Search Documents

By Wm. C. Phelps, R. E. Grace

b R.c c)nduciivity of slags and glasses is of particular interest when viewed as an activated ionic flow process. The ionic conductivity, for example, has been found to obey the Easch-

Jan 1, 1958

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By W. E. Brigham, P. W. Reed, J. N. Dew

STANDING COMMITTEES Executive-A. R. LEDOUX, chairman. Membership-GEORGE C. STONE, chairman. Finance-J. V. N. DORR, chairman. Library-E. GYBBON SPILSBURY, chairman. Papers and Publications--BRADLEY STOUGHTON, chairman. Nominations-POPE YEATMAN, chairman.

Jan 9, 1919

By H. S. Cannon, F. N. Rhines

The application of a static load to a copper powder compact during sintering at an elevated temperature accelerates the rate of sintering in such a way that a given load induces the same proportional increase in rate for all times of sintering. It is shown that sintering under a load is like creep under a fixed load in that the stress required to accomplish a given degree of densification is proportional to the logarithm of the sintering time. VIRTUALLY all of the theories of sintering that have been put forward within recent years have contained the assumption that the chief driving force of the process is the surface tension resident in the exposed surfaces and internal pores of the compact, or powder mass. An externally applied load might be expected to provide a somewhat equivalent driving force for sintering. It is known that the application of a compressive load, during sintering, hastens densification, but it is by no means clear whether sintering under the influence of surface tension alone and sintering under an applied load are fundamentally similar processes. The present study was undertaken in an effort to obtain an answer to this question and with the hope that the answer may contribute to an understanding of the mechanism of sintering. It has been found that there is a close relationship between sintering and creep processes. Copper powder compacts were sintered in hydrogen at 1000 °C under dead loads of 0 to 165 psi and the progress of sintering was observed by means of density measurements. Using a commercial reduced oxide copper powder, see Table I, cylindrical compacts Yz in. x x in. high were made at a pressure of 12,500 psi. For sintering, these were placed in a cylindrical graphite container into which they fitted snugly. A compressive axial load was applied to the compact through a graphite rod of similar diameter, which rested upon the upper end face of the compact; iron weights, in suitable amount, were placed upon the graphite rod to provide the load. This assembly was encased in a vertical silica tube within a resistance-type furnace capable of maintaining a substantially constant temperature within the working zone. After various predetermined times at temperature, the samples were removed from the furnace and their density was measured by conventional means. The heating-up and cooling-down times have been included in the computed sintering time, using the assumption that the sintering rate doubles for each increase of 10 °C in temperature. The experimental results are presented in Table 11. Upon metallographic examination of the specimens, it was found that there was no apparent change in the shape of the pores as a result of loading, i.e, no flattening, Fig. 1. Substantial contraction away from the container walls was observed in all samples sintered with loads of 10.5 psi and less.

