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By J. Waldman, M. B. Bever, A. K. Jena

The heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of one solid solution have been measured by tin solution calorimetry. The heats of formation are analyzed in terms of the quasichemical theory. If the enthalpy diffel-ence between a hypothetical fcc form and the hcp form of cadmium is taken into account, this analysis does not lead to the conclusion put forth in the literature that electronic effects make significant contributions to the heats of formation of silver-rich Ag-Cd solid solutions. The temperature dependence of the heats of formation is appreciable and negative near 78ºK, but decreases gradually to nearly zero abore 400°K. The relative partial enthalpies per grarn -atom of silver at 541°K and cadmium at 532" and 541°K in tin have also been determined. THE composition range of the silver-rich Ag-Cd solid solutions stable at room temperature extends to about 40 at. pct Cd. Heats of formation of these solid solutions at 308" and 723°K have been measured by solution calorimetry.1,2 Heats of formation for an average temperature of 800°K have also been calculated from vapor pressures.2,3 The heats of formation deviate from the values predicted by the quasichemical theory above about 30 at. pct Cd. This deviation has been attributed to electronic effects at the Brillouin zone boundaries.2 The heats of formation of Ag-Cd alloys are essentially the same at 308", 723", and 800°K; consequently the temperature dependence of the heat of formation d?H/dT = ?Cp is vanishingly small, although from the exothermic heats of formation a negative value would have been expected. In the investigation reported here the heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of 1 solid solution have been measured by tin solution calorimetry. The results are analyzed in terms of the quasichemical theory and the dependence of the heats of formation on temperature is discussed. The relative partial enthalpies per gram-atom of silver in tin at 541" and cadmium in tin at 532" and 541°K were obtained in the course of this investigation. The values of the temperature dependence of the relative partial enthalpies per gram-atom of silver in tin derived from the data reported by various investigators2,4-9 are contradictory. The literature contains only a value for 517°K of the relative partial enthalpy per gram-atom of solid cadmium in tin.2 EXPERIMENTAL PROCEDURES Samples of Ag-Cd solid solutions were prepared by melting weighed amounts of silver (99.99 pct pure) and cadmium (99.95 pct pure) in graphite crucibles under a flux of molten potassium chloride.10 The solidified ingots were sealed in evacuated Vycor tubes and annealed at 775°K for 10 days. The ingots were swaged and drawn into wires. The wires, sealed in evacuated Pyrex tubes, were held at 725°K for 5 hr and cooled to 365°K at an average rate of 2.5ºK per hr, followed by furnace cooling to room temperature. Chemical analysis of samples taken from different parts of each ingot gave no indication of segregation. Metallographic examination showed the samples to be homogeneous. Samples of the solid solutions or of the component elements were added to tin-rich baths in a calorimeter." At the start of a run the bath consisted of pure tin. Silver was used in the form of wire of 0.01-in. diam as supplied and cadmium in the form of lumps. Gold (99.999 pct pure) was added with the samples in order to reduce the endothermic heat effect of additions of Ag-Cd solid solutions. Samples of only one composition were added in a run and the ratio of the weight of alloy to that of gold was the same in all additions of a given run. In each run several calibrating additions of tin were made from 273°K. The heat contents of tin were calculated from the following equation, which is based on published data:12 (HTºK- H279º) = 6.70 T - 72,300/T + 20 cal/gram-atom; 505°K < T < 650°K The heat effect of each addition was plotted against the average of the sum of the atom fractions of solutes in the solution before and after that addition. The total concentration of solutes at the end of a run was less than 2 at. pct. In this range the heat effect was a linear function of the atom fraction of the solutes. The heat effect at infinite dilution and the composition dependence of the heat effect were obtained from the plots. RESULTS AND DISCUSSION Evaluation of Data. The linear dependence on composition of the heat effects of additions suggests that in the dilute range the enthalpy interaction coefficients other than the first-order coefficients of silver, cadmium, and gold are negligible, as shown in a concurrent publication.13 The heat effects at infinite dilution and the values of the composition dependence of the heat effects are listed in Table I.

