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By E. H. Wells, A. Andreas

Greater progress than in any previous year was accomplished by the oil industry in New Mexico in 1936. The total number of completions in the state was 631, of which 549 were oil wells, 21 were hydrocarbon gas wells, three were carbon dioxide gas wells, and 58 were dry holes. The total oil production for the year was 26,804,446 bbl. Compared with the production for 1935 of 20,228,947 bbl., this represented a gain of 32.5 per cent. Of the total production, 25,337,382 bbl. came from Lea County. The average daily nonmarginal well allowable for that county was 115 bbl. the first of the year and 86 bbl. at the close. Production was regulated by the New Mexico Oil Conservation Commission,

Jan 1, 1937

By Frances H. Clark

IN wartime, the fabrication and use of metals assumes increased importance, for a modern war of sizable proportions cannot be undertaken with- out a vast supply of this material. Light alloys of aluminum and magnesium, which were comparatively unknown in the last war, will play an important role in this one. Due to research on a vast scale in the interim of years, industry is today well equipped to fabricate metals on an enormous scale. Research for the past year has been most productive and a comprehensive survey in the space of this article would be impossible. It is hoped that the stressing of a few items here and there out of a great quantity of able work will indicate in a small way the advances made within recent times. Specific references to the literature will be omitted at the Editor's re- quest but some authors of papers that I have found of special interest are mentioned.

Jan 1, 1940

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By Otto H. Henry

The purpose of this investigation was to determine the equilibrium diagram of the lithium-magnesium pair as a first step in studying the possible usefulness of these alloys as ultra-light structural materials. Review of the Literature The behavior of lithium towards magnesium was first investigated by Masing and Tammann.(1)† In order to prevent oxidation the alloys were made in iron tubes under an atmosphere of hydrogen; temperatures were measured with a glass-protected thermocouple. These investigators found that lithium and magnesium form two series of solid solutions separated by a miscibility gap between 85 and 95 per cent magnesium; that the alloys with 81 and 95 per cent magnesium showed a homogeneous structure under microscopic examination, while the alloy with 89 per cent magnesium contained two distinguishable crystallites; that the curve indicating the beginning of crystallization rises from the melting point of lithium to that of magnesium; and that no compounds of lithium and magnesium are formed. The equilibrium diagram was not plotted because no definite data were obtained for determining the solidus and the position of the miscibility gap in the solid state. The difficulties encountered in this investigation were: (1) that it was necessary to heat them as high as the melting point of magnesium in order to obtain homogeneous melts; at such temperatures the alloys attacked the glass protecting the thermocouple; and (2) that at temperatures above 400" C. the lithium united with the hydrogen to form lithium hydride, thus contaminating the alloys. By applying the same methods as those used in the lithium-magnesium system, Masing and Tammann determined the equilibrium diagram of the

Jan 1, 1934

By H. M. Howe

On commencing the construction of the Orford Company's copper smelting works, at Bergen Point, N. J., I endeavored to convince our President, Mr. W. E. C. Eustis, by actual tests, that at the pressure of from 15 to 18 ounces per square inch, employed by us in smelting, less power was consumed in delivering a unit of blast by a Baker blower than by a fan blower. I attempted to prove this in the following manner: Across the mouth of a No. 5) Baker blower I firmly fastened a board with two round holes, 6 inches in diameter, cut in it. The board was fastened so tightly that no air could escape except through the holes. I then drove the blower at several differerent speeds, observing the pressure at which the air excaped through the two openings for each different speed of the blower, and also indicating the engine, whose only work at that time was to drive the blower. From this I calculated the quantity of power required to deliver, with a Baker blower, sufficient air to keep the pressure at a given point, while it escaped freely through the two six-inch apertures into the open air; or, in other words, to deliver air at a given pressure through these two openings. From the total power so consumed it was, of course, necessary to deduct the power which was required to drive the engine itself. This was ascertained by removing from the engine the belt which drove the blower, and then noting the quantity of power consumed in simply turning the engine over without any

