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By Anthony Lucas

THE discovery of oil in 1901 on the Spindletop dome, Texas, inaugurated a new industry on the Gulf Coast, an industry which has grown with the discovery of successive fields, until today it engages the services of thousands of workers and employs enormous capital. New fields are being discovered from time to time and doubtless some still remain to be found, though of late years discoveries have become more infrequent. Nowadays several hundred dry holes are drilled each year in a fruitless and blind effort to discover new fields, for as yet geologic science has developed no effectual method of locating the coastal oil deposits in advance of drilling. Moreover, despite the occasional discovery of new fields, the total production of the Gulf Coast is today no greater than it was in 1906, for the added production of the new fields has been offset by the rapid decline and more or less complete exhaustion of some of the older ones. Careful geologic work within the fields has in some cases increased the production temporarily, but has developed no really new supplies. The Gulf Coast oil industry seems to have passed its period of greatest expansion and to be declining at a fairly steady rate, and this condition is naturally viewed with alarm by the more farsighted operators. In my opinion, the time has come for the adoption of radical and aggressive methods of prospecting, and a fraction of the money wasted yearly in drilling shallow wells in hopeless locations might well be devoted to this purpose. Many facts lead me to believe that all the salt-dome oil has had a common origin; that it has migrated up from considerable

Jan 7, 1918

By J. H. M. Thomeer

A method is presented that provides a mathematical description of capillary pressure curves and, probably, of differences in pore geometry of samples. The technique is based on the observation that the location and shape of a capillary pressure curve reflect characteristics of the pore structure of the sample. INTRODUCTION It has been noted1-5 that the observed differences in shape and location of capillary pressure curves reflect some basic properties regarding the pore geometry of the samples. For example, according to basic concepts of capillarity, the following statements can be made regarding the location and shape of a capillary pressure curve.* The location of the curve with respect to the (Vb)pc and PC axes is a measure of the interconnected pore volume and of the cross-sectional area of the pore first entered by mercury, respectively. The shape of the curve depends on the interconnection of the pores and the sorting of the pore sizes. It has been the object of this study to use this information as a starting point in an attempt to find a unique mathematical description of the PC — (Vv)p, relations of different samples. It may be expected that parameters in such a relation can then be used to describe differences in pore geometry of these samples. For a practical description of the PC — (Vb)p, relation, however, it appears desirable to describe each curve (i.e., each sample) by a limited number of parameters so that the curves taken from all samples form a family, each member of which is uniquely determined by one single combination of values of all parameters.

By G. B. Gould, F. M. Gibson

IN DECEMBER, 1934, the joint Committee on Fuel Values, of the American Institute of Minim and Metallurgical Engineers and the American Society of Mechanical Engineers, submitted a preliminary report, which briefly stated its conclusion that it was not possible to devise any formula for the valuation of coal, based upon the various physical and chemical properties, that would be generally applicable. That report also listed those chemical and physical properties of coal that are generally recognized to have some effect on its use in steam plants, and those physical characteristics of steam plants which affect, in one way or another the relative importance of the properties of coal used in them. Since then, the Committee has considered and discussed in greater detail the interrelationship of the properties of coal and plant characteristics. The conclusions of the Committee are summarized below, with certain recommendations regarding engineering procedure, which will promote the collection of more easily correlated observations with respect to this subject, and thus advance more rapidly the accumulation of data capable of general application.

Jan 1, 1936

By C. McCulloch

OPEN-PIT mining of coal is relatively a recent innovation; men still active in the industry can trace its development. Re- viewing the growth of operations from the original horse-drawn scrapers, through the various stages of power equipment to the huge strip- ping shovels of today, one also notes changes in the methods of what the coal man calls preparation at the face. We really should not call it face preparation because, in contrast to underground mining, a face does not exist in strip mining. Further, preparation of the coal for market at the loading point has already, in but a few years, become largely of historic interest only and modern mines as well as old mines recently modernized rely almost entirely on separate and elaborate preparation plants to produce marketable coal. This practice was not voluntarily adopted by the producer but was forced upon him by the inadequacy of previous

