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By C. E. Shoenfelt

Operations ill Colorado oil fields in 1934 were not quite so extensive as in 1933, but much better results were obtained and one new oil field was discovered. In all, 26 wells were drilled, of which 9 were oil wells, 1 was a gas well, and 16 were dry holes. New oil production totaled 10,220 bbl. and new gas production totaled 33,714,000 cu. ft. This compares with new oil production in 1933 of 1238 bbl. and new gas production of 14,307,000 cu. ft. Dry holes in 1933 totaled 29 as conlpared with 16 in 1934. Oil was discovered in the Hiawatha gas field, Moffat County, in 1934 in the Mountain Fuel Supply Company's No. 4B Wilson, C. NE. NW. of sec. 23, 12N., 100W. This well was completed in a sand in the Wasatch (Tertiary) at 2304 to 2337 ft., after plugging back from 3797 ft. It made 20 bbl. of oil initially. No. 4B Wilson is the first well in the Rocky Mountain region to discover oil in commercial amounts in rocks younger than Cretaceous, and while it is not expected that Hiawatha will develop into an oil field of important proportions, eventually it may produce a considerable amount of oil as the gas pressure declines. The Hiawatha gas field was discovered in 1926, on one of six structures in what is known as the Vermillion Creek gas area. It is a northeast-

Jan 1, 1935

By John B. Hastings

THE occurrence of such a large amount of gold in the Hartsel granite, even though the surmised existence of similar areas is not new, brings freshly to mind the pegmatite type of magmatic differentiation lately brought again to attention by occurrences at Silver Peak, Nev., described by Spurr; and in Alaska, described by both Spurr and Brooks. In both localities graunitic rocks or dikes are thought to pass into metalliferous quartz-veins. An interesting association in this connection is the occurrence of diamonds in residual pegmatitic clay of San Juao de Chapado, Brazil, described by Derby :1 (P. 142) "Bodies of pegmatite are quite common in the older rocks of Brazil, both in the. diamond regions and elsewhere, occurring not only in the gneiss and granite, but in the schistose series as well. Those that have been examined are dike-like in their mode of occurrence and granitic in composition." (P. 143) "The question of the eruptive or secretionary origin of pegmatites has long been a subject of discussion among geologists. . . . The recent studies . . . seem to have clearly established that most if not all of them are essentially eruptive masses, though possibly modified in some way by aqueous agencies. Even before becoming acquainted with the literature of the subject this view had seemed to me to be the only acceptable one as regards the typical pegmatites of Brazil." What is pegmatite ? J. F. Kemp says ". . . veins or dikes-it is an open question which is the more correct term-are met formed of very coarsely crystalline aggregates of the same minerals that constitute granite. These are called pegmatite and in them is the home of graphic granite, the curious intergrowth of quartz and feldspar, such that a cross fracture of the blades of quartz suggests cuneiform characters. . . . In regard to the larger veins or dikes it seems improbable that true igneous fusion could have afforded such coarsely crystalline aggregates, and so we are forced to assume such abundance of steam and other vapors, i.e, mineralizers, as to almost, if not quite, imply solution."

Jan 5, 1908

By GEORGE D. RAMSAY

WHEN the Ironton blast furnace of the Columbia Steel , Co. was first put into operation the iron ore was mined frol11 the deposit near Iron Springs, Utah. This is principally a hematite with 12 to 20 per cent of magnetite finely disseminated throughout the ore. It varies from a fairly soft broken rock structure to that which is hard and compact. In the broken form it will weigh about 150 lb. per cu. ft., and in place the density is approximately 250 lb. per cu. ft. The first ore received for the blast furnace was crushed so as to pass through approximately a 4-in. square opening screen. A typical screen test of this ore is shown in Table 1.

