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By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By Douglas W. Fuerstenau, Kalanadh V. S. Sastry

Based on an analysis of green pellet size distributions and kinetic data on ball growth with taconite concentrates, a ballability index has been developed to quantify ball growth behavior as a function of moisture and bentonite additions. The applicability of the ballability index to such other particulate materials as pulverized limestone and ground magnesite is shown.

Jan 1, 1973

By Charles M. Cooley

A NOTED Prospector Passes-Stories of the grizzled old prospector that discovered what turned out to be a famous and highly profitable mine, only to die in poverty through the shenanigans of "the Interests," are legion. It is pleasant, therefore, to be able to report that the discoverer of one of Canada's most famous mines was more fortunate.

Jan 7, 1953

By H. A. Keller

After an absence of over two years, the writer returned to Leadville in March, 1890. The change which had taken place in the conditions of smelting during so short a time seemed almost incredible. Lead-carbonates had been still further replaced by refractory sulphides, and clean dry ores had been crowded out, to a large extent, by magnesian " fines."

Jan 1, 1893

By S. K. Tarby, V. S. Robinson III

A number of experimental determinations of the vapor pressure of liquid silver have been reported in the literature. 1-8 This communication presents additional data for the vapor pressure of liquid silver measured in the temperature range of 1450° to 1600°C and summarizes the results of previous investigations. The results reported here were obtained as part of a

Jan 1, 1969

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By Alan Stanley

THE Maclntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.1 Pigment plant production demands that the MacIntyre mill produce a 44.7 pct. TiO2 ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the Maclntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from one level to the next.. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the, physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO2 has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO2 has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the Maclntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO2 was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiO2 a constant gravity would invariably be obtained, and as the TiO2 value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct TiO2 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO2 value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO2 and as the specific gravity increased the trend was for the TiO2 assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. [ ] Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1952

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,&apos; research on the subject is still in an early stage of development."&apos; To the authors&apos; knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal&apos;s position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.&apos; Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By R. Schuhmann, E. J. Michal

Experimental measurements are reported for the oxygen pressures of iron-silicate slags in equilibrium with solid silica. CO2-CO mixtures were bubbled through the slags in silica crucibles to find equilibrium values of p co2/p co over the entire composition range of silica-saturated slags at 1250°, 1300°, and 1350°C. From the data, the activity vs. composition relationships were calculated for O, FeO, and Fe. SLAGS composed primarily of silica and iron oxides have particular practical importance in copper smelting,&apos; in acid steelmaking, and in accounting for the service behavior of silica refractories. These slags all contain both ferrous and ferric iron, so that, strictly speaking, they are ternary or three-component liquid solutions. For convenience, the components may be taken as the three oxides, FeO, Fe2O3, and SiO2. The constitution of the FeO-Fe,O,-SiO, system at slagmaking temperatures has been studied in a recent investigation described in a separate paper.&apos; This work showed the compositional ranges of iron-silicate melts at temperatures up to 1450°C and also the temperature-composition relationships for melts in equilibrium with various solid phases, including iron, wüstite, magnetite, and silica. Broadly speaking, the compositions of iron-silicate melts at a given temperature should be thought of as varying over a two-dimensional field. In the first place, the silica/total iron oxide relationship varies from maximum silica for silica-saturated melts to minimum silica for wüstite-saturated melts or, at higher temperatures, to zero silica for straight iron oxide melts. In copper smelting, for example, the converter slags approach the low silica limits while the reverberatory-furnace slags have intermediate silica contents, perhaps approaching silica saturation in some circumstances. Liquids formed in the pores of silica refractories presumably are close to silica saturation. The second type of composition variation is in the ferric/ferrous relationship, which depends on how oxidizing or how reducing the process conditions are. Relatively reducing slags, such as acid-steelmaking slags, are lower in ferric oxide and ap- proach saturation with metallic iron. Oxidized slags, such as copper-smelting slags, contain larger percentages of ferric oxides and approach or reach saturation with magnetite. Since these two kinds of compositional variations are closely related to two general properties of interest for all metallurgical slags, basicity, and oxidizing power, it is hoped that the thermodynamic study of iron-silicate slags eventually will throw further light on the significance and nature of these long-recognized but as yet poorly understood slag properties. Measurements of oxygen activity as a function of slag composition, using CO-CO2 gas mixture to fix oxygen activities, afford an experimentally convenient approach to the study of the thermodynamic properties of iron-silicate slags. In a preceding investigation,³ his approach was used in a systematic study of iron-silicate slags in equilibrium with solid iron. The present paper gives the results of a similar study of the iron-silicate slags in equilibrium with solid silica. The experimental work consisted in the determination of CO2: CO ratios in gas mixtures at equilibrium in the system: gas: liquid slag: silica Determinations were made at temperatures from 1250° to 1350°C for slags ranging in composition from iron saturation to magnetite saturation. Also, equilibrium CO,: CO ratios and slag compositions were determined for the univariant systems: gas: liquid slag: silica: iron gas: liquid slag: silica: magnetite Experimental Methods The experimental procedure was essentially the same as that used in the previous study of iron-silicate slags saturated with solid iron," but in order to work with the silica-saturated slags an all-silica crucible assembly was used. A liquid slag was prepared from pure prefused stock materials and brought to equilibrium with the silica crucible at the desired temperature. Then a mixture of CO2 and CO was continuously bubbled through the melt