Jan 1, 1970

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By A. J. Opinsky

THE purpose of this note is to indicate the locations and sizes of various interstitial holes in the orthorhombic uranium lattice based on a hard-sphere model. First, plane configurations of three and four atoms will be examined, and then the true interstices surrounded by four atoms in space and by five atoms in space will be obtained. The data and notation contained in a report by Tucker&apos; will be used. Plane Configurations Fig. 1 presents the orthorhombic uranium lattice made of spheres touching at the closest interatomic distance. The three light-colored spheres in the ab plane are illustrative of the first type of configuration to be examined. If one edge of the unit cell is taken as the origin, the three atoms can be represented by the vectors [Oi + Oj + Ok], [ai + Oj + Ok] and [(a/2)i + (b/2)j + Ok] where i, j, and k are respectively parallel to a, b, and c. In the future, this notation will be shortened to [000], [a00] and [a/2 b/2 0], respectively. A vector R = [r s t] de-scribes the position of the hole surrounded by the atoms. Since the center of the hole must be equidistant from the three atoms R2 = r2 + s2 + t2 = (r-a)2 + s2 + t2 = (r-a/2)2 + (s-b/2)2 + t2. R = [a/2 (b/4) - (a2/4b) 0] is the solution of these

Jan 1, 1955

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.&apos; It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,&apos; CrIr,,&apos; and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.&apos; In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By J. L. Martin, W. M. Campbell

A new electric logging method, called displacement logging, often gives a direct indication of the presence of mobile hydrocarbons in hydrocarbon-bearing formations. This method is based on the detection of a bank of connate water which is formed between the invading mud filtrate and virgin formation fluids in these cases. The existence of this phenomenon has beer, verified by laboratory studies and by actual field logs taken in known oil sands. INTRODUCTION During the past decade increasing use has been made of conventional electric logs to determine the amount of oil or gas in formations traversed by a borehole. This determination requires knowledge of several factors, such as true resistivity of the formation, formation factor, and water resistivity. Sometimes all of the factors necessary to make a reliable saturation calculation are not available. Also, the computations and corrections which are necessary in such a study often require the services of an experienced log analyst. It has long been the desire of exploration people to have a logging device which will locate hydrocarbon-bearing formations directly without requiring complex interpretation methods. The displacement log, while not completely fulfilling this desire, appears to be a Step in that direction. Basis for the Device The basis for this device stems from a phenomenon which occurs when mud filtrate invades a formation which contains displaceable hydrocarbons. As the mud filtrate invades the formation, most of the oil or gas is pushed out of the invaded zone, leaving residual oil. However, in addition to displacing most of the oil or gas, the connate water is also swept out, since the originally irreducible water is mobile in the presence of a water phase.1,2,3 Tonsequently, this irreducible water piles up as a bank between the virgin oil zone and the invading filtrate. If the mud filtrate is of higher resistivity than the formation water— as is commonly the case—the resulting annular zone, containing the bank of formation water, will be of lower resistivity than either the virgin oil-bearing formation resistivity or the invaded zone resistivity. This resistivity configuration, going from high to low to high again as the distance from the borehole increases, is found only in those zones which contain displaceable hydrocarbons. A device which would reliably detect this low resistivity zone would give a direct indication of mobile hydrocarbons. Illustrations This phenomenon is illustrated in Fig. 1 and 2. Fig. 1 shows a sketch of a zone containing salty connate water plus displaceable hydrocarbons, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 2 shows this zone, together with fluid content and resistivity graphs. after invasion by a fresh water mud. The resistivity pattern on moving away from the borehole is high: low: high. The absence of the low zone phenomenon in water zones is illustrated in Fig. 3 and 4. Fig. 3 shows a sketch of a zone containing salty formation water and residual oil, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 4 shows this water zone, together with fluid content and resistivity graphs, after invasion bv a fresh water mud. In this case the resistivity pattern on moving away from the borehole is high: low since there is no change in water saturation at the head ol