Jan 1, 1935

By Alfred Boyles

"Heredity"1 in cast iron has been a subject of much discussion. Numerous experimenters have found that the properties of gray iron may vary greatly without corresponding variations in composition or thermal treatment. The main structural difference in such cases is in the size and distribution of the graphite flakes and the explanations given usually attribute this difference to some chemical element not shown by ordinary analysis or to some physical factor, such as inclusions in the melt. It cannot be said that any of these theories is completely satisfactory. Much remains to be learned about cast iron and for this reason a study of the material was undertaken as a part of the program of fundamental research at Battelle Memorial Institute. A review of the literature indicated that very little systematic work had been done on the mechanism of freezing in cast iron. The experiments described below are largely concerned with that problem. Normal and "Dendritic" Cast Iron As examples of variation in type of structure, photomicrographs of two test bars of cast iron are shown (Figs. 1 and 2) and the composition and properties are given in Table 1. Both are common, unalloyed gray iron. Test bar No. 13 has normal graphite flakes while No. 49 has very fine, lacy graphite arranged in a dendritic pattern, the matrix in both being pearlite. These two types of cast iron are well known to foundry-men and need no detailed description.

Jan 1, 1937

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By C. Feng, C. Elbaum

Knoop hardness measurements were carried out on large grains of iodide titanium containing different amounts of oxygen. For each oxygen content the hardness is recorded ainingas a function of the crystal orientation and of the angle 4 between the indenter diagonal and the projection of the C (hexad) axis in the surface. The results can be expressed by the following relation; hardness = n-k cos 2ø, where n and k are constants for a given oxygen content and crystal surface orientation. A NISOTROPY of hardness is a well-known phe-nomenon and has been reported for many metals.1-3 At the present time, however, such information is not available in the literature for titanium. Consequently, a systematic study of the simultaneous effects of oxygen content and crystallographic orientation on the hardness of titanium was undertaken in this laboratory. Evaluations of oxygen content in titanium are frequently carried out through hardness tests. Although such procedures may be justified in small grain specimens, the results of the present investigation indicate that the anisotropy of hardness should be taken into account in the case of coarsegrained specimens as well as in the case of pronounced preferred orientation. Materials and Experimental Procedures Iodide titanium, 99.99 pet pure and containing of the order of 0.002 wt pet O, was used throughout this investigation. The metal was arc melted in an argon atmosphere and cold rolled into strips 1/16 in. thick. These strips were subsequently recrystal-lized and strain annealed in vacuum (10" mm Hg or better) at 850°C in order to produce crystals varying in diameter from 10 to 25 mm. Oxygen was introduced into selected large crystals by heating at 700°C in an atmosphere of pure oxygen under an observed pressure of approximately 50 mm Hg. Each sample was subsequently annealed in vacuum at 850°C for 100 hr, in order to homogenize the oxygen content throughout the specimen. It was found that longer annealing was not necessary, for no change of surface hardness in a given direction was detected after prolonged annealing. The oxygen content was determined by the difference in weight of the specimens before and after the oxidation-annealing cycle. The accuracy of oxygen determination is within ±0.1 mg in samples weighing 0.5 to 1 g. A vacuum fusion analysis of oxygen was performed on several samples and gave results in good agreement with the ones obtained by the weight change. It should be emphasized that expected weight losses through evaporation of the metal in vacuum at 850°C' are many orders of magnitude lower than the precision of these measurements. Following the annealing treatment, both oxidized and unoxidized crystals were carefully polished. All detectable traces of surface cold working were removed by repeated polishing and etching. Laue back reflection X-ray patterns were taken for each crystal for the purpose of determining the orientation and ascertaining the absence of substructures detectable by this method. Hardness measurements, using a 1 kg load, were subsequently carried out on a Tukon hardness tester equipped with a Knoop indenter. The Knoop indenter was used throughout this work because indentations obtained by means of a Vickers indenter are considerably distorted due to the anisotropy of the elastic constants in titanium. Such distortions are much less pronounced in the case of Knoop indentations, although for some orientations a cer-

