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Prof. H. O. Hofman, Massachusetts Institute of Technology, Boston, Mass. (communication to the Secretary): When Mr. Stetefeldt quotes me as saying that " silver-assays are uniformly made by scorification," he has evidently not understood that I was referring solely to the practice of silver-lead smelting-works. Everybody knows that silver-mills do not employ the scorification-assay for regular work ; and it is equally certain that in very few, if any, silver-lead smelting-works will the crucible-assay be found in use for determining silver. The second part of the quotation, "as it is adapted to all kinds of ores and gives excellent results unless organic matter is present," although, of course, also intended in a restricted sense, might very well be extended to a general one. Mr. Furman, in his Manual of Practical Assaying,* says, on page 123: "We believe that the Colorado practice is preferable, as most ores will yield higher silver-results by scorification." The fact that the scorification-assay is the accepted one in Colorado is strong presumptive evidence for its accuracy, as exactness would nowhere else be more jealously demanded. Mr. Stetefeldt cites Albert Arents- as a supporter of his preference for the crucible-assay, although I had already done so in favor of scorification. Looking up again the reference, I find that I was justified in quoting him, as, while Mr. Arents advocates the crucibleassay for low-grade gold ores, not on account of the greater accuracy of its results, but because it is quicker and less expensive, he condemns it§ for the assay of silver-ores, and prefers the scorifier for rich goldores, and for coppery ores, and in general for ores containing both silver and gold. As I, like Mr. Stetefeldt, have kept no detailed

Jan 1, 1895

By James W. Neill

Discussion of the paper of H. 0. Hofman, presented at the Canal Zone meeting, November, 1910, and printed in Bulletin No. 42, June, 1910, pp. 473 to 497. JAMES W. NEILL, Pasadena, Cal. (communication to the Secretary *) :-Professor Hofman's paper brings the art up to . date. As I was one of the pioneers in this business, I beg to give the following incomplete data regarding my efforts in this line. In the year 1883, while I was in charge of the smelting-operations at Mine La Motte, Mo., there was at the concentrator an unusually large production of a middle product, locally called "iron," which carried considerable values in nickel and cobalt, and which it was desirable, for this reason, to treat by itself. The works could not spare a furnace for the purpose; and to handle this product I improvised a "roast-hearth " from an old " lead-hearth." This was a small cast-iron furnace of the usual construction, about 2 by 4 ft. in dimensions, with a hollow cast-iron back, through which the wind circulated before entering the tuyeres. I had a cast-iron grate made to fit this hearth, and placed it flush with the lip, or apron, and above the tuyeres. On this grate, which had round holes about 0.25 in. in diameter, and a total surface of about 20 by 40 in., I roasted the nickeliferous pyrite product; starting the fire with kindling, then adding charcoal, and then gradually feeding the sulphides with a shovel, so as to cover the fire, choke down blow-holes, and get an even bed. Blast at a pressure of 3 or 4 oz. was supplied by a fail-blower. When a cake of roasted material had formed, it was removed with a steel bar, or fork, to the lip of the furnace, and thence into a wheel-barrow.. The fine material which had remained unmelted, but very hot, on top of the cake would promptly ignite when the cake was broken up and removed. The fire would then be covered with fresh material and * Received Aug. 29, 1910.

Apr 1, 1911

By D. E. Musgrove

The question of alternating current vs direct current has become an important consideration to the mining industry. Rising production costs demand lower investment, which, in many instances, can be realized by the use of ac mining machines. Generally ac motors, control systems, and distribution and power conversion equipment can be installed for approximately 50 pct of the first cost of their dc equivalents. This basic saving has made ac mining a serious competitor for the traditional dc mining systems. With the increased use of ac voltages underground, there has developed the problem of conveniently converting distribution voltages to usable 480-v power. Power at low voltages should not be carried for comparatively long distances, and the transformation should be made at the point of use. Otherwise, serious voltage regulation problems and objectionable line losses will occur.

