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By Charles R. Keyes

PAGE I. Introductory............ 140 II. Location and History...........140 III. Surface-Relief of the District....... 141 IV. General GeoloGic Features........ 142 1. Main Relationships and Map....... 142 2. Résumé of Geologic History..143 V. Geologic Formations Represented...144 1. Broader Considerations......... 144 2. Geologic Section.......... 145 3. Nomenclature.......... 146 4. El Pasan Limestones..146 5. Santa Rita Limestone.... 146 6. Silver Shales........... 147 7. Bella Shales........... 147 8. Berenda Limestone..147 9. Grande Limestone... 148 10. Lake Valley Limestone........ 148 11. Sierra Limestone.......... 149 VI. Unconformities........... 149 VII. Geologic Structure.......... 150 1. Main Characteristics......... 150 2. Folding........... 1.50 3. Faultings........... 150 4. Relations of the Eruptives...153 VIII. Geologic Relations OF the Ore-Bodies...... 154 1. Governing Factom......... 154 2. Position.......... 154 3. Relations to Foldings...155 4. Relations to Lines of Dislocation... 15.5 5. Relations to Present Surface.Relief..156 6. Relations to Eruptive Rocks...157 7. Relations to Lithologic Nature of the Rocks.... 158 IX. MINERALOGIC CHARACTER OF THE ORES...... 158 X. Origin of the Ore.Deposits..159 1. General Statement......... 159 2. Original Source of the 0re.Materials...160 3. Contact-Metamorphism of the Region... 161 4. Process of 0re.Concentration..162 5. Lowering of Ground-Water Level..162 6. Formation of Cerargyritic Ores...163 XI. Recapitulation........... 168

Jan 1, 1909

By Erwin Pink

It has been pointed out in a previous publication' that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e' the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E' is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson's ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By W. P. Sykes

IN CONNECTION with a study of tungsten steels, Honda and Murakami1 reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. MATERIALS The iron powder used in preparing the alloys was obtained as follows: Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000° C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 percent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon, The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly

Jan 2, 1926

By John B. Knaebel, Robert J. Grant

This paper outlines the trends in gold production since the discovery of America, in the world as a whole, and in the principal producing regions as well. World production climbed at an average rate of about 20,000,000 oz. per 5-year period until the record all-time output of 111,307,000 oz. in the period ending with 1915. Production fell off during the war period, but has been mounting since 1925, and will probably be nearly 100,000,000 oz. for the 5-year period ending in 1930. Total world production of gold from 1492 to the end of 1930, as closely as can be determined, is more than 1,061,000,000 fine ounces. More than one-half of this total, or about 575,000,000 oz., has been mined since 1900. In percentage of world production, the United States jumped from 4.8 per cent for the decade 1831-1840 to 44.5 per cent for the five years ending with 1855. This is the highest figure ever reached by this country, although, with the exception of the 10-year period ending 1865, it ranked first among the nationa from 1849 until the end of 1905. During the 5-year period ending with that year, the United States produced 24.7 per cent of the world's gold. The tremendous increase from South Africa following 1890 resulted in that country's becoming the largest contributor for the five years 1906-1910, a position it has held with increasing dominance ever since. Relegated to second place in the period 1906 to 1910, the United States produced nearly 20 per cent of the world's new gold until 1920. From 1921 to 1925 it averaged 13.6 per cent and since then it has continued to decline in relative importance, accounting for only 10.9 per cent in 1927. Final figures for 1930 may place Canada second among the gold producers of the world.

Jan 1, 1931

By Carl E. Johnson

INTRODUCTION A method for predicting water-flood oil recovery was reported by H. Dykstra and R. L. Parsons' in 1950. It is now generally known as the Dykstra-Parsons method and is widely used by petroleum engineers. The method is semiempirical and consists of a correlation of four fundamental variables. These are: V, vertical permeability variation;' a, mobility ratio; Sw initial water saturation; and R, fractional recovery of oil in place at a given producing water-oil ratio. The correlation extends over a wide range in each of these variables, and may be applied to all formations with initial oil saturations of 45 per cent or greater. The method of calculation originally outlined by Dyhtra and Parsons closely follows their derivation. And this is a convenient way of illustrating the development of some rather complicated ideas. However, in actual use it is more cumbersome than necessary. The purpose of this note, therefore, is to provide a simplified method for making Dykstra-Parsons predictions. A SIMPLIFIED GRAPHICAL SOLUTION The correlation between V, a, Sw and R, corresponding to a given producing water-oil ratio, can be shown on a single graph. This is best done by plotting V against a to show lines of constant R(1 - S, . WOR-0.2). Figs. 1, 2, 3, and 4 show these plots