Jan 1, 1882

By Max Boehmer

(Pittsburg Meeting, March, 1910.) AFTER 30 years of development and after an output of $350,000,000 in value of gold, silver, lead, zinc, and copper, there has not been published a satisfactory explanation of the origin of the immense deposits of the Leadville district. The original examination find survey of Leadville by members of the U. S. Geological Survey was a most magnificent piece of work, but their attempt to explain the origin of the ores was based upon the then-accepted theory of lateral secretion, originated by Sandberger, which theory was afterwards disproved in many cases by further development in numerous districts. This theory contended that the ore in the veins had been leached by surface-waters from the eruptive rocks in the immediate vicinity, and it had its origin in the fact that the neighboring eruptive rocks all contained, to an appreciable degree, the several metals found in the ore-deposits. But the practical miner, reasoning in a simple manner from the condition of things as he found them underground, soon discovered the fallacy of this proposition. He reasoned that, in the case of the Leadville deposits, this theory could not be true, because, if the ores were leached from the overlying eruptive rocks by surface-waters, they would as a matter of necessity be controlled by the action of gravity, and the main bodies would collect in- natural depressions of the underlying limestone, and at all points where such depressions existed. But this was not in accord with the channels of ore as he found there ; and hence the theory of lateral secretion in this district was never accepted. Another objection to it consisted in the fact that large areas within the ore-bearing district contained no ores whatever, although their formation was the same, and the same limestones were covered by the same thick sheet of

Feb 1, 1910

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

Jan 1, 1916

By Walter McDermott

This machine is an improvement on the well-known endless travelling belt used for dressing slimes in many mills; the chief point of difference, and constituting the essential advantage of the present over the old form, is the application to the machine of a secondary agitating or shaking motion, in addition to the ordinary progressive motion of- the belt. In the machine as heretofore made, the inclined belt or apron moved slowly up against a thin stream of water and ore, depositing the concentrations carried over in a tank placed below, through which the belt travelled, of course, in a reversed position. By reference to the accompanying drawings, it will be seen that in this main principle the new modification does not differ materially; but the means by which it is carried out are essentially different. The machine consists of a substantial frame of mood, F, Figs. 41, 42, and 43, within which hang the shaking frame and rollers, B B, A, Endless apron ; B, Apron frame and rollers ; C, Driving drum ; D, pulleys; B, Shaft and connecting rods; F, Wooden frame; G, Shaft of regulating Pulley; H, Yokes. supporting the upper half of the travelling apron, A, which passes below around the driving drum, C, in the water-tank, J. On leaving the water-tank, the belt passes over the guiding and tightener pulley, G. The ends of the shaking-frame, B, are provided with iron yokes, H H, bored to admit the shafts of the end rollers, and carrying a lug, by which attachment is made to the connecting rods,

By Walter McDermott

THIS machine is an improvement on the well-known endless traveling belt used for dressing slimes in many mills ; the chief point of difference, and constituting the essential advantage of the present over the old form, is the application to the machine of a secondary agitating or shaking motion, in addition to the ordinary progressive motion of-the belt. In the machine as heretofore made, the inclined belt or apron moved slowly up against a thin stream of water and ore, depositing the concentrations carried over in a tank placed below, through which the belt travelled, of course, in a reversed position. By reference to the accompanying drawings, it will be seen that in this main principle the new modification does not differ materially; but the means by which it is carried out are essentially different. The machine consists of a substantial frame of mood, F, Figs. 41, 42, and 43, within which hang the shaking frame and rollers, B B, A, Endless apron ; B, Apron frame and rollers ; C, Driving drum ; D, pulleys; El Shaft and connecting rods; F, Wooden frame; G, Shaft of regulating Pulley ; H, Yokes. supporting the upper half of the travelling apron, A, which passes below around the driving drum, C, in the water-tank, J. On leaving the water-tank, the belt passes over the guiding and tightener pulley, G. The ends of the shaking-frame, B, are provided with iron yokes, H H, bored to admit the shafts of the end rollers, and carrying a lug, by which attachment is made to the connecting rods,

Jan 1, 1875

Jan 1, 1969

By Evan Evans

IT is appropriate to evaluate 1947 in review as a year of a peacetime record production of about 676,000,000 tons of coal (anthracite and bituminous), closely approaching the extraordinary wartime output in 1944. Considering the general price-wage inflation, it is in point to note that the coal industry sustained the highest wages paid to workers in any major industry, but that coal prices at wholesale levels have risen much less percentage wise than the average for all commodities. The sellers' market continues to prevail. In addition to serving our own country's enormous needs, our coal industry is exporting extraordinary tonnages overseas. This unusual export demand is likely to continue for a while. Moreover, the demand in Europe for American coal mining machinery is a real tribute to the management efficiency of our modern mechanized coal industry. Competitively, the petroleum industry is concerned over its long-term supply, and already a synthetic fuels industry is being publicly advocated. In due time coal and lignite are bound to be

