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By Roland Kammel

For electrolytic recovery of silver from dilute aqueous solutions improved mass transfer is necessary to achieve favourable current efficiencies and high space-time yields. The many cell designs proposed for this application can be divided into two different groups: cells from which the silver must be redissolved and cells from which the deposit can be reclaimed as a metal. Introduction Electrolytic silver recovery methods have proven advantageous under technical and economic aspects for the treatment of rinse water, still rinses and spent silver solutions in the electroplating and surface finishing industry, of exhausted fixing baths from photographic processing, bleed electrolytes from silver refining processes and leach liquors. Examples of the compositions of typical dilute silver solutions are listed in Table I.

Jan 1, 1984

By O. W. Shimer, D. C. Helms, C. E. Brown

THE early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 334 million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20° to 90° and some are on the invert in, many sharp folds and faults. PLANNING The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been maintained. Locations of stripping areas are determined as follows: 1. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness and pitch of the beds.

Jan 1, 1944

By W. W. Dudley

Inflow of ground water is an important engineering and safety consideration during construction of large openings underground. The initial step in predicting groundwater inflow involves hydraulic tests in exploratory drill holes. Zones within the area of interest are isolated in the drill hole by inflatable packers and are tested by measuring the water level responses to applied hydraulic stresses. These responses may then be translated into significant hydraulic characteristics of the tested rocks such as transmissivity, hydraulic conductivity, hydraulic potential, and storage coefficient by using a type-curve solution. Once the geometry and necessary hydraulic characteristics have been determined for the rock in the vicinity of the proposed opening, a model can be developed using certain assumptions that will lend itself to treatment with available mathematical methods. The mathematical method applied to the model considers conditions of partial penetration and nonsteady-state, leakyartesian, constant-drawdown discharge of ground water. A type-curve solution results in a curve that gives the variation of discharge (inflow) with time. This technique of predicting ground-water inflow has been used in planning construction of cylindrical chambers for use in underground nuclear experiments by the U.S. Atomic Energy Commission. These chambers have been constructed in low-permeability rocks at depths as much as 6000 ft and under hydraulic heads of thousands of feet.

Jan 1, 1973

By I. H. Warren, E. Devuyst

A review of the physical and chemical aspects of the direct leaching of metal oxides has been given and com- pared to recent data of the authors and co-workers. The physical aspects, including the anisotropy of the dissolution, the hydration and the zero point of charge of some metal oxides are discussed first and then the kinetics of the dissolution of metal oxides are considered. A general mechanism of the leaching of oxides which describes most of the observed results is proposed.

Jan 1, 1973

By M. H. Mueller, P. A. Beck, W. P. Chernock

HARRIS introduced the term inverse pole figure for the diagrams previously used by Barrett' to represent the volume fraction p(a,ß) of material in various orientations with respect to the fiber axis in a specimen with fiber texture. The direction of the fiber axis with respect to the crystal lattice is specified by the two independent angle variables a and ß. In such a diagram p gives the fiber axis density distribution over the various crystallographic directions. The p(a,ß) may be given in a two-dimensional diagram by means of contour lines (p=con-stant) in a stereographic projection. The inverse pole figure incorporates in a single contour line diagram all the information given conventionally in pole charts for various (hkl) reflections and, therefore, it represents a considerable degree of condensation. Also, it gives this information directly in terms of the volume fraction of the specimen in various orientations, and it obviates the necessity of referring back and forth between the various pole charts in an attempt to interpret them in terms of orientations. Inverse pole figures undoubtedly represent the most adequate method for describing a texture in a quantitative manner and, at least in the case of fiber textures, this method is certainly a practicable one. Harris described1 a simple procedure for determining at least the rough outlines of a quantitative inverse pole figure. This method depends on the measurement of the intensity of X-ray reflections from various (hkl) planes lying parallel to the same specimen surface. In the case of a rod, reflections from a plane specimen surface perpendicular to the rod axis (fiber texture axis) are to be used. Harris has shown that the measured intensities I,,, reflected by crystal planes (hkl), aligned perpendicularly to the fiber axis of a specimen with unknown fiber texture, and the corresponding intensity Iu nkl from a random specimen are related to the p(a,ß) value for the unknown texture by the following equation IAkl/I°Aklw=c/c°.p(a, ß) [1] where C and C° re parameters depending on the crystal imperfections (extinction), surface preparation (e.g., thickness of oxide layer), the absorption coefficient in the specimen, effective line breadth, and instrumental factors. The values of the variables a and ß1 defining the crystal orientation, depend only on the indices hkl of the reflecting plane perpendicular to the fiber axis. Since p, as described by Harris1, is normalized in such a way that upon integration over the total orientation range its mean value is 1, the parameter C/C may be calculated approximately by the summation of Eq. l over all available X-ray reflections hkl, corresponding to a set of discrete orientations (rather than by integration over the complete range of orientations represented by the continuous variables a and ß). From the summation of Eq. 1 1/n SI AKL/I° Akl = C/C. SP(a,ß)/n is obtained where, as stated above 2p(a,ß) =1. n Therefore

