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By Eugene A. Stephenson

NUMBER of noteworthy events in the petroleum industry may be reported for 1941, of which the most spectacular was doubtless the rise in the daily rate of crude-oil production to a peak of approximately 4,300,000 barrels. This enormous daily rate did not ensue from the furor of flush pools but represented for the most part merely a slight additional daily delivery from many wells that had previously been operated on a more restricted basis, in line with good conservation practice and also from the adroit increase in the number of days per week by the Texas Railroad Commission. Another important fact was the increase in price throughout the Mid-Continent area from the static level of $1.02 for 36°, A.P.I., crude, to $1.17 per barrel. Efforts to elevate the price above this point have met with severe opposition from the O.P.A.. as has also a similar effort by the PennsyIvania Crude Oil Producers' Association, but the vastly increased costs for materials and labor may shortly give the industry the enhanced price which it has long deserved.

Jan 1, 1942

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By R. M. Barnes, A. H. Bell

The ideas set forth in this paper are proposed for consideration and discussion as the result of recent study of various plans for control and proration of gas and oil production from Kettleman North Dome oil field. They would be applicable to any oil field during its flush production stage. The problems of development and proration are so Fig. 1.—Ideal Cross-section, Kettleman North Dome Oil Field. intimately connected in Kettleman Hills and in many other flush fields that they have both been covered in this paper. Many are of the opinion that Kettleman North Dome oil field should be considered as containing only one zone to its present total penetrated thickness of nearly 1500 ft., and that the hydrocarbon content of this zone gradually changes from dark and relatively low-gravity oil with relatively low gas-oil ratios on the flanks and plunges to mostly light-colored and high-gravity oil with high gas-oil ratios in the higher structural positions, somewhat according to the idealized section shown in Fig. 1. At least the lower 400 ft. contains dark oil in the higher structural positions.

Jan 1, 1933

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By AIME AIME

THE report of the united. States Steel Corporation for the' year 1928 gives the, following ,figures of raw materials and' finished products . Raw materials, tons :

Jan 1, 1929

Discussion of the paper of, RICHARD H. RICE, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 89, May, 1914, pp. 721 to 743. S. G. VALENTINE, Oxford, N. J.-In a paper read at the New York meeting of the Institute last February I presented some notes taken from our experience with the turbo blower operating on a blast furnace. In connection with Mr. Rice's very interesting paper there are a few items that might be of further practical interest. The question of the reliability of this type of blower will naturally be presented. In this connection we would say that our turbo blower has been in practically continuous use during the present blast, which was begun June 7, 1912, with only three interruptions for repairs of any consequence. Soon after blowing in there was developed a tendency of the blower to surge or pulsate. This occurred on operating at a point considerably below the normal capacity of the machine, and was checked with comparatively little trouble by throttling the intake slightly and taking up a small lost motion on the governor connections, a legacy of the previous blast that had not been attended to. All this required only a few hours' time. In. March, 1914, the furnace being banked on account of a blizzard that cut off our freight deliveries for five days, the opportunity was used to replace the carbon packing on the steam-turbine shaft and to repack the steam inlet valves. In June, 1914, the blower was off 8 hr. to replace an oil ring and scrape a bearing. With these exceptions we have made continuous use of the machine and find we can depend upon it with entire safety as a piece of machinery.

Jan 4, 1915

By Robert Wamsley, W. E. Jones

ONE of the earliest problems in the life of any community is the provision of an adequate supply of water sufficiently free from all types of contamination to be suitable for domestic purposes. Generally speaking, the location of most communities is determined to a great extent by the availability of an adequate supply of satisfactory water. For a mining camp, that consideration cannot be foremost. Here, the ore takes first place, and the men who mine it must do the best they can under the existing conditions. If there is no local source of water, it must be brought from some distant source or must be found by sinking shafts or drilling wells. Fortunate indeed is the mining company that discovers a commercially valuable ore deposit beside a never failing creek full of pure water, with sufficient water rights available, because the acquisition of water in any other manner nearly always involves not only a considerable period of time but the expenditure of considerable money. The experience of Climax Molybdenum Co. demonstrates the measures that sometimes are necessary in order to provide a suitable supply of water. The Climax mine and mill are on the Continental Divide, about 13 miles northeast of Leadville. The elevation of the domestic part of the camp varies from a minimum of 11,320 ft. to a maximum of approximately 11,550 ft. above sea level, and, as is common at such altitudes, the near-by streams that might be suitable for a water supply are small and intermittent, usually flowing only during the summer months. The only streams of any size in the immediate vicinity of Climax are the Ten Mile and Arkansas Rivers. The headwaters of Ten Mile River are on the Company's property, and its water has been used for the domestic supply. The headwaters of the Arkansas River are about 2 miles distant and have not been used as a source of supply by the company. During the past 11 years of the production of molybdenum at-Climax, the number of families living there has increased from about 45 to 283, and the population has increased from about 200 to 1200 persons. Consequently, the capacity of the water-treatment facilities, and the amount of water available, had to be increased to meet the requirements of the camp. As early as 1932 it was recognized that the water in Ten Mile River would not continue to be adequate for domestic purposes and after considerable discussion it was decided to drive a drift through the major fault in an effort to find additional water. This drift was completed in 1935 and tapped sufficient water to make the supply adequate. This water was treated in a tank underground, where lime was added, and was then piped into the domestic supply lines. At about the time this line was completed, the presence of fluorine in harmful concentrations was discovered in the water. This problem was submitted to the International Filter Co. and in November 1937 a plant of its design was put in operation for treating the water to remove the fluorine. This plant proved entirely successful,