Jan 1, 1956

By J. L. Thompson

There are two basic forms of the LPG-slug process: the gas driven and the water driven. The pressure required for miscibility between gas and LPG prohibits the use of the gas-driven LPG process in shallow reservoirs. The water-driven LPG slug process normally exhibits good sweep efficiency. However, displacement of the LPG by water is poor. An improvement in this process appears possible by injecting a slug of carbon dioxide between the LPG slug and the water drive. Laboratory experiments were conducted in homogeneous linear systems to determine the effect of pressure on the various displacement zones. In the carbon dioxide-LPG displacement zone, the effect of pressure on the displacement efficiency is negligible above the miscibility pressure. However, the displacement efficiency decreases linearly with decreasing pressure below the miscibility pressure. With water displacing carbon dioxide, it was found that the recovery of carbon dioxide after water breakthrough can be predicted from its solubility in water. A displacement test was conducted with LPG and carbon dioxide slugs large enough to avoid interference between the oil-LPG, LPG - carbon dioxide and carbon dioxide - water displacement zones. Under these conditions, essentially complete oil and LPG recovery was obtained. However, a substantial amount of carbon dioxide was left in the core at water breakthrough. INTRODUCTION It has been shown in homogeneous linear systems that essentially complete oil recovery can be obtained by displacement with a miscible fluid such as LPG. Economic considerations dictate that the valuable LPG also be recovered. Methods proposed for recovering the LPG include (1) displacement with natural gas at a pressure high enough to make the two fluids miscible1 (the disadvantage of this method is that the required pressure of about 1,500 psi is too high for shallow reservoirs) and (2) displacement of the LPG with water2 (principal disadvantage is that a large amount of LPG remains in the formation because of poor displacement efficiency). This paper treats an improvement in the water-driven LPG slug process3,4 where carbon dioxide is injected between the LPG and water. Carbon dioxide is completely or at least partially miscible with propane and soluble in water; thus, displacement efficiency is improved at both ends of the carbon dioxide slug. To minimize effects of other variables, all experiments were conducted in linear core systems. GENERAL PROCESS DESCRIPTION The displacements of propane by carbon dioxide and carbon dioxide by water are considered separately, assuming enough of each is injected to prevent mutual interference. Displacement descriptions are confined only to the part of the pore volume containing mobile fluids unless otherwise specified. The schematic representation is given in Fig. 1. Starting at the producing well, a zone containing only oil is followed by a zone containing a single-phase mixture of propane and oil. The concentration of propane increases in the direction of the injection well and ultimately grades to pure propane. Then follows a zone containing a mixture of propane and carbon dioxide in continuously varying proportions until 100 percent carbon dioxide is reached. In this zone, the concentration of carbon dioxide in the immobile water phase also varies from zero to full saturation. Whether the displacement of propane by carbon dioxide is of complete or partial miscibility depends on pressure and temperature (Fig. 2). If the horizontal line representing the prevailing pressure intercepts the boundary curves of the phase envelopes for the prevailing temperature (i.e., if the pressure is lower than the critical

By J. J. Cosgrove, J. E. Warren

A general model which approximates the effect of cross- flow has been developed to give a practical method for predicting the waterflood behavior of a stratified reservoir. The model is based on a modification of Dietz&apos;s theory and allows for variations in both the permeability and hydrocarbon pore volume. In the particular cases considered, it is assumed that the permeability can be characterized by a log-normal distribution and the hydrocarbon pore volume by a normal distribution. A simple graphical method which enables the practicing engineer to predict the behavior of a stratified system is presented The results obtained by the proposed method are compared with those obtained by the Dykstra-Parsons method. As a result of this study the following conclusions have been drawn: (1) The effect of cross-flow in a stratified system can be appreciable, particularly at very favorable or very unfavorable mobility ratios; (2) Under normal conditions, the effect of variations in the hydrocarbon pore volume can be neglected; and (3) The failure to use all of the available permeability data can lead to large errors in the prediction of the behavior of a stratified reservoir. INTRODUCTION Various methodshavebeenproposedto characterize and to predict the waterflood behavior of a stratified reservoir. Most of the methods assume that the reservoir is composed of discrete homogeneous continuous layers. With this model, the degree of stratification can be measured by several parameters based on core-analysis data. Among these are the Lorenz coefficient1 and the variation of a log-normal permeability distribution? The behavior of stratified systems is usually predicted by the Stiles, Dykstra-Parsons method or some modification of these. In both of these methods the reservoir is divided into discrete homogeneous layers with no cross-flow between layers. In the Stiles method the mobility ratio is assumed to be equal to unity while in the Dykstra-Parsons method it is allowed to take on any value. Other predictive methods have been proposed; method allows for cross-flow between the beds and a method by Schmalz and Rahme6 correlate.s the recovery directly with the Lorenz coefficient. In this new approach, which is essentially a continuous analog of Hiatt&apos;s method, the effects of both mobility ratio and cross-flow between the beds have been included. It is assumed that the permeability can be represented by a log-normal distribution and the hydrocarbon pore volume or porosity by a normal distribution. These types of distributions have been observed by several authors, 1,2,4 and most field data seem to confirm their observations; e.g., if these distributions are assumed and there is a 1:l correspondence between porosity and permeability samples, the commonly encountered linear relationship between porosity and the log of permeability is obtained. Since, in many field cases the permeability and poro sity data are truncated or cut-off at predetermined upper and/or lower values, the effect of discarding part of the data was investigated with the proposed method. A better technique for truncating the data is suggested. THEORY In the derivation of the method to be described in this paper the following assumptions are made: 1. Capillary forces are negligible per se; their effects are only manifest in the relative permeability curves. 2. The fluids are immiscible, incompressible and homogeneous. 3. The reservoir is horizontal and uniformly thick; it is initially liquid saturated i.e., connate water and oil. 4. The reservoir is composed of discrete layers, each having its own permeability, porosity and connate water saturation; each layer is homogeneous,