Jan 1, 1959

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By J. B. Coher, M. B. Bever

COLD work destroys long-range order, as was first observed by Dehlinger and Graf.1 Dahl2 showed that the mechanical disordering caused by cold work produces changes in those properties that are affected by long-range order. The existence of order has a marked effect on tile manner in which an alloy deforms and therefore on its mechanical properties.L' The relation between order and deformation behavior however, is only beginning to be understood. Seemann and G1ander4 suggested that cold work reduces an ordered alloy to a kind of gruel of antiphase domains. According to Cottrell,5 superdis-locations and pairs of dislocations in a slip plane connected by a strip of anti-phase domain boundary provide deformation mechanisms which do not change the state of order. In general, however, slip may be expected to produce new domain boundaries and destroy order if dislocations move on intersecting planes or cut through existing domain boundaries. The yield strength of an ordered alloy may pass through a maximum with decreasing domain size.5"7 The reduction of domain size resulting from cold work may, therefore, lead to a maximum in strength properties. Flinn8 suggests that dislocations can climb by short-range diffusion during deformation and thus can generate domain boundaries not only on slip planes, but also on other planes which will be those with the lowest domain-boundary energy. It has long been known that the rate of strain hardening of an alloy in the ordered state is larger than in the disordered state.3'9 Also the slip bands in ordered CU3, AU10 and Ni3Mn" are finer than in the disordered alloys. The stress which causes initial yielding in Cu,Au passes through a maximum with decreasing domain size.6'12 A maximum has also been observed in the hardness of ordered Ni3Mn as a function of strain.' These observations suggest, but do not prove, that domain size reduction occurs during deformation. According to Fisher13 slip destroys short-range order and thus the strength of an alloy is related to the degree of short-range order present. Rudman and Averbach14 and Averbach et a1.,15 demonstrated that cold work reduces short-range order in copper-gold and gold-silver alloys. Destruction of long-range and short-range order by cold work implies slip on an appreciable fraction of planes. Yielding of an alloy in which short-range order exists or antiphase domain boundaries are present should be discontinuous because the first dislocations moving across the slip plane meet with the largest resistance.5 Such discontinuous yielding has been observed in CU3AU6,16 and Cuzn.l7 This phenomenon, however, can also be explained by mechanisms not involving order.b The published investigations of the effects of cold work on alloys with long-range or short-range order have not been covered thoroughly in reviews of order-disorder phenomena. These investigations, therefore, will be listed here. They have been concerned with strength properties> 2,3,6,8,9,12,16-21 electrical resistivity,2,4,18,19,21-26: thermoelectric power, magnetic properties,2,18,21,26 and X-ray strain'1,2,14,15,27,28 The slip systems and the appearance of the microstructure after deformation in ordered and disordered alloys have also been investigated. 6.10.ll,l7,23,29,30 The alloys used in these investigations were copper-gold. 1-4,6,9,10,14,16,18 23-26,28,29 copper-zinc. L7. 19. 20,30 nickel-manganese,2 11,21 iron-aluminum. iron-nickel,' copper palladium,4,18,22 gold-silver.4,18,22 and palladium-silver-copper.4 In the work reported here. the changes in properties of polycrystalline Cu3Au were investigated as functions of strain in wire drawing and rolling. Specimens were heat treated before deformation