Jan 1, 1952

By B. A. Eaton, R. H. Jacoby

This paper presents the depletion-performance correlations developed using data from PVT studies and well-completion tests of 27 rich gas-condensate and volatile-oil reservoir fluids. The PVT behavior for each fluid war determined experimentally in the laboratory, and the depletion performance of each fluid was then calculated. Well-completion test data consisting of reservoir pressure and temperature, initial total gas-oil ratio, and stock-tank oil gravity were used with the depletion-performance data to develop general performance correlations. Three correlations are presented. The first equation shows the empirical relation of gas in place per barrel of hydrocarbon pore space with reservoir pressure and temperature, and initial total gas-oil ratio. The second equation is the correlation of stock-tank oil in place per barrel of hydrocarbon pore space. The third equation relates stock-tank oil production (to 500-psia depletion pressure) with pressure, temperature and oil gravity. All three correlations are also presented in convenient graphical form. Gas production to 500-psia depletion pressure is approximately 92.6 per cent of the gas in place for each fluid, so no correlation was developed for gas production. INTRODUCTION The rate of discovery of shallow, low-pressure and low-temperature oil reservoirs in the United States has been declining in recent years. For this reason, the search for oil has gone to greater depths where high pressures and temperatures are encountered. A high-pressure and high-temperature reservoir is the environment in which many rich gas condensates and highly volatile oils are found. Because of this trend, the performance prediction of such reservoirs has become an important task of the reservoir engineer. The need and usefulness of a performance correlation based on field data that are available from the usual well-completion tests have previously been established. These earlier attempts have shown that the phase behavior of rich gas-condensate systems and volatile-oil systems can be correlated with fluid properties, pressure and temperature. However, very little information on gas-condensate depletion performance5 was available at the time of these earlier attempts. The availability of more recent data has made possible the development of an improved correlation. The data, as listed in Tables I and 2, are for 25 gas-condensate and two volatile-oil systems that were studied. The problem was to correlate the data for in-place fluids and the production data with the initial total gas-oil ratio, initial reservoir pressure and temperature, and stock-tank oil gravity. These correlations were obtained by multiple regression analysis, whereby the data were fitted to an equation by the method of least squared error. BASIS OF THE CORRELATIONS 1. The data used in the development of these correlations were obtained from depletion-performance calculations6 and well-test or production measurements. 2. All of the independent variables used in the correlations are available from the usual well-test completion data. 3. The reservoir volume considered is 1 bbl of hydrocarbon pore space (HCPS). 4. The gas-oil ratio used is the total standard cubic feet of gas (at 14.7 psia, 60F) coming off the entire separator train per barrel of stock-tank oil. This minimizes the effect of separator conditions which might vary from system to system. 5. The correlated pressures are the actual reservoir pressures which might or might not be the saturation pressure of the reservoir fluid.

Jan 1, 1966

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By Thomas H. Leggett

IN speaking of the mining and economic conditions prevailing at the present time on the Rand, it is not my intention to go into the details of the mining-practice, since this has been already well described both in the Transactions1 and elsewhere,2 but rather to take a more comprehensive view of the industry and its surroundings as a. whole, marking its general development and the lines of its future progress. In a. paper entitled Deep-Level Shafts on the Witwatersrand, with Remarks on a Method of Working the Greatest Number of Deep-Level Mines with the Fewest Possible Shafts,3 presented to this Institute in August, 1900, I drew attention to the great cost of sinking the very deep vertical shafts that were then being seriously proposed as necessary for the development of the deeper areas, pointing out the strong advisability of working this ground by means of inclines to be sunk from the existing shafts of from 3,000 to 4,000 ft. in vertical depth. In this paper it is stated (1:). 975): "In short, practice upon the Rand now tends towards fewer vertical shafts and more underground inclines, especially for the very deep mining about to be undertaken." In consequence, the 6,000-ft. vertical shafts, at one time so much discussed, have never been started, and they do not now seem likely ever to be. The necessity of placing all deep shafts further apart in order to make them control and exhaust larger areas was also dwelt upon. This economy was vitally necessary for both 1 Gold-Mining in the Transvaal, South Africa, John Hays Hammond, xxxi., S17 to 855 (1901). R Engineering and Mining Journal, vol. lxxxv., p. 53 (1908). ' Trans., xxx., 947 to 987 (1900).

Jan 5, 1908

By A. A. Steel

(Spokane Meeting, September, 1909.) DURING. the summer of 1905 I was employed by the U. S. Geological Survey to investigate the geology, Mining, and preparation of barite in most. of the fields of the United States. The Eastern districts have been more or less completely described ; the Virginia field in detail by Thomas L. Watson, in his paper, Geology of the Virginia Barite-Deposits,' and other fields in abstract., including statistics of production and references to current literature, by various authors .2 There have also been published a few details of the occurrence of barite in the lead-mines of Washington county, Mo.3 The other accounts of this district are erroneous and meager, and since this field is the most important one in the United States at the present time, a detailed description of the local geology seems doubly desirable. Barite-deposits are scattered over nearly the whole of Washington and adjoining counties, but. the product, is all mined from the areas indicated upon the sketch-map, Fig. 1, and is shipped from the stations of the St. Louis, Iron Mountain &. Southern railway, between Blackwell and Potosi, from 45 to 60 miles SW. of St.. Louis. The topography is for the most part gently rolling, with slightly graded streams, usually less than 200 ft. below the higher hill-tops. Along Mineral fork and Indian creek are :some steep bluffs and cliffs, affording good exposures of the

