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By D A. Shushkov

Analcime-bearing rocks are one of the varieties of raw zeolite material, although the characteristics of analcime are not as good as other kinds of zeolites such as clinoptilolite or mordenite. However, some fields of application of analcime-bearing rock have been found, eg a method of water purification has been developed and patented. Analcime-bearing rocks are rather widespread in the Timan region of the Komi Republic of the Russian Federation. They are represented by Upper Permian siltstones and mudstones. The analcime-bearing rocks have the following mineral composition (per cent): clay minerals (50 - 70 per cent), quartz (ten to 30 per cent), analcime (one to 30 per cent), feldspars (two to ten per cent), carbonates (two to five per cent) and pyroclastic material. Analcime aggregates encrust cavities and infill microfissures in rock. Both microcrystalline (crystals <0.01 mm in size) and medium-crystalline (~0.5 mm) aggregates are observed. The mechanical, gravitational, magnetic, sorption and ion-exchange properties of analcime-bearing rocks have been studied. They are characterised by a high index of grindability and a low index of abradability and crush resistance, low values of the benzol-based pore volume and toluene-based specific surface area, and a medium porosity value. The magnesium based ion-exchange capacity (IEC) ranges from 28.7 to 196 mg+equiv/100 g. Analcime-bearing rocks of the Timan region are characterised by low beneficiation potential. Preliminary ultrasonic treatment of the analcime- bearing rocks is efficient for the destruction of intergrowths along their boundaries and production of free analcime aggregates. The proposed beneficiation procedure yields 95 per cent analcime concentrate. In the Komi Republic, analcime-bearing rocks are utilised in agriculture. They are also used for domestic needs (eg as biotoilets for domestic animals) and the solution of ecological problems (regeneration of soil polluted by oil). We have completed experiments on the purification of potable and industrial water using analcime-bearing rock subjected to thermal treatment. The experiments demonstrated that it was possible to decrease water colouration by 20 per cent, turbidity by 79 per cent, permanganate oxidation by 30 per cent and total iron content by 70 per cent.

Jan 1, 2008

By J. Pereyra, M. DeMarco

"INTRODUCTION It can be vital that bolted joints holding subassemblies together remain secure. Bolts should resist the loosening effects of vibrations and dynamic loads yet need to be easily removable during maintenance. When a threaded fastener is subjected to vibration, the rapid movement causes a lowering of friction against the threads and a subsequent loss of preload. The loss of preload allows the fastener to vibrate loose and possibly fall out. As the diameter of fasteners increase desired preload becomes increasingly more difficult to achieve. Input torque requirements for achieving proper bolt preload is exponentially related to any given fasteners diameter. This means that specialized tooling or bolting practices are usually required to attempt the tightening of fasteners to reach their required preload. Traditional methods can cause problems with joint integrity and do not provide consistent bolt load across the bolted surface. BOLTED CONNECTIONS A failed critical bolted joint can lead to high maintenance costs, machine downtime, and risk to worker safety. Control of the clamp load in a bolted joint is vital. However, when faced with a problem joint, it is not surprising that the design engineer will not have an answer if asked about the clamp load. Torque calculations must always be based on the existing conditions that often are vague. Unless all parameters are correct, the calculation will be unreliable. Examples of parameters are: • Thread condition of the fasteners • Hardness of contact surface • Material (steel, aluminium, copper, etc.) • Extra friction from a locking fastener • Extra friction from an adhesive • Lubricant on the thread • Type of bolt head (flanged, regular or serrated) • Surface coating of the bolt • New or reused fastener During tightening, bolts are subjected to both tensile and torsional stress. The total stress in a bolt can be calculated using the formula: Total stress = vsx2 + 3txy2 In order to maximize the desired tensile stress (sx) it is vital to minimize the torsional stress (txy). Tensile stress (clamp load) is achieved when the bolt is axially elongated. Unwanted torsional stress (twisting) in bolts arises during tightening due to thread friction. High thread friction increases torsional stress and causes yielding at lower clamp load levels than normal. A lubricant is necessary to minimize the malign torsional stress. However, many commonly used bolt-locking systems are based on increased thread friction (deformed nuts, adhesives, etc). To minimize thread friction and concurrently safely secure the joint has often incorrectly been considered impossible. The use of locking systems that increase thread friction is the single most common reason why the full capacity of bolted joints is not utilized. The following example illustrates the problem."

