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By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By T. A. Rickard

Clement Le Neve Foster was born at Camberwell on March 23, 1841, his father being Peter Le Neve Foster, who was secretary of the Society of Arts for 26 years. As a boy of 12 he was sent to school at Boulogne, receiving a preliminary education there; and in 1857, when only 16 years old, he took his degree of Bachelor of Science from the University of France. In October of the same year he returned to London and entered the Royal School of Mines, which was then in Jermyn Street. He distinguished himself by winning a scholarship and a medal, and by securing his degree as Associate of the Royal School of Mines in the abbreviated period of two years. This was followed by a year at the Bergakademie at Freiberg; subseque1:tly he visited several mining districts in Germany and Hungary. On returning to England, in November, 1860, he received from Sir Roderick Murchison an appointment upon the Geological Survey. During five years he was engaged in field-work, first on the Wealden beds in Kent and Sussex, and then in Derbyshire and Yorkshire. At this time his evenings were largely devoted to reading for a degree from London University. In 1861 he matriculated, obtaining the Bachelor of Science in 1863, with honors in biology and a University scholarship in geology; in 1864 he passed the two examinations entitling him to the Bachelor of Arts degree, and in 1865 he received the degree of Doctor of Science. In 1865 he succeeded Mr. Richard Pearce as lecturer to the Miners' Association of Cornwall and Devon. At the same time he became the curator to the museum of the Royal Geological Society of Cornwall at Penzance, a member of the council in 1873, and a life-member in 1874; he made frequent donations to the museum, besides contributing several valuable papers to

Jan 1, 1905

Jan 1, 1970

By Randall L. Neal

This paper discusses the impact of taxes at the state and federal level on typical on-shore oil and gas exploration economics in the USA. Taxes considered are the windfall profits excise tax, state production (or severance) taxes, state income tax, and federal income tax. Also considered will be market prices for oil and gas in the USA. The effect of government take as a percent of revenue, on rate of return, discounted Payout, and discounted cumulative cash flow is shown on the attached tables. The conclusion drawn is that tax laws, while rarely the most important factor to be considered when drilling a well, can have significant impact on the profitability of oil and gas ventures, and should be considered when determining where to drill. Hypothetical exploration wells were analyzed for the impact of tax laws on project profitability. The results of this study show that when factors other than taxes are postulated to be the same (such as producing rate, capital, operating costs, and prices), cash flow can vary by as much as 68% due to the differences in the tax laws. Other significant findings for the cases studied include: (a) that discounted payout varied by as much as 1.8 years, (b) that rate of return differed by up to 67% and (c) the total tax rate as a percentage of revenue had a maximum variance of 33%.

Jan 1, 1982

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

William Kent, New York City: I regret that I have not had the time since the Cincinnati meeting to make as complete a study of Mr. Salom's paper as I wished. I regard it as one of the most important papers that have been presented on this subject, and worthy of complete study. I started out, on the limited time I had, on a system of study which I would recommend to any one else who has leisure to complete the investigation. I took the original report presented at the Cincinnati meeting, and selected from it' such tests as had the analyses reported along with the physical tests, giving the amounts of carbon, phosphorus, manganese, etc., taking only those in which all these elements are given.

Jan 1, 1885

By G. D. Rieck, G. H. G. Vaessen, D. L. Vogel

Both doped and undoped tungsten single crystals exhibit hardness anisotropy with respect to the direction of testing in each of the crystallographic phes investigated. The hardness anisotropy of undoped single-crystal tungsten is rather pronounced in (001) and (110) planes but very minor in (111) planes. The anisotropy in (122) planes of the doped and drawn tungsten after recrystallization is in accordance with a previously published concept of a stringlike distribution of the doping material in the metal. ANISOTROPY in mechanical properties of single-crystal tungsten was investigated by Rose et al., Garlick and Probst,2 and Beardmore and Hull. 3 Although data on the Vickers microhardness of tungsten have been published (see, e.g., Boosz 4 and the references cited by him), no data on the microhardness anisotropy are available. We report, therefore, some of our own results on the microhardness and its anisotropy. The microhardness has been determined of the following samples. A) Polycrystalline tungsten samples taken from: 1) powder metallurgical tungsten "normally" doped with potassium-silicon-aluminum oxides (final contents inppm: K, 100; Si, 100; Al, 20; Cr, 20; Fe, 50; Mo, 400; Ni, 10) and in the form of: a) a 10-mm-diam swaged ingot annealed at 1600°C, the grain sizes varying between 15 and 250 p; b) a sheet rolled at about 800°C and recrystallized at 2000°C7 the grain sizes varying between 15 and 150 p; c) a 2-mm-diam swaged rod, as-worked, with elongated grains (average diameter of about 25 , lengths up to 1 mm); 2) undoped electron-beam-melted tungsten with very large grains (contaminations in ppm: K < 10; Fe < 20; Cr < 10; Cu < 0.1; Ni not detectable; inter-stitial~ not determined). B) Single-crystal samples taken from: 1) pure tungsten grown on a Pintsch wire by the van Arkel procedure (main contaminations inppm: Mo, 100; Si < 10; Cu and Fe, 2; A1 < 2; interstitials not determined); 2) zone-melted undoped tungsten (analysis as under A2); 3) large crystals in secondary recrystallized tungsten