Jan 1, 1965

By B. E. Cornish

Most technical and statistical data published on pyrophyllite relating to production figures, uses, markets and sales, have in the past traditionally linked the mineral with talc and soapstone. This is due to several common superficial physical properties resulting in substitute uses and applications. However, these minerals are not similar in chemical composition and do not generally occur in a similar geological environment. Pyrophyllite now stands on its own in the marketplace-particularly in ceramic applications-due to the combination of excellent heat shock and creep resistance properties of the mineral. The increase in pyrophyllite use in the field of ceramics indicates the continuing realization of these marked unique properties. Several new fields of ceramic applications, previously the preserve of high-alumina materials, have been developed on the intrinsic properties of pyrophyllite. Pyrophyllite is an aluminum silicate with the molecular formula of AI2O34SiO2H2O. It would be more appropriate to group pyrophyllite with such materials as kyanite, diaspore, andalusite, and certain high-alumina clays in relation to its general applications (Stuckey, 1928). These materials all have good beat shock resistance properties at high temperatures and are widely used for the manufacture of refractories. For those reasons they are interchangeable in some applications. Pyrophyllite also has many uses in nonceramic applications, the most important to date being as a substitute for talc in fillers. The major pyrophyllite mining operations are located in the US, Japan, Korea, Canada, and Australia, where the mineral is widely used as a raw material for general ceramic, mineral filler, and dilutant applications. Commercial Applications Pyrophyllite was first used in the last century for lining stoves and fireplaces, and also in the carving and polishing of ornamental objects. The rise in industrial demand for new products and applications resulted in the introduction of pyrophyllite as an alternative, mainly for talc and soapstone. Industrial filler applications followed for paint, paper, cosmetics, rubber, pesticides, crayons and pencils, and bleaching soap. The first use of pyrophyllite in ceramic applications was prior to World War II, in the manufacture of ceramic cladding tiles in the US. This was followed by the production of kiln furniture refractories and whiteware when pyrophyllite was offered by suppliers in North Carolina as an alternative to some local clays. The largest tonnages of pyrophyllite used today are in refractory linings in steel ladles in Japan, as seen in Table 1. The consumption of pyrophyllite in Japan is second only to clay and chamotte among refractory raw materials used. Recently this technology has been adopted in Australia. Japanese and Australian practice has resulted in appreciable technical and economic benefits, particularly when pyrophyllite is used in combination with zircon. The potential growth for this application is substantial if US and European steelmakers follow. Investigation and research into the properties of pyrophyllite determined the following main advantages of pyrophyllite-based ceramics: high corrosion resistance for molten iron, steel, and slags; good heat shock resistance; good indices of deformation under load and hot creep resistance (refractories); and increase in mechanical strength of whiteware products promoted by a better distribution of mullite in finished products (also obtained at lower firing temperatures than normally required in production of triaxial ceramics). White cement

Jan 1, 1983

By T. Gleason

Problems involved in applying wet scrubbers to gas cleaning coal dust from thermal dryers are reviewed. Careful consideration of all the elements going into a modem coal preparation plant is required in view of the increasing difficulty of applying suitable gas cleaning equipment. This problem arises not only from the presence of finer coals to be handled, but also from the pressures applied by both the general population and the plant operators to improve the standard of gas cleaning performance. The Peabody scrubber is presented by the author as a machine designed to help improve this cleaning operation. Wet scrubbing of fine coal from thermal dryers poses a number of problems in adapting the gas cleaning equipment to the fine particulate matter. Among them are: 1) Dust in gases leaving the thermal dryer cyclones is often extremely fine with high percentages of total dust loading less than 1p in size. 2) Flue gas entering the scrubber is corrosive since the coal fired in the thermal dryer furnace is in the range of 0.7% by weight sulfur or higher. Therefore, comparatively high cost stainless steel alloys or corrosion resistant linings are required for a satisfactory service life. 3) Requirements for residual coal loadings leaving the gas scrubber are continually being lowered, while modern coal preparation operation is imposing heavier burdens on the collection system through introduction into the thermal dryer system of very fine coal previously not recovered. The advent of flotation systems in increasing numbers is typical of this trend. 4) Installation of a scrubbing system on thermal dryers is made primarily to reduce air pollution and product recovery value is of little or no value. Therefore, the operating costs of gas pressure drop and water requirements must be held to a minimum. We have, then, the basic situation which calls for comparatively high cost stainless steel alloy wet scrubbers, which must be highly effective in removing coal fines particularly in the 0 to 5-p size range. Further, the standards of scrubber performance are continually being raised towards the level where gas discharged from the scrubbers must be essentially free of any coloration due to residual dust. In view of the highly refractive nature of fine coal dust, residual loadings of 0.01 grains per cu ft or less are required to provide a color free discharge gas. In the present specifications under consideration a residual coal loading of 0.05 grains per cu ft would be considered color free, since the discharge gases are saturated in the range of 150°F. The steam plume acts as a masking agent at the point of discharge, and upon dissipation of the 150° saturated vapor stream, the effluent gas stream could be essentially color free. The specification under consideration calls for residual solids loading of 0.05 or less grains per cu ft, given a coal size distribution shown in the basic data in Table I. It is noted that the dust laden coal stream has a size distribution by weight of 33% in the 2 to 5-p size range and 55% in the 0 to 2-p size range. The particle size distribution given in the specifications does not detail the percent by weight less than 1-p in size, and more important, the size distri-