Jan 5, 1955

By Bruce A. Kennedy

The 1960's were an apparent turning point in the technological and social attitudes and awareness of the mining industry. From the late 19th century through to the early 20th century, one has always been presented with the picture of the rough and ready leaders of the mining industry who screamed for production and damned anything that got in the way of it. This attitude led to a certain alienation of the mining industry in the eyes of the general public. They saw an industry which was archaic in many of its practices and often heartless in its attitudes towards mankind. However, a gradual change spread through the industry and cracks began to appear in the hard facades of the mining companies. Resistance to change had almost become a standard operating procedure for many and consequently changes in technology had been slow in coming. The late 1950's and the 1960's saw a new awareness come into existence. As the mining company managements changed, there developed a realization that considerable efforts had to be made to bring the technology and social standing of the industry out of the dark ages and into the modern world. New advances were made in both metallurgical and mining technology. The 20th century technology of computers was accepted and became a standard tool of the industry.

Jan 1, 1971

By GEORGE O. SUMAN

IN THE operation of oil properties there are various difficulties with pumping wells which can often be overcome or greatly lessened if sufficient attention is, directed towards pump and tubing problems. The difficulties referred to are the wearing out of pumps, sanding up of pumps, and the sanding up of the hole. As the perforations in the oil strings are large and the oil and sand loose and unconsolidated considerable trouble is often encountered in pumping wells due to the ease with which' the sand can come into the holes. DETERMINING FLUID LEVEL In determining the proper depth at which to tube a well it is essential to first find out something about the behavior of the fluid in 'the hole: Facts in regard to this natter can be obtained by finding the fluid level on pulling the tubing, by making a pumping test on the well tubed to various depths, and by bailing tests during cleaning out work. In ordinary oil field operations it is customary to take the fluid level at the time of pulling the tubing. This 'can only be done when the pump is not sanded up. There are two methods used in obtaining the fluid level. One method is to note where the outside of the tubing starts, to be covered with fluid when pulling the

Jan 1, 1925

By H. M. O?Harra

Experiments have shown that the use of enriched air would be of particular benefit in the roasting of zinc ores for the manufacture of sulfuric acid. Enriched air increases capacity of furnace, decreases fuel consumption, and increases SO2 content of roaster gas. THE work here described had for its purpose the procuring of data from which some quantitative estimate might be made of the results obtainable by using oxygen-enriched air in roasting zinc ores on a commercial scale. The principal metallurgical advantages of using enriched air in roasting zinc ores would be: 1. The rate of roasting would be increased, with consequent gain in the capacity of the roasting furnace. 2. As less air would be required for roasting, the volume of hot gases leaving the furnace and the heat carried out of the furnace as sensible heat in these gases would be less per ton of ore roasted; partly for this reason and partly because of the increased quantity of heat generated in the furnace by the larger amount of ore that could be roasted, the consumption of fuel by the furnace would be lessened; and by the use of air sufficiently enriched with oxygen the necessity of using fuel might be entirely obviated. 3. Roaster gas having a higher SO2 content could be produced; this would make possible greater capacity and more economical operation of the sulfuric-acid plant. Certain phases of the application of enriched air to roasting can be worked out only by experimenting with a furnace of commercial, or at least semicommercial, size. Thus the precautions necessary to secure proper distribution of heat in the furnace;1 the volume of enriched air,

Jan 3, 1924

By O?Harra B. M.

THE work here described had for its purpose the procuring of data from which some quantitative estimate might be made of the results obtainable by using oxygen-enriched air in roasting zinc ores on a commercial scale. The principal metallurgical advantages of using enriched air in roasting zinc ores would be: 1. The rate of roasting would be increased, with consequent gain in the capacity of the roasting furnace. 2. As less air would be required for roasting, the volume of hot gases leaving the furnace and the heat carried out of the furnace as sensible heat in these gases would be less per ton of ore roasted; partly for this reason and partly because of the increased quantity of heat generated in the furnace by the larger amount of ore that could be roasted, the consumption of fuel by the furnace would be lessened; and by the use of air sufficiently enriched with oxygen the necessity of using fuel might be entirely obviated. 3. Roaster gas having a higher SO2 content could be produced; this would make possible greater capacity and more economical operation of the sulfuric-acid plant. Certain phases of the application of enriched air to roasting can be worked out only by experimenting with a furnace of commercial, or at least semicommercial, size. Thus the precautions necessary to secure proper. distribution of heat in the furnace;1 the volume of enriched air; and the proportion of oxygen in this air, necessary to give the desired increase in roasting capacity of the furnace and in SO2 content of the roaster gases;; and the most desirable frequency of raking, thickness of