Jan 1, 1939

By M. W. Strong

THE technique of handling drilling muds varies somewhat, partly because of personal factors but mainly because of differences in forma-tion, the type of problems met with, and the general drilling conditions in different localities. The much greater depths to which bore holes are now carried have made necessary closer attention to and great modifications of all aspects of drilling-mud technique. Increased depth means smaller hole, smaller drill pipe, smaller clearances, higher pumping pressures, higher differen-tial pressures between shows and the mud column, less accurate control of the weight of the mud column, delayed receipt of formation data, and poorer samples. It means longer delays and greater hazards in rectifying mistakes or dealing with accidental occurrences. Equipment on a larger scale is necessary and more pains must be taken with layout. Lastly, the budget costs of raw materials have risen to high figures and economy of time and of direct monetary expenditure have come to mean much more than formerly. A mud laboratory is now part of the essential establishment of a modern oil field and to it current problems can be submitted for the most thorough investigation. The detailed chemical properties of all mate-rials purchased or quarried have to be investigated. Detailed data on the physical properties have to be ascertained and research on improve-ment of material and its most efficient use has to be carried out. In this paper we propose to discuss the main mud problems with which we have to deal in Iran, some of which are peculiar to our local conditions while others are of the general type common to all workers in this subject.

Jan 1, 1938

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. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents3 or by starch.4 The object of this work was to study the floatability of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH.

Jan 2, 1954

D EC. 20-The spirit of Christmas and good will toward men has managed a few brief appearances on the front pages, welcome relief from man's usual ill-will toward man. A couple politicos did their best to brighten the scene by well-publicized romances. There was a general exodus to Florida to patch up nervous systems, and even the UNO quieted down as Mr. Vyshinsky departed for home via Eastern Germany. Before going he opened up a preliminary bombardment for the worldwide "communist peace offensive," and it is now the duty of the 600 million (according to the Cominform) ideological converts to press home the attack. In Washington, Mr. Lilienthal resigned as Chairman of the Atomic Energy Commission and demonstrated again the difficulty of government to retain the services of capable men. The President has yet to appoint another victim- possibly someone nicely noncontroversial and timid. So might the critics be appeased, but it would bode ill for the rapid exploitation of peaceful uses of atomic energy, the relaxation of excessive secrecy, wider sharing of developmental work with friendly nations and possible revision of the Acheson-Lilienthal proposals for inter- national control of the atomic bomb.

Jan 1, 1950

By J. H. Clemes

The process of leaching silver ores with sodium hyposulphite is comparatively new, and published accounts of the details and losses of the process are as yet very few. The following account of a careful series of experiments to determine the actual loss in this process may therefore be acceptable to members of the Institute. The ore treated was highly calcareous, and the principal sulphide present was iron pyrites. Following is an analysis by Professor Price, of San Francisco, of the ore treated : Per cent. Silica,..........15.13 Sulphur,.........13.31 Arsenic,.......... 9.82 Iron............ 17.33 Alumina,..........1.35 Zinc,...........4.92 Lead,..........1.78 Carbonate of lime,..33.78 Magnesia,.......... 2.58 100.00 Ten tons were crushed dry with a 30 X 30 screen = 900 holes per square inch. In order to feel our way with this ore, two experimental or "pilot" charges were roasted. Pilot Charge No. 1. Treated 1000 pounds in a four-hearth reverberatory. 8.30 p.m.—Entered fourth hearth, remaining there one and onehalf hours; sulphur began to burn. 10 p.m.—Changed to third hearth; ore became red-hot half an hour after entering; the fireplace was kept almost destitute of fuel. 2.30 A.M.—Changed to second hearth. Charge continued, giving off a large quantity of sulphurous fume; the fireplace was kept dark.

Jan 1, 1884

By Kenneth N. McLeod, Donald W. McGlashan

In the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle.