Feb 1, 1910

By Charles A. Anderson

Arizona and western New Mexico contain 17 of the 25 leading copper mines in the United States. Production of molybdenite, lead, zinc, and by-product gold and silver is important. Precambrian ore deposits are largely limited to the Yavapai Series in central Arizona and most of the metal production has come from massive sulfide deposits, dominantly pyritic but containing different amounts of chalcopyrite, tennantite, sphalerite, and galena. Their origin has been interpreted by some geologists as hydrothermal replacement of schist, and by others as syngenetic deposits later metamorphosed. Most of the important ore deposits are of Mesozoic and early Tertiary age, dominated by the porphyry copper deposits spatially related to stocks, plugs, sills, or dikes of quartzbearing porphyritic to granular rocks. Host rocks for these deposits include the associated intrusive rocks, Precambrian schist and granitic rocks, Paleozoic limestones, Mesozoic(?) porphyritic andesite, and Mesozoic arkose and siltstone. Chalcopyrite and pyrite are the dominant hypogene sulfide minerals in the porphyry copper deposits, accompanied by minor molybdenite. The Questa deposit in New Mexico is largely molybdenite. Supergene sulfide minerals are chalcocite and minor covellite. Some ore bodies consist largely of hypogene sulfides, some are dominantly supergene sulfides, and others are mixed hypogene-supergene sulfides. Supergene oxide-copper minerals locally are important. Intense hydrothermal alteration accompanied the metallization in all of the porphyry copper deposits; five types are recognized, ( 1) propylitic, (2) argillic, (3) potassic, ( 4) quartz-sericite (without clay), and (5) lime silicate. The origin of the closely spaced fractures that contain ore minerals in intersecting veinlets is debatable; some geologists favor tectonic forces and others suggest cooling of magma or shrinkage due to alteration. Breccia pipes, veins, and limestone replacements account for some important deposits of Mesozoic and early Tertiary age, and presumably these are genetically related to the various intrusive rocks of this age. The St. Anthony deposit of Cenozoic age in southeastern Arizona is unique, consisting of a lead-zinc vein associated with later molybdenum and vanadium oxide-minerals. Cenozoic manganese deposits in western Arizona are an important resource in the Artillery Mountains, but the extent to which they may be exploited is a metallurgical and economic problem.

Jan 1, 1968

By Robert K. Linn

The New ldria Mining District is in the southern part of the Diablo mountains of the California Coast Range, 140 miles southeast of San Francisco. The district, noted primarily for quicksilver, also has become important recently as a producer of short-fiber chrysotile asbestos. Between 1853 and 1966, the New Idria district produced 568,092 flasks of quicksilver valued at about $55,600,000, 99 per cent of which was recovered from one deposit, the New Idria mine. In 1944, the district was ranked third in all-time production of North American quicksilver districts, and, since that time, the New Idria mine produced an additional 129,045 flasks, placing the district and the New Idria mine second in all-time production. The major structure of the region is the northwest-trending Coalinga anticline consisting of an asymmetric dome of sedimentary beds ranging in age from Jurassic to Quaternary and marked at its northwest end by an oval body of sheared serpentine 14 miles long by 4 miles wide. The serpentine core, rimmed by Franciscan sandstone of probable Jurassic age, was uplifted in stages between Jurassic and Quaternary time and was intruded along a ring of faults into beds of the Panoche Formation of upper Cretaceous age. The core of serpentine and Franciscan rocks is the locus of about 20 quicksilver mines that rim the faultbounded core and lie within the serpentine mass. The host rock of the most productive deposits is altered Panoche shale and sandstone that lies intermittently along the perimeter of the core. Deposits of the New Idria group of mines and those of a few other small mines lie along the northeast contact in the footwall of the New ldria thrust fault, and a few others occur on steep normal faults around the south and southwest. The chief ore mineral in all quicksilver mines is cinnabar, but minor amounts of metacinnabar and native mercury are found in some of the mines. Ore shoots were deposited in fracture zones and stockworks in altered Panoche shale and sandstone and in definite fissure veins in Franciscan sandstone. Rocks made highly amenable to fracturing by hydrothermal alteration were fractured extensively by late faults. The resulting fracture zones, located along the late faults and at changes in strike or dip of the hanging wall or footwall, are the principal controls of most ore shoots. The largest and richest ore shoots are those of the New Idria mine. The major ore bodies occur in fractured shale and sandstone beneath the New ldria thrust fault at its junction with major tear faults.