Jan 1, 2015

By Fred N. Kissell, Jerry C. J. Tien, Edward D. Thimons

At coal mine working faces, simultaneous application of three basic elements reduces the methane explosion hazard: (1) adequate ventilation, (2) regular monitoring of gas concentrations, and (3) the elimination of ignition sources. This paper reviews the application of these elements in a manner relevant to Chinese coal mines. Adequate ventilation is provided by using the mine entries to convey air for the long distances between the mine portal and the working sections (main ventilation systems) and then using line brattice or ventilation duct (face ventilation systems) to convey air the last hundred meters to the working face where coal is broken and removed. The air quantity provided is enough to safely dilute methane and the air velocity is enough to prevent layering. Gas concentrations are regularly monitored in accordance with regulations using knowledge of the circumstances under which the highest concentrations are likely to be found. Ignition sources are eliminated by ensuring that electrical equipment does not ignite methane, that sparking from cutter picks is minimized, and that smoking by workers is strictly forbidden. Risk-reduction studies using fault-tree analysis have shown that large reductions in explosion risk only result from multiple preventive actions. For example, a ventilation upgrade or a methane monitor upgrade by itself offers risk reductions under 50 pct. A risk reduction of 90 pct. or more would typically require much more. Other studies have shown that the everyday vigilance of those working underground is as important as engineering design.

By Sandip K. Mukherjee

This paper describes the application of pressure foam to control respirable dust in a double-drum longwall mining section. The feasibility of passing an adequate quantity of pressure foam through the shearer drum was initially established in the laboratory. Thereafter, underground testing of the foam system to determine its effectiveness on an active operating longwall was conducted in a mine in West Virginia. The foam system proved superior to the water spray system. The de- tails of the laboratory and field investigations, the results obtained, and the degree of acceptance of this system by the mining company are discussed in this paper.

Jan 1, 1984

Relatively lower recoveries (60%) of coarse phosphate (-16 +35 mesh) particles are attributed to the difficulty in transportation of coarse particles from the pulp to the froth column and rapid drainage of these particles from the froth column to the pulp. Increasing the hydrophobicity of coarse particles by higher, more efficient coating of the collector and using larger froth volumes have been suggested to overcome these problems. In this study, the role of emulsification of the fatty acid-fuel oil collector on the flotation recovery of coarse particles was examined. It was determined that emulsification can not only increase the coarse particle recovery, but do so at higher fractions of fuel oil in the collector, thereby reducing the reagent cost as well.

Jan 1, 1989

By B Vernon, M Whiteley, T Robinson

The Western Australian gold industry has approximately 100 operating plahts, mainly CIP/CIL. The nature of the State's rapidly expanding gold industry gave rise to concerns over management of the  cyanide hazard, in that most plants are remote from major population centres, have a workforce with a high tum over and use highly saline process water. Approximately 4500 workers in the industry have the potential to be exposed to cyanide in the course of their normal work.   This paper outlines the risk management strategy developed by Government and industry to monitor atmospheric HCN gas in the work environment and the role of continuing education and training along with regular site inspections by Department of Mines Inspectors.