Jan 1, 1961

By A. G. Rozner

TRANSVERSE rupture tests have been commonly used in mechanical investigations of brittle materials. The specimens are simple, easy to prepare, and loading presents no difficulty. Owing to the complexity of stress distribution in bending1 one can determine stresses rigorously only for the elastic range. The bend-test results, however, are at times converted into tensile-strength data, determined as maximum fiber stress. The assumption is made that for small plastic deformations the linear stress-strain relation applies. This problem was experimentally investigated by Bach3 who tested cast iron in bending and in tension and found that the maximum fiber strength obtained in bending exceeded the experimental tensile strength by a factor depending on the geometry of the tested piece. The factor varied from 1.57 for a rectangular cross section to 2.12 for a circular cross section of the tested beam. Since this work was carried out 60 years ago, the cast iron used could be expected to have been highly brittle, thus the extent of plastic deformation prior to fracture very small. We have therefore carried out a number of tests on magnesium-modified cast iron with an average elongation of -5 pct. It was hoped that the data obtained from the tests would serve as a guideline for comparing data obtained in tension and bending for brittle materials. Mechanical properties were measured at room temperature on an Instron tensile machine at a crosshead speed of 0.05 in. per min. The three-point bend test employed cylindrical bars 0.20 in. in diameter with a 1.0-in. span. For the tensile test, cylindrical tensile specimens with a gage length of 0.85 in. and a diameter of 0.160 in. were used. Results are summarized in Table I. From Table I one can see that fracture strength

Jan 1, 1965

By L. H. DeWald

During the examination of various commercial brands of copper wire bars, which had exhibited different degrees of adaptability for being drawn into fine gages of wire by the present-day high speed machine, it was found that each brand had a more or less characteristic crystal macrostructure. The extremes of these macrostructures are similar FIG. 1.-EFFECT OF METAL TEMPERATURE IN CASTING ON CRYSTAL MACROSTRUCTURE OF BAR. Reading from left to right, metal temperatures were 1166" C., 1149" C., 1132" C.. 1121" C., 1093" C. to the maximum variation shown in the photomacrographs reproduced in Fig. 1. As the various brands did not differ materially in chemical composition, it was concluded that the differences in structure were the result of variations in casting technique.

Jan 1, 1931

By WILLETT G. MILLERS

GENERAL RECEPTION COMMITTEE.-Willett G. Miller, Chairman; F. G. B. Alan, Hon. Frank Cochrane, Eugene Coste, Thomas W. Gibson, Cyril W. Knight, J. C. Murray, 0. N. Scott, Alan Sullivan, J. B. Tyrrell, J. W. Wells, A. B. Willis. COBALT RECEPTION COMMITTEE.-Arthur A. Cole, Chairman; Will. Ask with, R. W. Brigstocke, Robt. Bryce, Fred Coombs, M. I. Culbert, I. R. Drummond, J. W. Evans, A. Ferland, F. N. Flynn, E. L. Fraleck, S. R. Heakes, Joseph Houston, D. L. Jemmett, I. R. Jones, Major Leckie, Capt. Jack Leckie, R. W. Leonard, W. H. Linney, Alexander Longwell, Frank Loring, Murdock McLeod, John Martin, D. B. Rochester, W. E. Running. COBALT RECEPTION COMMITTEE (Ladies).-Mrs. A. A. Cole, Mrs. A. Edwards, Mrs. R. Jennings, Mrs. S. H. Logan, Mrs. A. Longwell, Mrs. H. F. Marsh, Mrs. J. Smith. SUDBURY LOCAL COMMITTEE.-Mayor L. O'Connor, Chairman; S. Fournier, Secretary; A. H. Beath, W. J. Bell, F. B. Bennett, D. M. Brodie, J. S. Buchanan, F. C. Busby, Wm. Chalmers, R. Dorsett, W. A. Evans, John Frawley, J. S. Gill, A. B. Gordon, J. G. Henry, T. N. Kilpatrick, Major Leckie, Chas. McCrea, John McLeod, Wm. McVittie, R. Martin, R. S. Mitchell, J. H. Morin, J. A. Orr, James Purvis (President Board of Trade), C. R. Reid, Major Smith, W. W. Stull, J. F. Templeton, S. E. Wright. The first session, held in the Banquet Hall of the King Edward Hotel, was called to order Tuesday, July 23, 1907, at 2.30 p.m., President John Hays Hammond presiding. Prof. Willett G. Miller, chairman of the General Committee, introduced Alderman J. J. Graham, who, in behalf of the City of Toronto, extended a hearty welcome to the members and guests of the Institute. To this welcome, President Hammond replied in a few well-chosen and hearty remarks. In the hall in which the session was held there was exhibited a fine, full-length, life-size portrait of Dr. Rossiter W. Raymond, in 1871 Vice-President and acting President, in 1872, 1873 and 1874 the elected President, in 1876 and 1877 Vice-President, in 1883, by appointment of the Council, and for the last 24 years by annual election, Secretary, of the Institute. Dr. James Douglas, of New York, N. Y., on behalf of numer-

