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By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By F. M. Simonds, E. Z. Burns

The Rawley property is located in the Kerber Creek mining-district, Saguache county, Colorado, at an elevation of 10,600 ft. (See sketch-map, Fig. 1.) Ore was found in this vicinity as early as 1880, and claims covering a large area were located and in many instances patented. The ores, however, being of comparatively low grade, and the nearest railway station, Villa Grove, being some 20 miles away, it is extremely doubtful whether any considerable amount of ore was ever handled at a profit. It is safe to say that several hundred thousand dollars were spent (a large part in building mills) previous to 1902-03. About that time a very capable promoter gathered together a group of these claims and interested some New York people, who had had no previous mining experience, in the purchase of these claims. Following the organization of a company, this promoter became General Manager. As often happens under such conditions, the first step was to erect a mill to treat 100 tons per day. It may not be fair to this enterprise to say that the failure which followed might have been foretold, simply on general principles, but this much is certain—the water supply fluctuates in the course of a season through a wide range and for a considerable portion of the year was inadequate to run this mill at capacity. Further, it is currently reported that some of the mill foundations were placed on ice. However true this statement may be, it is a fact that, when first inspected by us, many of the belts in the mill were held on'their pulleys by means of idlers. A shut-down followed, with a material re-adjustment of interests, at which time we became consulting engineers for the company.

Jan 1, 1914

By Lynn I. Kelley

Potash is the primary industrial mineral produced in Saskatchewan, followed, in terms of gross value, by aggregate, sodium sulphate, salt, potassium sulphate, peat, clays, silica sand, calcium chloride brine and "clinker." Potentially economic deposits of kaolin, diamond and building stone are under evaluation.

Jan 1, 2001

By W. J. Wenger

Results of the analyses of 151 crude oils from 123 oilfields in the Williston basin are presented. Production statistics are compiled by geographical areas within the basin, by geological age of the producing zones, by States, and by field for the nine fields with the greatest production. Characteristics of the oils are tabulated, and correlations are included to show relationships between properties of the oils and some factors in the environment. Properties of the oils in some instances imply that there has been migration and mixing of the oils between productive formations of different geological time periods.

Jan 1, 1968

By S. R. Dunbas, D. C. Jillson, E. A. Anderson

THE present work was undertaken to furnish information, lacking in the literature, on the deformation mechanisms active in pure titanium at room temperature. Since it was started, Rosi, Dube, and Alexander' have indicated that slip can occur in coarse-grained (2 to 6 mm diameter) titanium on the {1010} and {1011} planes and twinning can take place on the {1072}, (1122) and (1151) planes. Liu and Steinberg,' working with titanium flakes produced by fused salt electrolysis, found evidence of twinning on the {1032$, {1121), {1122}, (1123}, and (1154) planes. The crystals used in the present work were substantially longer (up to nearly 2 in. in length) and possibly purer. Production of Large Crystals It was the purpose of this part of the work to provide single crystal or large grain specimens for use in the deformation studies rather than to study the mechanism of crystal growth. Accordingly, all further exploratory studies on methods were abandoned when it was found that cold-rolled bars sealed in vacuo in individual Vycor tubes and given three or more cycles of 4 hr at 1200°C and three to five days at 850°C, gave large grains. Eighteen specimens about 0.2 in. square x 2 in. long yielded 33 useful grains, ranging from Va in. to nearly 2 in. in length, with an agreeably wide range of orientations, Fig. l. The 0.25 in. thick strip from which the starting specimens were cut had been reduced 67 pct on 18 in. diameter rolls from a scalped, hot-forged (959" to 1000°C), arc-melted, iodide titanium ingot. Thc bar was at room temperature, but the rolls were at 200°C. Reductions of about 0.03 in. per pass were used. The bar was cut into four segments, each of which was rolled in a somewhat different manner. No effect on the growth of large grains was noted. The composition of the titanium, determined on turnings from the ingot scalping operations, is given in Table I. The Rockwell A hardness of the ingot was 26. The standard starting specimens, about 1/4x1/4x2 in., were milled on all four sides, hand polished on 280 and 400 mesh emery papers, etched for 3 min in a 50 HF-50 glycerine solution, rinsed, and dried in alcohol and ether just before sealing them in Vycor tubes. The average specimen weight was 7.5 g, and the tube volume was 6.5 cc. A vacuum of less than 1 micron pressure was applied. The specimen tubes were placed in an evacuated Inconel muffle to minimize the danger of collapse of the glass tubes at temperature. In practice the specimens were first heated to 1200 °C for 4 hr and then transferred fairly quickly to an 850°C furnace where they were held for three to five days. This cycle was repeated at least three times before the specimens were cooled, removed from the tubes, lightly polished and etched on one surface for examinstion. Those in which large grains had not developed were resealed in Vycor and returned to the cycling. Satisfactory specimens (about one out of every four cycled) were polished with emery paper on all four side;, then metallographically polished using ctchinz between wheels to remove distorted metal and, finally, given a very light etch to reveal the grain boundaries. This was necessary because the surface was roughened by the sublimation of titanium under high temperature vacuum conditions. Specimens were identified by TiXl numbers using supplementary letters to designate specific grains.

