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By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st'ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.'-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5'6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

By V I. McCallum

In 1954, Falconbridge Nickel Mines Limited began the program of deepening the Falconbridge mine workings for 2,000 feet below the bottom, or 4025, level in order to provide twelve new levels for production. Involved in this program were a production-sized internal shaft, .crushing, pumping and hoisting installations, the integration of the new shaft operations with those of existing shafts, and considerations of ventilation requirements and ground support at depth. This paper describes the major items of equipment, and the depth development of No. 9 shaft as a whole, and also emphasize the planning phases of the program. The factors involved and reasons for the equipment and layouts chosen are given. Introduction and History THIS paper describes the planning and development of that portion of the Falconbridge mine between the 4025 and 6050 mining levels. This mine, the oldest of several being operated by Falcon-bridge Nickel Mines Limited in the Sudbury district, has been a continuous producer for over thirty years.

Jan 1, 1964

By R. B. Elver

The level of steel consumption per capita is one of the principal indicators of a country's standard of living. It is no coincidence that the materially advanced nations possess viable iron and steel industries to provide a reliable and economic source of steal for the manufacturing industries. No other metal is as dominantly important in manufacturing as steel. The blast furnace - steel furnace complex based on coking coal, ferrous scrap and iron ore - continues to be the principal steel-producing method. Less important is the electric furnace method based on scrap, In recent years, there has been considerable interest in the many direct reduction processes that are not dependent on coking coal but usually produce a product for further refining in steel furnaces. No matter which series of processes are used, iron ore is essentially the only source of virgin iron units. Thus, to such a vital and capital-intense industry as steel, access to a relatively inexpensive, long- term supply of iron ore is essential.

Jan 1, 1964

By J. Wade Watkins

One potential peaceful application of nuclear explosives is stimulating the production of liquid or gaseous hydrocarbons from essentially nonproductive deposits of petroleum, natural gas, oil shale, and tar sands. Within the United States the appreciable difference between producible proved reserves and ultimate reserves and resources of hydrocarbon deposits is of such magnitude that much petroleum, natural gas, shale oil, and bitumen will not be produced unless significant technological progress is made in production techniques. The shattering effect of contained nuclear explosives and, to a lesser extent, the heat produced, have been considered as stimulative forces when the thickness, depth, and nature of such deposits permit considering the use of nuclear devices. Mechanical production problems would be less in an oil or gas reservoir than in an oil-shale or tar-sands deposit. Also, tar-sands resources in the United States may not be adequate to warrant serious consideration of applying nuclear-explosives stimulation. Gas reservoirs should present the least-radioactive-contamination problem. The technical feasibility of using nuclear explosives cannot be evaluated fully at present. Additional information is needed on the effects of pressure, heat, and radioactivity on the solids and fluids of hydrocarbon deposits, the nature and extent of induced fractures in different rock media, and the possibility of isolating and confining or removing radioactive contaminants. Final technical feasibility can only be determined by a field test. If technical feasibility is established, economic feasibility will depend upon the comparative cost of producing hydrocarbons by nuclear explosives and by conventional means. It is probable that an economic comparison would favor nuclear stimulation only where devices of relatively high yield could be used practicably and safely.

Jan 1, 1964

By C E. Gordon Brown

Aircraft utilization, weather and cost data are given for three separate projects north of the sixtieth parallel in the Northwest Territories and the Yukon Territory. These operations, carried out by helicopter-equipped geological and prospecting parties, have cost $24 to $30 per square mile, depending principally on the distance from the base. They provide adequate surface exploration of areas with 40 to 50 per cent rock outcrop. A good one-inch-to-one-mile geological map can be made. T HE exploration of the Canadian northland has been given increasing attention by the mining industry during recent years. In many cases, the initial problem is to make an adequate reconnaissance of a large area where existing geological information is meagre. The Geological Survey of Canada pioneered the use of helicopter-equipped geological parties for mapping at a scale of eight miles to the inch.

