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By P. Somasundaran

An experimental and theoretical treatment of the depressing effect of inorganic electrolytes on the amine flotation of quartz is presented. Experimental data obtained for the amine flotation of quartz as a function of pH with potassium nitrate as depressant was used to test the models for the effectiveness of inorganic ions as depressants. The validity of commonly used assumptions are examined. The surface tension data obtained for dodecylammonium acetate solutions as a function of KNO3, concentration indicated that the collector adsorption on bubble cannot be neglected in the treatments, since this adsorption changes significantly with the addition of the inorganic electrolyte. It also indicated the possibility of significant changes in the specific adsorption potential of the collector occurring with the addition of inorganic electrolytes.

Jan 1, 1975

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.'-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By P. W. Neurath

IN recent years the domain theory of ferromag-netism has been put on a sound experimental and theoretical basis. But its application to one of the most widely used high quality magnetic materials, the cold-rolled grain-oriented 3 pct Si-Fe used in transformer cores, has been rather difficult because of the complexity of the domain structure of the poly crystalline sheet material. This paper presents some experimental data for this material, showing the relation between plastic and elastic stresses, 60-cycle watt losses, and the domain structure as observed visually. Only a very tentative qualitative explanation of the effects will be attempted. Some initial results were reported earlier.'

Jan 1, 1957

W. H. BASSETT,* Waterbury, Conn. (written discussion ?).-The effect of reducing gases on hot solid copper has been known for many years in the copper industry, and precautions taken to guard against it in the general practice in copper heating and annealing. In view of the statement that Bengough and Hill, in 1910, were the first to suggest the possibility of the formation of gas within the copper itself, it is interesting to note that in Harper's Magazine for April, 1904, an article, "Life and Diseases of Metals," by Professor Heyn, illustrated the effect of reducing gases on copper by a photograph, which is shown in Fig. 1. This he entitled "Copper burst asunder by disease." After referring to the effect of hydrogen on steel, he makes the following remark: "Similar symptoms of poisoning, caused by hydrogen or gases containing hydrogen (as gas for lighting purposes), are apparent in copper when exposed to red heat. Not every kind of .copper is susceptible to this poisoning in equal degree. Copper per-fectly free of cuprous oxide is entirely exempt from poisoning. Most of the various coppers of commerce, however, contain cuprous oxide, formed during the smelting process while exposed to atmospheric influences. In such coppers, containing cuprous oxide, hydrogen causes a terrible disease on the copper being heated red hot. The copper bursts asunder and is permeated by cracks. This disease is practically incurable and can be eradicated by resmelting only. The results work destructively according to the amount of cuprous oxide contained in the copper." It must have been evident to Professor Heyn, as it was to us on reading this article, that the bursting asunder of the copper was clue to the formation of steam. Practical copper heaters have known for many years that it was quite possible to produce blisters, or large gas holes, in the interior of copper plates or bars by heating to a high temperature in reducing gases. These facts, of course, do not detract from the value of the study of the action of hydrogen gas that has been made by Mr. Pilling, but simply illustrate that the practical effect of reducing gases on furnace-refined copper has long been a troublesome factor in the heating or annealing of that metal.

Jan 1, 1919

By J. C. Irvine

Meramec Mining Co. has put into operation a crushing and conveying system on its newly established 2475-ft level, 200 ft below the lowest production. To develop this level without interrupting hoisting or mine haulage, a 15.8% decline was driven from the 2275-ft level. A 5-cu-yd LHD diesel loader and a diesel-powered drilling jumbo were put into operation midway down the decline, and were used to develop the remainder of the decline and the entire level. Development of the ore pass system to the crusher required the construction of Swedish-type dumps on the main haulage-ways of all production levels with a minimum disruption of ore haulage. Concrete was handled by both rail-mounted and rubber-tired vehicles. The system features four Swedish-type dumps with control chutes at the lower three dumps, a 42-in. gyratory crusher with attendant feeders, and an 1800-ft long roof suspended conveyor feeding two 5000-ton ore bins. The crushed ore from these bins is conveyed to the lower of the mine's two original loading stations for hoisting. The retention of the original dumping and ore pass system as an alternate route has given mine production a unique flexibility. Operation for 22 months has permitted evaluation of the system from a long-term standpoint.