Jan 1, 1963

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth&apos;s atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world&apos;s leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.&apos; Previous investigators&apos;&apos; have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana&apos; showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By J. J. Arps

n approach to the study of the electrical properlies of drilling muds, their cakes and their filtrates was made by treating the drilling fluid as a porous medium. Lluring this study it was found that the weight pararneter was omitted from previous investigations on electrical properties. Patnode in 1949 made a similar approach to ,his investigation. His work showed that there was a variation of resistivity relationships with per cent Puid present in a given suspension. This present study ex-tends Patnode&apos;s investigation to one in terms of the solids fraction of the drilling fluids. Previous investigations were made on low weight muds where the effect of the rolids fraction was obscured. The following equationr were fitted to data taken from 94 field muds and 47 laboratory muds (see Tables I and 2). The parameter, C, is a complex function of the solidr content, or mud weight, of a drilling fluid. It was also found that for all drilling muds examined. A nomograph is presented combining Eqs. I and 2. INTRODUCTION It is generally recognized that the materials present in drilling muds affect the relationship between mud filtrate and mud resistivities. However, most electric log interpretations proceed with the assumption that the mud resistivity and temperature are the only important parameters needed to obtain a filtrate resistivity or a mud cake resistivity. Lamont1 suggests that only average relationships exist between mud cake, mud filtrate and mud resistivities. He indicates that there is limited accuracy when these intercorrelated factors are used since no other measure-able variable is apparent. A previous paper by Patnode indicates that drilling fluids may be considered to be a system of fluids in solid particles which may be correlated electrically in a manner similar to rock solids. 1 he equation for the resistivity factor. F = (per cent fluid) is satisfied for a given clay type in water, but the value of m varies as different materials are used in the water. The resistivity factor is not constant for a given amount of clay. As is suspected it varies as the solids fraction conducts electrical current. Since both weighting material and clay solids are present in commonly used drilling fluids, it is expected that both materials contribute to the variation of the m factor in Eq. 3. An extension of Patnode&apos;s work is presented in this paper to show some of the interrelations which exist between the resistivities of mud cake, mud filtrate and mud. Use of these data enable a more accurate calculation of mud filtrate and mud cake resistivities if only the mud resistivity and weight are measured. EXPERIMENTAL The measurements of mud weight, fluid and solids resistivity, alkalinity, and chloride content of mud samples were made in this research. Mud samples representing drilling fluids from 94 Louisiana and Texas wells (Table 1) and 47 laboratory-constructed systems (Table 2) were used in the experimentation. The measurements of the mud properties were made both in the field and in the laboratory. The tests on the properties of weight, alkalinity and chloride ion were standard tests as described by API specifications. The resistivity measuring devices were constructed in the laboratory for this study. For details on the resistivity equipment see Fig. 1. The fluid cell

