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By Eugene S. Perry

The most outstanding event in oil and gas development in Montana during 1936 was the discovery of oil in the Baker-Glendive gas field, in the extreme eastern part of the state. Other notable achievements were small extensions in the Cut Bank oil field; continued favorable results of acidization in the Kevin-Sunburst oil field; and the discovery of oil and gas in commercial quantities about 20 miles southwest of Billings, on what is known as the Mosser dome. Several wildcat wells were drilled. For the coming year of 1937, it is anticipated that the main activities will be confined to drilling in or near known fields. During 1936 Montana had seven fields producing oil, but over 95 per cent of oil production came from four fields, which in order of importance are: Cut Bank, Kevin-Sunburst, Cat Creek and Pondera. Total production for the state was 5,850,893 bbl., which is 1,251,761 bbl. more than the total for 1935. Natural gas was produced and marketed from eight fields, most important being Cut Bank, Baker-Glendive, Kevin-Sunburst and Dry Creek. These four fields accounted for over 85 per cent of total state gas production, which is slightly greater than the 1935 production of nearly 18 billion cubic feet. Increase in gas consumption is due in part to increase in smelter operation. More detailed information pertaining to the various fields is given in Table 1. In the Baker-Glendive field a test 8186 ft. deep, 15 miles southeast of Baker, was completed by the Montana-Dakota Utilities Co. in 1936. The first gas-bearing sandstone (Judith Hiver horizon, Upper Cretaceous) was found at a depth of 528 ft., and a second sand at 1167 ft. Sandstones of the Dakota formation, in which occurred water, were found from 3724 to 3853 ft. White sandstone correlated with the Tensleep (Minnelusa) formation of Pennsylvanian age was found from 5631 to 5751 ft. deep. The lower 1900 ft. of the well (below 6278 ft.) was essentially in limestone and dolomite, and information on correlation of formations in this mass of sediments is not available at this time. The upper portion of this part of the well contained much anhydrite. Cherty and dolomitic limestone below 7000 ft. may be equivalent to limestones of the Madison formation. The thickness of strata beneath the Dakota formation was

Jan 1, 1937

By R. E. Lund, D. E. Warnes

SELECTIVE sulfation of individual constituents in ores or metalliferous products has received increased attention in recent years. The fluid-bed reactor with its advantages of close control of both temperature and atmosphere promises to have ap-

Jan 1, 1958

By J. M. Ohm, Carl M. Bunker

Two special tools for recovering gamma-ray probes and logging cable from drillholes have been designed by Ohm and Bunker and constructed by Ohm. Though intended specifically for U. S. Geological Survey equipment, they may be used with other equipment of the same general type. Fishing Tool for Probes: A fishing tool of the overshot type (Fig. 1) was designed to retrieve logging probes (sondes) that become disconnected from the logging cable and are trapped in the drillhole. When the tool slides over the top of the gamma-ray probe, studs on the bottom engage the shoulder near the top of the probe (Fig. 2), which is then pulled to surface.

Jan 10, 1959

Iraq Petroleum Co. together have produced more than 2,000,000 bbl. from all areas since 1927, most has been returned to the reservoir through the wells. Iraq Petroleum Company's small skimming plant at kirkuk supplies its operating requirements. Drilling Operations The Iraq Petroleum Co., since 1930, has discontinued exploratory drilling and concentrated on the exploitation of the Kirkrik field preparatory to filling its 84,000 bbl. pipe line. Drilling operations are on schedule and the I.P.C. expects to have its initial producing wells ready to turn into the line by April of this year. The Mosul Oil Fields Ltd., holding company of all the shares in the British Oil Development Co., after acquiring the "West Tigris Concession" in May, 1932, has completed a geological survey of its 46,000 square miles and is entering upon an exploratory drilling program with three cable-tool rigs. Petroleum in Iraq Transferred Territories in 1933* The Khanaqin Oil Co., which operates the Naft Khaneh field in the so-called Transferred Territories, has continued to supply the Iraq market with petroleum products during the period under review. The output of it's refinery at Alwand during the past three fiscal years ending March 31 has been as follows:

Jan 1, 1934

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,' the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

Some years ago the open Hearth Committee of the Institute reached the conclusion that the reading of "set" papers tended to preclude the specific and detailed discussion of specialized problems of current interest to those operating steel plants. As an innovation the Committee distributed in advance of the meeting in May, 1927, a questionnaire containing a list of 27 topics involving operating problems. The subsequent discussion of the questions, participated in by 37 members, was a conspicuous success. Semiannual meetings have been held since; and at the conference of November, 1929, at Chicago, 131 men were present and the minutes comprised a book of 133 printed pages, thereby, indicating the growing value of the conference in the eyes of both the metallurgists themselves and the companies that employed them. With this example in mind, the Directors felt that definite advantages would accrue to a similar conference to be participated in by smelter officials and metallurgists engaged in the operation of copper reverberatory furnaces. The settlement of the Carson litigation, which for several years had virtually stopped public discussion of reverberatory practice, offered an opportune time for launching the scheme. Although the Conference may become largely self-financing in the future, some funds were regarded as necessary to conduct the first meeting. The members of the Rocky Mountain Income Committee, in view of the fact that copper smelting was essentially an activity of the Rocky Mountain area, recommended the project be, in effect, underwritten by the Fund, and the directors approved an appropriation for this purpose. Invitations were extended to high executives of the various-companies interested to send representatives to an initial meeting to be held at Salt Lake City, May 26-27. The response was enthusiastic. Twenty-three metallurgists representing 12 different plants were present to discuss the comprehensive-program relating to construction and operating phases of reverberatory smelting. It was understood that the record was not to be included in the regular publications of the Institute but that it would be prepared for private distribution among the participants and the officials of their companies. That the exchange of views and experience was no less instructive and stimulating than it was frank, full and informal is indicated by the following transcript of the minutes of the meeting.

Jan 1, 1930

By Harold S. Davis

SURROUNDING the nuclear core of an atomic energy plant there are usually one or more thick walls of concrete, as required to protect instruments and personnel from the harmful effects of nuclear radiations. Sometimes these massive walls are of ordinary concrete weighing about 150 pcf. To reduce wall thicknesses, concrete weighing 200 to 350 pcf may be used. Such high densities are obtained by using natural aggregate processed from heavy ore, or by using steel slugs or iron shot in concrete. Mix data for a number of high-density concretes are summarized in Table I.1 High density at low cost is of prime importance in shields designed to absorb gamma rays. On the other hand, biological shields located near the reactor core must attenuate neutrons as well as gamma rays. In general, a biological shield should contain: 1) heavy elements to slow down high energy neutrons and to absorb gamma rays, 2) either light elements or hydrogenous materials to moderate neutrons of intermediate energy, and 3) materials to absorb neutrons once they have been slowed down to thermal energies. Some shield materials, iron and water for example, are effective in one or more of the above ways. On the other hand, some otherwise excellent shield materials have certain undesirable radiation properties that limit the ways or number of places they can be used. For example, when iron absorbs neutrons it emits secondary gamma rays of high energy. On the other hand, boron absorbs neutrons avidly without producing high energy gamma rays. In spite of its high cost, boron is sometimes used in concrete to minimize production of secondary gamma rays. In some shielding applications it is necessary to avoid materials that become radioactive when subjected to neutron bombardment, continuing to give off high energy gamma rays for long periods after being removed from a neutron field.