Sep 1, 1907

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By H. R. Cooper

Beginning from the point of view that process control of ore flotation can be approached by on-line analysis of processing behavior, an equation was developed which has characteristics useful for a multi-variable feedback loop. The application of this equation to optimizing control with a data acquisition system will be discussed in Part 11. OBJECTIVE OF CONTROL The purpose of developing a feedback method for concentrator control is to provide a means for determining ore processing behavior in order that data describing the ore can be used to make appropriate changes in control conditions while the ore continues to flow through the flotation circuit. In absence of simple linear relationships between pairs of variables in the flotation process, attention is directed to the need for a generalized relationship which possibly would incorporate all pertinent variables. It would be possible to apply such an equation to the control of variables in a concentrator in real time according to operational requirements as ore gradually changes in quality and processing behavior. To meet this objective, it is necessary to define relationships describing flotation performance in terms of performance variables capable of being measured on-line, either with on-line instruments and analyzers or with manual methods lending themselves to quick determination of meaningful information. Relationships derived to meet this objective form a model for the flotation process. The evaluation of flotation parameters of the ore and the execution of control on the basis of the derived information while the ore is continuing through the process would constitute a feedback control system. Data for the following control and performance variables can be made available: 1) ore feed rate, 2) collector addition rate, 3) lime addition rate, 4) pulp density, 5) assay or multiple assays in feed, tails, or concentrate sufficient for material balancing, 6) particle size distribution in flotation feed, 7) froth height, and 8) frother addition rate. Other process variables, such as flotation air input and mechanical agitation intensity, are usually not considered as control variables and were not taken into account in this analysis. Other data, such as that describing the ore, would be useful for concentrator process control. However, information of this type (such as ore hardness, grain size of the mineral, chemical species of the mineral, and ore surface properties) being not presently measurable in the on-line sense, has the effect of causing disturbances in the system which can be detected only indirectly. The process control system being sought must recognize disturbances by their effect on measured performance followed by determining control changes to compensate for them in meeting the objectives of improved performance (perhaps higher throughput, maximum return, etc.). A suitable model for the process having capability of recognizing the effects of ore disturbances should provide the means for introducing proper compensation through control changes. This would be done by processing on-line data with the model to calculate coefficients reflecting ore characteristics. This procedure can only be applied in a typical flotation system when on-line data can be processed at faster rates than the usual rate at which the ore in flotation feed takes on significantly different characteristics. For example, material balance data can be accumulated in approximately 5-min intervals using on-line X-ray fluorescence analysis. The flotation system time constant might be 15 min including grinding. Ore changes having time constants longer than 1 hr could be accommodated using on-line feedback control by this procedure. FORM OF A FLOTATION MODEL A suitable form for mathematical expression of the flotation process is an equation involving rates, when each of the components entering into the separation can be treated independently by a rate equation. A first-order, kinetic rate equation can be written on