Jan 1, 1990

"In addition to outstanding technical sessions and networking opportunities, the SME Annual Conference and Expo offers attendees a chance to see the latest and greatest technology that the industry has to offer. The 2017 SME Annual Conference and Expo was no exception as 575 companies filled 756 booths from Feb. 19-22 in Denver, CO. The following is a look at some of the vendors that were on hand.AIL MiningThe Edge, featured by AIL Mining at the 2017 SME exhibit, is a four-flange structural liner designed to be an alternative to structural plate’s traditional lapped seams and to help mine operators build more efficiently and safely. It is ideal for creating underground structures, such as mine shafts, ventilation raises and escape ways. The Edge is available on SuperCor structural steel plate — 10 times stiffer and five times stronger than traditional steel liner plate. It facilitates curved structures, both horizontal and vertical, and eliminates the need for ring beams. It is ideal for remote sites. For added safety, structures can be assembled from the inside, and the leak-resistant structures can be dismantled and removed easily. Brackets can be attached to mine shafts or vent raises to support Alimak rails or climbers. Similarly, brackets or hangers can be attached to drifts or tunnels to support mine air, water or electrical utility services.ArcadisMining companies spent nearly $12 billion on water infrastructure worldwide in 2014, reflecting the industry’s heightened concern about environmental issues and social, regulatory and political risks.So, with an increasing focus on water reuse and recycling, mining companies must have effective water management plans that include sustainable solutions. Also, many water quality issues fall under both state and federal regulatory jurisdictions. To solve these problems, Arcadis provides comprehensive ground- and surfacewater technical support in a complex hydrogeologic setting. It can characterize the nature and extent of mine-related constituents in ground water and surface water, as well as the complex interactions between the two waters, and prepare the operational permits needed by mine and tailings facilities. As an example, Arcadis constructed a hydrogeologic and geochemical conceptual site model that improved site understanding for a molybdenum mine in the western United States that spanned several watersheds. It also provided technical support for permitting and compliance issues, allowing the mine to return to active production."

Jan 5, 2017

By James E. Monsees

Extensive underground excavation will be required for construction of a mined geologic repository for nuclear waste. Hundreds of thousands of feet of drift will be required based on the conceptual layout design for each candidate nuclear waste repository. Comparison of boring and blasting excavation methods are discussed, as are special design and construction requirements (e.g., quality assurance procedures and performance assessment) for the nuclear waste repository. Comparisons are made between boring and blasting construction methods for the repository designs proposed for salt, volcanic tuff, and basalt. Differences in the geologic media and settings of the prospective sites influence the excavation method in terms of drift length, size of opening, drift slope, rock quality, and boreability. Support requirements, ventilation, and the ability of the geologic system to retard radionuclide migration are also directly impacted by the geology and excavation method.