Jan 1, 1973

Jan 1, 1931

By E. V. Potter, E. T. Hayes, H. C. Lukens

LARGE volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that ignite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.1.2 The close relationship between iron and man¬ganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. APPARATUS The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of I00 c.c. for a 60-cm. length. For larger changes in gas volumes; auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By W. B. Plank

I HAVE been asked by the Chairman of the Engineering Education Committee to outline what the engineering colleges would like the mining companies to do with the young engineer just, out of college. It has been suggested that, because my own personal experience has been almost entirely within the coal industry, I handle this subject from that view- point. Many thoughtful engineering educators are today wondering what effect the present employment policies of many industrial companies are going to have on the young man just starting out in his profession. Since before the World War large industrial concerns, such as those in the electrical and mechanical industries, have gone to the colleges to interview 'likely graduates until today there has developed in most of our engineering colleges, especially in the eastern part of the country, what appears to be a lively competition on the part of these companies in bidding for the young graduate engineer. The employers of mining engineers, with one or two exceptions, have not yet begun to enter this competition. It remains to be seen how serious this situation will become, how it will affect the training of other engineers, and what effect, if any, it will have on the mind of the young man about to enter college who may be inclined to take up mining engineering, but who gains the impression from this well advertised employment service just mentioned that there is no opportunity for him in the mineral industry as com- pared with the opportunities offered in say civil, mechanical, and electrical engineering.

Jan 1, 1929

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By M. R. Geer

THE increase in the number of coal-cleaning plants employing dense-medium processes occurring since 1946 is especially interesting when viewed historically. Both sand and magnetite were introduced as material for heavy mediums at about the same time, sand in the Chance process in 1921 and magnetite in the Conklin process in 1922, but from that point on their records diverge. The Chance process enjoyed a steady growth from its inception, whereas no additional magnetite plants were built in the United States for over 20 years. Then, following the close of the World War 11, magnetite was again introduced, this time with marked success. During the following years some 47 plants employing magnetite medium were built.

Jan 7, 1953

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By H. Reinhardt, P. Haglund, J. Rydberg, B. Lunden

As legislation to minimize pollution in effluent streams becomes stricter, it is important to treat used acid pickling baths before discharge. This is usually achieved by neutralization of the acids and precipitation of the dissolved metals in such a way that neither acids nor metals can be re-used. A process has been designed and tested on a pilot plant scale to recover both acids and metals from a stainless steel pickling bath leaving only Na2SOs in the effluent. In this process, H2SOr is added to the spent pickling liquor and the recovery of the pickling acids HN03 and HF is achieved by solvent extraction, using TBP in kerosene as the organic solvent. The extracted acids are stripped with water, giving an acid concentration high enough for direct use in the pickling bath. Molybdenum is also extracted by TBP and is recovered in a separate step. The other metals, Fe, Cr and Ni, are precipitated from the raffinate as hydroxides, dried and recycled to the metal process. In evaluating this process, comparative experiments with mixer-settler and pulsed column have been performed. The process described is being considered for use by a Swedish company pickling 70,000 tons per annum of stainless steel.

Jan 1, 1973

By William Barrett

IN order properly to evaluate the data related to geomagnetic surveys, it is highly desirable to have all the available information concerning the magnetic properties of the, involved media. This is true of surface as well as subsurface formations and becomes of increasing importance as advancement in instrumental and interpretative technique permits the analysis of relatively slight magnetic reflections of buried masses. Since the magnitude and areal distribution of the usually complex resultant magnetic field at the surface of the earth is a function of the susceptibility1 of the involved matter, it necessarily follows that susceptibility determinations will afford valuable data for geophysical correlation. The present method was developed to meet the need for routine analysis of specimens in the geomagnetic laboratory where it was felt that general utility, ruggedness, ease of manipulation and reproducibility of results was of greater importance than extreme sensitivity.

Jan 1, 1931

By M. J. Humenick, K. Garwacka

A laboratory experimental research project was conducted to evaluate the use of chlorine for the oxidative destruction of residual ammonia that may remain in ground water after in-situ uranium solution mining operations. The work tested the idea of injecting high strength calcium hypochlorite solution into the mining zone to convert ammonia to nitrogen gas as a final cleanup process for ammonia removal from the ground water system. This paper details ammonia removal efficiency as a function of chlorine dose, reactant, and product material balances, and how the concept may be used as a final ground water restoration process.

Jan 1, 1985

By Franz Wever

ACCORDING to Tammann,1 the explanation of the effect of mechanical deformation in producing changes in the properties of metals is one of the most important problems of physical metallurgy, taking rank with the study of the constitution of alloy systems; and this problem has long attracted-the attention of practitioner and scientist alike. Its solution was not advanced materially until Tammann2 set up his translation hypothesis with its crystallographic basis, while other hypotheses, such as the amorphous metal hypothesis of Beilby3 and Rosenhain,4 have been shown by more intensive studies to be less and less satisfactory. The principles of the Tammann translation hypothesis have proved to be useful even up to today and in spite of all of the recent accumulation of experimental data, while the differences of opinion which have arisen relate to the extent to which the hypothesis accounts for the observed changes in properties and to what extent further assumptions are necessary. Stimulated by the proposals of Tammann, there soon developed a lively experimental activity which aimed at the elucidation of the structural or crystallographic changes produced by the mechanical deformation of metals. Parallel movements of crystal "blocks" along definite crystal slip planes had already been observed by lowing and Rosenhain5 in 1900, in metals which had been moderately deformed but without shedding light on the crystallographic nature of the processes accompanying more severe deformation. The solution of this important problem was not advanced until a much later date, or until the methods of X-ray crystal analysis had become available. Shortly after the discovery of the diffraction of X-ray by crystals, symmetrical diffraction effects were

