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By E. R. Russell, N. E. Richards

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,' through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without

Jan 1, 1969

By T. Reed Scollon

Major interrelated factors to be considered in assessing the impact of air pollution control regulations on coal are: (I) the fuel and fuel-related limitations of such regulations; (2) the rate of adoption and areal scope of the regulations; and (3) the availability of fuels and fuel-burning equipment to meet the requirements. A growing number of regulations contain provisions limiting the emissions of sulfur oxides or the sulfur content of fuels or both. With few exceptions, these limitations have not yet become fully effective in those areas which have already adopted regulations, and pertinent details of future regulations or legislation for most other areas are unknown at this time. Sufficient information is not avail- able to determine the availability of low-sulfur fuels at various demand and price levels, and large-scale commercial feasibility of sulfur-oxides removal processes and equipment is believed to be some years away. Accordingly, with the many uncertainties and unknowns, it is possible at best to make only a rough assessment of the impact of such regulations or legislation on coal.

Jan 1, 1969

By Robert O. Vernon

Urban sprawl, and all its attendant problems, is upon us. In Florida, and much of the rest of the world, this has been intensified by a special problem - the coastal zone - a land of high-intensity urbanization localized where the sea and our citizens interact. Florida is blessed by a long coastline of beautiful beaches, indented by estuaries, lagoons and spring fed rivers. Rocky and sand covered islands invite habitation. A large and varied fauna and flora make recreation an avocation and work a pleasure. Accompanying these people are all the sustaining, and satellite industries that find the climate, labor, and commodity markets, cheap water transportation, and natural resources to be attractive. It is estimated that by the year 2008 a megalopolis will stretch down the Atlantic Seaboard from Georgia to encompass the Keys and extend along the Gulf to Alabama. This city will be fenced by the sea on one side and by the water management works, necessary to provide the water supply for this complex, on the other. What can we do about increasing the amount of water available for this population and decreasing the resultant wastes??? Rarely has there been tendered a more favorable opportunity for a coordinated planning and development project that will provide public access to beaches and multiple use of the coastal lands. Florida, as a peninsula swept by ocean breezes, having a largely indigenous water supply and only the beginning of the pollution of estuarine and coastal waters can cope with air, water and coastal dissipation and pollution, if we have a beginning at providing a constant water supply and at limiting pollution. This answer would appear to lie underground, where the porous limestones are interbedded with impervious fine-grained sediments and ground-water that circulates through these aquifers empty to the ocean and Gulf along the continental slopes.

Jan 1, 1969

By W. A. Haley

This paper discusses how a large wheel loader should be equipped, with particular attention paid to tires and tread life, and describes the several steps that can be taken to provide favorable working conditions and reduce over-all costs. A comparison is then made of wheel loader production and costs vs those of power shovels, and the present and possible future applications of the wheel loader are outlined.

Jan 1, 1969

By Mary A. Barrett

The Bureau of Mines conducted a laboratory-scale investigation of grouting mixtures containing iron or aluminum to determine the existence of health or explosion hazards, due respectively to oxygen depletion or hydrogen emission. Mixtures containing iron created an oxygen deficiency in less than 24 hours and released small amounts of hydrogen; a health hazard could occur but only under extremely unfavorable conditions. Mixtures containing aluminum released little hydrogen and consumed little oxygen; however, if improper on-site mixing yielded high local metallic aluminum concentrations, enough hydrogen might be released to produce an explosive atmosphere in a confined space.

Jan 1, 1969

By E. L. Burwell

Preliminary results of an in situ oil shale retorting experiment conducted by the Bureau of Mines in a shallow bed of Green River oil shale at Rock Springs, Sweetwater County, Wyo., are described. Eleven wells were drilled into a 20-ft-thick section of the shale lying between 68 and 88 It deep, and attempts were made to connect the wells through the shale with a fracture system created by application of high-voltage electricity (electro-linking), hydraulic fracturing, and explosive fracturing. Ignition of the shale through the central well was easily achieved with a propane burner, and shale oil began to collect in three wells within 3 hours. Propane injection was discontinued after 7 days, and combustion continues, although attempts to control the direction of the combustion front have been unsuccessful. Production rates as high as 4 ½ barrels of nil per day have been recorded, but too little is known about underground conditions to permit an estimate of recovery efficiency at this time.