Jan 1, 1959

By AIME AIME

IN many countries the lack of liquid petroleum supplies has centered interest upon the hydrogenation of coal and coal tars for the preparation of motor fuel. In the United States, hydrogenation has been of greater interest for grading up low-value petroleum fractions to the more valuable volatile fuels and for the preparation of a variety of premium products, including aviation gasolines, solvents, Diesel fuels, and lubricating oils. Chemically, the basic reason for this process is that, as shown in Table 1, the ratio of hydrogen to carbon (H/C ratio) in available raw materials is quite different from that characterizing the products sought.

Jan 1, 1936

By Philip D. Wilson

WHEN the United Nations win the war and the decision has been made to control future armament in the Axis countries, plans for the extent and operation of such control must have been prepared, to be ready to put into immediate execution. Such control to be effective must be premised upon complete military occupation of the two countries for a substantial period, with an arrangement at the end of such occupation for continued supervision of these industries into an indefinite future.

Jan 1, 1944

By R. J. Stevens

The Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft ('934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (I) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory furnaces in terms of tons of copper produced per ton of coal burned is high. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table I shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is suficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 22 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1949

The Candelaria deposit was first discovered by Spanish prospectors in 1863; but its silver ore was not exploited on a large scale until 1873, when the Northern Belle mine was opened. The first Northern Belle mill was built at Belleville, 13 km (8 miles) to the northwest. From 1876 to 1886 the Northern Belle paid over $1 million in dividends each year. In 1882 a 43 km (27 miles) pipeline was built to Candelaria from the White Mountains to the west to furnish water for the mills and town at Candelaria; it was 100 mm (4 in.) in diameter, hand- riveted, and made in England. Sections of this pipe are used. as claim posts today. At its terminus at Metallic City, above Candelaria, a large concrete reservoir was built and called Metallic Lake. It is being used today by Candelaria Partners. Production at Candelaria declined after the mid-1980s, revived for a short period in the early 1890s, and during the 1920s a 300 ton mill operated for three years. Candelaria Partners is owned jointly by Occidental Minerals and Congdon and Carey, with Occidental being the operator. An engineering study done in mid-1979 resulted in engineering for the plant commencing in late that year and heap leaching being started in September 1980. Two million tons of ore per year containing 108 g Ag and 0.28 g Au per mt (3.15 oz Ag and 0.008 oz Au per st) will be mined from the Lucky Hill and Mount Diablo .areas about 1.6 km (1 mile) up Pickhandle gulch from the heap leaching operation. Waste -to -ore ratio is about 2:l. Ore is mined by front-end loaders and hauled by 85 ton trucks to the primary crusher, a 1,070 by 1,780 mm (42 by 70 in. ) gyratory. Primary crushed ore is conveyed to a stockpile of 10,000 tons live capacity from which it is reclaimed by hydraulic reciprocating feeders and conveyed to the crushing and agglomeration facility. This unit is composed of a 1.8 m by 2.6. m (6 ft by 12 ft) double deck screen, a 2.1 m (7 ft) standard cone crusher, and three conveyors. At the conveyor transfer points NaOH and NaCN solution is sprayed on the ore as it falls through a row of 75 mm (3 in.) hanging steel bars. During this process of turning and dividing the ore, the fines agglomerate with the coarse ore to give better percolation for the leach solution on the heaps. Provision was made for the later addition of 2 kg per mt (4 lb per st) of cement to aid in the agglomeration. Agglomerated ore at minus 50 mm (2 in.) size is then conveyed to a 390 mt (430 st) loadout bin where it is transferred to 85 ton rear dump trucks for haulage to the leach pads.