Jan 1, 1953

By W. R. Webb, M. O. Peterson

WHEN men drive haulage equipment ranging up to 22 tons in an open pit operation, they must live with the realization that their safety is dependent upon the machines they drive and how well they operate them. The hazards inherent in their jobs must be recognized, met, and defeated. It comprises a never ending struggle toward perfection-an almost un- obtainable goal. The Jones & Laughlin Benson Mines, at Adirondack State Park in New York, created a safety program which resulted in only one three day lost time accident from April 1948 to April 1952. At the very start of the program, management of the open-pit operation recognized the hazards existing at Benson. The program was designed to meet each danger. With a knowledge of the problem faced, the process of minimizing each facet was planned along lines of maintenance of equipment and training of personnel. Its success is evident. In the ever-present struggle, care and maintenance of machines and application of experience to new equipment design are mainstays. Truck Haulage Benson produced 2.9 million tons of crude iron ore and 1.6 million tons of waste in 1951. To do the job, truck mileage reached 500,000 miles. The tremendous mileage emphasized to safety planners, the fact that the more work done, the greater the possibility of risk in haulage operations. Instrumenting the aim of the safest equipment possible is a methodical servicing program. Like other segments of the drive, the servicing program is based on greater production with fewer accidents. Every truck is serviced at least once per eight-hr shift. Examination includes inspecting and tightening wheel studs, checking tires, steering apparatus, lights, brakes, wipers, heaters, fire extinguishers, and refueling. A running history of the equipment&apos;s operating life is kept in the form of service and maintenance records. Machine operators are constantly on the alert for malfunctioning of units. At the first sign of trouble the truck is returned to the garage for exchange. No truck functioning incorrectly is kept on the line, regardless of its shift check schedule. The program resulted in a reduction of the number of costly overhauls and cut down the number of haulage accidents. Miscellaneous Mobile Equipment Auxiliary units, operating within the pit, have presented definite safety problems. The highest accident rate in the pit occurred on trucks carrying water and bits to the churn mills. The weight and awkwardness of bits and drill stems, combined with remote delivery points were direct causes of numerous accidents. Here, the problem has been one of equipment handling, rather than haulage. All air compressors for secondary drilling are truck mounted, facilitating mobility. In addition to making it easier to move the equipment, truck mounting has eliminated many of the hazards connected with relocating machinery. By making air compressors independent of other units, drilling operations have been speeded up considerably. Unseen rocks in the path of moving vehicles are a constant source of tire damage. At Benson the problem has been met by supplying each loading crew with a bulldozer for cleanup operations. The pitman directs the dozer operation, and when truck drivers back into loading areas, he serves as an extra set of eyes. Modern Truck Garage Provides Drive-Through Service Simplicity is the essence of any preventative maintenance program. At Benson, a modern garage, with a drive-through service bay simplifies servicing. Shift inspection of the 22-ton haulage units is accomplished with minimum delay and maximum thoroughness. Major repair work and periodic overhauls are done in the repair section of the truck garage. Crane facilities for handling heavy assemblies ease the job and add to the safety factor. Other mobile machinery,