Jan 11, 1924

By T. Cantwell, N. C. Rasmussen, H. E. Hawkes

Beryl is a mineral that may be difficult to distinguish from quartz by casual field inspection. The easily recognized green color and hexagonal crystal form of coarse-grained beryl are by no means universal, even in beryl from pegmatitic deposits. If it occurred as a fine-grained accessory mineral in an igneous rock, it would almost certainly escape detection unless samples were submitted for petrographic or chemical analysis. There may be substantial deposits of some beryllium mineral, other than beryl, that has been overlooked because that mineral also closely resembles the common rock-forming minerals. A reliable and simple method of identifying beryllium minerals and determining the beryllium content of a rock would be helpful in exploration. This article describes preliminary experiments in applying nuclear reaction to the qualitative identification of beryl and to the semiquantitative determination of the beryllium content of rock samples. Gaudin,1,2 the first to apply a nuclear reaction in detecting beryllium minerals, developed a method that irradiates the sample with gamma rays, which react with beryllium nuclei to produce neutrons. The neutrons are then measured with standard equipment. The cross section for this reaction is about 1 millibarn. The cross section is a measure of the probability that a reaction will take place, for example, between a beryllium nucleus and an incident gamma ray or alpha particles.3-5 At 1-millibarn cross section for the reaction, satisfactory performance required a source strength of the order of 1 curie (3.7 x 10"' disintegrations per sec, where each disintegration releases one or more gamma rays). The reactions will not take place if the gamma radiation is below a minimum energy, in this case 1.63 mev. The size of the source and the energy of the radiation made heavy shielding necessary for these experiments, both to reduce the background count of the neutron counter and to safeguard personnel. The original discovery of the neutron by Chad-wick in 1932 resulted from experiments with another nuclear reaction, induced by bombarding beryllium with alpha particles in which the products are carbon-12 and neutrons. The equation for this reaction is as follows:' " ,Be" + ,He'? 6C12 + 8,n' [1] re-particle neutron In the above nuclear equation (Eq. 1), the sub- script number indicates the number of protons in the nucleus (the atomic number) and the superscript the total number of neutrons and protons (approximately the atomic mass). For the alpha-neutron reaction the cross section is about 250 milli-barns, or 250 times that of the gamma-neutron reaction used by Gaudin. The positively charged alpha particle is repelled by the positive charge of the beryllium nucleus; it must, therefore, have a certain minimum energy in order to approach close enough to the beryllium nucleus to react. For reaction with the beryllium nucleus, the lower limit of the alpha-particle energy is 3.7 mev. The alpha-neutron reaction, with polonium-210 as an alpha source, was selected for the present experiments. Alpha particles are emitted by polonium-210 at 5.30 mev, which is adequate for the reaction with beryllium. Furthermore, this isotope of polonium emits alpha particles with negligible associated gamma radiation, thus eliminating the necessity of shielding. The half-life of polonium-210 is 138 days. Inasmuch as alpha particles carry a possible charge and are large compared with most nuclear particles, their energy is rapidly dissipated in passing through matter. Their range in standard air is 3.66 cm,3 and they penetrate only a few tens of microns into a mineral sample. The short range in air can be minimized by preparation of a flat sample surface that can be brought very close to the alpha source during analysis. On the other hand, short range of alpha particles in air lessens the radiological health hazard and makes it possible to use this method without shielding. It must be emphasized, however, that the alpha emitters are potentially very dangerous if they enter the human body. Polonium must be handled with extreme caution. The literature has reported experiments on the yield of neutrons from reaction of alpha particles with beryllium nuclei. Feld" reports that in intimate mixtures of polonium and beryllium, 3 x 106 eutrons per sec are produced per curie of polonium. Elsewhere in the same reference it is stated that a sandwich-type source yields about one third as many neutrons as an intimate mixture. A table of neutron yields for full energy polonium alpha-particles on thick targets as reported by Anderson7 is the basis of Table I. From Table I it can be deduced that the elements most likely to interfere, i.e., those that also produce neutrons when bombarded by alpha particles, are boron and fluorine. These data also show that it will probably not be possible to determine very small quantities of beryllium in rocks because of the masking effects of the major elements, sodium, magnesium, and aluminum. The neutrons emitted in the alpha reaction are detected by another nuclear reaction. Either of the

Jan 1, 1960

(Read at the Amenia Meeting, October, 1877.) THE Committee on a Standard Gauge have been constantly engaged, since their appointment, in the duties assigned to them.§ They have corresponded with different persons interested in the manufacture and use of gauges in this country, and have received from several of them important information. They have also entered into correspondence with the governments of England, France, Germany, and Russia through their Consuls, and with Austria directly. The Consuls of Germany and France * Transactions, Vol. V, p. 575. t Transactions, Vol. III, p. 43. + Transactions, Vol. II, p. 224. §See Transactions, Vol. V, p.,48.