Jan 1, 1987

By Claude P. Heiner

mountain region to M tht Coast points for domestic consumption and for export are shown in Table 11. There is considerable disparity in rates from both Rock Springs, Wyo., and Castle Gate, Utah, to the four coast cities where the slack coal is to be used for purposes other than export. The rate on coal to be exported is the same from either starting point to any of the four coast cities even though there is a difference of as much as 341 miles in the shipping distance. It is interesting to note that the freight rate between Sunnyside, Utah, and Fontana, Calif., on coking coal is $5.05 per ton and that coal up to 8 in. can be moved on this rate if it is suitable for coking. This rate was published late in 1942 on a contemplated annual movement of more than 500,000 tons. There have been decreases in freight rates since 1923 on movements of slack coal from Utah into Seattle and Portland due to pressure on the railroads and to greater. quantity of coal shipped. It is the author,', opinion that a movement of slack coal in excess of 3 million tons of coal per year from Utah to any point in central California would justify a freight rate equal to that puhlished for Fontana, Calif.. or $5.05 per ton. The movement of 3 1/2 million tons of coal per year on the basis of 240 mine working days per year would require that 14,600 tons be handled each mine working day. If it is assumed that shipments could be arranged for a 6-day week, the average railway movement would he 11,200 tons, or approximately 3 trains containing fifty-five 70-ton coal cars per day. Such movements of coal would require railroad equipment represented by the investment amounts stated in Table 12 and entail the services of 250 men. Table 12 ... Railroad Equipment and Investment Required To Move 11,200 Tons of Coal a Day from Utah to California Railroad Equipment Cost 2800. 70-ton coal cara at $6.000 each $16,800.000 32 locomotives at $310.000 each. 9.920.000 Miscellaneous eauiument:.......... .5;000:000 Total........................ $31,720,000 It therefore appears that, under presently known mining methods, the lowest price at which coal could be sold f.0.b. the mine in amounts of 3 1/2 million tons per year for generation of power in central California would be $4.60. It also appears that the lowest freight rate that could be expecled between intermountain points and the central California area would be $5.05 per ton, making a total cost of coal delivered at a plant site of $9.65 per ton. Conelusions The following are the author's conclusions: 1. Coal mines in Utah and in the Kemmerer and Rock Springs districts of Wyoming could increase annual production by 6 1/2 million tons per year. 2. Under present conditions coal could probably be delivered to any steam electric plant in central California at a price not to exceed $9.65 per ton. 3. The use of coal at such a price, while higher than the equivalent present price of fuel oil, is entirely feasible. 4. There are adequate railroad facilities for movements of large quantities of coal from the intermountain region to the Rest Coast. 5. In a national emergency it probably would be extremely difficult, if not impossible, to obtain sufficient oil to meet requirements of the greatly expanded West Coast steam electric generatsing capacity. 6. The intermountain region contains ample coal reserves to supply all conceivable demands for West Coast power generation for a number of generations. 7. Increasing demands of labor threaten to lessen, if not eliminate, savings in cost of coal production through the use of new mining machinery. 8. Continuation of experiments in socialism by the Federal Government through construction of hydroelectric generating plants, particularly those unrelated to land-use reclamation, defies justification. Rates under this concept of a governmental function are subsidized through greater taxation of its people. Private capital is available to construct steam plants, or hydro plants where feasible, and should be permitted to continue in order to preserve the principles of our free enterprise system. DISCUSSION (L. C. McCabe and Robert P. Koenig, presiding) C. C;. BALl*—I was asked to lead off the discussion, but it is not with the thought that I might be able to add anything to the paper. The thoroughness with which it was prepared rather forestalls the asking of many questions. Your treatment, Mr. Heiner, is a very valuable contribution. I do want to suggest—that although you have limited your study to this specific question, with certain geographic limitations, many of the things in your paper apply just as well to the eastern coals. I want to agree 100 pct with your final conclusion concerning government-subsidized construction. Id. C. McCabe*—It is certainly worthwhile to take stock occasionally to see where we are going in problems of this nature. I agree with Mr. Heiner that ultimately the only reliable source of fuel that the West Coast has is coal hut the time factor is the difficult element to evaluate. Just before I came here I discussed this subject with N. B. Hinson, Vice President and Executixe Engineer of the Southern California Edison Company, and Chairman of the West Coast Inter-Power Exchange Committee. He has given much thought to utilities' fuel supply and it was very helpful to me in preparing a discussion of the paper to talk with him beforehand. Stock taking and forecasting of future development are essential to the continuing success of any enterprise. Mr. Heiner has called attention to the unprecedented growth of central and southern California and to the increased demands for fuel and power which have accompanied it. He discusses the increased fuel oil and natural gas requirements and the probable limits on the future use of these fuels and of hydroelectric power. In contrast to the calculable limits of these sources of electric energy, the author points to the availability of enormous reserves of coal in the Rocky Mountain States adjacent to the Pacific Coast which can be utilized for power generation. That there will be increased use of coal for power generation in the area under discussion is generally accepted hut it is in the timetable of such development that there is not complete agreement. In a recent report, Mr. Hinson reviewed the future power outlook for the Pacific southwest area. He pointed out that the use of steam plants in connection with water power plants in this region has made the maximum use of hydroelectric energy possible, and that the correct balance between hydro and steam generating plants produces the most economical overall system. Steam plants in the area which had been installed to protect against deficiency in hydro energy in dry years were used to carry war loads. Fortunately, no dry

Jan 1, 1950

By M. A. Giralico

A new generation of hydraulic efficient pumper and auxiliary impeller designs is the result of an extensive research program focused on improving the overall performance of optimized SX/EW plants. Combined with the proper scale-up, these optimized designs will greatly reduce aqueous and organic entrainment losses, reduce or eliminate air entrainment and crud formation, enhance mass-transfer and maximize the overall copper yield. Currently, these new pumper and auxiliary impellers are installed full-scale in numerous plants ranging in flow rates from 90 to 15000 G.P.M. and developed heads up to 51 inches. Operational results reported by the independent metallurgist at each processing plant are reporting the lowest entrainment results in the industry. Further R&D has just been completed on a new mixing configuration that separates the systems mixing and pumping requirements. Results from the system pilot test document further improvements in reduction of both chemical entrainment and crud formation, while keeping mass transfer stage efficiencies.