Jan 1, 1964

By Edward E. Hicke, Charles A. Stickels

The dihedral angle of liquid-lead inclusions in solid nickel has been measured as a function of temperature from 371 to 816 C at zero pressure. and as a function of pressure up to 50,000 psi at 317 and 593 C. Thermodynamic expressions are derived for the temperature and pressure coefficients of interfacial tensions in this system. A method is presented for obtaining relative tempmature and pressure coefficients from dihedral-angle data, and the resulting values are used in conjunction with the thermodynamic relations to calculate excess properties of the solid-liquid interface. Defining the position of the solid-liquid interface by the condition that the excess concentration of lead is zero, the excess concentration of nickel and the excess entropy at the solid-liquid interface are: where y(593) is the interfacial tension of the nickel grain boundary saturated with lead at 593C and zero pressure. These values are considered reliable to within a factor of two. While similar calculations are not possible for the nickel grain boundary, it is shown that the expwimental results imply that the excess concentration of nickel at the boundary and the excess entropy of the boundary are negative. THE temperature and composition dependencies of interfacial tensions in metal systems have been reported by several authors in the last 15 years.'-' No measurements of the effect of pressure on inter- facial tensions in metals have been reported, although measurements made on nonmetallic gas/liquid and liquid/liquid systems suggest that a measurable effect should exist.6-l2 The purpose of these experiments was to determine the influence of temperature and hydrostatic pressure on dihedral angles in the Pb-Ni system. The equilibrium dihedral angle is expressed as a ratio of interfacial tensions by2: where 8 is the dihedral angle, yGB is the Ni-Ni grain boundary tension, and SL is the solid Ni-liquid Pb interfacial tension. Three sets of ex- periments were run to determine: a) the effect of temperature from 371" to 816°C on the dihedral angle at zero pressure; b) the effect of pressure up to 50,000 psi on the dihedral angle at 371° and 593°C. THERMODYNAMICS The properties of interfaces of most direct concern are the interfacial tension, excess concentrations of various components at the interface and the excess entropy of the interface, S°. These quantities are defined following Gibbs. Consider an interface separating phases a and 0. Construct two surfaces C, and C such that all properties of phase a remain uniform up to C, and all properties of phase 0 remain uniform up to C. The region between C, and Cp is the interfacial region. Let a "dividing surface", D, be constructed in the interfacial region such that it passes through all points "similarly situated with respect to the condition of the adjacent matter."l3 Surface D divides the interfacial region into a portion a' adjacent to phase adjacent to phase . Let a closed curve, C, enclose an area A in D. Erect normal lines to D along C; these lines and the surfaces C,, Cp, and D then enclose volumes V and V' in the two halves of the portion of the

Jan 1, 1964

By A Falter

Gyroscopic surveying instruments, which apply the physical law of a gyroscope, are being used for deter-mining the azimuth of lines with a high degree of ac-curacy. In the past ten years, gyro-theodolites have been introduced widely for underground orientation in the mining industry of Russia, Germany and South Africa. Gyroscorpic methods eliminate awkward procedures of conventional shaft plumbing, and provide more safety, excellent control and the highest precision at any point under-ground without interference with hoisting operations. The advantages of gyroscopic orientation in geodetic surveys become obvious in primary and secondary triangulation, in the determination of co-ordinates of single triangulation points, using the method of trigonometric re-section and intersection, and when traversing over long distances or in areas with obstructed view. Other fields of application are found in geophysical surveys and in the orientation of technical objects; e.g. radar stations, relay stations and ballistic missiles.

Jan 1, 1964

A field method combining solvent extraction and paper partition chromatography permits a simple and rapid semiquantitative estimation of gold in siliceous, argillaceous and sulphide ores. The method will facilitate the eyaluation of prospect samples in which the gold is too fine for separation by panning.Ethyl alcohol-hydrobromic acid mixtures are suitable for chromatographic development of the gold complex, and give clear reproducible definition of the gold zone. Substitution of commercial "methylated spirits" for the ethyl alcohol gives equally good definition, improving the potential of the method for field use.A batch of six samples in the range of 0·5 to 5·0 dwt/ton can be completed in two hours. The range may be extended by simple modification to higher or lower values.INTRODUCTIONIn a chromatographic method described previously (Lever 1958, Nevill and Lever 1959), gold from a standard volume of ore clamped between -plate glass was extracted by aqua regia on to the paper. After cautious drying the chromatogram was developed by an ethyl acetate-nitric acid-water mixture and gold was identified by spraying with stannous chloride solution. Sensitivity of the method in the low range was poor. The brown line obtained in the 1-3 dw/j ton range, caused by movement of gold in the reduced form, was not considered to be a satisfactory confirmation of the presence of gold. It was felt that the method would be improved by using a more elegant extraction and applying developing conditions which would produce a well defined purple line at all gold values. Iron was a limiting factor, and a method of eliminating its interference was needed.The method now developed overcomes these shortcomings, and gives a reliable result with a purple line for assay values of 0·5 dwtjton and over. Gold is dissolved from an...

