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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

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.' The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5'6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS' on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n', the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By Merlin H. Aylesworth

THE subject assigned to me is peculiarly appropriate to the anniversary of the birth of Abraham Lincoln. If we applied to our present problems the ideals and methods of the Great Emancipator, the future of American institutions would be so definitely assured that there would be little need to discuss the matter. The only inquiries would relate to the pace of progress, not to the possibility of progress. As a nation we have grown more and more to revere the memory of Lincoln, to honor his character, to extol his teachings and to eulogize his concepts of democracy. We rec-

Jan 1, 1940

By Arthur F. Taggart

PROGRESS in a technical art is of several kinds. It springs .from many diverse sources. It comprises invention, mechanical improvement, operating advance, analytical study, education. Invention is, by definition, a relatively great, essentially individual step, taken quickly. Operating advance is the slow, cumulated march of practice; in contrast, it moves at the pace of the tortoise, but over, the years its effects rival and, in some cases, surpass those of invention. Mechanical improvement- is a usual concomitant of the reduction of invention. to operating practice; thereafter it is a primary tool of operating advance. Analytical study is the process of mental digestion of the fruits of invention and practice. Its purpose is to render these into a form assimilable by the art as a whole, and by the perennial crop of would be practitioners. Education, disseminating the results of such study, consolidates and maintains the positions gained. Thus, slowly at first, but continuously accelerating, the tide of progress grows- to flood. Such growth, in mathematical parlance, is expressible in the general form y = mxn, where x is time, n is some positive number greater than one, m is another positive number, and y is the state of the action at instant x. When n is 2, the readers will recognize the graph of the equation as one branch of the familiar square parabola, whose property it is to become parallel to the y-axis; i.e., to move at an infinite rate, in that never-never

Jan 1, 1947

By T. Egleston

The Boston and Colorado Smelting Works are situated in the town of Black Hawk, Gilpin County, Colorado, on the Clear Creek Narrow Gauge Railway, 55 miles from Denver, in the Rocky Mountains, at an altitude of 7800 feet. It was one of the first works erected for the metallurgical treatment of gold ores, and the only one established in Colorado on a large scale which has been uniformly successful. Both gold and silver ores are treated, and gold, silver, and copper produced. The lead is not separated from the ores nor paid for, if it exists, and is entirely lost in the residues. The works were planned and built by Professor Hill, formerly Professor of Chemistry in Brown University, Providence, R. I., and is still managed by him, assisted by Mr. Richard Pearce, formerly professor in the School of Mines at Truro, England. They are very advantageously situated with regard to the ore-producing regions, having Boulder County on the north, which produces, besides ordinary gold ores, a series of tellurium minerals, such as altaite, sylvanite, and hessite, which are very rich in gold and silver. They are associated with copper and iron pyrites, blende, galena, and the carbonate and oxides of iron. Gilpin County itself produces for the most part the pyrites of iron and copper rich in gold, with a small quantity of galena and blende, which is rich in silver. In

By T. PH. D. Egleston

THE Boston and Colorado Smelting Works are situated in the town of Black Hawk, Gilpin County, Colorado, on the Clear Creek Narrow Gauge Railway, 55 miles from Denver, in the Rocky Mountains, at an altitude of 7800 feet. It was one of the first works erected for the metallurgical treatment of gold ores, and the only one established in Colorado on a large scale which has been uniformly successful. Both gold and silver ores are treated, and gold, silver, and copper produced. The lead is not separated from the ores nor paid for, if it exists, and is entirely lost in the residues. The works were planned and built by Professor Hill, formerly Professor of Chemistry in Brown University, Providence, R. I., and is still managed by him, assisted by Mr. Richard Pearce, formerly professor in the School of Mines at Truro, England. They are very advantageously situated with regard to the ore-producing regions, having Boulder County on the north, which produces, besides ordinary gold ores, a series of tellurium minerals, such as altaite, sylvanite, and hessite, which are very rich in gold and silver. They are associated with copper and iron pyrites, blende, galena, and the carbonate and oxides of iron. Gilpin County itself produces for the most part the pyrites of iron and copper rich in gold, with a small quantity of galena and blende, which is rich in silver. In * By consent of the council of the Institute, this paper was first published in London Engineering, from which the engravings are here reproduced.

Jan 1, 1876

By Henry Mulryan

THE largest and purest known deposit of diatomite is being actively mined and processed 3 ½ miles south of Lompoc, Santa Barbara County, Calif., by the Johns-Manville Products Corporation. The workings FIG. 1.-LOCATION OF DIATOMITE DEPOSIT AT LOMPOC. cover 4000 acres, the depth of economically recoverable diatomite being 1000 ft. (Fig. 1). Lompoc, a community of 2500 population, is situated in the Santa Ynez River Valley 10 miles inland from the Pacific Ocean. It is 44 miles

Jan 1, 1936

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,' and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,' the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,' who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By J. J. Foster

MOST of us will, I think, agree that never before in the history of the coal industry has the human side of our business been so important as today. Since, even in wholly mechanized mining, labor cost is such a large percentage of out total cost we are all deeply concerned not only about the present attitude of our employees but particularly about the future, when the industry returns to a "survival of the fittest" basis. Many things could and should be done about our employee relations in the coal business. Failure to recognize these obligations and do something about them may lead to serious consequences, the least serious of which will be the loss not only of many of our better employees but a large portion of our potential employees, as they graduate from our schools to other in¬dustries. Some of these things should be handled by the industry as a whole whereas others should be done by individual companies. Due to varying conditions and size of organizations it would, at best, be necessary to vary a program to meet the individual needs of each operator.