Jan 5, 1957

By R. L. Huntington, Frank P. Vance, George F. Russell, Robert Thompson

With the advent of higher pressures in the operation of natural-gas transmission lines, the removal of water vapor from the gas has become increasingly important in order to prevent condensation or formation of gas hydrate from slowing down or stopping the flow of gas. Intelligent design of these dehydration or gas-drying plants has been hampered through the Iack of experimental data on the water vapor content of natural gas at elevated pressures. In view of this need, this present investigation was sponsored by the Southern Natural Gas Co. in the Chemical Engineering laboratories at the University of Oklahoma Research Institute. Experimental results were obtained on the water-vapor content of natural gas up to 2000 lb. per sq. in. at atmospheric temperatures. The water content at 2000 lb. is approximately two thirds as much as it is at 1000 Ib. Deviations from the ideal gas laws vary directly with pressure and indirectly with temperature. Introduction The removal of water vapor from natural gas is an important operation in connection with the production and transportation of this commodity because: I. Liquid water accelerates internal corrosion of a pipe line. 2. Accumulation of water at low points in a pipe line reduces markedly its capacity. 3. Gas hydrates, icy snowlike growths, form readily under high pressure in the presence of the lower hydrocarbons and water, often plugging up the pipe line. In order to design dehydration plants for stripping the gas of its water content, it is essential that the engineer. have a knowledge of the saturated or equilibrium water-vapor content of the gas to be processed. With the gradual increase of operating pressures around gas-producing wells and pipe lines, it was observed that the quantity of water recovered from dehydration plants or condensed in colder lines was considerably greater than had been expected from calculated contents, based on vapor-pressure data taken from steam tables. This observation prompted a number of investigators, for instance, Laulhere,3 Dea-ton,l and Hammerschmidt2 to carry out experimental work at pressures up to 600 lb. per sq. in. in order to determine quantitatively the water content of various gases. Sage, Lacey, et al.4,5 have recognized more recently the need for such data at higher pressures, but their work was done at temperatures of 100ºF, and higher. Since hydrate formation usually, if not entirely, occurs at temperatures below 100ºF., the present investigation was confined to the . lower temperature range at pressures from 600 to 2000 lb. per sq. in. gauge.

Jan 1, 1945

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).-This interesting paper throws additional light on a question about which differences of opinion have apparently existed in the past, and the writer would like to record in this connection the agreement of his experience with that of Primrose and Prof. Smart in regard to the effect of quenching on the properties of gun-metal bronze. The writer's results have been published, so that there is no need for a detailed report, here, but his in-vestigations resulted in showing that both gun metal and manganese bronze are ruined by quenching in water from a red heat, apparently because they cannot stand the strains produced by the sudden cooling. The lines, mentioned by Prof. Smart, in a polished and etched section of the quenched metal have also been noticed by the writer, who however has not found them any different in quenched specimens than in annealed specimens. Since they appear only after etching, it would seem most probable that they are merely grain boundaries in most cases, though Prof. Smart's idea that they are indications of strains is by no means impossible. Fig. 1 shows how these lines appeared on the author's speci-mens of annealed gun metal, etched with ammonia and hydrogen per-oxide, and magnified 100 diameters.

