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By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By Karl S. Kurtenacker

In attempting to find a rapid and economical means for solving many of the subsurface problems that confront the highway engineer, the author for the past two years has utilized a Megger Ground Tester on resistivity surveys in conjunction with highway construction. Electrical surveys in connection with highway work are largely shallow depth surveys, thus differing from most other types of resistivity work. Consequently, the readings are affected by a great many qualifying factors such as the density and moisture content of the media under observation and the amount of weathering and leaching. In most cases the surface layer is decidedly heterogeneous in character, and, because of the great number of side hill cuts, the second layer, which in most cases is rock overlain by some sort of surface soil, silt, or debris, seldom lies in a horizontal position. Shallow strata, lacking homogeneity and not lying in a horizontal position, do not lend themselves readily to accurate theoretical interpretations, therefore the author has used empirical rules to a large extent in interpreting depth soundings. The following empirical rules of interpretation are surprisingly adequate for highway work, since much of the work is in the nature of reconnaissance surveying and the results are construed to be approximations. The writer is careful not to risk interpretation on some special feature of the curve, since such features are usually due to random errors or lack of homogeneity among the subsurface strata. Effect of Surface Medium A resistivity depth sounding taken to a depth of 200 or 300 ft. is not much affected by superficial conditions, but these conditions have a great effect in depth soundings to 25 or 30 ft. In shallow soundings the character of the surface medium has a very marked effect on the entire resistivity graph. Fig. 1 illustrates a very striking example. Graphs A and B are depth soundings taken in approximately the same place. The surface stratum is a clay loam but at the place where graph B was taken

Jan 1, 1934

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

NEW MEMBERS. The following list comprises the names of those persons who became members during the month of June, 1913: Members. ANGERER, VICTOR, Vice-Prest. and Genl. Mgr., Wm. Wharton, Jr. &, Co., Inc., 25th St. and Washington Ave., Philadelphia, Pa. BULLOCK, ALLYN, Min. Engr., Hazleton, Pa. CUNNINGHAM, NOEL Met. Engr. Hollinger Gold Mines Ltd., Timmins, Ont Canada ESTABROOK, EDWARD L., Supt. of Colliery 426 Center St., Ashland, PA. GATES A. O. Instructor Purdue Univ. La Fayette Ind. 1 LUDLUM, ALBERT C., Prest., New York Engrg. Co., ,2 Rector St., New York, N. Y. MILLER, HERBERT F., Met. Engr P. O. Box 142, Verona, Pa. MORTON, ELMER T., Min. Engr Clifton, Ariz. MURFIT, RICHARD H.. Fdv. Asst Hess Steel Castings Co., Bridgeton, N.J. QUAYLE, THEODORE W., Chief Sampler, Metcalf Mines, Arizona Copper Co., Metcalf, Ariz.

Jan 7, 1913

By M. C. Chang, J. Dasher

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to bene-ficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly —24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant. The three major problems encountered in this system became acute when the mine switched from track-mounted machinery to the more economical off-track equipment. The quality and uniformity of product declined, too much slime accumulated in the circuit, and waste pond disposal became highly impracticable. Lowering of Quality and Uniformity: Since the filter cake was not beneficiated in any way, addition of this material, which contained about 18 pct ash. would certainly lower the quality of metallurgical coal. Difficulties of handling the high-ash, high-moisture cake were compounded by the lack of adequate blending facilities at the mine, making it impossible to maintain uniform feed for the coke ovens. For a two-month test period, to verify the source of trouble, all filter cake was excluded from the metallurgical coal. The excluded filter cake was stocked in the yard. Slime Buildup: The moisture retained in the coarse coal products and the filter cake provided daily the only means of slime bleed from the circuit. As this bleed was not enough to offset the incoming fines in the raw coal feed, there was excessive buildup of slimes. To operate at all, it was necessary to purge the system each weekend by pumping all the solids from the thickener to a waste pond. The slimes built up during the week progressively increased the apparent viscosity and density of the circulating plant water, so that hydroseparators and hydrotator units had to be constantly adjusted. Uniformity, yield, and quality of the metallurgical coal suffered in consequence, and the filter cake ash and moisture contents increased from Monday to Friday. Limited Waste Disposal: Location of the plant does not permit unlimited waste pond area. Maintenance of a waste pond for the purpose of emptying the thickener during weekends became a costly burden that could not be tolerated. HOW THE PROBLEMS WERE SOLVED The flowsheet (Fig. 1) chosen to overcome these difficulties is considered the one most economical to install and operate. In a preliminary change made before the flotation circuit was installed, the cyclones and thickener were first operated in series, the overflow from the 3-in. cyclones, after flocculation, being discharged into the thickener and the thick-