By R. W. Olson, A. L. Benham

Viscous fingering was studied as it occurred in an open Hele-Shaw model (1 ft x 4 ft x 1/16 in.); it was also studied in the same model packed with 80-mesh glass beads during miscible displacements under unfavorable viscosity ratio conditions. It was determined that the lengths of 20 elements of the front were distributed normally around the average position of the combined elements under all conditions. Represented by the normal distribution, the length of the viscous fingers grew linearly with the distance traveled from the point of finger formation, increased with displacement velocity, and increased with increasing mobility ratio. Results obtained during the first few inches of displacement were of little or no use in predicting finger growth and/or finger length throughout the 4-ft model since the point of finger initiation cannot be predicted and would often occur several inches from the point of injection with either positive or apparent negative coordinates. The fingering occurring during a miscible slug displacement was much greater than would be predicted based upon the actual mobility ratios between in-place fluid and slug and between slug and following fluid, using the results described above for miscible displacement in the absence of a slug. Many of the experiments in the packed model showed that the rate of growth of the viscous fingers was diminishing toward the end of the displacement in the 4-ft long model, indicating that microscopic mixing, such as diffusion or dispersion, was decreasing the viscous fingering effect. INTRODUCTION Viscous fingering is a manifestation of a finger-shaped interface between displaced and displacing fluids occurring during typical miscible displacement projects for oil recovery. Its cause may be traced to the instability of a viscous fluid being displaced by a more mobile fluid. Viscous fingering takes on important significance in the miscible slug process 1.2 where it may be a dominant factor in determining minimum slug size. Experimental1-3 and theoretical4-7 studies of viscous fingering have been made by other investi- gators. However, an exhaustive study of the variables affecting viscous fingering had not been made. The present study was undertaken in an effort to determine the effects of some of the more obvious variables—such as mobility ratio, displacement velocity, distance displaced, and packing—upon viscous finger length and growth in a small laboratory model. It does not necessarily follow that conclusions reached by studying the results of this model study may be applied to the field. Future studies would have to evaluate the effect of model size on extension of these results. EQUIPMENT AND EXPERIMENTAL PROCEDURES A flow diagram for the equipment used in this study is shown in Fig. 1. Basically, it consisted of (1) a constant-rate pump for the injection of displacing fluid into (2) a model made up of two flat transparent plates spaced a small distance apart and (3) provisions for the production of fluid into a calibrated graduate. The displacing fluid contained a dye which allowed visual observation of finger spacing and length. The pump performed at rates from 2.5 cc/hr to 480 cc/hr, while pumping a light mineral oil into a bladder in a closed glass container holding the displacing fluid. The model was made up of two plates of 1-in. Plexiglass with dimensions 1-ft wide by 4-ft long. These were spaced 1/16 in. apart so that the internal model dimensions were 1-ft wide x 4-ft long x 1/16

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.&apos; The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast&apos; reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By R. V. Colligan

[CONTENTS PACE Educating and Training Economic Geologists of the Future. By C. H. BEHRE, JR. (TP 2278, Min. Tech., Nov. 1948. Discussions by R. V. COLLIGAN and EVAN JUST) ....... I Mercury Industry in Italy. By EDWIN B. ECKEL. (TP 2292, Min. Tech., Jan. 1948. Discussion .............................. by C. N. SCHUETTE) 3 Chert in the Kingsport Formation at Mascot, Tennessee. By ARTHUR T. ALLEN. (TP 2299, ............... Min. Tech., Jan. 1948. Discussion by M. M. BUTLER) 5 Wall Rock Alteration at Butte, Montana. By RENO H. SALES and CHARLES MEYER. (TP 2400, Min. Tech., May 1948. Djscussions by C. D. HULIN, W. D. JOHNSTON, JR., and L. C. ................................... GRATON) 5] Educating and Training Economic Geologists of the Future R. V. COLLIGAN*-I can best illustrate my opinions by drafting another five year plan (Table 2). This plan is set up following the same stipulations outlined by Dr. Behre, namely: (I) the student is preparing himself for commercial work as a mining geologist; (2) he is attending an institution with a sufficiently broad curriculum (that is, engineering school and mining school as well as liberal arts college) to furnish the courses listed; and (3) he is not planning to continue his studies through to a doctor&apos;s degree before going into commercial work. A comparison of my study plan (Table 2) and that submitted by Dr. Behre (Table I) will at once point up the basic similarity, due to the obvious fact that there are so many essential courses which must be included in any outline of study. However, a more detailed analysis will show up certain differences, which, in fact, are only certain refinements on Dr. Behre&apos;s program. These I plan to discuss in order of their importance. The first and most important change is the addition of 12 hr of optional subjects, making a total of 24 hr of optional subjects as against a total of 12 hr under Dr. Behre&apos;s schedule. This of course entails the elimination of certain courses, which I shall discuss later. However, I wish to make it clear that I suggest eliminating these courses not because I feel that they are unnecessary, but rather because I feel the optional courses are more necessary to the complete education of the individual. I appreciate that Dr. Behre recognizes the importance of the cultural side of education, but I take issue with his thesis that the student will get it without credit and in his spare time. I do not think that the average college student, and certainly not the college freshman, is mature enough to know what he needs and where to get it in his spare time. I think it must be "spoon-fed"; he must be oriented through specific courses. University life (or should I say "college life") is too full of athletics, fraternity activities, dances, "bull sessions," and countless other enjoyable distractions, all of which contribute to the "full man." I fail to see how the average young American male can possibly sandwich in a necessary complement of "cultural activities" in his spare time. Since these latter activities do not fall within the pattern set by the "group," and show less promise of immediate return in enjoyment, or increased social status on the campus, they are bound to suffer in competition with the more popular, "group" activities. No doubt much of the criticism levelled against arts colleges, namely, that the cultural courses are useless, is well taken, for the culture