Jan 1, 1964

From March to May of 1963, the Bureau of Mineral Resources carried out an experimental aeromagnetic survey at Cobar, New South Wales, to field test a proton-precession magnetometer installation in the Cessna aircraft VH-GEO. The Cobar area was chosen as considerable information was already held on the Earth's magnetic field there, which was known to provide a range of anomalous areas that are not excessively disturbed.A procedure for survey flying and methods for processing data were developed during the survey. Contour maps of the aeromagnetic results were produced in the field. The experimental survey was successful in outlining magnetic anomalies in detail.INTRODUCTIONSince 1951 the Bureau of Mineral Resources, Geology and Geophysics (B.M.R.) has carried out an airborne magnetometer exploration programme with DC.3 aircraft carrying fluxgate magnetometer equipment. Recently a proton-precession magnetometer was developed by the Design and Development Group of the B.M.R. for observatory use. One unit modified for airborne use was installed in the Cessna light aircraft, VH-GEO. The Cessna was modified structurally to take the magnetometer, associated bird, and winch gear.The proton-precession magnetometer has many good features.1. It utilises the transistor and associated solid-state devices in its electronics, and hence is light and small.This is the basic feature allowing its installation in a light aircraft. The transistor circuits have a high reliability factor and owing to the card sub-unit...

Jan 1, 1964

By H P. Tardif

This paper briefly describes some of the phenomena encountered when materials are submitted to extremely high pressures, such as those produced by the detonation of an explosive charge placed in contact with the material. It was found that extensive changes take place in the? microstructure of iron and steel. Diffusion-controlled processes, such as the transformation of lamellar pearlite, the recrystallization and grain growth of ferrite, and the homogenization of the pearlite-ferrite structure, can take place within micro-or milliseconds. Mechanical twins can propagate without deviation from ferrite to pearlite, thus indicating a proeutectoid ferrite-pearlite-ferrite orientation relationship. The propagation and interaction of intense stress waves in materials was demonstrated with the use of Armco iron. Finally, a comparison is made of the damage produced in metals by the formation of craters made by explosive shock and by hypervelocity impact. D DRING the last few years, exceptional development has taken place in the field of explosive metallurgy, i.e., the

Jan 1, 1964

By H. R. Hardy

Whether the mining engineer is concerned with stress problems in a mine at depth, the development of a new drill bit, or the efficiency of a comminution process, the mechanical properties of the rock with which he must work are of the utmost importance. One of the most popular topics in rock mechanics circles today is ?Is it possible to utilize directly parameters determined from laboratory tests on rock specimens in the analysis of mining engineering problems?? It is the author's opinion that laboratory and .field investigations have not yet reached the stage of development where this question can be answered with any degree of certainty. At present, great difficulties are involved in applying the results of laboratory tests to a mining engineering problem. However, this is due in part to the lack of detailed measurements of stress and deformation in the field and in part to the lack of development of satisfactory structural theories to correlate laboratory and field measurements. Furthermore, if mechanical properties measured in the laboratory are to be directly applied to the analysis of mining engineering problems, the critical mechanical properties must be identified, reliable test procedures must be developed and extensive test programs must be carried out.

Jan 1, 1964

By G Anders

The effectiveness of two types of powder used in long-wall slashing was compared. The evaluation of the results can serve as a good example of how the application of statistical methods to underground test data can help to minimize the number of tests to be carried out. The conclusions are stated concisely, including a definite assessment of the reliability of the tests. Introduction AN assignment at the Algom Nordic mine called for a performance comparison between 70 per cent Cilgel B and 75 per cent Dygel in longwall stope slashing, particularly taking into account, in both cases, the build-up of bootlegs as dependent on hole deviation. Stopes were usually 8 to 10 ft. high and inclined at about 17 degrees. Starting from a raise, they were widened by consecutive longwall slashes to 60 ft., and, al-lowing for drift pillars, were approximately 300 ft. in length along the incline.