Jan 1, 1954

By Paul Weaver

OF the four papers that comprise this TECHNICAL PUBLICATION, three are case histories of individual geophysical prospects, subsequently tested by drilling. The bibliography of Dr. Barton's published scientific papers† includes investigaions in physiography and surface geological mapping, as well as his geophysical papers, and from this list it is to be observed that he early recognized the place of different types of geophysical prospecting methods in the search for geological structures of economic importance. Moreover, his viewpoint was not merely that the structures should be found, but that the geophysical data should be examined quantitatively to determine the geometry of the structures. In other words, that although these data are insufficient to deduce a unique form for the structure that caused the effects measured in the data, the engineering computations should be carried-out to give as much of a definite configuration to he structure as the data permitted, in order that the testing of the structures could be conducted in the most economical manner and with the idea that the experience so gained could be later incorporated in the study of structures subsequently found. Dr. Barton continually emphasized the quantitative use of geophysical observations, whereas at the time that he began his specialization in geophysics it was considered sufficient to use observations only qualitatively. He, more than any one else, was responsible for -the first volume on geophysical prospecting issued by the Institute in 1929, and his three articles in that volume stressed the quantitative use of geophysical prospecting. The fourth article in this present TECHNICAL PUBLICATION is a further contribution to this branch of geophysical interpretation, and is a supplement to the paper in the 1929 volume, "Calculations in the Interpretation of Observations with .the Eötvös Torsion Balance." From the successful' demonstration by Dr. Barton of the usefulness of quan-

Jan 1, 1944

By J. Ander

About fifteen years age some mines in western Canada commenced using Diesel engines, partly for development work but also for operations on quite a large scale. In the Eastern mining field, the Diesel engine made its appearance some eight years ago and has since, at quite a number of mining plants, proved to be a reliable and economical prime mover. As a result, it is today used more extensively than could have been foreseen only a few years ago, and it is reasonably safe to predict that the next few years will see the Diesel engine utilized to a still greater extent in the Canadian mining industry. It is not much more than thirty years since the first Diesel engine was put in operation. During the early years of this century, the Diesel engine took, so to say, its first faltering steps in public service. Since then it has reached a high state of perfection, and its importance has grown in a most remarkable way, until today it is used in practically every field where power is required. It is slowly but surely superceding steam for a great many purposes, as, for instance, for ship propulsion. While in 1921 only about 8 per cent of all tonnage launched was motor-driven, the proportion had grown to 38 per cent in 1927, and for 1929 it was slightly over 45 per cent. Some of the finest passenger liners afloat are Diesel-driven. In the early days, Diesel engines were built only in comparatively small units. Today engines with a capacity per unit of up to 10,000 horsepower, or even more, are being built for marine and stationary purposes.