Jan 1, 1968

By R. A. RAGATZ

THE preparation of specimens for microscopic examination from metal articles of relatively large cross-section offers no particular difficulty. It often happens, however, that articles submitted for examination are so thin that specimens satisfactory for microscopic examination can not be successfully pre- pared by the methods commonly employed when working with larger articles. Ordinarily, the preparation of metallographic specimens involves the following operations : (1) cutting the small specimens to be examined out of the larger mass of metal, (2) cleaning and electroplating, (3) mounting to furnish support during the grinding and polishing operations, (4) grinding and polishing to produce a scratch-free surface, (5) etching and drying. All of these operations must be carried out in such a manner that when the specimen is finally examined under the microscope, the structure seen is a true and well-defined representation of the structure that the larger mass of metal possesses at the place where the small specimen was removed. It is important that the deformation involved in cutting out the specimen be as slight as possible, in order that the subsequent grinding and polishing operations will completely eliminate the cold- working effects in the vicinity of the cuts. It is also important that the specimen never be allowed to attain a temperature high enough to alter its structure; the maximum permissible depends on the metal being handled. With some metals, zinc for example, consider- able care must be taken to avoid heating; with other metals, annealed steel -for example, no particular pre- cautions need be observed because there is no tendency for structural change to occur at relatively low temperatures.

Jan 1, 1929

By Herty, C. H.

The effect of temperature on the physical properties of structural materials has been the subject of many investigations during the past decade. The literature on the effect of elevated temperatures. is voluminous, and during the last four years a great deal of experimental work has been carried out on the effect of low temperatures on the impact properties of steel. For many engineering purposes it is important to know the shock resistance of steels at low atmospheric temperatures, and with the ever-developing field of refrigeration and separation of materials at low temperatures, the normal limits of atmospheric temperature have been exceeded in practice. Iron and its alloys in the unnotched condition have a high impact strength at low temperatures, but in practice variations in type of notches result either from design or accidentally through scratches and surface or internal defects. A study of notched bar impact tests is, therefore, highly important to the engineer. A survey of the literature on low temperature impact testing indicates that chemical composition, heat treatment and method of testing have been the variables which have been considered in most previous work. In only a few instances has any mention of the steel- making method been mentioned and in these the comparison was between steel-making processes and not between steel-making methods on the same process. In view of the wide variations in impact properties at room temperature, in quench and strain ageing and in grain growth of steels of identical chemical composition, (by this is meant the usual five element analysis reported), it was felt

Jan 1, 1957

Coal Transport Via Pipe Line Claimed Feasible Moving coal via pipe line is a project proposed by the U. S. Bureau of Mines. A pipe line 100 miles long capable of transporting 5000 tons of coal a day with water could be built for about $10 million. The cost of moving the coal 100 miles would be between $1.28 and $2.01 a ton.

Jan 9, 1951

By M. M., Fine

In a laboratory study of grinding and classification' of silica sand, a satisfactory means of producing the medium-fine specification sand desired by producers of flint-glass containers was developed. The best procedure consisted of ball-mill grinding and double classification, which gave a properly sized sand containing less iron than the feed.

