models for many different coverings and packings constructed from equal, discrete, uniform, and log-normal distributions of particles. In addition to the loose random assemblies, dense random covering and packing constructions were simulated whose properties are ideal upper limits for those of the loose random coverings and packings. The properties of the dense random coverings and packings, heretofore only obtainable by theoretical analysis, were also simply obtained. The statistical geometry of loose random coverings and packings was studied, and several new interpretations of the area-covering or space-filling requirements in these systems were made. In two dimensions, it was found that the properties of all loose random coverings are predictable by taking suitably weighted averages of the corresponding properties of just four kinds of polygons whose edges are defined by connecting the centers of mutually tangent circles in the covering. The distributions of these polygons that permit area-covering were determined, and empirical equations for predicting the density, average coordination number, and average pore area in loose and dense random coverings were formulated. The properties of loose packings were determined by performing a simplicial division of the computer-simulated assemblies to produce a unique set of minimum volume, space-filling tetrahedra whose edges connected the sphere centers in each packing. A simple empirical equation was formulated that permits the calculation of the average number of contacts in any sphere packing, random or regular. Some of the statistical geometrical properties of the simplicial tetrahedra in the computer-simulated packings were analyzed. The tetrahedron edge length distributions in all the loose random packings were nearly identical when the edges were presented in terms of sphere diameters, regardless of the sphere population in the packing. Moreover, the gap lengths in the loose packings were to an excellent approximation representable by a uniform distribution of sizes. The distributions of spheres in tetrahedra resulting from the simplicial division of the loose random packings also existed in the tetrahedra in dense random packings. These observations were employed in developing a unique method for predicting the geometrical properties of loose random packings without simulating the assembled packing. Instead, the space-filling simplicial graph could be predicted for any given density of packing of any sphere population. The cumulative packing properties of these tetrahedra were shown to be nearly identical to those calculated by all loose random packing simulations attempted in this investigation. The simplicial tetrahedra completely describe a packing and can therefore be used to predict all properties of interest.

Jan 1, 1971

By W. Spencer Hutchinson

THE relative importance of mineral production in British South Africa is about as follows: Gold, $200,000,000; diamonds, $40,000,000; coal, $18,-000,000; asbestos; $3,000,000; chrome ore, $2,000,000. In 1926 the gold mines paid $42,000,000 in dividends, the diamond mines $13,000,000, coal nearly $3,000,000, others less than $500,000. The recorded history of South Africa starts with the visits of the Dutch and the English in the sixteenth century, followed by the settlement of Cape Colony by the Dutch East India Company in 1651: The English acquired Capetown in 1806 and conflicts between English and Boers were a part of the history, from that, time on. Transvaal was settled in 1835, following the Great Boer Trek. The mining of diamonds became im-portant in 1870; the production of gold from the Rand in 1890;' the export of chrome ore in 1910; and the dis-covery of platinum in 1925. South Africa has a race problem, resulting not alone from the disparity of numbers between whites and natives, more than seven blacks to each white, twenty to one in Southern Rhodesia, and three. hundred to one in Northern Rhodesia; but because of the division of the white race between English and Cape Dutch or Afrikaans. The natives are also of many tribes.

Jan 6, 1927

By P. A. Riveros

This paper describes the leaching of the common copper minerals tennantite (Cu12As4S13), tetrahedrite (Cu12Sb4S13) and enargite (Cu3AsS4) in acidic media using Fe(SO4)1.5, FeC13 or 02 as oxidizing agents. At temperatures <100°C, tennantite dissolves slowly in Fe(SO4)1.5-H2SO4 media, and the rate is directly proportional to the area of the sized tennantite. The rate increases sharply with increasing temperature and the apparent activation energy is 69 kJ/mol. Increasing Fe(SO4)1.5 concentrations slightly increase the tennantite leaching rate. The kinetics of dissolution of disks of synthetic iron-bearing tetrahedrite in Fe(SO4)1.5-H2SO4 media are linear; the leaching rates are slow but increase significantly with increasing temperature, with an apparent activation energy of 120 kJ/mol. The dissolution of sized particles of natural Ag-bearing tetrahedrite in FeC13- HC1 solutions proceeds according to the shrinking core model, and both Cu and Ag dissolve at about the same rate, provided that the total chloride concentration of the solution is sufficiently high to solubilize the AgC1 reaction product. The leaching rates are slow, and the apparent activation energy is 116 kJ/mol. The addition of sulphate ions to the FeC13-HC1 system reduces the tetrahedrite leaching rate to values similar to those realized in the Fe(SO4)1.5-H2SO4 system. At <100°C, enargite dissolves slowly in either Fe(SO4)1.5 or FeC13 media, and the dissolution rate obeys the shrinking core model. The rate increases with increasing temperature and the apparent activation energies are 50-64 kJ/mol. The rate increases slightly with increasing FeC13 concentrations in 0.3 M HC1 media. The leaching of enargite at elevated temperatures and pressures was also investigated. Potentially useful leaching rates are achieved above 170°C, at which temperature sulphate, rather than sulphur, is produced. Lower temperatures (130-160°C) lead to fast initial leaching rates, but the dissolution of the enargite is incomplete because of the coating of the enargite particles by elemental sulphur.