Jan 1, 1948

By E. H. Rose

IN the realm of ore dressing the most pregnant feat of all time was announced in 1945: the winning of the mineral raw materials which made the harnessing of atomic energy possible. Lost in the stupendous implications of the end result, in the two billion dollar hugeness of the project, and in the famous names attached thereto, the fact that crude uranium ores had to be concentrated received relatively little notice in the press. Only the final link in the concentrating chain was publicized-ether extraction of uranyl nitrate, developed by Hoffman and carried on by the Mallinckrodt Chemical Works, or methods developed by the Ames group under Spedding. Some of the earlier links represented less glamorous but equally difficult and exacting research. One may only speak a word of admiration for those who worked hard, accomplished much, and said nothing. The universal lament for most of the year was "man shortage." A group of Canadian engineers expressed it as "being so short of labor that no labor was available to develop laborsaving devices." . Despite this, an outstanding amount of mineral-dressing progress was made in 1945. Necessity allowed no alternative. The insatiable demand of war for minerals forced the exploitation of lower and lower grade ores, and of others not before considered of commercial character or use, requiring the mineral dresser to fight for and win new bridgeheads on the home front.

Jan 1, 1946

By J. D. Lubahn

Prior tests by Dorn, where the strain rate in a tensile test was suddenly changed, have shown a small, but definite rate-history effect to exist. If this effect is neglected in the calculation of creep behavior from tensile results, an error should occur. This paper shows that this error is smaller than experimental scattering, and may be neglected. DORN1 has found a small but definite rate-history effect in the aluminum alloy 250 at liquid-nitrogen temperature using tensile tests with an abrupt rate change. Such an effect is to be expected from pre-viously known2-6 temperature-history effects, together with general experience that effects produced by changing the strain rate a large amount are simi-

Jan 1, 1959

By Gordon B. Brox, Joseph F. Mcaleer, Charles C. Goddard, Edward P. Shea, Robert G. Ingersoll, Lester G. Zeihen, George J. Burns, John M. Guilbert, Richard N. Miller, Charles Meyer

The Boulder batholith is a composite intrusive in which the Butte quartz monzonite is the dominant rock type. Quartz porphyry dikes intruded the quartz monzonite in directions which were subsequently followed by the eastwest- striking Anaconda system of veins, the earliest major veins in the district. Anaconda veins are faulted by northwest-striking veins of the Blue system, which are most prominent in the central third of the district. Anaconda veins are the major producers in the western third of the district and also in the eastern third, where the "horsetail" zones break off from them. Individual oreshoots are thousands of feet long as well as deep on both systems of veins, but they are generally more persistent and thicker on the Anaconda veins. Viewed broadly, the mineralization in the big veins is arranged in crudely concentric zones of zinc and manganese around a central zone of copper. Only slightly offset from these zones, but earlier structurally, is a zone in which quartz-molybdenite veinlets are prominent. This zone tops at about the 2800 level and widens downward. The pattern of distribution of Cu-Fe-S series minerals in the large veins of the copper zone is not symmetrical with respect to the metal zones. There is a fringe of chalcopyrite-bornite all around the copper front. However, within the copper zone, pyrite-chalcocite-enargitecovellite- digenite assemblages are prevalent near its eastern edge from the 3800 level to the surface, whereas deep on the large Anaconda veins in the western part of the copper zone, chalcopyrite is dominant. Here the chalcopyrite grades upward into bornite-chalcocite ores and eastward into the high-sulfur assemblages of the Leonard mine. Sericite-biotite-K-feldspar alteration envelopes, containing up to about 2 per cent copper as chalcopyrite, are present on some of the quartz-molybdenite veinlets at deep mine levels in the molybdenite zone. These envelopes contrast sharply mineralogically and chemically with the later sericitic and argillic alteration envelopes around Main Stage veins. K'0-Ar'0 ratios indicate that they may be older by about 4 m.y. Secondarily enriched copper ores are mined in the Berkeley pit in the southeastern part of the district. At the present time they account for about half of Butte's production of copper.