Jan 1, 1952

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman&apos; by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman&apos; five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By K. J. Brondyke, P. D. Hess

Two processes have been developed for improving the quality of molten-aluminum alloys before casting. The Filtration Process. which involves passing molten metal through a packed bed of granular filter material, is a rapid means of removing finely divided particles. It has the most potential in those instances where removal of inclusions is of primary importance. The Combination Fillration-Inert Gas Fluxing Process inuolzles introduction of an inert gas so that it will diffuse countercurrent to metal flow through the filter bed of granular material. Dissolved hydrogen is removed from the metal in addition to removal of finely divided particles. The Combination Process is most useful where both inclusion removal and attainment of conistently low-hydrogen-content metal are important. Metal treated by the Combination Process is of higher and more uniform quality than heretofore attainable with prolonged chlorine fluxing. Costs of the Combination Process can, for the most part, be offset by savings derived from high recoveries and increased production of superior-quality products. IMPROVEMENT in the quality of molten-aluminum alloys is secured generally through the use of some fluxing practice in a crucible, holding furnace, or ladle involving either gaseous or solid fluxing media. Typical fluxing agents may include the gases nitrogen, argon, or chlorine used either singly or as mixtures and the solids aluminum chloride or hexachloroethane. Regardless of the fluxing means used, the primary objectives are the adequate removal of both metallic and nonmetallic inclusions and reduction of hydrogen content to an acceptably low level. The ultimate goal is to produce ingots and cast products of high quality free from inclusions and porosity. The development of ultrasonics for measurement of internal quality, tightening of quality controls, and the application of the aluminum alloys to new or different commercial fields have been responsible for an ever increasing demand for improvement of quality of both cast and fabricated products. This demand for high quality has not been restricted to any single type of product. On the contrary, the demand encompasses about the entire variety of products including those for fabrication, those to be machined, buffed, or finished for decorative purposes, and those for critical applications where both surface and internal quality is of utmost importance. In many instances products acceptable in the 40&apos;s would now be scrapped as unacceptable by these higher present-day standards. With this ever increasing demand for higher quality, it became apparent at Alcoa that conventional means of melt treatment were inadequate in many instances and new approaches were necessary. Consequently the research program was intensified with attention focused on metal treatment during transfer in order to reduce the furnace processing time to a minimum in an effort to attain the desired results at a minimum of additional expense. As a result of this intensive research program which covered numerous variations and adaptations of conventional methods in addition to new methods of melt treatment, several new processes were developed, two of which will be described here. The first of these, a method of melt filtration, was patented in February, 1959.l The second process involving combination filtration—inert gas fluxing was patented in June, 1962. 2 Other melt-treatment processes developed during this period of investigation were patented as listed.3 FILTRATION PROCESS General Description. The Filtration Process, which involves passing molten metal through a packed bed of granular filter material, is a rapid method of effectively removing finely divided particles. It is an impingement-type filter; hence the size of the particles removed from the metal are considerably smaller than the interstices of the