Jan 1, 1878

By Robert L. Zerga

Mining equipment and systems have been incorporated into the San Manuel mine to meet the requirements of ore development and extraction. A general discussion of the existing equipment as it relates to the specific methods is presented. A comparison is made between original and present equipment, and future equipment needs. The problems, successes and failures of mining equipment adaptation for the San Manuel mining system are highlighted.

Jan 1, 1981

By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot's reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.'' The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

By Richard E. Chism

SAN DIMAS, in the State of Durango, Mexico, on the frontier of the State of Sinaloa, is the centre of an extensive and rich mining region, which has been exploited for over a hundred years; and the patio process for working silver ores has there attained the highest perfection of which it is capable. Local modifications have been engrafted upon the underlying principles of the process, but, as a whole, the San Dimas practice so fully illustrates its typical capabilities, that I have undertaken to describe its workings in the hope of lightening, to some degree, the labors of my professional brethren who may have occasion to visit Mexico." As is tolerably well known, the patio process, like all other systems of free amalgamation, is not successful with ores containing more than a trace of zinc or lead, the presence of zincblende being especially obnoxious. Iron and copper in small quantities are not particularly disadvantageous. The process succeeds very well with all sulphide ores which do not contain much more than a trace of arsenic and antimony, provided the tailings are concentrated, although, of course, it is best adapted for free milling ores. For suitable silver ores that contain small amounts of free gold the process is still a good one, but where the gold is combined with sulphurets, a considerable and even an excessive loss is inevitable. Hitherto the Mexicans have submitted to this loss, but, since the introduction of American mills, they are gradually abandoning the patio process in favor of the other. The San Dimas ores have a gangue of quartz and feldspar. They are composed principally of silver sulphides, with some chloride and

Jan 1, 1883

By E. A. Holbrook

IN view of what has happened in - the past three years, it seems incredible that industrial corporations continue to write to engineering and mines schools for "promising members of the graduating class," or, indeed, that they even send representatives to the colleges to interview engineering graduates. Certainly, by this time, every company should be aware of the fact that recent engineering graduates are almost nonexistent and the number is not likely to increase within the next several years. At the February, 1945, annual meeting of the Local Section delegates of the A.I.M.E. in New York, W. B. Plank, professor of mining engineering at Lafayette College, summarized well the situation of the colleges by titling his talk "The Lost Generation of Engineers."

Jan 1, 1945

By John L. Schroder

The demands for increased productivity on the 1967 coal industry have generated new operating trends and fresh approaches to old methods, which have enabled the industry to keep pace with the expanding economy. Changes, while not radical in concept or design, have been plentiful and are marked by the refinement of the already tried, tested and proven. Perhaps not since World War II have there been demands on equipment manufacturers to design and deliver such diversified types of machines as those required by the industry in the past year. Equipment developments-following a plan which calls for higher productivity, lower maintenance costs and greater machine availability- have tended more toward increased horsepower and heavier, more rugged equipment. Electrical and mechanical components, designed in many instances with maximum reliability rather than initial costs as the main criterion, have contributed to the improvements in over-all performance. High-strength, specialty steels are finding use in a wide range of equipment applications. The horsepower capacity of electric motors being installed is more frequently being rated on a continuous basis rather than the former one hr or less and, as a result, fewer failures now occur because of overloading. These developments reflect the pyramiding cost of equipment down-time and represent definitive progress in reducing the magnitude of the problem.