Jan 1, 1930

By T. Egleston

THE ores of mercury of North California are composed of metallic mercury and cinnabar. They are found in serpentine, and are very often associated with chalcedony, in masses more or less irregular, often concentrated enough, however, to furnish ores yielding from three to ten per cent., and sometimes richer. This deposit makes its appearance in Vallejo where it has been worked. North of here the mines are more developed. Most of the quicksilver mines, how¬ever, are situated in Sonoma and Napa Counties. On its outcrop the serpentine rocks have become decomposed, and have often been washed away to a considerable depth, so that in many cases in their neighborhood, what is apparently nothing but ordinary dirt, will frequently contain from two to three per cent. of metallic mercury, with but a trace of cinnabar, in which case, as at the Sonoma mine, it is made up into adobes and distilled. Such material does not require to be mixed with dirt to be made into adobes. Very often, also, the outcrop of the rock, where it is not decomposed, is filled with metallic mercury, so that by striking a pick into it, as at the Rattle-snake mine, a pound or more of mercury at a time will sometimes spurt out. Such rock as this is found in several localities in every stage of impregnation, and usually makes very rich ore. There is generally, however, very little of it, and it is found only in the first workings ; the ore in depth is always cinnabar. At the Rattlesnake mine near Pine Flat, where large quantities of metallic mercury are found, the rock contains so much petroleum that it has been necessary to make special arrangements to burn the carbides of hydrogen, since the distillation of the petroleum causes an extra quantity of poor soot to be formed in the condensation-chambers. At the Geysers the ore is associated with large quantities of sulphur and gypsum, so that in a hand specimen there is often more sulphur than cinnabar, which is a serious impediment to working, especially for the modern style of furnace with iron condensers, and causes so much soot to be formed that it has been known to penetrate as far as the blower, and to so completely clog it as to prevent its revolution. The ore coming from the mine is more or less hand-picked. In one or two cases attempts have been made to treat the poorest, and especially the very fine ores, mechanically as at the California works.

Jan 1, 1875

By F. S. Kendorski

Several startup or longtime underground stone mines have experienced unanticipated roof control difficulties due to the variable geologic character of the roof strata. Careful mapping of roof conditions, and identification of controlling geologic and mine geometric factors, lead to an understanding of the mechanisms causing roof problems. Factors such as unexpected rolls of the roof strata resulting in a gradual change from strong to weak roof; encountering open water-filled master joints; roof strata delamination due to internal water pressures; local karst features with mud, sand, and water hazards; and sudden loss of limestone roof due to paleo-channel erosion are some recent problems described. Strategies for overcoming these problems are discussed and detailed.

Jan 1, 2002

By H. B. Humphrey

In the 39 years from 1891 to 1929 , gas and dust explosions in the coal mines of Tennessee caused 413 deaths , or one- third of the fatalities in the mines for that period . Inasmuch as explosions caused but about 15 per cent of mine fatalities for the whole United States for this same period it is evident that the Tennessee coal mining record is by no means good , as far as explosion fatalities are concerned . Since 1926 , Tennessee has had a clear record as to fatalities from explosions ; this fact may be credited very largely to the improved conditions and safer practices in Tennessee's coal mines which have been brought about by the work of the State Inspection Department and of the Southern Appalachian Coal Operators Association directed toward adoption of safety precautions and practices most of which are advocated by the United States Bureau of Mines . Chief among these improvements are the replacement of black powder and dynamite by permissible explosives , improved ventilation , and the installation of rigid methods of inspection for gas . With the present tendency for operations to pass into the hands of responsible and informed management , and with unrelaxed care and inspection , the good record of the past several years should be maintained .