Jan 1, 1964

By Shiou-Chuan Sun

SHIOU-CHUAN SUN (author&apos;s reply).-Thanks are extended to Professor Hassialis for his recognition of the usefulness of a new tool, the cataphoretic cell, as an adjunct to the bubble machine and the abstraction test. His questions concerning adsorption, dielectric constant, floatability, activation, and depression are interesting and worthy of discussion. I According to Mueller,28 it is questionable that any of the present formulas gives absolute values of zeta potentials which are completely accurate. The problem is further complicated by the question" of whether the "dielectric constant" has any meaning at all for such a microscopically thin layer. With these in mind, the results in this paper should be considered in the relative sense as a first approximation and not as absolute quantities. Adsorption Referring to item a of Fig. 8, the dielectric constant and the viscosity of the xanthate solutions are the same for galena, sphalerite and quartz. If dielectric constant and viscosity (but not the adsorption) were the first-order variable of the cataphoretic system, as claimed by Professor Hassialis, then the magnitudes of zeta coefficient of galena, spha)erite and quartz would have been similar to each other. These are not. The big difference of zeta coefficient of these three minerals in the same xanthate solutions is not altogether unjustified to be attributed to their difference in adsorption of xanthate ions. This is supported by the results of chemical abstraction tests reported by Ince.14 Again, the big difference of zeta coefficient between wollastonite, calcite, and fluorite in the same laurylamine hydrochloride solutions (p. 118, Figs. 58, 59, and 60 of ref. r5) also indicates that the cataphoretic system is not governed chiefly by the dielectric constant. Beside the data shown in Fig. 8, other experimental evidences15 which support the idea of correlation between adsorption and zeta coefficient are: (I) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of various concentrations of sodium cyanide, (2) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of constant concentration of copper sulphate at different pH values, and (3) there is a qualitative parallelism between zeta coefficient curve and chemical abstraction curve of quartz in solutions with constant concentration of barium chloride at different pH values. The above mentioned experimental results are generally in agreement with Gouy&apos;s double layer theory,1-5 and support this idea that the concentration and the kind of ions adsorbed at the mineral surface and in the adjacent surrounding liquid chiefly govern the electrokinetic phenomena. Dielectric constant and viscosity of the liquid medium may be of somewhat lesser importance. It follows that the correlation between the coefficient and adsorption as claimed in this paper is justified. Dielectric Constant The term "dielectric constant " was first introduced into the electrokinetic equations by Perrin.30 In a footnote of his publication he states that Holmheltz has forgotten to include the dielectric constant. The conversion of the moment29 to the zeta potential involves an additional difficulty and confusion not involved for the moment, namely, assigning a value to the dielectric coefficient. This is conventionally assumed to be constant and equal to the dielectric constant of the bulk liquid. 21 The published literature 10, 12 indicates that the values of dielectric constant for dilute chemical solutions have been assumed as those of pure water.

Jan 1, 1947

By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.&apos; As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,&apos; reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

By Peter J. Szabo

INTRODUCTION The time period from the detailed feasibility study to the post investment audity usually ranges from three to eight years depending upon the nature of the mining project considered. It is the only after the post investment audit that we know the adequacy of the assumptions made concerning operational risk assessment in the detailed feasibility or acquisition economics. The post investment audit results from numerous mining projects can best be described by a verse by John Greenleaf Whittier&apos;s Maaud Muller. It reads "For all sad words of tongue or pen the saddest are these &apos;It might have been!"&apos; Dissecting the negative results of numerous mining projects we find faulty assumptions concerning markets, geology, capital investment and operational risk assessment. Although in hindsight many of these assumptions could have been considered impossible or impracticle to have forecast with any degree of certainty, we find that refined assumptions concerning operational risk assessment could have been made with only a modicum of additional "Due Diligence". Anyone who invests in a mining property should employ a much higher discount rate of future cash flow, (usually in the minimum range of 25%-30%), than he would expect from such safe investments as Treasury Bills or high grade Utility Bonds. The nature of this steep discount translates to a large uncertainty concerning the timing and actualization of assumptions contained in the detailed feasibility study. We must remember that when a project gets beyond 20 years, any contribution to the value of the project of cash flow is minimal due to the nature of the discounting process. Thus for each full or partial day lost in the development or early operation stage of a project, the financial impact will be greater than similar lost days later on in the project. Adequate operational risk assissment is particularly critical when bidding on competitive tenders for coal deposists in remote locations such as the Bowen Basin in Queensland, Australia. Because of the market attractiveness of these coal deposits for supplying end users in the Far East, Middle East and Europe, state governments require competitive tender biddings via the Authority to Prospect process. Front end bonuses and super royalty payments must be commited before the actual mining conditions are known. Time to submit firm offers from the actual request for proposal vary from 90 to 120 days. Thus any operational risk assessment must be detailed, realistic and reflective of the actual project. When one searches the literature, one finds limited qualitative data on operational risk assessment in valuation papers. Usually this facet of valuation takes a secondary role to such areas as reserves, markets, and environmental considerations. When one comes to the question of operational risk assessment more often than not one finds the use of "rules-of-thumb", such as tons per man shift, average production, average seam height, etc., are used to forecast results on which banks and other financial institutions are required to make investment decisions. Because of the extremely competitive environment of the 1970&apos;s and 1980&apos;s numerous financial institutions approved loans without adequate "Due Diligence", and are currently paying a steep price in terms of non performing loans and charge offs. One must always remember that each operation is unique with its own characteristic