Jan 1, 1969

By C. F. Gleeson

"Geochemical stream-sediment reconnaissance can be a useful exploration tool from the point of view of rapidly and cheaply evaluating the mineral potential of an area. This is particularly true of rugged and mountainous areas such as are found in Gaspé. For the past two years, SOQUEM has been carrying out such surveys over favorable geological regions in the Appalachians of northern New Brunswick and Gaspe. To date, about 4,000 square miles of terrain has been systematically covered by reconnaissance geochemistry. Jeeps have been used as a means of transportation in the easily accessible areas and a helicopter equipped with a winch has been used to lower crews into the more difficult-to-reach regions. Such surveys have been successful in finding metallic mineralization which otherwise might not have been detected.Electronic computation of analytical information has been used to construct regional metal maps, rolling mean maps and residual metal maps. These maps have helped in evaluating anomalies, in relating the regional geo-chemistry to the regional geology and in comparing the distribution patterns of metals. To date, some 30,000 stream-sediment samples have been collected from the Gaspe region and analyzed for Cu, Pb, Zn and Mn. These analyses are being subjected to computer analysis."

Jan 1, 1969

By F. T. M. White, W. A. Bardswick

"The parameters of airborne minerallic particulates which create industrial dustiness, together with the physiological hazards caused by their inhalation, are reviewed. Various techniques of dust sampling are discussed and analysed, and the parameters referred to above are classified as the basis for methods of assessing the physical, chemical and mineralogical characteristics of dust-particle suspensions. The paper surveys those methods of assessment currently accepted by various statutory authorities, and reviews other methods that warrant attention and newer techniques that are being developed."

Jan 1, 1969

By James S. Browning

Mica mining in the United States is confined largely to pegmatites and schists in a few well-defined areas. The largest region extends from central Virginia southward through western North and South Carolina, northern Georgia, and east-central Alabama. 1, 2, 3 Whereas in western North Carolina these pegmatite dikes are weathered to only a shallow depth, they are deeply weathered in the Carolina Piedmont and in Georgia and Alabama. Particularly in Georgia and Alabama, mica is found in the decomposed slates and schists adjacent to the pegmatites, and in deeply weathered granites. Most flake mica is obtained as the major marketable product by crushing and milling pegmatites.4 To a lesser extent, mica is produced as a byproduct of feldspars and spodumene.6 Past research by the Bureau of Mines has developed two methods for mica flotation. One method utilizes acid-cationic flotation for recovery of mica." This method requires thorough desliming of the ore with consequent fine mica losses. The other method utilizes an alkaline-anionic-cationic process for recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials but not so drastically as to remove the fine mica. 8, 9, 10, 11, 12, 13 The latter process has also been successfully applied to a micaceous schist ore from California.14 This report summarizes the results of these research studies. Both of the flotation processes developed by the Bureau of Mines have been adopted by the mica industry and are being commercially utilized separately and in combination for flotation of mica from weathered pegmatite ores.

Jan 1, 1969

By L. G. Wilson

In order to comply with time limitations imposed by this symposium, a very narrow but nonetheless interesting segment of the market has been chosen for discussion of the preparation of a tailor-made product to meet a specific need, and in view of the fact that the barite market is one of the oldest and one of the broadest non-metallic mineral markets in the world, it is necessary that we place this in perspective. Of a recent world annual production; (i.e., 1966 figures released last year in MINERALS YEARBOOK), of some four million tons, the United States consumed over 1/2 million tons, of which approximately 950,000 tons were produced domestically and approximately 700,000 tons were imported. Of this total, something approaching 90% was used for drilling-mud weighting, and of the balance, all but about 60,000 tone is consumed in the production of glass, barium chemicals, aggregates, and other minor uses; thus we are really taking a look at a very minute, however important, and very selective, portion of the total barite-market. The real meat of this paper, after eliminating all irrelevant uses of barite, and delineating the area of discussion, resolves itself into the approach to a favorable marketing area and a specific attack on that area. Cost, to the user, has been, patently, a function of distance, as the basic price of barite has varied very little over the years until recently, and freight rates have been the governing factor. Conversely, the seller of barytes must make concession in the plant price to compensate for distance, if he is to successfully compete.