Jan 1, 1964

By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Oregon, and Washington) ferrous scrap-industry operations, principally those in Oregon and Washington, points out factors influencing the supply and consumption of scrap materials, such as the complete dependence of steel ingot producers in these States on scrap as a metal raw material and the sizable quantity of scrap exported from Seattle and Portland to Japan. The pattern of the industry is presented as a movement of materials from their diverse sources to the consuming market. The geographic locations of the consuming industries in relation to the areas generating scrap materials and the movement pattern of the supply from source to destination strongly influences the cost of the commodity. The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price. Scrap availability is not finite, because the return of materials as scrap is secular and influenced by constantly varying market conditions. Steel ingot producers use 75 percent of the approximate 500,000 tons of scrap consumed in Oregon and Washington; steel foundries take 15 percent of the total; and iron foundries, ferroalloy plants, and other miscellaneous consumers utilize the remainder. Also, from 1955 to 1960 an average of about 200,000 tons has been exported annually from Oregon and Washington. The foreign exports are supplemented by lesser shipments to other steel producing States, principally in the western United States. From 1955 to 1960 the preferred and higher value heavy melting scrap grades accounted for about 60 percent of total withdrawals which varied between 600,000 and 950,000 tons annually. Total crap withdrawals from Oregon and Washington are projected to 1.8 million tons by 1985, 60 percent (1.1 million tons) of which will be heavy melting grades. No. 1 heavy melting scrap is most attractive to scrap consumers at $35 per ton or less. Price-supply relationships compared with projected scrap requirements indicate future prices possibly over $35 per ton. High prices over a long period could motivate the Pacific Northwest scrap consumers to produce steel from iron ore. However, technologic changes taking place at integrated steel plants could reduce scrap withdrawals from the Pacific Northwest, which might keep the scrap price sufficiently attractive to obviate production of competitive iron products by the Pacific Northwest scrap consumers.

Jan 1, 1964

By G Anders

Underground tests of slusher cables at first might seem to be quite simple and inexpensive. They do, however, take a long time and give results that may be ambiguous and unreliable. Also, because underground test conditions are not exactly duplicable, tests carried out at different times or in different mines could not be compared. An attempt was made to develop a laboratory test method that would provide for all factors affecting slusher cable performance underground in such a way as to make it possible to achieve comparable results from different series of tests by exactly duplicating test conditions. Such a method should also make it possible to vary individual factors systematically in order to give a proper assessment of the effect of changing conditions on cable performance. A set of tests, comparing the same two types of cable both underground and in the laboratory, is described. AN assignment at the Algom Nordic mine called for the comparison of two types of %-in. slusher

Jan 1, 1964

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By C. Wert, P. Bunn

Determination of the solid solubility of gases in metals is usually done by one of two methods. The first is an additive method, in which measurement is made at temperature of the maximum amount of gas absorbed by an initially degassed piece of the metal. Gas additions are made until the dissolved gas first comes into equilibrium with a compound. This method is most useful at relatively high temperatures where the amount of gas absorbed is relatively large and where equilibration of the dissolved gas with the gas atmosphere can be achieved in a relatively short time. The second is a precipitation method. A supersaturated solution of the gas in the metal is held at temperature until equilibrium is established between the gas atoms in solution and a compound. The quantity of dissolved gas is then determined by some physical measurement which is sensitive only to the gas in solution. This method is generally useful in low temperatures. This paper describes measurement of solubility of nitrogen in tantalum whereby measurements at low temperatures using internal-friction methods are plotted together with existing measurements at high temperatures. The solubility is thereby known from less than 0.5 at. pet at 350°C to near 13 pet at 2300°C. Several measurements have been reported of the solubility of nitrogen in tantalum. These are collected in Fig. 1. Three single determinations by Ke,1 Andrews,2 and Brauer and zapp3 are plotted along with a series of measurements by Vaughn, Stewart and schwartz4 and Gebhardt, Seghezzi, and Fromm.5 Although not much doubt exists about the solubility being in excess of 10 at. pet above 2000°C, the solubility indicated at low temperatures depends on whose data are selected as being most reliable. The variation is enormous, being at least an order of magnitude at 500°C. Accordingly, a measurement was begun to examine this discrepancy. The method of measurement finally selected was that of internal friction. A solid solution of nitrogen in tantalum was prepared by heating a tantalum wire in a dilute at-