Jan 1, 1969

By B. W. Frazier

Jan 1, 1882

By H. O. Hofman

Jan 1, 1896

Jan 1, 1968

Prof. Henry S. Jacoby, Cornell University,Ithaca, N.Y. (communication to the Secretary): When a simple beam supports any given load, the lower fibers me in tension while the upper fibers are in compression, and if its cross-section is rectangular the neutral surface, where the stresses pass through zero from tension to compression, is at mid-depth, provided the elastic limit is not exceeded. In addition to the longitudinal stresses, there are horizontal shearing-stresses between the fibers which have their maximum value in the neutral surface, and which equal zero at the upper and lower surfaces, while there are also vertical shearing-stresses. Let another beam of the same dimensions be placed on top of this one, and the load be doubled, it then produces stresses in each beam of the same character, magnitude and distribution as in the preceding case, provided there be no friction between the adjacent surfaces of the beams. Next let these two beams be so firmly united that there will be no motion between them when the same load is again applied. All the fibers in the upper beam are now in compression, and those in the lower beam in tension, while the maximum stresses in the outer fibers are only one-half as large as before. The strength of the combined beams is therefore doubled. If, however, some motion occurs between the beams, then the stresses in some of the lower fibers of the upper beam pass from compression to tension, and those in some of the upper fibers of the lower beam from tension to compression, while the stresses in the outer fibers have a magnitude between the two values previously stated. These fundamental facts relating to the flexure of beams indicate the necessity of carefully designing the keys or brace-

Jan 1, 1898

By Ezequiel Ordonez

MOST spectacular of Nature&apos;s contributions to the making of the postwar world is the Paricutin volcano, in Mexico, which I described in the July issue of this magazine last year, a few months after it was born. Now, after more than a year of continuous eruption, it is still and perhaps will remain a comparatively small though no less interesting volcano. The cone on April 1 had an altitude of nearly 1200 ft. above the level of the small flat field from which it began to grow on Feb. 20, 1943. This cone is now almost entirely surrounded by the lava flows that poured out at different dates, from its base or from outlets on the slopes near its base. To the north and northwest these lavas were

Jan 1, 1944

Jan 1, 1961

By H. H. Richardson, E. H. Dix

Of all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations would have been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 525" C. to about 1 per cent. at 300" C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540" C., and that this amount decreases to about 3 per cent. at 20" C. In the same year Ohtani and Hemmi3 reported a solubility of 4.8 per cent. copper at 520" C., 2.6 per cent. at 460" C. and 1.5 per cent. at 420" C.

Jan 1, 1926

By M. C. LAKE

THE industrial development of the United States has been stimulated by the presence of high-grade iron ore in the Lake Superior district. These great deposits have been susceptible to economical extraction and are conveniently located for cheap lake vessel transportation to the great consuming centers. The district furnishes from 80 to 85 per cent of the iron ore annually consumed in the United States, and a full understanding of the available supply of this great commodity is so important that it is well to consider whether or not the industrial supremacy and national independence attained as a result of the abundance of cheap ore are permanent. The enormous deposits of high-grade ore available in the Lake Superior district have been the foundation upon which the vast industrial structure of the steel and allied industries has been built. It is extremely important to the country as a whole, and especially to those States and communities now dependent on Lake Superior ore for their prosperity, that their industries shall retain the particular advantages with which they are now endowed, and that a generous supply of high-grade raw material be available for their consumption at a satisfactory cost. The steel industry is so basic and fundamental that any fluctuation in the cost of its finished products as determined by the supply and cost of the raw materials involved in its manufacture will necessarily affect the business of a wide variety of industries which are dependent on it.