Jan 1, 1960

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Curtis L. Graversen, J. H. Hamilton, John C. Nixon, John R. Lewis

RECENTLY there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1.2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his' paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulfides under varying conditions. To date we have studied the oxidation of galena, 5 sphalerite, and chalcocite. It is a well known fact that copper sulfide minerals are oxidized slowly by weathering agents, so that the sulfides of copper which find their way into a tailing pond are gradually changed into watersoluble and acid-soluble compounds. Commercially, the oxidation of copper sulfide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple-hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°°C. EXPERIMENTAL Preparation of Chalcocite (Cu2S) Natural chalcocite is not pure. Minerals such as bornite, covellite, and chalcopyrite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and finely divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. To this was added a slight excess of

Jan 1, 1948

By A. J. Shaler, J. Prieto Isaza, John Wulff

TANTALUM metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involving high temperatures in vacuo some of the refractory metals become brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element columbium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum- columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen- containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides, one of the authors under- took4 an investigation of the thermo- chemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exothermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the process should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonlv made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tantalum, either in the metallic state or combined

Jan 1, 1947

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By J. Elmer Thomas

The evolution of the oil business is one of the great industrial romances of modern times. First used as a medicine, then as a lubricant, then as an illuminant, and finally as a motor fuel, each change in its principal usage caused large increases in consumption. Producing Successes The producing branch of the industry responded ably to the demands made upon it. Never was there a famine, rarely any threat of scarcity, and stored inventories were gradually accumulated to form comfortable working stocks. Originally an erratic and hazardous undertaking, the discovery and development of oil fields has made such strides as to classify now as a science. When storage stocks were low, production in close balance with consumption, and demand trending sharply upward, considerable concern was expressed over future needs. Price was very responsive to fluctuations in supply under those conditions, and quotations for crude and refined oils exhibited wide swings. A very different situation exists today. Consideration of the statistics only since the war will show how recent has been this change. In the 10-year period from 1918 to 1927 inclusive, we produced in the United States 6,100,000,000 bbl. of crude and imported 900,000,000 bbl., our total supply being 7,000,000,000 bbl. The consumption was 6,600,000,000 bbl., thus adding to stocks 400,000,000 bbl., an accumulation of somewhat less than 6 per cent. of the total supply. During that period virtually every field was promptly developed as soon as discovered and nearly every well in the country was producing at full capacity. With the maximum production of the wells required to take care of the rapid increases in consumption, with storage stocks moderate and proven reserves very slight, the producing division of the industry acquired a tempo not needed now. Potential Surplus Today the situation is vastly different. The economic consumption is about 2,700,000 bbl., with current production slightly in excess of that.

Jan 1, 1930

By H. Ries

THE stabilization of a gravel road with soil is a method of treatment developed in recent years by the United States Bureau of Public Roads for the purpose of binding the constituents together better, and maintain-ing a more durable surface. The process consists in adding to the gravel or crushed stone and sand, a soil mortar, so-called, of fine sand, silt and clay, mixed in the proper proportions. The coarse gravel and sand supply structural strength and hardness; the fine sand adds embedment support to the coarse sand; the silt acts as a filler to prevent the granular particles from rocking; while the clay serves not only as a binder but also provides pores minute enough to cause connecting moisture films which are supposed to have high cohesive properties1. It will be recognized that the clay is an important ingredient both when wet and dry, and should not show excessive expansion when wet, nor correspondingly high shrinkage in drying, as otherwise there is danger of unseating the nonplastic particles. Such a stabilized road, although an improvement on one with a floating surface, will in course of time be subject to wear, and become dusty when the clay dries out and breaks up. It has been found that if some salts are added to the road mixture they tend to maintain the soil moisture and prevent dustiness of the road or raveling of the road surface. In addition to this, it is claimed that these dissolved salts cause a thinning of the moisture films on the particles, thus permitting greater compaction of the road mixture, and thereby increasing its density. This fact can be proved by noting the increased compaction which a road mixture shows when certain salts are added to the soil water. Since certain chemical substances such as sodium chloride are electro-lytes, the question arises whether they cannot have some effect on. the qualities of the clay in the soil mortar, and perhaps improve them. In view of the fact that certain salts seem to exert a favorable effect on the road mixture it is desirable that they be held in the road soil as long a time as possible.