Jan 1, 1957

By Francis Clark

WHEN 60:40 brass is heated to 825° C., given a drastic quench to obtain the beta solid solution, and reheated, various changes take place in the structure. Reheating at 200° C. causes a fine, granular, sorbitic structure to appear which has been considered alpha solid solution. These particles coalesce at higher temperatures of reheating, and at 470° C., the alpha forms twins. A further study of these transformations was considered worth investigating. EXPERIMENTAL WORK The object of the experimental work was to study the effect of mechanical work on rolled 60:40 brass, quenched and reheated, and the mechanism of twinning in the alpha reeds of a furnace-cooled specimen. It was desired to determine the effect of mechanical work on the transformations taking place on reheating the quenched material, both at 200 and at 470° C. A study of the nature of the structure resulting from the breakdown of the beta at 200° C. and a study of the mechanism of twinning above 470° C. were considered problems for investigation. The question of the twinning of the alpha reeds was also an important phase of the work. With high-power magnifications, there was hope of following these processes.

Jan 1, 1927

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By B. S. Butler

The principal ore deposits of Arizona are in the southern, cen-tral, and western portions of the state, which physiographically are part of the Basin and Range province, southwest of the Colo-rado Plateau (Pl. I). The Basin and Range province is characterized by numerous subparallel mountain ranges separated by plains or valleys. Most of these ranges trend northwest to north, parallel to the margin of the Colorado Plateau; but in southeastern Arizona, southern New Mexico, and northeastern Sonora, they trend northward, transverse too the edge of the Plateau. The mountains rise abruptly from plains or valleys, the margins of which in many places are pediments cut on hard rock. Some of the plains form closed basins (bolsons, playas), but most of them are drained. The Basin and Range province in Arizona is divisible into the Mountain Region and the Desert Region4 (Pls. I and II). The Mountain Region forms a belt 60 to 100 miles wide that contains most of the large ore deposits. Its longest range measures about 55 miles, the widest 20 miles, and the highest peak more than 10,000 feet above sea level or 7,000 feet above adjacent valleys or plains. Broad plain-forming valleys are exceptional, but several with maximum widths of 20 to more than 30 miles appear in the southeastern portion. In the Desert Region the mountains are relatively low, narrow, serrated, and steep, with sharply angular profiles. There are a few exceptionally large ranges of which the longest measures nearly 100 miles and the widest 18 miles. The highest peak is some 7,000 feet above sea level, and the maximum local relief amounts to about 5,400 feet. Broad and comparatively low desert plains form 50 to 75 per cent of the area.

Jan 1, 1939

By Lester Uren

WITH the depletion of our older, and relatively shallow, oilfields and the necessity for securing new production from deeper horizons, much attention is being given to the improvement of oil-well pumps in order that they may function satisfactorily under the more difficult conditions imposed by increased depth. Until recently, practically all of the world&apos;s petroleum was secured from wells less than 3000 ft. deep, whereas horizons are now being explored to depths of from 5000 to 7000 ft. in some of the more prolific fields, and it seems probable that the greater part of the future supply must come from depths in excess of 3000 ft. While much of the early production in a new field is obtained by natural-flow methods, when the stimulus of high gas pressure fails, recourse must be had to some method of pumping. The perfection of a pump capable of economically and efficiently lifting oil from depths ranging from 3000 to 7000 ft. is therefore a matter of prime importance to the oil-producing industry. This paper is offered as an estimate of the present state of development of the oil-well plunger pump and as a review of the general principles involved in its operation in deep-well pumping. A design for a new type of oil-well pump embodying several novel features, is also described.

Jan 9, 1925

By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By J. Gordon Parr, L. P. Srivastava