Jan 11, 1919

By R. O. Harma

Introduction Wet autogenous grinding is utilized in three iron ore concentrating plants operated by the Cleveland-Cliffs Iron Company (CCI). This paper will trace some of the development in converting from the use of metal grinding mill liners to the use of rubber and will update the current performance of rubber liners in these applications. The Cleveland-Cliffs Iron Company is a natural resources firm with major interests in iron ore mining and processing and oil and gas contract drilling. The company also has interests in oil shale, uranium, forest products, and Great Lakes shipping. The three operations discussed in this paper are the Empire and Tilden Mines on the Marquette Iron Range in Michigan's Upper Peninsula and the Sherman Mine in northern Ontario, Canada. The Empire Iron Mining Partnership is managed by The Cleveland-Cliffs Iron Company and is owned by Inland Steel, McLouth Steel, The Cleveland-Cliffs Iron Company, and International Harvester. The Tilden Iron Mining Partnership is also managed by The Cleveland-Cliffs Iron Company and is owned by Algoma Steel Corporation, Ltd., Jones & Laughlin Steel Corporation, The Cleveland-Cliffs Iron Company, Steel Company of Canada, Wheeling-Pittsburgh, and Sharon Steel Corporation. The Sherman Mine is a joint venture managed by Cliffs of Canada, Ltd. and owned by Dominion Foundries and Steel Company, Ltd. and Tetapaga Mining Company, a wholly owned subsidiary of The Cleveland-Cliffs Iron Company. The concentrators at all three mines utilize two stage autogenous grinding. Empire and Sherman process magnetic iron ores (Table 1) and utilize magnetic, hydraulic, and flotation concentration methods. Tilden processes an oxidized iron ore (martite, goethite, and hematite) and utilizes a selective-flocculation desliming and flotation concentration flowsheet. Final grind particle sizes are 90% -325M (43k) at Sherman, 90% -500M (25,u ) at Empire and 85% -500M (25 µ) at Tilden. Developmental History The success of using rubber mill linings in Scandinavia led to the first rubber mill lining used by CCI. It was installed in a conventional primary ball mill at Republic Mine in 1964 as reported by Lindroos (1970). This was followed by additional rubber liners for both primary and regrind ball mills. Generally these rubber linings provided about twice the service life as compared to the Type I Ni-hard liners previously used. Grinding efficiency of rubber was found to

Jan 1, 1982

By Harrison A. Schmitt

One of the great copper-producing areas of the world is comprised of five U. S. western states and northern Sonora, Mexico. The Southwest province of this area, covering southern Arizona, south- western New Mexico, and northern Sonora, produces some 55 pct of U. S. copper output and the equivalent of 15 pct of world production. In 1956 the area produced about 550,000 tons. Tucson is approximately the center of the oval- shaped province, which measures only 300 miles on its east-west axis and about 200 miles on its short axis. Northwest of the oval, and forming a tenuous connection with the Utah and Nevada copper fields, is an important operating mine, Bagdad, and also the now inactive United Verde. Along its north- south axis, running from Globe, through Tucson, to Nogales, ten moderate to major copper properties have been discovered or revived during the past 15 years, and five of these in only the past seven years. The latter five properties lie in an area 25 miles in diameter, centering 20 miles south of Tucson. In order of discovery, or revival, they are: Banner's Mineral Hill and Daisy; Cyprus et al's Pima; Duval's Esperanza; Asarco's East Pima (now called Mission mine) ; and Lewisohn's Peach. Total tonnage is estimated at about 250 million tons averaging some 0.90 pct Cu, but ultimate production may exceed this amount since some of the reserve is open ended.

Jan 6, 1959

By William E. Ford, Edward Salisbury Dana

447. Minerals, as regards their chemical constitution, are either the uncombined elements in %native state, or definite compounds of these elements formed in accordance with chemical laws. It is the object of Chemical Mineralogy to determine the chemical composition of each species; to show the chemical relations of different species to each other where such exist; and also to explain the methods of distinguishing different minerals by chemical means. It thus embraces the most important part of Determinative Mineralogy. In order to understand the chemical constitution of minerals, some knowledge of the fundamental principles of Chemical Philosophy is required; and these are here briefly recapitulated. 448. Chemical Elements. - Chemistry recognizes about eighty sub- stances which cannot at will be decomposed, or divided into others, by any process of analysis at present known; these substances are called the chemical elements. A list of them is given in a later article (452) ; common examples are: Oxygen, nitrogen, hydrogen, chlorine, gold, silver, sodium, etc.

Jan 1, 1922

Jan 1, 1890

By Alfred H. Bell, Charles W. Carter

In 1942, Illinois produced 106,590,000 bbl. of crude oil, or 7.6 per cent of the entire amount produced in the United States. It ranked fifth among the oil- producing states. The production for 1942 declined 20.5 per cent from the previous year's total of 134,139,000 bbl. Tie daily average production for 1942 was approximately 292,000 bbl., or 74,000 bbl; less than the 366,000 daily average for 1941. At the beginning of 1942 the daily production was 367,000 bbl. This production declined steadily to 282,000 for June and to 246,000 for December. This steady decline was caused partly by the reduction in drilling resulting from Federal Conservation Order M-68 and partly by the fact that no major pool was found during the year. Discoveries Forty new fields (Fig. 2, Table 2), 48 extensions (Table 3), and 45 additional producing zones in existing fields (Table 4) Were discovered in 23 counties in Illinois during 1942. Of the 40 new fields, three