Jan 2, 1968

By Walter W. Bradley, OLAF P. JENKINS

IN April of this year the California State Division of Mines (formerly known as the State Mining Bureau) observed its 50th anniversary. The Division serves as a bureau of information and, an encyclopaedia of California's economic minerals. Its primary function is to make economic surveys of the mineral resources of California, their development and utilization. Geological studies also constitute a related part of the work as being necessary in tracing and out- lining ore deposits and the most likely areas in which to find them. The results of the Bureau's data-gathering are published in the form of annual reports of the State Mineralogist, and in bulletins on specific substances. The Division is just completing a series of reports on the mineral resources of the State arranged by counties.. It is now starting .a new series of reports arranged according to substances particularly the so-called non- metallic commercial groups. Of these the following are now available: clays, barite, and mineral paint. These will be followed by reports on feldspar and silica, diatomaceous earth, limestone and others

Jan 1, 1930

WHEN Magma Copper Company in 1952 set about finding $100,000,000 to finance the project of developing and equipping the property of its lusty progeny, the San Manuel Copper Corporation, A. J. McNab, president and guiding genius for both companies (and incidentally a mining engineer by profession), determined that he would avoid the mistake frequently made in such circumstances, of underestimating the cost, and thereby running short of funds before the job was completed. The fear that this might happen was one of the reasons why insurance companies, one potent source of "big" money, were reluctant to finance the enterprise. How, they asked themselves, would Magma, a relatively small company, get additional money in such a contingency? Insurance officials' thumbs were turned down. Conditions Imposed by R.F.C. The upshot was the negotiation by Mr. McNab for San Manuel of a contract with the Reconstruction Finance Corporation, dated July 10, 1952, whereby needed monies in amount up to $94,000,000 would be advanced as a loan, bearing 5 per cent interest. Arrangements were made for the separate financing of the new $10,000,000 town, needed for the project, through the Del E. Webb Construction Company of Phoenix, Arizona, and M.O.W. Homes, Incorporated, of Los Angeles. Thus the $94,000,000 drawing account was believed ample to provide for building the railroad, the mine plant, the concentrator, and the smelter, as well as for the underground development of the mine needed to start production. As a matter of fact, only

Jan 1, 1957

By O. C. Wheeler

In order that the series of reports on oil and gas in Colombia may be complete, the report for the year 1941, which was not available for Volume 160 of the TRANSACTIONS, is given here. The report for 1945 begins on page 4o6.

Jan 1, 1946

By John B. Miles

THE present period of depression in the iron industry, with the resultant close approximation of the cost of production to the selling-price of pig-iron, should make the discussion of this subject at this time not only interesting but, profitable. It is possible that it may result, in the collection of data, which when added to those set forth in this paper will clearly indicate the influence of the rate. of driving a blast-furnace upon its fuel-economy. The question is not whether an excessive rate of driving (meaning a rate definitely in excess of the average rate in the United States) results in, an increase in the fuel-consumption, but rather whether a rate considerably less than the average does not result in a marked decrease in the fuel-consumption. The commercial and metallurgical sides of. this problem must be kept separate. With a large margin between the cost of production and the selling-price of pig-iron, and a plant already in operation, it is frequently profitable to sacrifice a couple of hundred pounds of fuel per ton of pig-iron in order to secure the greater gross profits resulting from a larger tonnage. When this margin decreases with a plant in operation, or when the determination of the size of a new furnace intended for a certain production . confronts the management, a clear understanding of the effect of the rate of driving upon fuel-economy becomes necessary. If it be granted that slow driving leads to low fuel-consumption, it should he borne in mind in the design of a new plant for the production of a certain tonnage that the adoption of an economical rate of driving increases only the size of the furnace proper, whereas, due to the decrease in quantity of blast required on account of the decrease in fuel burned, the stoves, the blowing-engines, the boilers and the piping may be de-

Sep 1, 1908

By J. B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about 1/2-in. water pressure. No loss of air was evident. Fig. 2 presents typical data for a standard Denver sub-A 24x24-in. unit cell operated at impeller speeds from 0 to 710 rpm. Each plotted point represents the average for five readings distributed over the entire cell surface. Readings were taken with only water passing through the cell. Results of this type have been used in a study of the influence of operating variables on cell performance and in detecting inherent differences in the operating characteristics of cells of various kinds. Although the information presented in Fig. 2 resulted only with water passing through the cell, the apparatus is suitable for use during flotation of coal when various reagents are present. Possible modi- fications that might prove convenient under special circumstances include varying the size and shape of the receiver and substituting a calibrated, inverted, water-filled carboy or other gas-measuring device for the wet-test meter. If such modifications result in excessive back pressures, some form of draft should be applied at the discharge end of the measuring system.

Jan 1, 1959

By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969