Jan 1, 1969

By Noel W. Kirshenbaum

Difficulties and costs of transport markedly affect Canadian mineral producers because of distance from markets, weather conditions and rugged terrain. The chemical and physical nature of sulphide concentrates presents additional difficulties in handling and transport, resulting in higher costs which are ultimately borne by the mineowner. Troublesome properties include the thixo-tropic character of wet concentrates, freezing, susceptibility to autogenous heating, and fine particle size causing spillage and dusting losses. Canadian mineowners and shippers must contend with these problems and with stringent regulations governing the maritime shipping of concentrates. A "systems approach," in which complementary techniques in materials preparation, handling and transport are integrated, could reduce freight costs and losses for those selling concentrates, facilitate operations for those carrying and handling them and, in some cases, improve metallurgical processes in smelters receiving them.

Jan 1, 1969

By Sidney Katell

This report, covering the period January 1968 through December 1968, is a continuation of a series that began with the publication of Information Circular 7516 in October 1949. It is the tenth in a series of reports prepared in cooperation with the American Association of Cost Engineers. The abstracted articles are concerned with all phases of cost of engineering in the field of chemical and petroleum plants and related subjects. They are from the following sources: 1. American Association of Cost Engineers Bulletin. 2. Bureau of Lines Information Circulars. 3. Bureau of Mines Reports of Investigations. 4. Chemical Engineering. 5. Chemical Engineering Progress s 6. Chemical Week. 7. Coal Age. 8. Coal Mining and Processing. 9. Cost Engineering. 10. European Chemical News. 3 11. Hydrocarbon Processing. 12. Industrial and Engineering Chemistry 13. Oil and Gas Journal. 14. Petroleum Engineer. 15. World Oil.

Jan 1, 1969

This study was done to evaluate the economic and technical considerations of using pozzolanic materials in order to guide cement manufacturers, pozzolan producers, contractors, Government organizations, and others interested in concrete construction work. Five hundred and thirty-eight samples of pozzolanic raw materials were taken from 27 central and western States. These samples were evaluated by petrographic procedures, and about 200 of the most promising ones were given a complete series of physical tests (American Society for Testing and Materials) to evaluate further their suitability as a pozzolan. This investigation showed that deposits of natural pozzolan materials were widely dispersed in the central and western parts of the United States but that exploiting these deposits would depend on whether they could compete economically with an increasingly abundant industrial waste product--fly ash.

Jan 1, 1969

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By H. L. Retcofsky

Carbon-13 nuclear magnetic resonance (18CNMR) spectra of nine 2-substituted pyridines, seven 3 -substituted pyridines, and nine 4-substituted pyridines have been obtained and analyzed. Substituents included both electron-releasing groups and electron-with hawing groups. Substituent effects on the magnetic shieldings of the ring carbons, except for those in the 2-positions of 2-substituted pyridines, were found to be quite similar to the effects reported for the monosubstituted benzenes, Thus, at least to a first approximation, the two classes of compounds have similar shielding mechanisms. Shieldings of the carbon atoms in the 5-positions of 2-substituted pyridines and those in the 6-positions of 3-substituted pyridines were found to reflect electron release or withdrawal by substituent groups, The pyridinium cation and the compounds 2,2'-dipyridyl and benzonitrile were also investigated.

Jan 1, 1969

Applications of helium in aerostatics, cryogenics, space, and undersea work are described in papers from the Helium Applications Symposium. Specific subjects include investigations of X-ray sources by means of balloon-borne instruments, meteorological soundings by balloons, powered lighter-than-air flight, tethered balloons, refrigeration techniques, large superconductive magnets, electronic devices, superconducting transmission lines, high-precision thermal conductivity analysis, He3-He4 dilution refrigerators, uses of helium in the atomic energy program, helium-cooled nuclear reactors, power- plant applications for high-temperature gas-cooled reactors, helium welding of stainless steel tubing and pipe, development of helium-shielded arc welding, helium as a diluent in spacecraft atmospheres, helium utilization in the Saturn-Apollo program, and helium utilization in diving environments. Papers from the Helium Centennial Symposium at the national meeting of the American Chemical Society cover the history of the discovery of helium, the history of its development by the Bureau of Mines from a laboratory curiosity to an important item of commerce, the source of helium in natural gases, the world of liquid helium, and liquid helium-3.