Jan 1, 2007

By Eden Santos Silva

Usando os testes de torção a quente isotérmico contínuo e relaxação de tensão determinou-se as curvas de escoamento plástico e de relaxação de tensão, juntamente com a evolução mecânica e microestrutural do aço inoxidável austenítico ISO 5832-9 segundo as condições de deformação expressa pelo parâmetro de Zener-Hollomon (Z). Equações constitutivas foram usadas para avaliar e prever o amaciamento dinâmico. Verificou-se que os níveis de tensões são elevados com alto valor de energia de ativação aparente e descolamento da deformação crítica e de pico para as condições de alto Z. A tensão crítica encontra-se muito próxima do pico de tensão produzindo um retardo no início da recristalização dinâmica. Além do pico vê-se que o estado estacionário de tensões é alcançado para grandes deformações evidenciando um atraso no amaciamento dinâmico. Este comportamento é consequência da moderada valor de energia de falha de empilhamento (EFE), átomos de soluto em solução sólida (Nb, N, Mo) e presença de partículas de precipitados da fase Z (NbCrN) reduzindo a mobilidade das discordâncias e contornos de grãos retardando a cinética de recristalização.

Aug 16, 2017

By H. B. Hill

The Salt Flat field, formerly called the Joe Bruner field, is located northeast of the town of Luling in Caldwell County, Tex. This field, which is a fault structure, approximately parallels and is about 5 miles east of the Old Luling field. The proved area is approximately 1,280 acres, on which 332 producing wells (September, 1930) have been drilled. The majority of the wells are producing from the Edwards limestone at an average total depth of 2,700 feet. A few wells are producing from the Austin chalk or from other formations above the Edwards limestone. The Wilcox formation is exposed, and the fault trace in places is scarcely evident. The strike of the structure is approximately N. 20 to 45° The displacement of the fault is probably 200 to 500 feet. The discovery well was completed in the Austin chalk by the Lutex Oil Co. during April, 1928. In October, 1926, the Sun Oil Co. completed the discovery well in the Edwards pay. This well was an important discovery, as it indicated the potential oil possibilities of the Edwards limestone in echelon fault structures. The discovery led to the development of the third fault field in the Edwards limestone and opened up a large area for future prospecting.

Jan 1, 1931

By Animesh Jha, Catherine Davey

"Carbothermic reduction and nitridation reactions using synthetic kaolinite mineral were investigated for the formation of silicon based nitrogen ceramics. The temperature dependence of the reaction rate and its effect on phases formed are reported. The effect of the reactivity of carbon on the kinetics of formation of AIN and ShN4 is discussed. Using the standard Gibbs free energy values for the formation of nitrides and oxides of aluminium and silicon, a log po2 verses I/T diagram is constructed. The experimental data results are discussed and compared with the predicted phase equilibria. We also report the influence of sub-oxide gaseous species on the microstructure of the ceramic phases produced.IntroductionSynthetic kaolinite is a clay containing alumina, silica and water of crystallisation, and has a chemical formula 3(Al2O 3.2SiO2.2H2O). This mineral is relatively inexpensive and, is therefore an ideal candidate for use in the production of ceramic powder mixtures for example silicon nitride and aluminium nitride for composite material formation, When the mineral is heated, the water of crystallisation from the crystal lattice is lost via the 3(Al2O 3.2SiO2.2H2O) = 3(Al2O3.2SiO2) + 6H2O reaction. It has been shown [1·2j that on further heating to 1673K, the anhydrous kaolinite decomposes to a mixture of mulllte and silica, 3(Al2O3.2SiO2) = 3Al2O 3.2SiO2 + 4SiO2 which is consistent with the alumina-silica phase diagram, shown in figure 1.The binary alumina-silica phase diagram has a well-defined sub-eutectic immiscibility dome and this characteristic dernixing behaviour is reflected in the thermal decomposition of anhydrous kaolinite consequently the microstructural features resemble the spinodal decomposition process. It is well established that the spinodal decomposition process raises the nucleation frequency due to their low free energy barrier, (?G). The small magnitude of this barrier consequently promotes the evolution of a very fine microstructure. The process of spinodal decomposition is therefore expected to be influential during the reduction-nitridation of kaolinite minerals."