Jan 1, 1945

By Lawrence B. Wright

THE Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 following installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticline and a cross anticline recumbent against Cretaceous granodiorite, and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to oremaking materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937. The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about 1 to 4 and in the disseminated and breccia ores, 1 to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene.

Jan 1, 1947

By David T. Day

IN 1897 I published a proposed explanation t for the variation in color and specific gravity of Pennsylvania oils. A resume of this subject was also presented at the First International Petroleum Congress, in Paris, in 1900. Since that time much experimental work bearing upon this explanation has been carried on by myself, in the United States Geological Survey, and under my direction, by Dr. J. Elliott Gilpin, Marshall P. Cram, and 0. E. Bransky, at the Johns Hopkins University. The experimental results thus accumulated seem to throw considerable additional light upon the variations in color and specific gravity of petroleum, as found in different parts of the world, and also upon the variations in chemical composition. Therefore, it seems as if a, summary of the evidence thus obtained might be of value to those members of the Institute who are interested in the examination of oil-fields. The summary is here presented for that purpose. The phenomenon has often been observed in many oil-fields that oils of different color, specific gravity, and chemical composition may be found within short distances of each other. A conspicuous example of this is the occurrence at Jennings, Welsh, and Anse la Butte, La., of petroleum chemically somewhat similar to Russian petroleum; that is, characterized by the presence of naphthenes. Another characteristic is the presence of considerable percentages of asphaltic compounds, sufficient in quantity to disguise the presence of solid paraffin wax, and perhaps also to render that paraffin wax more soluble * Published by permission of the Director of the United States Geological Survey. 1 Proceedings of the American Philosophical Society of Philadelphia, vol. xxxvi., No. 154, pp. 112 to 115 (January, 1897).

Jun 1, 1910

NEW MEMBERS The following list comprises the names of those persons who became members during the period Sept. 10, 1916, to Oct. 10, 1916. BLOOMFIELD, EDWIN CHARLES, Min. Engr., 1012 Standard Bank Bldg., Vancouver, B. C., Canada. BRINGS, HENRY, Min. and Met. Engr., Chief Engr., and Geol., Mollet-Mesrine, 1212 Mills Bldg., El Paso, Texas. CHASE, MARCH F., Vice-Pres., Commercial Acid Co., 1906 Boatmens Bank Bldg., St. Louis, Mo. CUMMINGS, ALVIN M., Asst. Mine Supt., Witherbee, Sherman & Co., Inc., Mineville, Essex Co., N. Y. DOUGLASS, GEORGE M., Genl. Safety Inspector, Amer. Smelt. & Ref. Co. 120 Broadway, New Fork, N. Y. EMRICH, CLARENCE T., Chief Chemist, Old Dominion Copper Min. & Smelt. Co., Box 1163, Globe, Ariz. GARDANIER, SUTTER ALBERT, Assayer, Mgr., Douglas Assay Co., Douglas, Cochise Co., Ariz.

Jan 10, 1916

By B. M. Blake, R. S. Reppert, A. F. Keiser, E. J. Trinkle

The southern West Virginia coalfield was formed in a rapidly subsiding depositional basin associated with deep-seated growth faults. Subsidence began to the southeast during deposition of the Pocahontas Formation, and then shifted to the northwest during deposition of the New River, Kanawha, and Allegheny Formations. Rocks of all the coal-bearing formations grade into massive sandstones to the northwest. For the No. 3 Pocahontas, Sewell, Campbells Creek, and No. 5 Block coals discussed in this study, the overall sulfur and ash values of each coal seam increase gradually toward the northwest. The thickness of each coal tends to increase toward the southeast. These trends are partly a reflection of the differential subsidence of the coal basin along with varying degrees of peat accumulation and degradation. The northwest side of the coal swamps underwent relatively less subsidence and, thus, more degradation due to increased aerial exposure, with a resulting increase in the sulfur and ash values of the coals, and a decrease in the thickness. The open sea existed to the west of the coal swamps, and this marine environment also contributed to the higher sulfur values to the northwest. Coals of the Pottsville Group in the southern West Virginia coalfield generally have sulfur values between 0.6-1.0% with some as high as 2-3% on the northwest edge of the coal basin.