Jan 1, 1985

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author&apos;s presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author&apos;s presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By C. F. Weinaug

In recent years, several methods have been proposed for correlation of physical properties and behavior of hydrocarbon systems. These correlations were found to be unsatis. factory for predicting differential gas liberation and shrinkage data now obtained experimentally. To achieve the desired accuracy, methods were developed to adjust the correlations with two experimental pieces of data. The required data are the saturation pressure at reservoir temperature and the specific volume or density at these conditions. The saturation pressure is used to adjust the vapor-liquid equilibrium-ratio correlations. The density measurement is used to determine the apparent density of liquid methane. With these adjustments, differential gas liberation and shrinkage are predicted within the experimental error. EQUILIBRIUM RATIOS Equilibrium ratios published by the National Gas Assn. of America&apos; were used as a basis for the calculation. The convergence pressure for the sample was determined by using a hypothetical binary system, with methane as one component and the remainder of the system lumped together to form the other component. For the critical temperature of the heavy constituent, the weight average of the critical temperatures of the ethane and heavier components was used. The correlation of pseudo-critical temperature, density and molecular weight of Matthews, Roland and Katzl was used in this calculation for the hexane and heavier fractions. Points for the critical properties of methane and the hypothetical heavy constituent were placed on a chart of the critical loci of hydrocarbon systems. A critical loci for the hypothetical binary system was drawn, and the critical pressure of this system was determined at the reservoir temperature. This critical pressure became the convergence pressure for which equilibrium ratios were read from the NGAA4 charts. The NGAA equilibrium constants for C, through C, were used for the C,; through C, fractions since they were separated on the bases of normal paraffin boiling points. The correlation of Hoffman, Crump and Hocott5 as used to estimate the equilibrium constant for the C fraction. The NGAA eauilibrium-ratio charts are based primarily on paraffin systems and have to be corrected for the presence of naphthenes and aromatics. The correlations in the literature proved too unsatisfactory for determining these corrections. EXperimental data, the saturation pressure, is used with the correlation of Soloman2 to make this adjustment. The correction factors of Soloman were cross-plotted so that the factors for ethane and heavier components were made a function of the factor for methane. a2 = 0.7927 at + 0.1646 .........(1) where a, = correction coefficient for for methane NGAA equilibrium ratio, and a2t = correction coefficient for ethane and heavier NGAA equilibrium ratios. This equation and the equation for the bubble point are solved simultaneously for the correction coefficients. The bubble-point equation is anKnXn = 1.0 . . . . (2) The equilibrium constant for the saturation pressure at reservoir temperature is used. This procedure not only corrects for the relative volatility between components, but also assures that the results will be directly related to the experimental saturation pressure. METHANE DENSITY After determining a set of equilibrium ratios, the apparent density of condensed methane at 60°F and 14.7 psia was estimated. This was found to be necessary because the correlations of Standing3 ere found to be unsatisfactory. The law of additive volumes was employed to make this calculation.