Jan 1, 1943

Colorado today is the largest coal producing state west of the Mississippi River. Developments around Denver began about 1860, and the building of railroads created a good market for the new industry. The development of the smelter and steel industries near Pueblo increased the demand. The available records are not complete, and all the data found are shown in Table 76. [ ]

Jan 1, 1942

By J. C. Allen, E. V. Herring

CHILE EXPLORATION CO's. oxide plant at Chuquicamata, the largest of its kind, started in 1915 with initial operations at the rate of 10,000 tons of ore per day. Anaconda Copper Mining Co. acquired the controlling interest in 1923 and in the next few years modernized the plant and mine, extending operations to a nominal capacity of 490 million lb of electrolytic copper yearly by 1942. Plant production averaging 495.7 million lb of copper per year was maintained for the eight-year period extending from 1941 to 1948 inclusive. During the World War II production reached its highest level when in 1944 the output was 531.8 million lb. The maximum production for any one month was 49.6 million lb, achieved in May 1947. E. A. Cappelen Smith, consulting metallurgist for M. Guggenheim's Sons, worked out the first process for the treatment of Chuquicamata copper oxide ore about 1913, and directed a staff of 20 young engineers operating a pilot plant at Perth Amboy, N. J., on three shifts for an entire year. The copper is extracted from the oxide ore by a hydro-metallurgical treatment described in detail by T. A. Campbell in AIME Transactions, Vol. 106, Copper Metallurgy, 1933. The Oxide Plant is divided into five main operations as follows: (1) Crushing, (2) Leaching, including dechloridizing and sulphur dioxide treatment, (3) Tailing disposal, (4) Electrolytic precipitation, (5) Smelting and melting. Crushing The present Primary Crushing Plant has been in operation 25 years, during which time 4,342,112 cars of 70 tons net capacity have passed through the dumpers. The ore as received from the mine is frequently blocky and up to 5 feet in section. It is reduced to 9-in. size by two 60-in. gyratory crushers, and transported to the east and west ore bins by 60-in. conveyors. In the secondary crushing operation the ore is first reduced to 2 to 3-in. size by five standard 7-ft cone crushers and two No. 10 gyratories. This product is then reduced to 3/8-in. size by fifty-two 48-in. vertical Symons disc crushers and is transported by belt conveyors to the loading bridges from which it is charged° into the leaching vats. Conveyor belt No. 14 which serves the eight vats in the east section of the leaching plant has transported over 125 million tons of ore, which is a record for any type of conveyor. This 60-in. belt travels at a speed of 600 fpm and carries loads up to 5500 tons per hr. Leaching The ore is leached in 14 vats, averaging 13,500 short tons net capacity each. These vats are lined with a natural mastic which adequately resists the sulphuric acid leaching solutions. The leaching process as presently conducted comprises soaking the ore with successive volumes of leaching solution and spent electrolyte and withdrawing successive volumes of enriched solution from the vat to a total of approximately 3.2 million gal. The first 1.6 million gal of this volume withdrawn is called strong solution and contains about 35 parts of copper per 1000. The balance of 1.6 million gal subsequently withdrawn is stored in a

Jan 1, 1952

Jan 1, 1934

By Jonathan Ludlow, Paul J. Guay

Based on two studies that were funded by the U.S. Department of Energy, the authors provide an overview of the benefits expected from mining deeper webs on United States longwalls. The first study, completed in November 1979, identified the limits and potential gains from taking deeper webs with presently available equipment. The second on-going study discusses the conceptual design and benefits of a future system for taking very deep webs.

Jan 1, 1981

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968