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By T. W. Beck

Roof bolter occupations in underground coal mines continue to experience overexposure to respirable dust. One potential source of dust in roof bolting operations is the exhaust from the roof bolter dust collection system. A wet exhaust conditioner (water box) has been developed to reduce dust emissions from the exhaust of the vacuum dust collection system on roof bolting machines. The exhaust conditioner consists of a muffler chamber and a water chamber with four internal partitions to direct airflow over the surface of the water. The National Institute for Occupational Safety and Health conducted a series of laboratory tests to assess the respirable dust capture ability of this device as compared to the standard exhaust muffler. To determine the dust collection efficiency, both devices were placed in the exhaust stream of a simulated roof bolter dust collection system. Gravimetric samplers were operated upstream and downstream of the exhaust conditioner and muffler to evaluate the ability to capture both respirable coal and limestone dust. Researchers observed a 41 % reduction in dust concentrations for the water exhaust conditioner in the laboratory configuration. Significant levels of dust deposition in the sampling chambers may have contributed to this effective capture rate.

Jan 1, 2012

THERE is at least one concrete indication that Soviet Russia's two most important iron ore producing centers are seriously depleted. While keeping in mind Russia's penchant for reverse propaganda, one piece of evidence indicates that Magnitugorsk in the southern Urals and Krivoi Rog in the Ukraine have been mined to a point where lower grade ores are being recovered. An article in Pravda, Soviet newspaper, by I. P. Bardin. a Russian metallurgist, says that ore presently mined must undergo an expensive enriching cycle before it can be used in blast furnaces. Com- pounding Russian metallurgical troubles is the low quality of coking coals. High ash and sulphur content typifies the coal Badin talks about. Coal from the Ukraine, Eastern Siberia, Kazakhstan, and the Far East requires extensive treatment before it can be used, according to the article in Pravda.

Jan 7, 1953

By VlNTON H. CLARKE

Diamond-drill blasthole sloping has now been used for a long enough time to permit us to discuss fairly its problems from the ore-breaking angle and to attempt to peer into its future. To do this we have gathered information from many properties through questionnaires. The operators have indicated fairly well in their answers what they think of the method. The many variations of methods have by now been fairly well developed, and performance rates and. mining costs are well established at each property. All this can be laid down on paper with fair completeness. Now. knowing all this, what will the future of the method be? To attempt to look into the future of a mining method immediately brings to light many problems and variables. For instance: why were diamond drills used in the first place? What has the cost trend been? In what type of deposit has the method proved most advantageous? What will the future cost of diamonds be? What are the possible substitutes?

Jan 1, 1949

By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

By C. Chamberlain

The Telfer Project, Australia's newest, largest, and most remote gold mine treats 480 kt of ore grading 9.33 g/t derived from open pit mining operations. Coarse gold is recovered by gravity concentration with jigs and further upgraded wing a continuous strake launder table, and by amalgamation. Remaining gold is recovered in a cyanide circuit and incorporates flat bottom air agitators, counter current decantation (CCD) and stellar filters for clarification and precipitate removal. Overall recovery into a bullion averages 98%. The mill incorporates a number of design features that allow for maximum efficiency and security wing a minimum number of operation personnel.