Jan 1, 1926

By AIME AIME

ON the morning of Monday, Nov. 9, 1936, two motorcycles, with sirens screeching, - escorted a procession of 70 automobiles from the Colonia Railway Station in Mexico City to the Hotel Geneve. Riding in&apos; the cars were just over 200 visitors- members of the A.I.M.E. and their guests. They had come, via St. Louis, in two special trains from 24 different states for the 146th General Meeting of the Institute. During the morning they and 200 others, who had come from the United States by automobile or from various cities and mining camps in Mexico, duly registered with !efficient Mme. Irma Ordoiiez de Obregon and her assistants. Then started a week of strenuous but delightful activity that will never be forgotten by the participants. They were to cover more than 500 miles by automobile, always with a motor escort, and often

Jan 1, 1937

By Perry Olcott .

THE Taka oil field is in the northern part of Titus and Franklin Counties, in north- eastern Texas. The small town of Talco, from which the field derives its name, is on the P. & Mt. P. R. R., about 15 mi. north of Mt. Pleasant, the county seat of Titus County. The oil field extends east and west from the town of Talco, the approximate center. In May, 1924, R. L. Cannon, while doing surface geology for the Humble. Oil & Refining Co., mapped the surface trace of this fault structure as evidenced by Upper Midway faulted down against Lower Midway. In the interval of sixteen years between the original surface work and the recent productive well completion, approximately eight wells were drilled into the Woodbine sand without success. The structure was well defined by those tests and all of the wells en-

Jan 1, 1936

By Henry M. Howe

PART I. § 1. Introduction. After giving certain definitions, this paper gives the reasons which led to Roozeboom&apos;s form of the diagram of the freezing-point curves and general equilibrium of the iron-carbon compounds, steel and cast-iron ; and then those which led to replacing it with the present or double diagram, in which graphite is at all temperatures held to be the more stable and cementite the less stable (metastable) form of carbon. Next in § 10 the evidence supporting this greater stability of graphite is examined, then in § 17 that which seems to oppose it, and in § 22 a summary of the evidence is presented. The second part of the paper considers the topography of the graphite-iron diagram, rejecting summarily the solubility-lines based on the data of Charpy and Grenet and of Mannes-mann, on the ground that the data even on their face do not really point toward these lines, and that they are wholly incompetent to determine any solubility-lines whatsoever, because they report together with the dissolved carbon also an indeterminate quantity of cement-carbon, and because even such carbon as is actually dissolved, only in part represents the solubility of graphite, and in another and indeterminate part represents the solubility of cementite, or at least of carbon in presence of cementite as distinguished from graphite. It might be thought that graphite is but slightly soluble in iron, because of the absence of any suggestions of eutectoid graphite, corresponding to the eutectoid cementite of pearlite in very many cases in which the cast-iron seems to consist of ferrite and massive graphite only, and because of the micrographs of Goerens and Gutowsky. In these the primary austenite of cast-iron quenched but little below the eutectic freezing-

Jan 7, 1908

By C. Y. Wen, H. O. HOPMAN

l. INTRODUCTION. IN casting a thermal balance of the heat generated and absorbed in a blast-furnace treating lead-, copper- and similar non-ferrous ores, assumptions have always to be made for the values of the heat of formation of slag. ? Considering that the larger part of the charge introduced into the furnace comes out in the form of slag, the significance becomes apparent of a lack of heat-values for the singulo-silicate, which is the type of slags commonly made. The aim of the present investigation is to supply these heat-values as far as possible with the apparatus and the time available. The heats of formation of the ferrous and manganous bi-silicates have been determined by Le Chatelier; 1 those of some silicates other than iron and manganese by Tschernobaeff:2 finally Richards 3 gives a figure for a copper blast-furnace slag of known composition. The existing data and those resulting from the present investigation are assembled in Table VI. II. MATERIALS USED. The materials used in the experiments were silica, ferrous oxide, and calcium carbonate. Silica.-The silica sold in the market as chemically pure usually contains small amounts of magnesia, lime, and alumina, and is therefore not suited for the work. The pure material was obtained from clear quartz crystals from Arkansas, broken in a diamond mortar and ground in an agate mortar to pass 1 Comptes rendus, vol. cxx., p. 623 (1895); vol. cxxii., p. SO (1896). 2 Revue de Métallurgie, vol. ii., p. 729 (1905); Electrochemical and Metallurgical Industry, vol. iv., No. 2, p. 72 (Feb., 1906). 3 Electrochemical and Metallurgical Industry, vol. v., No. 7, p. 266 furls?, 1907;) ; Metallurgical Calculations, vol. iii.,.pp. 474, 475 (1908).

Jul 1, 1910