Jan 1, 1983

E1 Teniente made blockcaving look easy. Ore rolling out the Teniente 5 level has the appearance of nicely screened riprap ready for road dressing. Actually it has been mostly size-reduced by nature abetted along the way by the occasional nudge of a double jack wielded by a buitrero (grizzly-man). It is the famous upside-down mine at Sewell, where the ore flow is down and the people flow is up. Sewell (rhymes with jewel) is the impossible cluster of dwellings clinging to a high Andean spur where 13,000 inhabitants find that staircases must substitute for sidewalks. There is no mining man who is not familiar with the picture of Sewell-by day a pyramid of barracks huddled on the high ground out of harm's way and by night a surprising Christmas tree against the mountain top. Until April 1967, Kennecott's Braden Copper Co. rocked along producing a not inconsequential amount of copper, 180,000 tpy (all tonnages cited here are short tons), attributable to its not unspectacular mountaineering and engineering achievements. These latter included expertness in building avalanche-control fencing; operation of a 35,000-tpd concentrator on the Sewell mountain spur; a spectacular aerial tramway to move 1600 tpd of concentrates to the smelter at Caletones, and occasionally to provision Sewell when snow blocks the road; a cliff hanger of a railroad 43 miles down to the rich bottom land at Rancagua; and last but not least, a 40-mile tailing launder that sweeps across deep valleys on trestles that rival those of the Romans.

Jan 11, 1969

By A. A. Terchick, J. C. Anderson, D. T. King

During 1972-1973, U.S. Steel acquired an existing southern West Virginia high volatile coal mine property including a 150 tph heavy media feldspar jig preparation plant. Expansion of production from the property required an increase in plant capacity to 300 tph, replacement of the feldspar jig with a hydrocyclone circuit, and inclusion of a water clarification thickener system. The rugged and restrictive nature of the terrain adjacent to the plant facility indicated prohibitive construction costs and severe site congestion would be encountered if a conventional water clarification thickener were installed. A high-loading, small-volume thickener, developed initially for the sugar beet industry by the Enviro-Clear Co. of New York, was investigated by U.S. Steel Research for possible coal preparation application, utilizing bench scale and small scale pilot plant evaluation methods. Results of testing at existing U.S. Steel preparation plants indicated predictable successful application of the Enviro-Clear thickener, so a 35-ft-diam unit was installed. The two-phase thickener system, utilizing presettled bottom sludge as a filter-clarification media, has successfully performed since commissioning in April 1973, producing clarified water competitive with conventional thickener systems with freedom from usual thickener operational problems.

Jan 1, 1976

By A. N. Khayyat, R. G. Temple, R. Skelton

The fluid energy mill has been in use since the 1930's when an early patent was granted to N.H. Andrews in the USA. The microniser design has been basically unaltered since that date and current designs such as the Airfilco "Micronizer" have been progressively developed from results based on wide experience. The authors have been engaged in a research programme to establish optimum design and operational parameters for the Micronizer so as to provide a more quantitative basis for scale-up prediction of results. An introductory section will first trace the development of fluid energy milling including reference to other designs which have developed alongside the micronizer (especially the “Jet-o-miser"). With regard to design features the number of fluid injection nozzles and their size was investigated to establish the optimum range. Injection angle and, the consequent diameter of the internal "tangential circle" was carefully studied to determine the effect of this parameter on product size. The research was carried out using fine limestone as the test material with air as the grinding medium. Feed size fractions of 0-120µm, 0-250µm, 0-500µm, and 300-600µm were milled and product size analyses were carried out using the Coulter Counter technique.

Jan 1, 1980

By Homer Turner

COALS, other than anthracite, have been so thoroughly studied under the microscope during recent years, that we now know what kinds of plants and what parts of plants form the bulk of lower rank coals from peat to bituminous coal. The microscope has also shown the state of preservation of such vegetation as well as the nature and distribution of products of plant decay. These and further details have been ascertained mainly through the employment of two methods of attack, section cutting and maceration. Anthracite has failed to respond to these methods, so well adapted to the study of lower rank coals and, therefore, has been neglected by investigators to such an extent that there is much doubt as to its microscopical characteristics. The object of this paper is to lift anthracite from its realm of obscurity by demonstrating the wealth of microscopical detail that is revealed when reflected light is used on a properly polished and etched surface and, further, to show the relationship between anthracite and bituminous coal.