Jan 1, 1983

Discussion of the paper Of JAMES JOHNSTON, presented at the New York meeting, February, 1914, and printed in Bulletin No. 85, January, 1914, pp. 107 to 133. CHAIRMAN E. GIBBON SPILSBURY.-I would like to call attention to the fact shown in this paper that less than five years or perhaps seven years ago nobody had thought it possible to cyanide with success silver ores. The cyaniding of silver and gold ores was first of all started in Mexico, and gradually extended to this country in the case of the silver ores alone. The average extraction, I think, for the metals in Mexico, in the case of the silver ore, is less than 85 per cent., whereas here, in the case of a very complex ore, carrying a high percentage of sulphur and arsenic, and other objectionable elements, the ore has been treated so as to extract an average of 95 per cent. of the silver contents of the ore. It is really a phenomenal revolution in the metallurgy of silver ores which has been demonstrated and worked out at the Nipissing mines. GEORGE A. PACKARD, Boston, Mass.-I would like to suggest a slight modification, perhaps, of the statement which is made that no one considered cyaniding of silver ores up to five, or perhaps seven years ago, because in 1897, when I was at Mercur, Utah, one mill near there was operating on silver ores. It did not operate very successfully from a commercial standpoint, because they did not have a great deal of ore, but the extraction, I was told, was very satisfactory, and I am quite confident that it was, because, as suggested by the name, Chloride Point, the ores were silver chloride ores, and of course very easily soluble. Some years before that, in 1892, I made some tests myself. I spent three months making tests on more or less complex silver sulphide ores at Virginia City, Mont., and while our tests on the plain sulphide ores, finely ground, were quite successful, on account of the presence of a small amount of copper we did not work out a satisfactory solution of the problem at that time; although since then a cyanide plant has been erected and for at least eight years these ores have been treated by cyaniding at Virginia City, and the mill is still in operation. The period of five to seven years should, therefore, be modified considerably, in justice to the pioneers in the cyanide processes. REGINALD E. HORE, Toronto, Ont., Canada.-I hoped that there would be metallurgists from Cobalt here to present and discuss Mr. Johnston's paper. In their absence a few remarks from me may help to make clearer to you what they have accomplished.

Jan 6, 1914

By R. HAYDEN, H. B. HALLOWELL, H. O. Hofman

THE object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe in his classical paper "Contributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks.2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker' and Addicks.4 The absorption of gases has received' attention by Hampe,5 Stahl 6 and Heyn.7 The effects of casting-temperature have been noted by Stahl.8

Mar 1, 1907

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman. EDGAR RICHARD, Vice-Chairman. D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman. JAMES G. CARLETON, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass., W. E. C. EUSTIS. G. A. PACKARD. Columbia Holds four sessions during year. Annual meeting n September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON, S. SHEDD. Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman. I. F. LAUCKS, Vice-Chairman. CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT

Jan 7, 1917

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICHARD, Vice-Chairman D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer JOHN V. N. DORR LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of. Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman I. F. LAUCKS, Vice-Chairman PERCY E. WRIGHT, Secretary-Treasurer, 2012 L. C. Smith Bldg., Seattle. Wash. GLENVILLE A. COLLINS JOHN N. POTT

Jan 11, 1917

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, Jr., Chairman EDGAR RICKARD, Vice-Chairman D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer JOHN V. N. DORR. LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of Technology, Cambridge,Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY. Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. 0. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman I. F. LAUCKS, Vice-Chairman CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS JOHN N. POTT

Jan 10, 1917

By Thomas R. Stauffer

The principle that conventional schemes for taxing petroleum or mineral resources are "inefficient" is illustrated using simulation calculations tested against an "ideal" system. Inefficiency is defined as the relative success in maximizing expected government revenues from the resources. Most systems fail because: 1) they leave oil in limbo, i.e. unproduced because of excessive fiscal burden; or 2) they unnecessarily increase the variance in the explorationist'c, rate of return by undertaxing large fields and overtaxing smaller but infra-marginal fields. This increases his discount rate and reduces taxable surplus. An "ideal" tax system is specified which maximizes government revenues while minimizing risk to the operator. Two criteria are developed: 1) the tax falls to zero on fields which yield only the minimum necessary rate of return ("marginal" fields); and 2) the after-tax present value of all fields is the same for all fields above a threshhold size. In particular, marginal fields, while contrib- uting little to expected values, do contribute to reducing variance and hence risk praemia by distributing the exploration costs over a higher probability of successful outcomes.