DUWEZ1 has shown that pure titanium and pure zirconium transform martensitically during rapid cooling at temperatures about 30° and 15°C re spectively below their To temperatures. Holden et al.2 determined M, temperatures of Ti-Cu alloys by a metallographic technique applied to isothermally treated samples. Their results, superposed on the McQuillan3 version of the partial Ti-Cu diagram are shown in Fig. 1. Sources of metals were: Titanium: Iodide bar; Foote Mineral Co. Ltd. Zirconium: Iodide bar; Foote Mineral Co. LM. Copper: Spectrographic Standard; Johnson Matthey and Co. Ltd. Alloys were prepared by levitation melting under argon to the following nominal compositions:* 0.5, Quenching, at rates to about 8000°C per sec, was performed by cooling in a stream of helium (99.999 pct pure) a 3/64 in. cube of material previously heated by a tungsten coil in a system operating at. 10-5 mm Hg. Cooling rates below 200°C per sec w were obtained by controlling the current to the heater coil. The specimen was supported on a 32 gage Pt, Pt-Rh thermocouple attached through a DC amplifier to an Edin magnetic oscillograph (Model 8082) with a maximum chart speed of 250 mm per sec. Transformation temperatures were read off the oscillograph charts at the location of the beginning of the thermal arrest. The same specimen was quenched several times, and all runs were repeated on new samples. Regular calibrations of the oscillograph against a potentiometer were made between quenching experiments. The criterion of martensite formation was the effect of surface rumpling. Previously polished samples that showed a rumpled surface after transformation are assumed to have undergone martens itic transformation: transformations of a diffusion type produce no surface disturbance, Figs. 2 and 3. Electrochemical measurements were made in a cell described elsewhere4 whose electrodes were the martensitic and the diffusion-transformed materials in the following electrolytes:

Jan 1, 1962

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite&apos;" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By F. N. Rhines

Despite the large amount of study which has been devoted to the subject our present knowledge of the copper-oxygen system remains incomplete and unsatisfactory .in many respects. This applies particularly to those regions in which solid metallic copper exists. The primary object of the present paper is the contribution of new information relative to the solid solubility of oxygen (or cuprous oxide) in copper at atmospheric pressure, together with certain observations in the low-pressure regions of the system. It seems appropriate also to present a brief summary of the outstanding previous work on the constitution of mixtures of copper with its lowest oxide in order. to show the relation between the new facts and the system as a whole. The earliest recorded investigations of the copper-oxygen system are those of M. S. Lucas(l) $ and of M. Chevillot(2) in 1819 and 1820. Lucas believed that liquid copper is capable of dissolving its oxide, but neither he nor Chevillot was able to furnish convincing proof of this property. It was not until 1866 that T. Graham(3) definitely established the existence of such a solubility. Nine years later W. Hampe(4) measured its extent and roughly outlined the copper-rich portion of the system. The first really precise examination of the constitutional relationship between copper and cuprous oxide, however, was that of E. Heyn(5) who in 1900 published a temperature-concentration diagram covering the range from 0 to 10 per cent of cuprous oxide at atmospheric pressure. Within these limits of composition cuprous oxide was found to dissolve in liquid copper, forming at 3.4 to 3.5 per cent a eutectic which melted at 1065" C. R. E. Slade and F. D. Farrow(6) extended these studies to mixtures of higher oxygen content. They discovered that between 20 and 95 per cent of cuprous oxide the metal and oxide form two liquid phases at a monotectic reaction of 1195" C. The span of the biliquidal region diminishes slightly

Jan 1, 1934

By B. A. Kulp, R. R. Reeber

Lattice parameters for the wurtzite form of&apos; CdS mere measured by powder X-ray diffraction techniques over the temperature range 26° to 1000 K&apos;. A negative thermal -expansion coefficient was determined parallel and perpendicular to the c axis below 13.5°K. Near 808°K, the curves of the a, parameter, the differential thermal expansion, and the resistivitv vs absolute temperature exhibited a reversible discontinuity. j\. direct determination of the lattice parameters of CdS over an extended temperature range is of particular use in interpretation of the effects of high pressure on the band structure of semiconductor materials. For example, Langer&apos; has studied the effects of pressure on the absorption edge of CdS from 77°K to room temperature. In order to properly interpret his results it is necessary to know the change in lattice constants as a function of temperature for the wurtzite, zincblende, and rocksalt2 modifications of this material. Thermal-expansion measurements for CdS, wurtzite phase, have previously been determined over a limited temperature range.s74&apos;5 The zincblende phases, of other compounds with similar bonding, have been investigated by Novikova et a! .&apos;&apos; Previous thermal-expansion measurements for metals with hexagonal symmetry have for the most part used bulk sample techniques for low-temperature result. Most X-ray measurements at low temperature have been on materials with cubic symmetry.&apos;jQ The use of X-ray powder-diffraction techniques offers a convenient and accurate method of measurement over a wide temperature range. The X-ray method, besides measuring unit cell size, also provides information about change in structure type and the nature of some of the stacking defects present. I) EXPERIMENTAL PROCEDURE The thermal expansion was measured by X-ray powder-diffraction techniques. Lattice parameters for the range 300" to 1000°K were determined in a 19-cm Unicam camera. From 26" to 300°K a 34-cm back-reflection camera with the Van Arkel" film arrangement was used. The sample was bonded to a copper cold finger below a helium, hydrogen, nitrogen, oxygen, dry ice, or ice brine bath in a metal cryistat. che inner bath was surrounded by another one for radiation shielding. Nitrogen was used in this outer bath for the very low-temperature runs while dry ice and acetone was used for the 195°K point. CuKa X-rays, filtered with a nickel foil, entered the cryostat through a 0.001-in.-thick aluminum window. During a typical 9-hr exposure the sample was continuously rotated through a 30-deg arc. Heat losses from the sample holder limited the minimum temperature attained to 26°K with helium in the inner dewar. Temperature calibration between 25" and 125°K was determined with an Allen Bradley 300-ohm carbon resistor. The resistor was attached to the back of the copper finger with a thin layer of silicone grease. Liquid He, HZ, N2, and O2 baths were used to calibrate the resistor. Temperature variation is estimated to be *2"K with a slightly higher uncertainty at room temperature and 264°K. The thermal expansion of high-purity germanium from 373" to 900°K was measured as a calibration for the Unicam camera. This value was compared with the known value1&apos; for the thermal expansion. A discontinuity in the thermal-expansion coefficient of the CdS a, parameter was observed. Similar discontinuities in the resistivity and differential thermal analysis at the same absolute temperature indicate that the temperature error is *5°K in the temperature range above 500°K. Temperature errors in the Unicam camera below 500°K are appreciably higher due to large gradients in the resistance furnace. II) SAMPLE PREPARATION The CdS was Eagle Picher ultrapure grade. The crystallite size range of the as-received powder