Jan 1, 1968

By A. CHESTER BEATTY

MAGNESIUM oxide is by far the most refractory of the common oxides, since it has a melting point of 5072 deg. F. as compared with 3110 deg. F., the melting point of silica (crystobalite) ; 3722 deg. F., the melting point of alumina (corundum) ; and 4127 deg. F., the melting point of chromite (Cr2O33FeO). Its large-scale use in the lining of metallurgical furnaces dates back to the latter part of the nineteenth century, when extensive deposits of magnesium carbonate were discovered in southern Austria in the province of Styria. Before the development of Austrian magnesite, calcined dolomite, a mixture of lime and magnesia, was used in basic steel-making furnaces. The lime in the dolomite was quite objectionable, since it slaked on exposure to the atmosphere, and dolomite therefore could not be made' .into permanent furnace bottoms or into brick. The Austrian magnesite, with its very low lime content, was free from these objections and soon displaced much of the dolomite. With the extensive development of basic steel-melting, the rise of the copper industry, and other metallurgical and chemical processes which dealt with chemically basic substances, the use of magnesite grain and magnesite brick increased rapidly.

Jan 1, 1931

By W. E. Field

In the Coast Mountains approximately 110 miles north of Vancouver, the gold mine of Bralorne- Pioneer Mines Ltd. lies at an elevation of 3500 ft. The deepest or 41 level in the mine is at an elevation of 1400 ft below sea level, and the rock temperature on this level is 122.5°F. The thermal gradient is 1 "F increase in temperature for each 67.5 ft increase in depth. The mine produces between 500 and 600 tons per clay, utilizing an adit two internal shafts, and one service shaft from surface. The Queen shaft, extending from the 26 to the 41 level, IS the deepest, and most production now comes from this area. Stoping in by cut and fill using mill tailing hydraulic backfill.

Jan 12, 1963

Born, March 28, 1853 Died July 23, 1916 On July 25, 1916, the Board of Directors adopted the following minute and directed that it be entered upon the records of the Board & published in the Bulletin of the Institute, and thereof be sent to the family of Mr. Kirchhoff: Charles Kirchhoff was one of the oldest, most widely known and most highly esteerned members of the American Institute of Mining Engineers. On his return in 1875 from a European course of study, to begin a highly successful professional career, he joined the Institute, then just commencing to acquire both national and international recognition. He became at once, and-for more than 40 years continued to be, its earnest , and active supporter, serving it as Manager, Councilor or Director for terms aggregating 9 years,-as Vice-President for 2 years, and twice as President for a year. During the critical period of the erection of the United Engineering Society's building, and the transfer of the Institute to permanent head-quarters therein, Mr. Kirchhoff was its efficient representative in the United Engineering Society, and on the Building Committee. In 1910, amid the congratulations of colleagues, employees, and innumerable friends, Mr. Kirchhoff retired from active business as Vice- President and General Manager of a great technical publishing company. Yet he sacrificed of his well-earned leisure yet one more year, to serve the Institute as President through 1911.

Jan 9, 1916

By J. David Lowell

For his contributions to the field of mining geology, a striking example being his brilliant inte.rpretation of the complex geologic history of the San Manuel District (Pinal County, Arizona) which resulted in the discovery of the Kalamazoo orebody, and for his lecture, "Copper Resources in 1970." On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radiocarbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy. Evolution of the Copper Industry The copper ore mined by the ancients was high grade, and the copper produced was expensive. The copper industry began with narrow high-grade veins, but has evolved to the point where massive earth-moving equipment can be operated in huge, low-grade open pits. Indian pits dug before 3000 B.C. in the Lake Superior district were in ore which averaged 15% Cu. His- torical research done by Arthur Brant has shown that copper cost in the Middle East in 1840 B.C. in terms of 1970 labor dollars was about $25 per lb. The copper mined in northern Europe in 1540 in the time of Georgius Agricola averaged about 8% Cu, and the cost in 1970 labor dollars was about $10 per lb. Average ore grade had dropped to about 6% Cu in 1890, and the cost of copper in the U.S. in 1970 dollars was about 45¢ per lb. Butte, Mont., was a good example of the efficiently operated vein mines of this time. In 1906, Daniel Jackling made a dramatic entrance into the copper scene with the Bingham Canyon open-pit copper mine and proved that more profit was possible mining 2% porphyry copper ore on a

Jan 1, 1971

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday's constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960