Jan 1, 1947

By J. B. Scott, J. L. Popham, H. F. Coffer, J. J. Reynolds

This paper concerns field experiments to define the areal extent, orientation and thickness of an artificial fracture in the Sacatosa field, Maverick County, Tex. The fracture was made by a sand-oil treatment of 176,-000 gal of lease crude containing a fluid-loss additive and 270,000 lb of 20-40 mesh subangular Poteet sand. The well was perforated with a jet gun, consisting of six shots in a single plane. Fourteen test holes were drilled at various locations around the fractured well. Drill-stem tests, Micro and Sonic Logs, coring and sampling of formation cuttings were used to determine the presence of the fracture in these holes. The test holes were drilled at distances up to 250 ft in a radial pattern around the fractured well. In addition to fracture areal extent and orientation, sand grain size before and after fracturing, erosion of perforations and fracture thickness were studied. INTRODUCTION The orientation,12 areal extent3, 4 and thickness5-9 of artificially induced fractures in reservoir rock by hydraulic means have been discussed in great detail in the oil industry in recent years. Methods for initiating vertical"&apos; and horizontal" fractures have been tested in the laboratory and the field. Although the methods used give successful well stimulation, good field data on the physical characteristics of the fracture are lacking in the literature. It is recognized generally that properties of a fracture, such as thickness, sand placement in the fracture" and shape, may vary from reservoir to reservoir. This paper gives data on size, orientation and sand placement in a large fracture initiated in a single plane in Sacatosa field, Maverick County, Tex. It is not intended as a speculative study; rather, it is restricted to actual field data on fracture properties. No attempt is made to prove that the same type of fracture occurs in all wells. The field procedure was to drill 14 test holes at various locations around the fractured well. By employing several different testing techniques, the presence of the fracture and some of its characteristics were determined. These techniques as well as the results obtained are discussed in detail in this paper. DESCRIPTION OF FRACTURE TREATMENT N. J. Chittim Well No. 37-1, completed in the San Miguel No. 1 sand, Sacatosa field, Maverick County, Tex., was chosen for the field study. The San Miguel sand is a tight, well consolidated sandstone with an average porosity of 23 per cent. The permeability ranges from 0.1 to 10 md, with a median permeability of 2.3 md. The sand thickness averages 23 ft and is located at depths of 1,150 to 1,700 ft throughout the field.I3 The fracture treatment performed on Well 37-1 was as follows. 1. The well was drilled to a depth of 1,438 ft with native mud, and 51/2-in. casing was set and cemented to the surface. 2. The casing was perforated at 1,349 ft with a fracture-initiating jet gun. This gun consists of six shots, 7/16-in. diameter in a single horizontal plane. The jets were oriented in two groups of three, 180" opposed. The perforating device was designed to initiate a fracture perpendicular to the wellbore.