Jan 1, 1945

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By Sherwin F. Kelly

THE joint meetings of the Mining Geology Committee and the Society of Economic Geologists proved to be deservedly popular, and the interesting papers drew an attendance which strained the capacity of one of the large meeting rooms.. As might be expected these days when even the Supreme Court can't keep away from the subject of gold, the discussions opened on Thursday morning with several papers devoted to questions of structural and mineralogical relationships of the deposits of this metal. The presentation of Ira B. Joralemon's paper, "Veins and Faults in the Bralorne Mine," by Reno Sales, elicited considerable discussion on the relation of mariposite to gold, and the situation of the gold deposits with respect -to the Coast Range batholith. H. V. Warren stated that lie had observed mariposite always to be associated with gold in this region, but that gold was not always associated with mariposite. He pointed out that there is a series of veins on the west side of the batholith with a different mineralogy that, because of their richness but small size could quite easily make good, small mines. John A. Dresser concurred in this, and said lie thought this region was one of great promise for the mining geologist. He also reported having found mariposite associated with gold values below commercial limits, in the Appalachian regions.

Jan 1, 1935

By RALPH HAYES SWEETSER

ONE per cent. of ash in a ton of coal has been so little considered that in many circles it has been positively ignored. Even P. T. Barnum had never heard of it, or he would have had one on exhibition alongside the Cardiff Giant and the White Elephant. One per cent. of ash is closely related by both those freaks of Barnum in that it is "stone" and, in its aggregate, it is the greatest "White Elephant" that the American public now supports. Some of you may have paid Mr. Barnum for a look at the "petrified man" (named the Cardiff Giant by the gullible wise men of the early seventies); but it is certain that everyone of you is now paying for the support of the great White Elephant that is being constantly carried by our railroads all over the country-at the public's expense. " One per cent. of ash in a ton of coal" requires 120,000 open-top railroad cars each year to transport this use- less stone giant from its native bed in the coal seams of the bituminous regions to the coal bins of the consuming public.

Jan 1, 1924

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By Lawrence B. Wright, Lester G. Morrell

On the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly condemned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings. HISTORY AND PRODUCTION Little interest_was_evidenced-in this-distriet until the building of the railway in 1893 provided easy access and the discovery of the Ymir mine in 1896 attracted attention. As a result, the Ymir Yankee Girl group of claims was staked in October 1899. In 1907, an American syndicate took over the property and subsequently extended the 50-ft. drift and opened the present 400 and 540-ft. levels. In 1908, the Syndicate, without recording any shipments in the meantime, dropped its lease, which was taken up by H. L. Rogers, who bonded the Yankee Girl group. Rogers shipped 2622 tons of ore, mainly from the uppermost stope in the mine, which is reported to have yielded

Jan 1, 1940

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By AIME AIME

APPARENTLY unperturbed by any misgiving as to ill luck connected with the mystic number thirteen -for there were exactly that number of Directors on deck-the Board held two sessions on Tuesday, Feb. 21. , . Between the executive session at 5:15 p. m. and the general session at 8:30 p. m., 28 Section and Division delegates were wests of the Directors at dinner. Committee chair- " men and past officers brought the attendance to 75. Messrs. McAuliffe, Merica, Mudd and Tally had expressed their intention to be at the Directors' meeting, but each was prevented unavoidably at the last minute. At the executive session of the Board, J. V. W. Reynders was unanimously chosen to fill the unexpired term of Dr. Becket as Director: and Eugene McAuliffe in like " manner was selected to become Vice-president to fill the vacancy created hy Dr. Becket's assumption of the Presidency. Upon nomination of President Becket the following Executive Committee was appointed: Frederick M. Becket, chairman; Howard N. Eavenson, H. A. Guess, J. V. W. Reynders and William Wraith; and the Finance Committee was appointed as follows: Henry Krumb, chairman; Paul D. Merica and H. G. Moulton. Karl Eilers was reelected Treasurer and A. B. Parsons was re- elected Secretary to serve for the ensuing year, whereupon the executive session was adjourned.

Jan 1, 1933

By Sidney H. Haughton

WHEN the white pioneers of the eighteenth and nineteenth centuries advanced from the coastal settlements of southern Africa into the interior of the subcontinent, they found it inhabited, more or less sparsely, by brown or black peoples mainly of pastoral habits but equipped with a fighting spirit and certain fighting weapons. Some of the tribes were smiths, others were miners and metallurgists; all used fuel, either industrially or domestically. Some of that fuel was wood, some cattle dung, and in some places the natives mined outcrop coal. Coal was first discovered by Europeans in Natal about 1840. After proper deliberation and after allowing due time for a consideration of all the implications, the Natal Government decided in 1881 (40 years after) to import an English expert to investigate and report on the discovery. Things then moved rapidly, and in what to a geologist is the remarkably short space of eight years, Natal collieries were producing at the rate of nearly 30,000 long tons per annum or 100 long tons per working day!

Jan 1, 1945

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

The binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-A~ili~r~ony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Ti11 These three systerrls are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the