Jan 1, 1936

By W. F. Stowasser

A downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in co-operation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace.

Jan 5, 1955

By J. F. Wolff

CARL ZAPFFE, Brainerd, Minn. (communication to the Secretary*).¬Unless one has actually directed explorations for iron ore, it is doubtful whether the importance of Mr. Wolff's paper, the value of the information contained, and the large amount of detail work involved in what is set forth can be fully appreciated. It is indeed rare to get such a com-

Jan 3, 1917

By AIME AIME

Russell B. Paul, Chairman of the Special Committee on Divisional Relationships, presented the interim report of his Committee which was published in the September, 1945, issue of MINING AND METALLURGY and a copy of which is incorporated in the official minutes of this meeting. The following specific actions were taken by the Board of Directors in relation to the six recommendations in the Summary of the Report as published: (1) Mr. Haider, Chairman of the Petroleum Division, presented the formal request of his Executive Committee that the headquarters of the new Secretary of the Petroleum Division be established in Dallas, Texas. After lengthy discussion in which the point was made that the success of this program would depend upon effective co-operation between the Chairman of the Division, the Secretary of the Petroleum Division, and the Secretary of the Institute, the request was approved. The new secretary will be selected by the Division and will be employed by the Institute in the capacity of an Assistant Secretary. (2) The following item in the report was approved:

Jan 1, 1945

By Will Clark

HE who enters a mining claim within an Indian reservation of the United States of America acquires no rights thereby, because of the fact that the lands within such Indian reservation are not a part of the public domain, and cannot be located or acquired as mineral land. However, where such an entry is authorized as to a particular reservation by an Act of Congress, such claims as may be entered under such authorization are thereby segregated from the reservation, and the Indian title is extinguished. Under the Choctaw Constitution, any citizen of that nation, in other words any Choctaw Indian, who discovered a coal mine, acquired an exclusive right to all coal within a radius of 1 mile. The laws of the Chickasaw nation provided for the formation of corporations to develop coal and other mines, with authority to contract with others to develop and work the mines. Under these laws, leases were made; but Congress subsequently abrogated all existing leases, prohibited all persons from receiving royalties from such mines, and provided that all coal within the nation should remain the common property of the tribes. Such leases are now expressly prohibited by an Act of Congress (32 United States Statutes at Large, 655). All leases of mineral lands upon Indian reservations must now be made under regulations promulgated by the Secretary of the Interior, and the royalties must be paid into the United States Treasury for the benefit of the tribes. In Canada the Indians have no rights to the royal mines and minerals, and the government can make no stipulation with the Indians which would affect the rights of the Province in which the lands are situated. Therefore, while it is true that under our present law no rights can be acquired to a mining claim within an Indian reservation, it seems to be fully within the authority of Congress to make laws, giving such rights to mineral locators as it may deem necessary or expedient.

Jan 6, 1914

By Arnold Hague

In the short time allotted to me* I can only hope to present to you a brief sketch of the main geological features of the country which you are about to visit. My remarks must, of necessity, be more or less incomplete, as my desire is not so much to elucidate any special problem connected with the many interesting geological questions to be found here, as rather to offer such a general view of the region as will enable you, during your five days' trip through the Park, to understand clearly something of its physical geography and geology. The Yellowstone Park is situated in the extreme northwestern portion of the Territory of Wyoming. Its boundaries, as determined by the original Act of Congress setting apart the Park, are very ill-defined. At the time of the enactment of the law establishing this national reservation, the region had been but little explored, and its relation to the physical features of the adjacent country was but little understood. Since that time, surveys have shown that only a narrow strip, about two miles in width, was situated in the Territory of Montana, but it was also found that a still narrower strip extended westward into the Territory of Idaho. The question of properly establishing the boundaries, -based upon our present knowledge of the country, is now before Congress, and an Act has already passed the Senate, proposing to make the northern boundary coincide with the boundary between Wyoming and Montana, and the western boundary coincide with the Wyoming and Idaho line. The Act under consideration extends the southern boundary of the Park to the 44th parallel of latitude, carrying the area of the reservation southward nine and one-half miles. The eastern boundary is made to coincide with the meridian of 109' 30') adding a strip of country about twenty-four and one-half miles in width along the entire eastern side of the Park.

Jan 1, 1888