Jan 1, 1965

By J. W. Cloud

years ago upon the effect of having the rails always rolled in the same direction, and also of having them rolled backwards and forwards, and showed that under the latter course there were of necesshy weak spots somewhere near the centre of the rail, yet in all this discussion the methods of rolling have been passed by almost in silence. Mr.. Sandberg in his paper mentions the idea of using a regietering dynamometer attached to the punching machines, and of det.erminit~g the quality of the metal by the resistance which is shown. I think the&apos; first idea of this kind was published by Professor Langley, then of Pittsburgh, who, while making some investigations for Mesrs. Miller, Metcalf and Parkin, announceti as tile result of a series of dynamometric experiments that abrasive resistance was the term which should be wed in regard to steels of different wearing qualities. I have had extremely delicate dynamometers attached to the instruments of precision with which I am making the iuvestigation on the fatigue of metals, and hope soon to communicate the results of the iovegtigation- made with them to the Institute. I wish again to call attention to the fact that we are wing the words " hardener " and " hardness " without any real idea of the meaning of these words. When we say hard and soft, as we have hen constantly doing during this discussion, is it quite sure that every one has exactly the same meaning in his mind ? Certainly, when hard is used in distinction from soft*, we mean not the capacity of wear, but the capacity of resistance to peuetration, to fracture, or some other resistance, and do not always meau the capacity of resistance to abrasion or crushing, which the discussion would sometimes seem to imply were the only qualitiw requisite to constitute a god rail. J. W. Cloud, Altoona, Pa. : I would call the attention of the Institute to the title of Dr. Dudley&apos;s interesting and valuable paper, —" The Wearing Capacity of Steel Rails in relation to their Chemical Composition and Physical Properties." Here are two separate and distinct questions: lst, The wearing capacity of steel rails in relation to their chemical content; and 2d, the wearing capacity of steel rails in relation to their physical properties. The discussion has been almost exclusively confined to the former question, on which there may be many differences of opinion in matters of detail without greatig affecting the result. The latter

Jan 1, 1881

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young&apos;s modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

Furnace Builder. Engineer with extensive experience in furnace building. Position with well-established firm, branching into new fields. Location Ohio. 11-1343. Erecting and Operating Engineer to take charge of erection of gas-producer equipment and to teach customers how to operate such equipment. Location Ohio. Salary $250 per month. R-1339. Assistant Professor in Mining School, for instruction work; must have had experience in ore dressing and metallurgy. Location Missouri. Salary $1500-$2100 per school year (8 mo.). R-1332. Consulting Engineer, familiar with construction of artesian wells to act in a consulting capacity. Location New York City. R-1324. Mining Engineer and Investigator to do non-metallic mineral investigations in both field and office for United States Government. Position will last at least a year, and may become permanent. Location Washington, D. C. Salary $1800-$2700 depending on qualifications of appointee. R.-1317. Crushing Plant Superintendent, cement mill and construction experience essential. Prefer man who has had limestone crushing experience. Location New York. R-1314. Assistant Professor of Coal Mining, must be a graduate of mining engineering and have had some coal mining experience. Location Philadelphia.. Salary $2200 for school year of 10 months. R-1312.

Jan 9, 1919