Jan 1, 1950

By George A. Laird

I. INTRODUCTION. THIS old and once famous district played, through its enormous production of silver and gold, an important part in the history of the State of San Luis Potosi. According to a pamphlet prepared under the direction of the Governor of the State, Sr. Don Blas Escontria, and presented to the visiting members of the Institute during the Mexican meeting of 1901, this district is situated 20 km. east of the city of San Luis Potosi, in a range of mountains of moderate height, extending 135 km. N. and S., and 16 km. E. and W.; and the mineralized area hitherto developed is about 600,000 sq. m. The history of the district,. as given by the record dated 1778, and formerly kept in the San Francisco convent, says that it was discovered in 1575 by Sr. Don Pedro Irarte, and adds that the city of San Luis Rey de Francisco del Potosi received its name (in allusion to the famous Potosi mines in Bolivia) by reason of the remarkable productiveness of its gold- and silver-mines in the first period of their exploration, during which they paid to the Crown, as " quintos " (the fifth part of the product), $97,000,000, as appears from the accounts of the royal treasury. The amount of the quientos paid during the " bonanza period " of 80 years was $72,000,000. The larger sum first mentioned probably represents a longer series of years. But either will suffice to indicate the great wealth of the mines. In 1663, the decadence of the industry began with the caving¬ in of several mines, concerning which the record of 1778, al¬ready cited, says, in substance, that on Good Friday one of the owners in the enterprise, in view of the unfavorable prospect of a lawsuit in which he was engaged, set fire to the timbers supporting the underground galleries and workings of the San

Jan 1, 1905

By AIME AIME

Gentlemen, we have ten questions on our list and a number of us here probably have other questions to ask. Therefore, we arc going to allocate the time to these different questions so that we will try to be finished by 4:30; from then until 5 o'clock, if any of you have any questions on subjects not related, you will be free to ask them. Mr. Morton and I have changed the order of the questions. Instead of what is now first, we have put No. 3 first, progress on basic-roof construction, inasmuch as we feel that it is quite important. At this time, H. S. Robertson, of Harbison-Walker, is going to give you a short talk, with slides, on what has been done to date on this subject.

Jan 1, 1940

By Benj. E. Shackelford

THE present paper is concerned with typical temperature values experienced in lamp-filament measurements as made on regular factory and engineering products. It deals with the relations existing between temperature, efficiency, lamp size, and life of incandescent lamps, insofar as they affect the rating of the product and its use by the individual consumer. The temperatures measured lie in that range covered only by the general method of radiation pyrometry, as opposed to direct methods used under contact conditions. The range of temperatures ordinarily experienced extends from about 2125° K., for the now almost extinct carbon-filament lamp, to 3200° K. for the comparatively new tungsten-filament motion-picture lamp. Most of the more common sizes of tungsten lamps have temperatures ranging from 2500 to 3000° K. Because of the high temperatures involved and the relatively small area of the sources used, we are practically restricted to two methods of measurement, both of which depend on the light radiated front the filament. The first and more usual method is that of the Morse pyrometer, dependent on the variation in temperature of the amount of light of a given color range yielded by the filament. In this case, the measured temperature is that of a small part of the incandescent body, that is, the part which is focused on the comparison filament. The second method, known usually in this country as that of "color match" and in England as "color-identity" is based on the color of the total light yielded by the filament, the comparison being facilitated by the use of an ordinary photometer- head. A more definite idea of the temperatures involved in the case of filaments of various vacuum and gas-filled lamps, is given by Fig. 1. The size of the lamp, in watts, is plotted along the horizontal axis and the temperature of the filament is plotted along the vertical axis. The lamps concerned are regular product, rated for 1000 hr. life. The temperature values for the old 16-candlepower carbon lamp and the new motion-picture lamp are shown by the cross and circle respectively.

Jan 9, 1919

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

Meeting of June 26, 1914.-The President was authorized to appoint Advisory Committees to co operate with the United States Bureau of Mines. The President announced the appointment of Edward H. Benjamin and W. C. Ralston as additional members of the Committee on Arrangements for the San Francisco meeting, 1915. H. T. Van Ells and Judd Stewart were appointed to represent the Institute on a joint committee of several technical societies to consider the standardization of graphical methods for the presentation of statistics. The President announced the appointment of H. Foster Bain to succeed Edward H. Benjamin, resigned, on the Committee of Management of the International Engineering Congress, 1915. The Secretary was authorized to issue a new circular advertising the sale of back Transactions and to sell back Transactions, bound in cloth, at a price of $35 for 46 volumes, provided sufficient orders were received to warrant the special binding. The sum of $177.50 was contributed to the San Francisco Local Section. Upon recommendation of the Committee on Membership, 70 Members, 4 Associate Members and 7 Junior Members were elected to their respective classes; there was also one change of status from Junior Member to Member.

Jan 8, 1914