Jan 1, 1981

By E. W. Pehrson, J. W. Furness

THE method of presentation in the accompanying charts is based upon the well-known formula: production plus imports minus exports equals apparent consumption. Thus for each area for which data are shown there are two columns of equal height, one representing production plus imports, the other apparent consumption plus exports. Usually no account has been taken of increases or decreases in stocks. All columns and flow lines are drawn to a linear scale which is supplemented by figures showing the actual quantities represented. Owing to the small area occupied by the European countries on the world map it was impossible to show the details of the trade of the individual countries. All of Europe (except Russia), therefore, is shown as a single unit. However, statistics of production and consumption indicated elsewhere on the charts show the degree of self-sufficiency enjoyed by the major European powers.

Jan 1, 1936

NEW MEMBERS The following list comprises the names of those persons who became members during the period Sept. 10, 1916, to Oct. 10, 1916. BLOOMFIELD, EDWIN CHARLES, Min. Engr., 1012 Standard Bank Bldg., Vancouver, B. C., Canada. BRINGS, HENRY, Min. and Met. Engr., Chief Engr., and Geol., Mollet-Mesrine, 1212 Mills Bldg., El Paso, Texas. CHASE, MARCH F., Vice-Pres., Commercial Acid Co., 1906 Boatmens Bank Bldg., St. Louis, Mo. CUMMINGS, ALVIN M., Asst. Mine Supt., Witherbee, Sherman & Co., Inc., Mineville, Essex Co., N. Y. DOUGLASS, GEORGE M., Genl. Safety Inspector, Amer. Smelt. & Ref. Co. 120 Broadway, New Fork, N. Y. EMRICH, CLARENCE T., Chief Chemist, Old Dominion Copper Min. & Smelt. Co., Box 1163, Globe, Ariz. GARDANIER, SUTTER ALBERT, Assayer, Mgr., Douglas Assay Co., Douglas, Cochise Co., Ariz.

Jan 10, 1916

By A. W. Hale

IN a work published in 1838, De Morgan, the author of the article on "Probabilities,' in the Encyclopedia Metropolitana, says " The method of least squares is not yet introduced into the affairs of common life,….that many things which are demonstrable only by the higher branches of mathematics are looked upon as useless." And he mentions an instance in which "a method was suggested for estimating the relative importance of boroughs, by considering their population and contributions to the revenue com-

Jan 1, 1881

By AIME AIME

WHEN Russell B. Paul was born in Russell Gulch, Gilpin County, Colorado, that district was the state's leading gold producer. The son of Dr. Henry Paul, who had gone to Colorado from Missouri during the golden era following the Civil War, and had joined the Institute in 1889 when he was manager of the famous Aspen mine, young Paul's early life was steeped in a mining atmosphere from which developed his selection of mining engineering as a profes¬sion. After receiving his E.M. degree from the Colorado School of Mines in 1902, Mr. Paul worked in Colorado and Honduras. Returning from Central America he was married to Mary Ellen Gilmour, daughter of a prominent Central City mining man;

Jan 1, 1943

By Bernard MacDonald

Introduction. OF the treatment of the slime-pulp of gold- and silver-ores by cyanidation, agitation is an essential part. When prepared for treatment, this pulp, consisting of ore reduced to such fineness that approximately 80 per cent. of it will pass through a 200-mesh screen, is mixed with a certain proportion of water, carrying in solution the quantity of cyanide (KCN) and other chemicals required. The water-constituent of the pulp thus prepared usually ranges from 1 to 2 parts by weight to 1 of the dry ore. Thus constituted', the pulp is charged into treatment-tanks, the shape and capacity of which vary, according to the quantity of pulp to be treated daily and the method of agitation to be employed. Tanks have no other function in a cyanide-plant than that of being economical and convenient containers or receptacles for holding the pulp, solution, or water used in the operations. It is by agitation that the solids in the pulp charged into the tanks are kept in suspension in, and mixed with, the solution in the proper proportions required for the treatment. If the proper mixture of solution to solids be determined to be 2 to 1 by weight (which is, approximately, 5 to 1 by volume), this proportion should be maintained in every part of the charge ; -that is, each solid particle of the pulp, whether it be of 180- or 400-mesh size, should, be surrounded by five times its own volume of solution throughout the whole period of treatment. The reason is, that the amount of chemicals ascertained to be necessary for dissolving the gold and silver contained in the solids, is held in uniform solution in the water-constituent of the pulp, and, therefore, the determined proportions of solution and solids must be maintained at all times during treat-

Apr 1, 1912

By A. W. Schlechten, R. F. Doelling

Parkes' process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,' raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes' crusts by one of the authors' gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes' process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes' crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper' on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned' supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By S. C. Hollister

An evaluation of the function of the engineer, so that means whereby education can best serve his needs can be adopted.