By J. F. Evers, S. Sadiq, F. W. Preston, G. W. Swift

Proper scaling of unsteady-state flow in laboratory gas reservoir models can be achieved if the permeability/fractional porosity ratio is less than 0.5 md. Porous media meeting this specification can be obtained from mixtures of sand and Portland cement provided (1) the water/cement ratio is in the range of 0.35 to 0.40, (2) the sand/cement ratio is in the range of 1/1 to 2/1, (3) the sand grain size is in the range of 48-100 to 18-28 mesh, (4) the mortar curing time is 7 days or more and (5) the cured mortar is dried under vacuum to reduce the temperature level employed during the drying process. The areal homogeneity of the mortars tested is reasonably good, although significant trends in vertical permeability were noted. The Klinkenberg and non-Darcy coefficients of mortar are such that proper scaling of these effects in the laboratory model could be expected. INTRODUCTION A long term deliverability prediction for a gas well is generally based on data determined from flow tests that are of short duration relative to the producing life of the well. These data, together with an estimate of gas reserves in place, form the basis for establishing the parameters of the mathematical model used to predict performance at future times. Results obtained from a mathematical model represent only an interpretation of the physical process being modeled. Experimental verification of the production process from discovery to abandonment is needed where production occurs under carefully controlled conditions. Ideally, one might consider such an experiment to be conducted in the field. Even if the cost of such an experiment could be justified, the time required would make it impractical to consider. However, if the time scaling problem could be handled properly, an experimental model of the gas reservoir production process could provide the necessary data to study the mechanisms of the production process in a reasonable time period. An experimental model has been designed and constructed using the data of this study as a basis. The model reservoir system consists of one producing well located at the center of a right-circular cylinder of porous material. Ten to 15 observation wells are located at strategic offset positions from the producing well. These wells, and the producing well, are fitted with pressure transducers so that the pressure-time history can be recorded at various radial and azimuthal positions in the drainage area during the entire production life of the system. Time is scaled in the model so that the time required to produce gas from discovery pressure to abandonment pressure is about 2 hours. This compares with a 20-year producing life in the model&apos;s field counterpart and gives a time scale factor of approximately 1:100,000. DESIGN CRITERIA To establish design criteria for the experimental model, the reservoir is considered to be a finite right-circular cylinder of radius rr, and height h with a producing well of radius rw located at the center and completed through the producing formation. This reservoir consists of a porous medium which has a uniform permeability k and gas porosity and the gas contained in the reservoir has density p, viscosity µ and molecular weight M. Initially, the pressure at all points within the reservoir is uniform at po. and the reservoir temperature is T. Since the reservoir production process has been demonstrated to occur in two distinct transient modes for either Darcy or non-Darcy flow,l it is

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori&apos; molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,&apos; using the data of Parravano and Malquori.&apos; Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By Bengt Helmerson

A new tankhouse was started in January 1959 at the Copper Refinery of the Boliden Co., Skelleftehamn, Sweden. In early 1961 a semiautomatic machine for looping and straightening of starting sheets was introduced to substitute previous manual operations. The machine as well as consequent, racking and handling is described. Finally, economic benefits achieved and new constructions for the future are discussed. HISTORY Tankhouse operations at the Boliden Co. &apos;s Smelter in Skelleftehamn started in 1932 on a scale that since then has been gradually increasing. In order to rationalize the operations, a new tankhouse was erected. It went into production in January 1959 and was designed for a yearly production of 35,000 metric tons at a current density of 16 amps per sq ft. Already from the beginning, however, the tankhouse has been run with a current density of 21.5 amps per sq ft, corresponding to a maximum capacity of 50,000 tons a year. During the time of planning of the new tankhouse, due consideration was given to the possibilities of mechanizing the operations. New ideas could be and were actually tested on full or pilot plant scale in the old tankhouse. In that way we developed a system for the cathode handling including washing, weighing, and transportation. A system using forklift trucks in combination with trailers and overhead cranes has been developed for transportation and racking of anodes and also for handling of anode scrap. With respect to the electrolyte, circulation and temperature control are partly automatic. Special attention was paid to the production of starting sheets, which operation normally requires a great number of man hours, and it was made the object of a particular survey as to the best ways of straightening starting sheets, attaching loops to the sheets, and so forth. As a result, a machine was designed during 1957-58 and built in our own shops. After a period of tests, the new equipment was put in operation commercially on the 10th of April, 1961. Since this date the machine has produced about 2 million starting sheets without interruption and has been the only source of looped starting sheets for the tankhouse. GENERAL DESCRIPTION Fig. 1 shows all the major parts of the system. These parts are: slitting machine with feeding table (I), standard roller leveler, type Ungerer (2), tilting roller table (3), conveyors for sheets and suspension bars (4, 7), storage of suspension bars (51, punching and stitching machine (6), two lift-turn-tilt tables (8) for discharging the starting sheets, two rack conveyors (9) for sheet assemblies. Included are a hy-daulic pump station and panels for pneumatic and electric controls. SLITTING AND STRAIGHTENING The machine is fed by hand by a man sitting in front of the slitting-machine table, Fig. 2. This operator inserts one sheet at a time into the slitter. After being trimmed, the sheet is automatically conveyed to the following step of handling, straightening. The slitting machine cuts away about 8 mm of the upper and lower parts of the sheet (in relation to its original position in the stripper section) for two reasons. The first one is to give the machine sheets of uniform dimensions; the second one is a matter of quality. Normally the starting sheets as stripped have a thick edge at the bottom end. This part would collect anode slimes and might also cause short circuits when inserted in the cells without trimming. The straightener used is of German construction

Jan 1, 1967