Jan 1, 1964

By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Ore on, and Washington) ferrous scrap-industry opera ions, principally those in Oregon and Washington, points out factors influencing the supply and consumption of scrap materials, such as the complete dependence of steel ingot producers in these States on scrap as a metal raw material and the sizable quantity of scrap exported from Seattle and Portland to Japan. The pattern of the industry is presented as a movement of materials from their diverse sources to the consuming market. The geographic locations of the consuming industries in relation to the area generating scrap materials and the movement pattern of the supply from source to destination strongly influences the cost of the commodity. The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price. Scrap availability is not finite, because the return of materials as scrap is secular and influenced by constantly varying market conditions. Steel ingot producers use 75 percent of the approximate 500,000 tons of scrap consumed in Oregon and Washington; steel foundries take 15 percent of the total; and iron foundries, ferroalloy plants, and other miscellaneous consumers utilize the remainder. Also, from 1955 to 1960 an average of about 200,000 tons has been exported annually from Oregon and Washington. The foreign exports are supplemented by lesser .shipments to other steel producing States, principally in the western United States. From 1955 to 1960 the preferred and higher value heavy melting scrap grades accounted for about 60 percent of total withdrawals which varied between 600,000 and 950,000 tons annually. Total scrap withdrawals from Oregon and Washington are projected to 1.8 million tons by 1985, 60 percent (1.1 million tons) of which will be heavy melting grades. No. 1 heavy melting scrap is most attractive to scrap consumers at $35 per ton or less. Price-supply relationships compared with projected scrap requirements indicate future prices possibly over $35 per ton. High prices over a long period could motivate the Pacific Northwest scrap consumers to produce steel from iron ore. However, technologic changes taking place at integrated steel plants could reduce scrap withdrawals from the Pacific Northwest, which might keep the scrap price sufficiently attractive to obviate production of competitive iron products by the Pacific Northwest scrap consumers.

Jan 1, 1964

By Chester O. Ensign

The White Pine Mine is situated in the southwestern portion of the Keweenaw Peninsula of Upper Michigan approximately 6 miles south of Lake Superior (Fig. 1). It is east of the Porcupine Mountains in Ontonagon County. The ore deposit is about 70 miles southwest of the famous native copper deposits of the "Copper Country" lying northeast of Houghton. Geological conditions are different at every mine and create a special set of problems in dilution control. This paper is largely intended to describe the techniques applied in mine dilution control (grade control) at White Pine, and present results of the program. For necessary background information major geologic characteristics of the deposit, particularly those that exert control over the distribution of ore, are briefly discussed. Mining methods are described in considerable detail since applied grade control techniques are adapted to these.

Jan 1, 1964

By R. B. Anderson

As a part of a Bureau of Mines program on the conversion of coal to liquid and gaseous fuels, the kinetics of the Fischer-Tropsch synthesis on iron catalysts was investigated. Nitrided catalysts were studied at 21.4 atmospheres using feed gases ranging from 2H2+1CO to 0.25H2+1CO, and at 7.8 to 21.4 atmospheres using 1H2+1CO gas. The overall apparent activation energy increased with increasing carbon monoxide content of the feed gas from 19.5 kcal/mole for 2H2+1CO to 23.7 for 0.7H2+1CO. The rate of synthesis with 1H2+1CO feed increased linearly with operating pressure from 7.8 to 21.4 atmospheres. A semifundamental rate equation of the form [r=a'PH2 0.6pco 0.4- ?r0.5PH200.5] was shown to fit the data satisfactorily. The relative usage of hydrogen to carbon monoxide decreased with increasing conversion, passed a minimum, and then increased. Apparently water is the principal primary product and carbon dioxide is produced by subsequent water-gas shift reaction. In another group of experiments water, carbon dioxide, argon, and methane were added to 1H2+1CO feed to a nitrided iron catalyst. Argon and methane were only diluents. Carbon dioxide was a slight inhibitor and water vapor was a strong inhibitor to the rate of synthesis. Water accelerated the water-gas shift and usually increased methane production. Important factors of catalyst geometry in determining rate were found to be particle size and extent of reduction. Apparently the active portion of the catalyst is confined to a layer of 0.01 to 0.02 cm from the external surface of particles. A special solution was made of differential equations relating re¬action at the catalyst surface to diffusion in pores of the catalyst for spherical particles with an active layer surrounding an inert core. The equation derived expressed the experimental data reasonably well. Diffusivities determined by this equation varied from 3 to 24X10-6 cm2/sec; these values are of the same magnitude as observed for the diffusion of gases in liquid. The appendix presents a group of synthesis experiments at pressures of 21.4 to 103 atmospheres. In this range the rate of synthesis on nitrided iron catalysts increased with pressure to the 0.74 to 0.84 power.

Jan 1, 1964