Jan 1, 1931

By C. S. Allen

With increased coal production and mechanization of coal mines many transportation problems arise. The main objective is to bring the coal to the tipple or dump it as quickly as possible. Larger and faster haulage locomotives or two locomotives connected in tandem have been adopted to solve the problem. Motor equipment, gears and control systems of locomotives to be placed on these hauls are carefully studied to meet these requirements, by an analysis of motor characteristic curves with the corresponding tractive effort curves, in order to determine the correct load for maximum efficiency and to determine the approximate schedule. Control equipment is usually considered to be the controller and resistance. Sometimes accelerating curves are calculated in order to obtain smooth starting in the least possible time without slipping the wheels. Train control is very important, but why limit this to acceleration ? Deceleratien-or-retardation of the locomotive is a part of the train control and should be given as much consideration as the control for acceleration. Types or Braking Common braking systems for mine locomotives utilize screw-type mechanical brakes, dynamic braking and the air brake. For gathering and haulage locomotives, the srrew-type mechanical brake is regarded as standard. A brake of this kind cannot be applied without much effort and lapse of time. Motormen, like other people, follow the path of least resistance, and therefore have their brakes ready for instant application—which means that the shoes are virtually dragging. Even then, a motorman bucks and plugs the motors to gain time and avoid as much physical effort as possible. "Bucking of motors" consists in turning the reverse cylinder of the controller to parallel position corresponding to the opposite direction of travel while the locomotive is in motion, without applying power from an external source. When this occurs, both motors tend to act as series generators, because the armatures are revolving and there is residual magnetism in the field circuit. Owing to slight differences in motor manufacture, one of these will generate a slightly higher potential and will overcome the generated voltage of the second and tend to drive it as a motor in the reverse Direction.-This action retards the locomotive but is very severe on the segments of the reverse cylinder and on the motor commutators. "Plugging motors" is the application of power to the motors corresponding to the opposite direction of travel. In order to "plug" the motors it is necessary first to "buck,, them (which reverses the connections to the motors) and then to apply power. Theoretically, this should be done only in an emergency, but locomotives in mine service are frequently thus treated., Dynamic braking is retardation of the locomotive by the motors acting as generators, which take no power from the line.

Jan 1, 1942

By C. S. Allen

With increased coal production and mechanization of coal mines many transportation problems arise. The main objective is to bring the coal to the tipple or dump it as quickly as possible. Larger and faster haulage locomotives or two locomotives connected in tandem have been adopted to solve the problem. Motor equipment, gears and control systems of locomotives to be placed on these hauls are carefully studied to meet these requirements, by an analysis of motor characteristic curves with the corresponding tractive effort curves, in order to determine the correct load for maximum efficiency and to determine the approximate schedule. Control equipment is usually considered to be the controller and resistance. Sometimes accelerating curves are calculated in order to obtain smooth starting in the least possible time without slipping the wheels. Train control is very important, but why limit this to acceleration ? Deceleratien-or-retardation of the locomotive is a part of the train control and should be given as much consideration as the control for acceleration. Types or Braking Common braking systems for mine locomotives utilize screw-type mechanical brakes, dynamic braking and the air brake. For gathering and haulage locomotives, the srrew-type mechanical brake is regarded as standard. A brake of this kind cannot be applied without much effort and lapse of time. Motormen, like other people, follow the path of least resistance, and therefore have their brakes ready for instant application—which means that the shoes are virtually dragging. Even then, a motorman bucks and plugs the motors to gain time and avoid as much physical effort as possible. "Bucking of motors" consists in turning the reverse cylinder of the controller to parallel position corresponding to the opposite direction of travel while the locomotive is in motion, without applying power from an external source. When this occurs, both motors tend to act as series generators, because the armatures are revolving and there is residual magnetism in the field circuit. Owing to slight differences in motor manufacture, one of these will generate a slightly higher potential and will overcome the generated voltage of the second and tend to drive it as a motor in the reverse Direction.-This action retards the locomotive but is very severe on the segments of the reverse cylinder and on the motor commutators. "Plugging motors" is the application of power to the motors corresponding to the opposite direction of travel. In order to "plug" the motors it is necessary first to "buck,, them (which reverses the connections to the motors) and then to apply power. Theoretically, this should be done only in an emergency, but locomotives in mine service are frequently thus treated., Dynamic braking is retardation of the locomotive by the motors acting as generators, which take no power from the line.

Jan 1, 1942

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961