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By G. V. Cullen, N. G. Siviour

It has previously been reported that metal loadings of up to 6.8 m. eq/g. of dry coal can be obtained by contacting brown coal or lignite with ammoniacal solutions of ammine forming metals. Application of equilibrium expressions to further experimental results indicates that the extraction is by ion exchange, that the exchange is divalent-univalent for Zn, Cd and Ni, but is mainly univalent-univalent for Cu, and that to obtain reasonably uniform values for the equilibrium constants correction formulae must be applied to compensate for multiple functionality of the coal and its pH dependence in ion exchange. The results are shown to be consistent with the hypothesis that metal ammine complex cations are exchanged for protons derived from carboxyl and/or phenolic hydroxyl groups in the coal.

Jan 1, 1981

The following is a, partial list of members and guests who called at Institute headquarters during the period Aug. 10, 1917, to Sept. 10, 1917. L. P. Barrett, Ann Arbor, Mich. Milo W. Krejci, Great Falls, Mont. H. J. Brown, Ridley Park, Pa. Chas. N. La Porte, Peoria, Ill. George M. Cheney, Guayaquil, Ecuador. Askin Nicholas, Bismuth, Australia. W. Lorrain Cook, Chicago, Ill. C. Edwin Nighman, Butte, Mont. John J. Croston, Atlanta, Ga. W. L. Remick, Norfolk, Va. A. F. Duggleby, Santiago de Cuba. T. C. Roberts, Jerome, Ariz. Geo. A. Easley, La Paz, Bolivia. Burr A. Robinson, New Haven, Conn. Burr J. French, Magdalena, Jal., Mex. J. L. Schueler, Peoria, Ill. A. D. R. Galloway, Komfrodua, W. Af. Walter L. Steele, Van Horn, Tex. P. R. Hines, Milwaukee, Wis. F. J. S. Sur, Denver, Colo. T. H. Jenks, Wickenburg, Ariz. C. A. Thomas, Dawson, Y. T., Canada. Paul S. King, Wilmington, Del. E. E. White, Ann Arbor, Mich. Harry Wolf, Golden, Colo. L. W. Bahney has left the Sheffield Scientific School, Yale, to become metallurgical engineer with the Scovill Manufacturing Co., Waterbury, Conn. H. B. Barling, formerly chief engineer of Breitung & Co., of New York, has been appointed manager of the mining department.

Jan 10, 1917

THE paper on "Specific Efficiency of the Blast Furnace" by Richard Franchot, which was pub-lished in the September issue of MINING AND METALLURGY, was presented for discussion at the Pitts-burgh meeting. The session opened with a discussion among S. P. Kinney, Mr. Franchot, and J. N. Reese as to the methods and results in sampling for cyanides in the blast furnace. This is covered in detail in writ-ten discussion below. T. T. Read objected to the use of the term specific efficiency as likely to be confusing. The blast furnace has to perform the function of reducing Fe, 03 to Fe as well as that of fusing the metal and, since the reduc-tion of Fe, 0? involves a CO equilibrium, it seems mis-leading to calculate efficiency on the basis of burning the , all carbon to CO? since it is not possible. Mr. Franchot replied that he used the term in the sense defined by Richards in his "Metallurgical Calculations;" but a subsequent search failed to reveal the term in Richards, who says (page 245, 1st edition): The practical conclusion is that a blast furnace generates in itself not much over 40 per cent of the calorific power of the fuel used, and rejects nearly 60 per cent; by using part of the waste gases to heat the blast, however, some of this rejected heat, to an amount representing net 5 to 10 per cent of the calorific power of the fuel used, is returned to and injected bodily into the furnace, thus rendering available for the purpose of running the furnace about 50 per cent of the calorific power of the fuel as a maximum. The efficiency with which the furnace applies this 50 per cent usefully to the objects of the reducing and smelting is another question for investigation.

Jan 2, 1927

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

Jan 11, 1917

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By Cyril Stanley Smith

The method of thermal analysis, so important in the development of metallographie science, has of recent years been falling into disuse owing to the development of other physical methods which give result's easier of interpretation and which can be used for the study of either equilibrium or transitional conditions because they do not require a continuously changing temperature. Nevertheless thermal analysis remains useful in the study of reactions that take place rapidly, and the simplicity of the experimental technique and the general availability of the apparatus involved are point's in its favor. Theoretically, thermal analysis is capable of giving specific and latent hat measurements and therefore should permit the study of reactions on a more fundamental basis than any other method. It is, however,difficult or impossible to obtain quantitative heat measurements from cooling curves obtained in the usual way. Even if the furnace containing the sample is cooled or heated at a linear rate, or if a gradient furnaec is employed to maintain a constant rate over a large range of temperature, the heat flow from or to the specimen depends on its previous history, for the difference of temperature between the specimen and its surroundings varies. The emissivity of the specimen surface, moreover, is unlikely to be constant. The able mathematical analysis by Russrll,1 although it prevent,s misinterpretat,ion of data, has an effect rather the reverse of that intended, and leaves the reader doubtful of the possibility of ever obtaining quantitative results from thermal curves. Nothing can be done to apply thermal analysis t'o the study of equilibrium conditions of reactions that arc not completed at rates of temperature change above about 1° C;. per minute, and this unfortunatetly excludes most solid transformations in alloys.† For the determination of liquidus