Apr 1, 1931

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By Baafi EY

Open cut mining in Australia is facing the greatest challenge in its history in attempting to compete not only with other operations internationally, but also with underground operations domestically. Most flat dip and shallow depth surface-mineable coal reserves have been depleted during the last two decades and new open cut operations must extract deeper coal deposits. As open cut coal mines move into deeper areas and the stripping ratios increase, the relative cost of overburden removal also increases. It therefore becomes even more important to design the mine around the optimum overburden removal scheme. The deeper mines are usually multi-seam operations with a more complex geology and with more geotechnical and hydrological problems. Deeper mines are subjected to greater problems requiring more detailed mine planning and design, such as selection of the optimum mining method and pit layout. In planning and design of such operations, the number of alternative methods which need to be considered is consequently greater.Dragline productivity and its stripping capabilities are directly affected by the selection of digging method, strip layout and pit geometry. Every mine has a unique combination of geological conditions. The operating methods that work well at one mine may not necessarily work at another site. Selection of an optimal stripping method, strip layout and pit geometry for a given dragline must be considered with respect to the geological conditions of the mine. With increasing geological complexity of Australian strip mines, it is becoming more important to use sophisticated techniques such as computerised mine planning methods to assist in optimising dragline operations.

Jan 1, 1998

By L C. Taylor, H U. Lesiste

This paper provides a preliminary description of the properties of the output pressure (shock) wave of an end initiated, cylindrical charge of low height to diameter ratio in saturated sand. The properties of primary interest are the pressure wave velocity, peak pressure and rate of rise of peak pressure to within 1.4 charge diameters from the output end of the charge. The behavior of these properties is seen to be quite different from their behavior at more customary ranges in water.

Jan 1, 2013

By R. Patrick

As a unique South African organisation, CSIR: Division of Mining Technology (Miningtek) strives to support the mining industry by improving health, safety and productivity through developing, adapting and transferring technology. Considerable effort is currently directed towards the development of potential non-explosive mining methods with the potential to allow continuous mining in narrow reef conditions. Besides improving productivity, continuous mining results in concentrated mining which has a significant impact on reducing infrastructural costs. Impact Ripping and Water Pulse Rock Breaking have been tried on gold mines, whereas Activation, Mini-Disc? cutting and the Plasma Holemaker are currently being tested on platinum mines. The organisation?s many years of experience in novel rockbreaking, together with its world-wide collaborator network, has placed it in a unique position to assist the mining industry and manufacturers in developing and/or adapting existing technologies for application underground. Currently a range of technologies are being investigated, which have reached different stages of maturity. The main technologies under investigation are; - Impact ripper system - Water pulse rock breaking - Activated undercutting rollers - Mini disc cutters - Electric rock breaking

Oct 1, 2001

By David Whittle

When does a project with questionable viability, warrant further investment? There are cases in which projects, which evaluate to a negative mean probable value, are worth investing in. There are also cases in which projects that evaluate to a positive mean probable value, should not be invested in. The author will present a model for ?project-control?which includes an adaptation of a well know grade-control concept. Comments on Resources and Reserves ?Resource and Reserve estimates are based on positive information (43-101). ?Reserve and Resource confidence qualitatively assessed. ?U.S. Geological Survey (USGS) recognizes Undiscovered Resources (U.S. Geological Survey 2003).