Jan 1, 1982

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 John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By Arthur Notman

THE raw material men in all industries, and copper is no exception, are accustomed to think of them- selves as the whole show, and not without justice, for if there were no copper mines the world would have no copper. Nevertheless, many different things costing money and resulting in profits must be done to their product before it is ready for the world's use. In other words, they are making the frequent mistake of Chinking in terms of partial costs. Nobody really uses electrolytic copper. Possibly that is why nobody seems willing to pay anything for it. The manufacturers, being canny, do not buy any more electrolytic than they feel that they can work up and sell profitably, although they like to make the raw material men Chink that they will take all that can be produced. This is a state of affairs that has aroused my sympathy and curiosity, and has induced me to study the financial history of the copper wire and brass industry of the country or such portion of it as publishes any records readily available to the curious minded. About 60 per cent of the electrolytic copper used in this country is drawn into wire and consumed by the electrical industries. The remaining 40 per cent is

Jan 1, 1926

By WALTER B. JONES

IN ALABAMA there are three distinct groups of bauxite deposits, as follows: (1) Cambro-Ordovician contact with the principal-deposits located in Talla-dega, Calhoun, DeKalb, and Cherokee Counties, and in adjacent portions of the State of Georgia. (2) Midway-Nanafalia contact, with the principal deposits in Barbour and Henry Counties, and in adjacent portions of Georgia; also in North-eastern Mississippi. (3) Mississippian - Cretaceous contact, with a group of deposits centered around Margerum in Colbert County. For the purpose of more clearly describing bauxite mining in the state, past, present and possible future, these three groups will be described separately.

Jan 1, 1934

ANNUAL meeting of the Woman's Auxiliary of the American Institute of Mining and Metal-lurgical Engineers convened on Tuesday morn-ing, Feb. 20, the president, Mrs. H. W. Hardinge, presiding. President Hardinge, in opening the meet-ing, said: "I have the honor and great pleasure to welcome you to our seventh annual meeting. It has been a happy year, though I started in fear and trembling. My fear is partly gone and my trembling becomes less as time goes on. Never has a chairman had such splendid cooperation and harmony in her work; no. matter how much was asked nor what the task, I have always received the same answer, `We are with you, of course we can do it.' Often the road has been untried and the way full of snares, but we have all pulled together. Is it any wonder we have had a prosperous year? I cannot thank the governing -board and officers enough for their help." Mrs. Hardinge described her trip through the West last summer, during which she visited many of the local sections of the Auxiliary. She also spoke of the work of the Rossiter Raymond memorial library which has been started as an activity of the Woman's Auxiliary. Mrs. Reynders read the minutes of the last annual meeting, and Mrs. Kemp read the treasurer's report. The latter showed that on Feb. 1, 1922, there was a bank balance of $683.61 and on Feb. 10, 1923, the bal-ance was $947.93. Mrs. Westervelt expressed the sorrow of the Auxiliary for the death -of Mrs. Florence Howe Hall and of Mrs. Levi P. Holbrook.

Jan 4, 1923

By A. T. Shurick

THE NRA Administrator's casual reference to the coal code as the next "pineapple" to be fixed was a conservative estimate of his job. This thorny and adamantine morsel now looms as a critical test of NRA. A failure in coal supplies would have the gravest potentialities in the Administration's program at this time. And the loss of prestige from a breakdown of the enforcement machinery in this initial large-scale test of strength would accentuate the incipient indications of insurrection in other directions. General Johnson has had a difficult task. It involves problems festering for a quarter of a century. A succes¬sion of Presidents have been glad to tide over their respective regimens with inconclusive expedients; they have been baffled by the complexities of the technical angles and hopelessly irreconcilable concepts of powerful conflicting interests with large issues at stake.

Jan 1, 1933

By Michael J. Fiannnaca, Michael M. Easdon

Disseminated epithermal gold metallization occurs within a breccia unit interpreted to be a submarine debris flow. Gold is associated with oxidized pyrite, fluorite, and jasperoidal silica. A minimum of 8 Mt (9 million st) of open-pittable mining reserves will be cyanide heap leached as run-of-mine ore at a rate of 0.9 Mt (1.0 million stpy 1. Careful evaluation of the combined results of successive sampling projects has established the pit plan, minable reserves, and process metallurgy of the operation. The sampling procedure utilized for a given test depended upon geological interpretation as well as the procedures, successes, and failures of previous tests. This paper summarizes the sampling and testing procedures of the development effort in light of the project goals and attendant problems in achieving them.

Jan 1, 1985

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

Jan 1, 1942