Mar 1, 1956

By Lawrence Addicks

THrough the courtesy of Dr. James Douglas I am permitted to give a summary of some of the results obtained in leaching slimes tailings in a series of experiments conducted under my direction at Douglas, Ariz., during the past year. While the test run for which the data are given deals with a particular case, much of the work is general in its application and may therefore be of interest. This work was done upon the ores of the Burro Mountain Copper CO. A description of the geology of the district will be found in the paper by R. E. Somers published in this volume, p. 604. The mineral is pyrite and chalcocite very finely disseminated throughout the gangue and a characteristic of all the ores is the large amount of alumina present. A representative analysis of the particular ore under consideration would be about as follows: Cu, per cent..................... 2.35 S, per cent...................... 3.0 Ag, ounces per ton.............. 0.05 CaO, per cent.................. 0.5 Au............................ None K2O, per cent.................... 4.0 Fe, per cent..................... 1.50 SiO², per cent.................... 70.0 Alz²O³, per cent....................13.OO The leaching of the ore direct was early dismissed from consideration for the following reasons: 1. The ore would have to be quite finely crushed to liberate the mineral for leaching; concentrating after crushing would cost but a few cents a ton; and a higher total reeovery would result from leaching tailings rather than ore. 2. Rough concentration would yield a suitable material for roasting to make sulphur dioxide or sulphuric acid in connection with the leaching scheme. 3. Such a program put the question of cost vs. recovery on a basis where flotation and discarding of tailings were directly comparable. Concentrating experiments already available indicated that the tail-

Jan 1, 1916

By B. T. Brady

Experimental data 1,2 on the energy dissipation in polycrystalline materials over a large frequency spectrum (10-2 cps to 106 cps) suggests that the quality factor [(e= Q )] is independent of the frequency providing both fluid-saturated and ferromagnetic materials are excluded from the test data. Additional data 3 suggest that the quality factors are less at high pressures than at low pressure, i.e., Q increases as the pressure increases. Observations on the dissipation of single quartz crystals with their polycrystalline counterparts indicate that the energy dissipation is less for the single crystal than for the aggregate .2 Both of the above observations, particularly the latter, are indicative of the fact that the dissipation increases with increasing surface contact within the polycrystal, i.e., a frictional attenuation scheme may be operative. Knopoff and MacDonald 4 have shown that a friction model gives rise to a quality factor frequency independence property. A partial listing of some values of Q, observed for both metals and non-metals, is given in Tables I, II, and III. In Tables I and II, the data all show Qs>Qp, i.e., the energy loss per cycle for compressional body waves is greater than that for shear waves of the same frequency. Most samples in Table III show the same effect. It is objective of this paper to suggest: (1) a frictional attenuation scheme may account for the observed losses incurred during the propagation of low amplitude stress waves in dry brittle rock and, in particular, that such a scheme can account for the observed relative magnitudes of the quality factors for P and S wave motion; (2) a friction scheme can readily explain the difference between the dynamic and static moduli in dry brittle rock; (3) a friction scheme, while in itself an intrinsically

Jan 1, 1968

ON FEBRUARY 4, 1952, the Phelps Dodge Corporation signed Contract GS-00P(D)-12068 with the United States Government. This interesting document dealt with the "Bisbee East" project as part of the Government's program to increase the supply of needed copper by encouraging private enterprise to expand production. The ore deposit involved was a relatively small body of low-grade ore lying east of the remnants of the old Sacramento Hill deposit that was exploited with indifferent success from 1923 to 1931, as related in THE PORPHYRY COPPERS. Planning for the entire enterprise had been directed from the start by Harrison M. Lavender, who in 1945, succeeded Percy G. Beckett as vice-president and general manager for all of Phelps Dodge's Western mines and smelters. The untimely death of Mr. Lavender in 1952 prevented him from seeing his plans brought to fruition; but in his honor the mine was fit- tingly named "The Lavender Pit" and was so dedicated on August 7, 1954. The Copper Queen Branch operates under- ground mines at Bisbee (production in 1955 was 28,000 tons) ; but, as this volume is concerned only with Porphyry operations, this chapter deals only with the Lavender Pit project, or as the Government knows it, Bisbee East. My reason for going into some detail regarding the floor-price contract is that it is fairly typical of contracts made by the Government in connection with a half-dozen other copper-expansion projects; and, incidentally, with various projects involving other strategic metals. Phelps Dodge did not seek a loan or other financial aid. The only encouragement asked consisted of (a) the privilege of a five-year write-off (commonly called rapid tax amortization)