Jan 1, 1998

By Michel Épiney, COREM, Mario Drapeau, Caroline Olsen, Claude Bolduc, Benoit Levasseur

"Several metal sulfide minerals (such as copper, zinc and iron), generally abundant in precious metal-containing ores, are known to dissolve during the cyanidation process. These unwanted reactions consume a significant amount of cyanide and oxygen, which is required for the extraction of gold and silver. Leaching kinetics of sulfide minerals are very fast in contact with oxygenated cyanide solutions. Therefore, the solution quickly becomes charged with oxidation products that are mostly metal ions, metallo-cyanide complexes, metal oxides and other sulfur species including thiocyanate, sulfides, polysulfides, thiosulfate, sulfites, sulfates, etc. COREM’s Extractive Metallurgy team has been conducting a research program on the improvement of the gold cyanidation process. As a part of this program, the current study aims to investigate the effect of certain operating parameters on the reactions involved during pre-oxidation and cyanidation. The effect of pre-treatment under ozone was investigated using an industrial pulp recreated from process water (charged with thiocyanates) and homogenized flotation tailings material from Agnico Eagle's LaRonde mine. In terms of mechanisms, the ozone treatment provides a complete deactivation of the material surface (characterized by EDTA extraction) and the solution (characterized by Ionic chromatography). This resulted in a lower reactivity of sulfide minerals that led to substantial gains in terms of consumption of cyanide and thiocyanate formation during the cyanidation process. The ozone-pre-treatment edges the classical pre-oxidation treatment (such as oxygen, hydrogen peroxides, etc) providing a quicker deactivation of the sulfide matrix and higher reagent savings in subsequent cyanidation process.INTRODUCTIONThe presence of sulfur in the process of gold leaching by cyanidation is a major drawback to optimizing the reagents consumption with suitable operating conditions. The coexistence of sulfide mineral species, such as pyrite, chalcopyrite, pyrrhotite or sphalerite along with the gold-bearing ore have, indeed, a negative impact on the extraction of precious metals by cyanidation (Bayat et al., 2003), (Azizi et al., 2010). These minerals are known to dissolve with cyanide under alkaline conditions and release in the slurry different kinds of sulfide by-products like polysulfides, thiosel, sulfite and sulfate (Seal II & Hammarstrom, 2003) (Breuer et al., 2008a), (Marsden & House, 2006) (Ghasemian Langeroudi et al., 2013). Once these sulfide by-products are released in solution they react with cyanide to form thiocyanate (Marsden & House, 2006) (Breuer et al., 2008b). The consequence of the dissolution of these cyanicides, is a significant increase in cyanide consumtpion as well as a slow-down of gold extraction."

Jan 1, 2016

In late May, at its final session in Nairobi, Kenya, the UN Conference on Trade and Development (UNCTAD) narrowly rejected the US proposal for a new International Resources Bank suggested by Secretary of State Henry Kissinger. The proposal was defeated by a roll-call vote of 33 to 31, with most of the nay votes cast by communist countries, and with 89 of the less-developed countries abstaining or absent.

Jan 7, 1976

The high pressure acid leach process (HPAL) is being commercially used in four plants around the world to treat limonitic laterites. The two major operating costs of the HPAL process are the sulphuric acid and the energy required to heat the pulp to the desired temperature (>240°C). As an alternative to acid injection and steam heating, the in-situ generation of sulphuric acid and heat, produced during the high temperature pressure oxidation of sulphur-bearing materials blended with laterites, has been investigated at the laboratory scale. Various sources of sulphur have been examined, in particular, elemental sulphur, pyrrhotite and a Cu-Ni low-grade bulk concentrate. Under the proper blend ratios, all sulphur sources tested generated sufficient acid to result in equivalent nickel and cobalt dissolutions. A significant improvement to the process economics can result from the addition of sulphur sources containing valuable by-products, such as nickellcobalt andlor precious metals (gold and PGMs). This is especially true in the latter case, when the HPAL can be operated under Platsol conditions (i.e. with the addition of 5-10g/L of chloride), to dissolve the base metals and precious metals simultaneously in the autoclave. Various examples of the application of this concept are presented, together with a brief discussion of its implication on the autoclave design and the downstream processes to recover the values from the leach solutions. Keywords: limonite, co-treatment, acid consumption, sulphur, sulphur compounds, pressure acid leach (HPAL, PAL), Platsol process