Jan 1, 1996

By Clarissa Hadad de Melo, Jean André François Dille, Rosa Maria Sales da Silveira, Rafaella Martins Ribeiro, Leonardo Sales Araujo, Luiz Henrique de Almeida, Alessandra Vieira Guimarães

Este trabalho tem por objetivo investigar o efeito do Y na precipitação da fase δ na superliga de níquel 718 e correlacionar a caracterização microestrutural com a precipitação/dissolução das fases, por análise térmica. As ligas A, B e C solubilizadas e superenvelhecidas foram caracterizadas por microscopia eletrônica de varredura e de transmissão, com o auxílio de EDS para identificar as fases presentes nas ligas. A caracterização microestrutural foi corroborada com técnica de calorimetria diferencial de varredura. Resultados mostraram que a adição de Y influencia no tamanho de grão e consequentemente na fração de δ precipitada. A adição de Y modificou a cinética de precipitação de δ, que variou de acordo com o teor de ítrio adicionado.

Oct 13, 2019

By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By Rafael de Araujo Silva

As ligas ß-Ti têm sido consideradas materiais com potencial para armazenagem de hidrogênio no estado sólido. A adição de elementos de liga estabilizadores da fase ß, tal como o Nb, retém esta fase metaestável em temperatura ambiente. Neste trabalho a liga Ti-40Nb (at.%) foi produzida via fusão a arco e suas características microestruturais foram caracterizadas visando avaliar os efeitos da aplicação da deformação plástica severa (SPD, severe plastic deformation) e da hidrogenação. A laminação a frio sob atmosfera de Argônio foi a técnica de SPD escolhida. Os resultados principais mostraram que é possível hidrogenar a liga fundida Ti-40Nb em temperatura ambiente após laminação a frio. Os efeitos da deformação plástica severa na microestrutura da liga, como a introdução de discordâncias, foram importantes para o aperfeiçoamento da cinética de absorção em temperatura ambiente (25 °C). Após a dessorção da fase hidreto (CFC) a microestrutura volta a ser constituída pelas fases ? (CCC) e ?” (ortorrômbica).

Aug 17, 2017

By M. C. Irani

This study is a survey of supply and demand for minerals, metals, alloys, and compounds used by the chemical industries in the Ohio River Basin (ORB) area of Ohio, Pennsylvania, and West Virginia during 1967. Data for the study were obtained from completed questionnaires received from chemical manufacturers and from interviews with officials of chemical companies and mineral producers and distributors. The information includes kind, quality, quantity, values, sources, specifications, uses, and methods of transportation. Results of the study show that of the total value of mineral materials consumed by the chemical industry, manufacture of inorganic chemicals consumed 46 percent; fertilizers, 22 percent; and soaps and detergents, 19 percent. Fifteen commodities accounted for 91 percent of the total value of mineral materials consumed. Five of these--phosphates, potash, salt, sulfur, and titanium dioxide--accounted for 59 percent of the total.

Jan 1, 1970

By A. C. Fieldner

All technical facilities of the Bureau of Mines have been geared for more efficient use and conservation of mining equipment, developing plans for safety, improving the quality of coal through better methods of preparation, studying the problems of coal storage and utilization, and extending the uses of coal5/ for the war and postwar economy. The Bureau is now analyzing all of the coal purchased by the Army and much of that required by the Navy. Work on boiler feed water was doubled over last year to meet the increased demand made by the War Department for protecting vital boiler plants in many new camps and defense plants. Progress has been made in safely storing coal to reduce dangers of spontaneous ignition to a minimum and to preserve coking power. Mixtures of oil and coal to be used as a substitute fuel have been investigated. Technical service on the conversion of plants to other fuels has been given to government agencies and private consumers. The possibilities of making motor fuel,

Jan 1, 1944

By R. E. Hershey

1. Reserves were estimated for three coal beds: Lantana, Sewanee, and Richland. 2. Known measured and indicated reserves for all beds, based on a minimum thickness of 14 inches and on 1,800 tons per acre-foot of coal in place, are estimated at 34 million short tons as of Januray 1, 1954. Of this total, 15 million short tons represents coal 28 inches and more thick. Areas in the beds were omitted from the estimate because available data relative to the bed characteristics were insufficient to permit making an estimate conforming with the definitions of measured and indicated coal adopted for this study. Should future drilling or development prove reserves in these areas, such reserves should be added to the total estimated reserves determined by this investigation.

Jan 1, 1956

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,&apos; b) by solution calorimetry with liquid tin as the solvent,&apos; 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