May 1, 2006

By Richard Stayner

Suspended seats perform two functions: Reduce effect of occasional large bumps; Reduce more continuous vibration at a lower level. The former needs high damping. The latter needs low damping. For most mobile work machines the inevitable compromise is generally better than a simple cushion seat, because that amplifies vibration at around 4 Hz which is a sensitive frequency for human vertical WBV. Why have standard tests for seat suspensions? • Seat suspensions are non-linear so any measure of performance depends on operating conditions. For comparison these need to be defined. • Seat manufacturers need benchmarks for product development; • Machine makers choose dynamic characteristics appropriate to their products; • Occupational health specialists wish to control operator exposure to Standard tests should be representative, repeatable and reproducible. These requirements are reviewed in relation to the history of seat test standards and the current position. Current position and history The current position is that we have standard tests for seats for agricultural tractors, earthmoving machinery, industrial (fork-lift) trucks. These tests comprise measurement of vibration transmission and of the rate of damping. Current standards developed as the technology developed, starting around 1960: 1. Test on machine driven over standard surface1. 2. Test on shaker reproducing standard surface. 3. Shaker input replaced by representative spectrum2. 4. Human subject replaced by dynamic dummy. (Not yet settled). Are standard tests representative? The development process has gradually moved seat tests further from reality. 4 hr samples of work exposure suggest that seats do not on average provide large reductions of vertical WBV3. For specific magnitudes of vibration they can work well. For low vibration, performance is reduced by friction and for severe vibration by length of travel. Recent work has led to a new test to quantify how a suspension controls over-travel 9.

Jan 6, 2006

By J. P. Sancho, J. M. Duart, J. I. Verdeja, J. O. García

Following a short review of the history of rails used in the transport of passengers and goods, this paper describes the process for rail fabrication, rail structure, and properties, and summarizes the fatigue test curves carried out on rails used today. Also reported is the process for “continuous rail” production using aluminothermic welding via the introduction of weld metal in onsite casting, as a homogeneous melt. Weld characteristics of aluminothermic welding using different preheating procedures—fusion zone, heat-affected zone, microstructure, hardness, slow bend test, and fatigue test resistance (Wöhler curves)—are related to preheating and welding procedures of 700, 900, and 1,100 MPA rail grades. The Locati method is preferred over the staircase method for ascertaining the fatigue limit due to its simplicity. Macrographic and metallographic inspection of broken specimens reveals the reliability of welding techniques and the good metallurgical quality of welds.

Jan 1, 2007

By François Baillargeon

Two types of ore deposit provide the bulk of the world nickel production. They are the hypogene magmatic massive sulfide deposits and the supergene lateritic deposits. Platinum group elements (PGE) are also extracted from magmatic sulfide deposits. Recent sky-rocketing price of palladium has prompted the mineral industry to seek alternative resources. In such a manner has emerged the Lac-des-Iles type of target, a very low sulfide-bearing bulk tonnage type of deposit. Furthermore, unconventional (e.g. non-magmatic) types of deposit are now sought more intensively (Wilde et al., 2003). Considering both this trend of the PGE Industry, and that only a few magmatic deposits account significantly for the world nickel production, someone may wonder if a diversification of the hypogene nickel resources base would not be needed in the near future. Laterites are residual deposits developed on ultramafic rock under wet tropical climate. Are all ultramafic protoliths equal to generate high-grade lateritic deposit? Are some preweathering processes important to generate favourable ultramafic protoliths? The mineralogical heterogeneity of some ?dry? lateritic nickel deposits renders their ore beneficiation difficult. Is the type of nickel-bearing mineral found in the protolith a significant factor influencing the laterite heterogeneity? To contribute to answer all these questions, we have undertaken a research project on the nickel occurrences of the southern Quebec serpentinite belts. Why choosing this specific region for such a project? First because, due to continuous mining of asbestos ore since 1870, the serpentinite belts of this region are among the best exposed and studied in the world. Secondly, this region host a complete spectrum of nickel deposits that have been described before in the scientific literature. Furthermore, this region is slightly to moderately metamorphosed which make it perfectly suited to study the departure from magmatic nickeliferous paragenesis through various metamorphic conditions. As a matter of fact two orogenic events affected this region, the Taconian, in Ordovician time, and the Acadian during the Devonian. The magnitude and the timing of these dynamo-metamorphic events vary considerably through the region (Gauthier et al., 1994). These variations are now well constrained due to precise age dating.

May 1, 2003

By O. L. Culberson, J. J. McKetta

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By J. J. McKetta, O. L. Culberson

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951