Jan 1, 1957

By Michael Hoch

The phase diagrams of binary systems of some of the transition elements of Groups IV, V, and VI were used to compute the partial free energies of these elements and the free energy of formation of their Laves-type compounds. From these data, isothermal sections of ternary phase diagrams were calculated and compared with experimental results. DURING the investigation of ternary and quaternary high temperature systems formed by the transition elements of Groups IV, V and VI, the binary phase diagrams for these elements available in the literature were studied. In this study, the free energies of formation of the compounds formed in these binary systems were calculated; these values were then used to determine the general shape of the ternary and quaternary phase diagrams. Above 900°C, the transition elements of Groups IV, V, and VI are all bcc and form only Laves-type compounds in binary systems. The investigation was based on the binary phase diagrams published by Hansen.1 The Cr-Nb system was constructed from the data of Elyutin and Funke.' Several unpublished phase diagrams were taken from Schmidt'sLo and English'sl1 compilations. THE BINARY SYSTEMS valuations of the Thermodynamic Functions. Rostokers evaluated the boundaries of the (a + b) field in Ti-base alloys with a two-constant equation. The authors' interest is mainly in the center of the diagrams; therefore the miscibility gaps in the Zr-Nb, W-Cr, Ta-Zr, Ta-Hf, and Ti-W systems were used to evaluate the thermodynamic behavior of the binary systems. Lumsden's4 Equations 29.2, 32.1, and 33.1, page 287, were used for the excess integral free energy FeX, and for the excess partial free energies Fx and replaces b and b replacesP in Lumsden's notation):

Jan 1, 1962

By Charles P. Williams

BY PROFESSOR CHARLES P. WILLIAMS, ROLLA, MISSOURI. During the fall of the year 1873, attention was redirected to the occurrence of lead ores in Southwestern Arkansas (chiefly in Sevier County), and somewhat extensive explorations of the deposits have since been made in the hope of finding the ores sufficiently argentiferous to be profitably worked. How far the expectations have been realized I am not authentically advised, but samples of the galena ore, yielding 62.09 per cent. of lead, gave on assay at the rate of 15 3-10 ounces of silver to the ton of ore. This was the highest result obtained by myself, though I am informed that higher yields have been obtained by others. Among the samples of ores from this locality, forwarded to me in January last, was one specimen which I at once recognized as stibnite, and, on notification, other specimens of the same from Sevier County were forwarded me. The first specimen of the several received contained 11.51 per cent. of gangue, 57.62 per cent. antimony, 4.57 of bismuth, with small amounts of arsenic and iron. The latest result from a portion of another hand specimen I append in full, with duplicate estimations of the arsenic, bismuth, and gangue. The analyses were all conducted by Mr. C. R. Winters, under my direction, and in the case of those given below the ore mas separated as closely as possible from the gangue before analysis. The results are for the mineral freed from hygroscopic moisture, and are as follows: I. 11. Mean. Sulphur,.. 28.618 .. . 28.518 Antimony,.68.576 .. . 68.676 Arsenic,..6 47 .474 .497 Bismuth,..521 .498 .509 Iron,.......762 .. ..762 Gangue,..944 .948 .946 99.868 99.808 This result indicates that the ore is stibnite.

By John Cogan

INTRODUCTION Lake tapping is a method of blasting an intake into a body of water from below the natural water surface without first lowering that surface or installing a protective cofferdam around the tap hole. Lake taps are done by first excavating a tunnel almost to the water/rock contact and then blasting out the final protective rock plug at one time to allow water to suddenly inflow into the tunnel from the lake. This procedure can be done "dry" or "wet." In the dry method the tunnel is empty of water before the final plug blast while in the wet method it is partially filled with water. This paper describes a wet method lake tap as performed at Alaska Power Authority's Tyee Lake Hydroeletric Project in southeast Alaska. The Tyee Lake project is located approximately 40 miles southeast of Wrangell, Alaska, in a glacially formed valley called the Bradfield Canal. The project consists of a powerhouse located at sea level on the canal, a system of tunnels and shafts connecting the powerhouse to Tyee Lake at elevation 373 m (1225 ft), and an 129 km (80-mile) electrical transmission line leading from the powerhouse to Wrangell and then Petersburg, Alaska. Tyee Lake itself is a natural lake gouged out of the rock by glacial ice during the last ice age. The objective of the project was to tap into the lake and use the water as a source for power production. The techniques used for lake taps have been developed in Norway where conditions are favorable for their use in hydroelectric proj¬ects. Over 100 have been performed. In the United States the Tyee

Jan 1, 1984

By W. L. Crentz, E. E. Donath, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951