Jan 2, 1950

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [(MG) l 2M +G2 = 2MG K = Ma X Pa, [I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Kl Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + SO2 = Cu2S + 2Cu20[3] K _ Cu2S X (Cu20)2 (Cu)6(Pso2)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [8 =KI = Pte, or VSO2= K2 '~/PeO, [S]]

Jan 1, 1941

By C. R. Clark, G. Swift, D. S. Roberts

The purpose of this investigation was to measure PVT behavior of various types and combinations of heavy hydrocarbon components from the paraffinic, naphthenic and aromatic classes where the relative proportions Of the various components were selected to approximate those of natural gas or gas condensate systems. Synthetic mixtures were used so that the compositions Of the various components could be measured accurately. n-Heptane, methylcyclohexane and methylbenzene were used to represent the paraffinic, naphthenic and aromatic components of the heavy fraction. In the mixtures studied, the heavy fraction composition was held constant at O. O5-mole lraction, the balance being methane except for one mixture where 0.10-mo1e fraction of an intermediate component, propane, was added. The PVT data for the mixtures were determined in a variable-volume, constant-mass apparatus at psuedo-reducedtemperatures from 1.84 to 2.00, over a pseudo-reduced pressure range from 2.3 to 12.0. The experimental results showed that, regardless of the type of heavy material (paraffinic, naphthenic, aromatic, or combinations thereof) mixed with methane or methane and propane, the compressibility factors at equal values of pseudo-reduced temperature and pressure varied by less than 2.2 percent. INTRODUCTION PVT data is used for natural gas and gas condensate fluids in determining reserves of reservoirs and performance of wells, in metering produced fluids, and in recombining samples for laboratory studies. While there are vast amounts of PVT data reported for natural gas and gas condensate systems from which useful correlations have been developed, ' the compositional analyses for these systems and the resultant correlations typically were made with components analyzed through some arbitrary carbon number, usually C6, with the residue reported as a lumped "heavy" fraction. The heavy fraction was stoichiometrically recombined on the basis of an apparent molecular weight to give the final compositional analysis. It is virtually impossible to make a systematic analysis of the effect that variation of the relative amounts of paraffinic, naphthenic and aromatic constituents of the heavy fraction of natural systems might have on PVT behavior. Because there is considerable latitude in the relative amounts of these constituents, one speaks of crudes or condensate liquids as being "paraffin base", etc. It is of interest to determine if changes in the relative amounts of these three types of hydrocarbons in the heavy fraction cause significant changes in PVT behavior. If so, steps should be taken to describe better the nature of the heavy fraction in PVT correlations. If not, more confidence can be placed in the correlations presently employed. DESIGN OF THE EXPERIMENTAL INVESTIGATION We attempted to determine if changes in the base of the heavy fraction would cause significant changes in the PVT behavior of gas or gas condensate fluids. Synthetic mixtures were used to enable us to systematically vary the base of the heavy fraction and to analyze accurately the fluids. We found that the heavy fraction of naturally occurring condensate systems seldom exceeds 0.05-mole fraction. Thus, the mole fraction of the heavy fraction in the synthetic systems studied was set arbitrarily at 0.05, to maximize whatever deviations in PVT behavior that might occur. Further, we judged that since the C7 hydrocarbons normally are present in greater quantities than higher carbon number hydrocarbons in naturally occurring systems, the use of n-heptane, methyl cyclohexane, and methylbenzene to represent the paraffinic, naphthenic, and aromatic species in the heavy fraction would be most appropriate. Finally, to enable us to compare our

Jan 1, 1970

By Charles Maier

IT has long been supposed that when crystalline materials are com-minuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1. The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chem-ical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the cor-rected heat of solution was less for fine material than for coarse. Con-tinuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by

Jan 1, 1936