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By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8'10'11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

By J. D. Forrester

Developments of the year make geologist's industrial position even more secure and important-Professional shortage remains acute-

Jan 2, 1953

Constraints in the location, process selection, and operation of the modern zinc refinery brought about by the heightened environmental awareness of the public were explained by Sanjoy Shome, project engineer for Kaiser Engineers Inc.

Jan 11, 1977

By R. N. Stevens

Any consideration of the errors involved in determination of ?gb by previous workers should discuss their experimental methods in terms of the appropriate theoretical equation; this the authors have not done in a number of cases. To facilitate the present

Jan 1, 1969

By A. M. Ribe

Briefly stated, the mission of the traffic manager (currently called a transportation services manager) is to enable his firm to utilize to its best economic advantage the various systems and modes of transportation available to it to bring in its raw materials and ship out its finished products. The function of the transportation services manager is perhaps of more relative importance in industrial minerals operations than in industry and trade generally.

Jan 1, 1970

Jan 1, 1903

By M. B. Ramachandra Rao

THE occurrence of copper ores at Garimenapenta, 14° 59 min 30 sec N Lat., 79° 33 min 10 sec E Long., in Nellore district, Madras State, India, has been examined and investigated on numerous occasions during the past two centuries.1 No tangible orebody was ever located as a result of all the ex-

Jan 4, 1953

Jan 1, 1913

By James Douglas

Once—and fortunately only once—before this occasion, was it my sad duty to express the loss we had sustained in the death of an eminent member. Dr. T. Sterry Hunt* was a student of chemistry who, by his investigations into the properties of the elementary bodies, had assisted emineiltly in the progress of the technical arts, and, more than any American of his generation, had helped to lay the foundations of chemical geology. William Earl Dodge, whose death we deplore to-day, occupied a rank not les~ importaiit in the army of industrial workers

Jan 1, 1904

Jan 1, 1920

By Paul Weaver

DURING 1932 the amount of geophysical surveying carried out as a part of oil-field development in¬creased, particularly in the Gulf Coast of Texas and Louisiana. Here the most intensive geophysical activity was displayed in the discovery of domes and prospects several years ago, after which there was a period of relative inactivity. This year many of the leases required development and geophysical methods were used to obtain pictures of the detailed structures. These were almost exclusively gravity and reflection-seismograph surveys and for the first time this latter method was generally used by oil operators to construct subsurface contours. The total number of geophysical troops in this territory increased from 16 to 40 during the year.

Jan 1, 1933

Jan 1, 1885

By J. H. McCarthy, J. M. Botbol, R. B. McCammon, G. H. Gott

Four areas have been identified as favorable drill site locations for determining whether a suspected porphyry copper deposit exists in Rowe Canyon, NV. Favorability is bated on the similarity to a deposit model constructed from geochemical data for the porphyry copper deposit near Ely. Favorability is defined as the coincident number of positive anomalies for zinc, silver, aresenic, antimony, and iron. The favorable areas coincide with an observed magnetic high and areas in proximity to major faults.

Jan 1, 1983

The regular activities of the Institute are financed mainly by income derived from members' dues, from advertising in MINING ENGINEERING, JOURNAL OF METALS, and JOURNAL OF PETROLEUM TECHNOLOGY, and from the sale of publications to the public In addition, collateral activities and special projects are financed each year by means of income - from endowed funds controlled and administered by the Institute. An active effort is being made to increase the endowment funds of the Institute through a standing committee, of which Wilfred Sykes is Chairman, and of which the other members are N G

Jan 1, 1952

By Roshan B. Bhappu, George M. Potter

The chemistry involved in the recovery of gold and silver from natural resources through hydrometallurgical and pyrometallurgical processes is reviewed. Process metallurgy for the cyanidation, activated carbon adsorption, carbon stripping, and electrowinning of gold and silver is discussed. The application of zinc sodium sulfide use for silver recovery from cyanide solutions is covered. Electrooxidation, other oxidation methods and roasting processes for problem ores and concentrates containing organic carbon and impurities such as arsenic, antimony, and tellurides are summarized. The smelting of cathodes, precipitates, and other products, and the various wet and furnace steps in separating dore metal are also reviewed.

Jan 1, 1981

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman A. D. BEERS, Secretary, 55 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. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. 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.

Jan 3, 1917

By L. D. Lash

The key to successful liquid-liquid extraction is the solvent. First, and most important, it must be highly selective for the metal desired and yet reject other metal ions present; second, the ideal sol- vent is completely insoluble in the aqueous feed liquor; third, it has rapid phase separation and will not form emulsions; and, fourth, low cost is desirable, since losses occur even though the solvent is recycled. For this application a solvent known as DDPA (dodecyl phosphoric acid) was chosen since it closely met these requirements. DDPA is a long-chain alkyl phosphate developed for AEC by Oak Ridge National Laboratories, Dow Chemical Co., and the U. S. Bureau of Mines. The long chain contributes to low solubility in the aqueous phase and to high extracting power from acidic sulfate solutions, whereas the alkyl phosphates generally exhibit high selectivity for uranium solutions.

Jan 11, 1958

By Carlos Kovacs-Figueroa

Complying with air pollution regulations created the need to dispose of increased sulfuric acid production by the Morenci smelter. As a result, a two-module leaching plant was constructed to leach Morenci flotation tailings. The leaching plant was equipped to perform the following operations: leach feed pumping, agitated leaching, two-stage countercurrent decantation, neutralization of leached tailings, and copper precipitation. Ancillary facilities were provided for neutralizer and flocculant preparation as well as precipitant handling and recovery of precipitates. Plant control is automatic from a central control panel supervised on a shift schedule by one operator and two helpers. Construction of the first module was initiated in April 1973 and leaching of tailings commenced in November 1974. Construction of the second module began in January 1975 and was completed in November 1975.

Jan 1, 1977

By K. H. Nimerick, G. P. Laflin

Laboratory data and field tests indicate that substantial losses of valuable coal can be caused by wind erosion. Wind tunnel tests show the effects of wind velocity and particle sizing on the amount of coal lost while in transit. Different coals were evaluated to determine the variables associated with wind erosion. The erosion losses can be substantially reduced by using a binder, or crusting agent, to consolidate the surfaces of the coal into a solid mass which resists erosion. This not only reduces economic loss but minimizes polllution.

Jan 1, 1980