Jan 1, 1967

By S. A. Falconer

The benefication of non-sulfide or non-metallic minerals by froth flotation has been practiced commercially for at least 30 years. In the pioneer stages of development of this flotation art, most of the promoters investigated were fatty acids or soaps that had been found to float sulfide minerals. When commercial application of froth flotation started to assume importance in the late 1920' s and 1930's, a great deal of fundamental research work was done in the laboratory (11-14, 19, 22, 23, 26, 29, 32). Among other subjects, this work included studies of the relative effectiveness of the different fatty acids and their salts on the flotability of various non-sulfide and non-metallic minerals. The successful present-day use of fatty acid and petroleum sulfonate type promoters results from better understanding of the principles of non-sulfide flotation plus the developnent of effective selectivity modifying agents. Many investigators have contributed to a greater appreciation of the numerous interrelated factors involved in fatty acid and soap flotation of non-sulfide minerals. Of these, mention should be made of recent fundamental studies by Tagart and Arbiter (31); Wolstenholme and Schulman (35); Schulman and Smith (28); Wark and his co-workers(3,4) Du FIietz(l5); and J. Leja(24). According to J. Rogers, K. L. Sutherland and E. E. and I. W. Wark(27), "the basic requirements for a 'collector' in flotation are that it shall form a film over the surface of the mineral to be floated and that this film should be oriented so that hydrocarbon (non-polar) groups form the effective surface." When modified in that way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince (33)that such a film can be produced only if the collector compound contains an active (polar) group to be attracted to the mineral surface, as well as the non-polar group. The commonly used anionic-type promoters for non-sulfide, non-metallic and metallic oxide ores include: 1. Fatty acids, and their soaps and emulsions. 2. Fatty acids residues — "pitches" and "foots." 3. Sulfonated and sulfated fatty acids and so-called "petroleum sulfonates." 4. Paraffin chain salts — sulfonated and sulfated higher alcohols. 5. Cyclic organic acids or salts, such as naph-thenic acid and naphthenates. Certain fatty acids are more effective than others as promoters for particular minerals under certain specified conditions. Some of the more costly fatty acids or collectors of the paraffin chain salt type may give improved selectivity in some instances and are being used commercially in a limited number of operations. Local availability may dictate the choice of the fatty acid used — for example, the use of palmoil fatty acid for flotation of copper carbonate ores in the Belgian Congo. Coconut oil fatty acids have also found limited use.

Jan 1, 1961

By Charles Jones

IN the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous, pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining ,journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T.J . Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world's deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world."

Jan 10, 1913

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By H. T. Kennedy, S. M. Avasthi

An equation developed for gaseous hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 0.73 percent when applied to 264 natural gas and condensate systems including 2,043 PVT points. Another equation developed for liquid hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 1.12 percent when applied to 346 crude oil systems including 1,759 PVT points. Both equations require composition of the mixture to be expressed as mole fraction of methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide, together with the characteristics of the heptanes-plus fraction in addition to the temperature and pressure. The equations cover wide ranges of the variables involved, and their accuracy is considerably better than that of other available methods. The equations were differentiated to allow calculation of the coefficients of isothermal compressibility and isobaric thermal expansion. (In this paper the coefficient of isothermal com-pressibility and the coefficient of isobaric thermal expansion will be expressed as compressibility and thermal expansion coefficient, respectively.) Equations to calculate these quantities are presented. INTRODUCTION Calculations of reservoir performance for petroleum reservoirs require accurate knowledge of the volumetric behavior of hydrocarbon mixtures, both liquid and gaseous. Compressibilities are required in transient fluid flow problems, and thermal expansion coefficients are important in thermal methods of production. An accurate laboratory investigation of the PVT behavior of each reservoir fluid encountered would be costly and time consuming. For this reason various correlations for predicting fluid properties have been developed and recorded in recent literature. Correlations have been presented in the form of graphs, tables and equations. Since an increasing number of studies are being conducted with the aid of electronic computers, recent efforts have been directed toward development of correla-tions suitable for computer programming. Application of computers permits the use of more complex correlations which otherwise are not feasible. Moreover, methods for predicting reservoir performance, particularly those based on the compositional material balance, depend upon the capability of accurately expressing the molal volumes and other fluid properties as functions of pressure, temperature and composition. The coefficient of isothermal compressibility c is defined by

Jan 1, 1969

By B. E. Warren

Jan 1, 1965