Jan 1, 1969

By Haskiel R. Shell

While the original purpose of the Bureau of Mines work on fluorine micas was to synthesize large single crystals or film suitable to replace natural muscovite or phlogopite, the objective was broadened to include development of the many possible fluorine micas as a class of new, unique materials. Several methods were developed for the synthesis of the fluorine micas at atmospheric pressure: Solid state reaction, melting in crucibles, internal resistance electric melting, and arc resistance electric melting. The latter two methods are now med commercially. A variety of fluoromicas were synthesized by isomorphic substitution including disilicic, trisilicic, and tetrasilicic. Fluorophlogopite, KMg3AlSi3O10F2, is the fluoromica most widely used. While most of the fluoromicas are completely stable to water, many water-swelling fluoromicas and fluoromontmorrilonoids were synthesized. Single crystals or film of the fluorine micas were grown to 2 inches or more by a number of methods, but none has as yet proved economical. In the report, detailed data and descriptions are given on compositions, syntheses, products, and uses, and on the properties including physical, dielectric, chemical, X-ray, optical, and structural.

Jan 1, 1969

By Frank B. Fulkerson

Barge traffic on the Nation's inland waterways over the past 15 years has been increasing at a rate much faster than intercity freight traffic by all modes, largely due to the growing consumption of mineral commodities, development of more powerful towboats and large and more specialized barges, improvements to loading and unloading facilities, and competition among bargelines for contract shipment of bulk commodities. The Bureau of Mines, in a study to determine barge traffic projections for inland waterways in the South-Central States to the year 1980, gathered data on origin-destination patterns by commodity, quantity moved, equipment used, and rates charged; the trend of each of these factors over time; and the extent of competition between water trans-port and other means of transportation. The Mississippi River and the Gulf Intracoastal Waterway, which together carryover half the Nation's barge traffic, are major carriers of coal, crude petroleum, steel, marine shells, sulfur, salt, cement, and alumina. Greater quantities of these products will be transported by barge; however, oil pipe-lines and unit trains for coal are expected to limit increased barge traffic of these two commodities. Increasing quantities of fertilizer materials will be transported upstream. Although congestion at certain locks is a current problem, the Mississippi River below St. Louis and other open-river stretches have the capacity to handle the increasing number of barges for the foreseeable future.

Jan 1, 1969

By W. G. Park

Long-range projection of demand for domestic crude oil indicates a continued upward movement and accentuates the need for increasing the recovery from known crude-oil resources to supplement expected future discoveries. Consequently, the industry and Government have given special attention to the viscous or heavy-oil deposits because they offer the distinct possibility of large order increases in ultimate recovery. This report presents data pertaining to 150 heavy-oil reservoirs in Arkansas including oil characteristics of samples from 38 of these reservoirs. To January 1, 1967, about 600 million bbl of heavy oil has been recovered from the 150 reservoirs in 63 oilfields; however, about 4.5 billion bbl, or 88 pct, of oil remained in the ground. Of prime importance is that much of this heavy-oil resource is in reservoirs having characteristics considered favorable for thermal-recovery operations. Data for the thermal projects initiated [thus Ear are presented in individual field discussions. Also discussed is the t crude oil supply-demand situation in the State.

Jan 1, 1969

By David W. Smith

"This paper is devoted mainly to a discussion of the hydrocarbon potential of the offshore, with a few brief remarks concerning the inorganic mineral potential.OFFSHORE OIL AND GAS POTENTIALIN ORDER TO HAVE HYDROCARBON ACCUMULATIONS, we must satisfy three basic requirements. First, we re-quire a sufficient thickness of sedimentary rocks which contain some porous and permeable formations to act as reservoirs. Second, we require some type of trapping mechanism, such as faulting, folding or stratigraphie trapping. Finally, we require that large quantities of hydrocarbons have been generated within the sedimentary rocks and have migrated to the traps."

Jan 1, 1969