Jan 1, 2004

By Tian Li

Molecular crystal growth during gibbsite precipitation from caustic aluminate solutions under different flow regimes was investigated in three different laboratory precipitators. The gibbsite precipitation experiments were conducted at the same temperature, initial liquor composition and seed type. The Taylor-Couette precipitator and the stirred tank precipitator were operated, respectively, under the laminar and turbulent flow regimes, while the bottle roller precipitator was operated in a complex flow regime, where fluid flows are generated by the end-over-end rotation of the bottles. Comparison of the growth rate estimates from the different flow regimes showed good agreement, which suggests that the hydrodynamic regime has little or no effect on gibbsite crystal growth under the operating conditions employed in this work. The growth rate estimates from the current precipitation study showed a second order dependency on supersaturation and is consistent with a screw dislocation growth mechanism. The findings of the current work are in agreement with previous gibbsite crystal growth studies published in the literature.

Jan 1, 2003

By Tony Amis

There is very limited information relating to the potential impact of temperature cycles, outside the variation that occurs naturally, on the behaviour of foundation piles. Such thermal loading occurs when piles are used as heat exchange elements within a Ground Sourced Heat Pump system, in addition to carrying building loads to competent strata. An investigation has been undertaken where a conventional load test has been extended to include a period in which the load is maintained and temperature cycles applied. Instrumentation was installed in the test pile, an adjacent borehole, two of the anchor piles and the heat sink pile in order to be able to develop an understanding of the temperature variation and associated strain changes within and between the various elements. Conventional electronic strain and temperature gauges have been used in conjunction with optical fibre sensors which also measure strain and temperature changes. The results have confirmed the validity of the assumption made in the thermo-dynamic design of the system, the compatibility of the differing measurement systems and differing installation methods for the optical fibres, and initial assessment suggests that the load-settlement response of the pile is not adversely affected by the temperature cycles applied.

Jan 1, 2008

By William E. Dennis

"INTRODUCTION The San Antonio Canyon prospect was examined by engineers 3/ of the Bureau of Mines in March 1943 and again in October 1944. In July 1944, the United States Geological Survey mapped the prospect and submitted a report 4/ recommending core drilling by the Bureau of Mines. The drilling project, which was supervised by the author, was started on January 10 and completed on May 10, 1946.ACKNOWLEDGMENTSIn its program of investigation of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of our mineral resources to the end that they make the greatest possible contribution to national security and economy. It is the policy of the Bureau to publish the facts developed by each project as soon as practicable after its conclusion. The Mining Branch, Lowell B. Moon, chief, conducts preliminary examinations, performs the actual investigative work, and prepares the final report. The Metallurgical Branch, O. C. Ralston, chief, analyzes samples and performs beneficiation tests. Acknowledgment is made to W. D. McMillan, engineer in charge of the Austin field office, and to J. H. Hedges, chief of the Tucson Division, Mining Branch, for general direction and advice. The samples were analysed in the laboratory of the Metallurgical Branch at Rolla, Mo., C. Travis Anderson, chief."

May 1, 1947

Jan 1, 1912

By C. I. Wilmot

FMC's Paradise Peak Mine was discovered in July 1983. The deposit at discovery contained 11,340 ,000 tonnes (12,500,000 tons) of ore grading 3.71 glt (0.108 oz/ton) Au and 120 glt (3.5 oz/ton) Ag. A feasibility study was completed by Davy McKee in May 1984, with detailed engineering starting in June 1984. Construction of the facility started on January 2, 1985 with plant start-up taking place on April 14, 1986, two and one half months ahead of schedule and more than 10% under budget. This paper describes the status of the operation approximately 1-1/2 years after start-up including revisions and additions to equipment and process.

Jan 1, 1988

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-' "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~' for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang's value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- ' mole per cal, and a Cdil value of 2.3 x 10' ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-' per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang's value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-' mole per cal, which is much

Jan 1, 1969