Jan 2, 1925

By Richard P. Rothwell

Fires in mines are so serious in their consequences and of such frequent occurrence, that their causes and the means of extinguishing them are certainly questions of the greatest interest to a large part of the engineering profession. We have already, in this country, many mines which have been burning for years, and though our hard anthracite is so difficult to ignite that for a quarter of a century after it was first discovered it mas not known how to burn it except with the aid of an artificial blast, yet most of the fires which have occurred underground have been in anthracite mines, and in the coal itself. The injury which these fires have caused to properties in various parts of the anthracite regions, and the cost of extinguishing them, would amount to many millions of dollars, and they have also occasioned the loss of many valuable lives. It is not surprising, therefore, that the subject has already attracted much attention, and the exercise of great ingenuity; and the present communication is made less with the expectation of announcing anything new, than with the object of putting upon record the present state of our knowledge on this subject, or, in other words, of indicating how defective are the present means of combating underground conflagrations. Causes of Mine Fires.—Even upon the surface, fire is a terrible foe to contend with, and there is probably no other which inspires such thorough and well-founded alarm. With what feelings, then, must we look upon this destructive element, when its field is in the narrow galleries of a mine, where the poisonous products of combustion, spreading in every direction, protect, in the most effectual manner, the fire itself from the attacks of extinguishers, while, if the face of attack be ventilated so as to enable then] to approach the seat of the fire, the air current simply increases the extent and violence of the conflagration. Fires underground originate in as various ways as those on the surface, and it is scarcely necessary to say that, except in the rare cases where they are the result of design, they are invariably classed as " accidents," and most generally as " unavoidable accidents." In reality, by an intelligent understanding of their causes and with due precautions, they can almost always be prevented. Ignorance and

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

INTRODUCTION Conditions for formation of porphyry copper deposits appear to have been propitious in the Appalachian orogen from the end of Precambrian into Middle Ordovician, and again from Middle Devonian into Mississippian. In the Appalachians we can now record the evolution of a porphyry copper province within a developing orogen, one that reached metamorphic and structural maturity by the end of Devonian. Fig. 15, after Irwin and Coleman (1972), locates that portion of the Appalachian orogen included in this study, and Fig. 16 illustrates general geology of the area. Deposits mentioned in Table 3 and in the text are shown in Fig. 16. Data presented summarize personal observations by the author, published descriptions of specific areas noted in the bibliography, and abstracts from Provincial assessment files. Sources of previously published data are acknowledged. Few comprehensive descriptions of individual porphyry copper deposits in this area exist, so much of the data presented is new to the literature. Porphyry mineralization has, for this chapter, been restricted to porphyry copper de- posits, although porphyry molybdenum de- posits (Clark, 1972) are also shown in Fig. 16 (Hollister, et al., 1974). Copper- molybdenum and tungsten-molybdenum skarns are also omitted to simplify discu sion, though each is known in the area studied. Gaspe Copper is included, however; min- eralization in this deposit is present in the intrusion as well as in the skarn adjacent (Bell and Scott, 1954). Porphyry deposits listed in Table 3 are included because of some important feature, although other deposits have been reported (e.g., Kirkham and Soregaroli, 1975 ) . Clearly, no table now compiled could be complete. The pace of exploration insures that new occurrences will probably be found. Summaries of features exhibited by intrusions shown in Table 3 should remain valid, however, since they appear representative and are based on an adequate number of deposits in the area studied. Paleozoic porphyry copper prospects (shown in Fig. 16) are more common, apparently, in the northeastern part of the orogen, rarely having been found south of Catheart or west of the Logan Line. Occurrences of molybdenum and other associated lithophile elements are, however, known to the south and west as well as further north. Killeen and Newman (1965), King (1970),

Jan 1, 1978

By A. L. Holley

THIS process is performed in the Pernot puddling furnace; it removes from 75 to 80 per cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has prod uced over seventeen thousand tons of washed metal for the open-hearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There are 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The washing of pig for puddling, however, is not a practice at Krupp's works, because pure pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given herewith. They also brought hone many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 12g pounds of iron with 1 pound of coke. The metal is run by a spout from the fore-hearth into an opening at the side of the main door of the washing-furnace. The Washing furnace.-This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers have 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880

By A. L. Holley

This process is performed in the Pernot puddling furnace; it removes from 75 to 80 pel. cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has produced over seventeen thousand tons of mashed metal for the openhearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There arc 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The mashing of pig for puddling, however, is not a practice at Krupp's works, because pore pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given berewith. They also brought home many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 124 pounds of iron with 1 pound of coke. The metal is run by a spout from the forehearth into an opening at the side of the main door of the washingfurnace. The The washing-furnace.—This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers hare 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880