Jan 1, 1940

By Cyril Stanley Smith

The method of thermal analysis, so important in the development of metallographie science, has of recent years been falling into disuse owing to the development of other physical methods which give result's easier of interpretation and which can be used for the study of either equilibrium or transitional conditions because they do not require a continuously changing temperature. Nevertheless thermal analysis remains useful in the study of reactions that take place rapidly, and the simplicity of the experimental technique and the general availability of the apparatus involved are point's in its favor. Theoretically, thermal analysis is capable of giving specific and latent hat measurements and therefore should permit the study of reactions on a more fundamental basis than any other method. It is, however,difficult or impossible to obtain quantitative heat measurements from cooling curves obtained in the usual way. Even if the furnace containing the sample is cooled or heated at a linear rate, or if a gradient furnaec is employed to maintain a constant rate over a large range of temperature, the heat flow from or to the specimen depends on its previous history, for the difference of temperature between the specimen and its surroundings varies. The emissivity of the specimen surface, moreover, is unlikely to be constant. The able mathematical analysis by Russrll,1 although it prevent,s misinterpretat,ion of data, has an effect rather the reverse of that intended, and leaves the reader doubtful of the possibility of ever obtaining quantitative results from thermal curves. Nothing can be done to apply thermal analysis t'o the study of equilibrium conditions of reactions that arc not completed at rates of temperature change above about 1° C;. per minute, and this unfortunatetly excludes most solid transformations in alloys.† For the determination of liquidus

Jan 1, 1940

PRESIDENT AND DIRECTOR SCOTT TURNER WASHINGTON, D. C. PAST PRESIDENTS AND DIRECTORS WILLIAM H. BASSETT WATERBURY, CONN. ROBERT E. TALLY JEROME, ARIZ. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1932

By D. Watson, T. J. N. Grainger-Allan

A technique for studying the mechanism of the froth flotation process in which continuous froth removal does not take place but, instead, an equilibrium is reached between froth and pulp is described. A flotation cell, specially designed to facilitate equilibration, and froth and pulp sampling procedures are described. The main advantage of the technique is that the ability to measure the steady-state froth height allows froth-stability effects to be separated from pulp-process effects. In the flotation of hematite front quartz, linear relationships are found between airflow rate and froth height and between airflow rate and the ratio at equilibrium of mass of values in froth to mass of values in the pulp. A simple mechanistic interpretation of these results is given. It is suggested that froth-stability effects may play a more important role than hitherto allowed. In particular, the way in which concentration and size distribution of gangue particles may affect overall flotation rate is shown.

Jan 1, 1975

By M. E. Wadsworth, R. D. Groves, B. W. Madsen

Experimental results obtained from large-scale (7 ton), long-term (500 days) leaching of low-tenor copper sulfide ores were interpreted by a geometric model involving the movement of a reaction zone through the ore fragments. The postulated leaching mechanism involved mixed kinetics and included diffusion of the reacting species through the host rock and a chemical reaction at the surface of the mineral particles. Ore properties which were considered were Ore particle size and shape, grade of ore, and mineral content. Excellent agreement between the mixed kinetic model and the laboratory leaching results was obtained when -1/2-in. ore particles were not included in the leach. Also, a satisfactory prediction of copper recovery from +1/2-in. ore with a different particle size distribution was made; however, it was necessary to modify the shape factor in the model. Prediction of copper recovery from an ore sample which included the -1/2-in. fine fraction and leaching for 460 days was 56.5%, and the recovery from leaching was 47.0%. The presence of fines caused solution channeling and a deficiency of oxygen which inhibited the leaching rate. Also, compaction of fines around coarser particles interfered with circulation around the ore particles, and bulk solution transport probably was a rate controlling factor.

Jan 1, 1976

By R. F. Shurtz

The author proposes a method used with some success on a magnesite deposit at Gabbs, Nev. He believes this procedure to be more sound than the blind practice of assigning uniform quality to large, soinetimes vast blocks or ore on the basis of analyses made of a small number of samples. When an ore deposit is evaluated on the basis of core sampling, questions always arise as to how much weight should be given the various sample grades and how the deposit should be divided into specific volumes assigned to corresponding grades. For a tabular deposit it is customary to use the so-called zone-of-influence. This zone is usually defined as the polygon in the plane of the deposit having corners halfway between a given core drill intersection and each of the nearest neighboring intersections. The volume of the ore in this polygon is assigned the analysis obtained from the drill core taken at the intersection. In massive or irregular deposits, volumes of various shapes may be defined with respect to the locations of drill core samples. These volumes may be regarded as three-dimensional zones-of-influence; the theory involved in assigning the values of the central analyses to the ore in the volumes is the same as that used in the case of a tabular deposit. The zone-of-influence method was used in evaluating one of the magnesite deposits at Gabbs, Nev.'-"

Jan 1, 1960

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By Thomas M. Drown

The process for determining phosphorus in iron now in most general use in the laboratories of iron and steel works, is, I think, the one proposed bv Mr. Emmerton." In this process the solution of the iron for precipitation by ammonium molybdate is effected by treating the iron with nitric acid, evaporating to hard dryness in a dish, taking up with hydrochloric acid and driving off the greater portion of the hydrochloric by nitric acid. This procedure accomplishes, first, the destruction of all the carbonaceous matters; and, second; it renders all the silica insoluble. Experience has proved the former—the complete oxidation of the carbon—to be absolutely essential; but the explanation usually given, namely, that unless the carbon compounds are destroyed they will have a solvent action on the yellow precipitate, I am inclined to

Jan 1, 1890

[Trans. No. Place Date Vol. Page 1, Wilkes-Barre, Pa.* .... May, &apos;71.. 1 3 2. Bethlehem, Pa Aug., &apos;71.. 1 10 3 Troy, N. Y Nov.,&apos;71.. 1 13 4. Philadelphia, Pa Feb., &apos;72.. 1 17 6. New York, N. Y •.... May, &apos;72.. 1 20 6. Pittsburgh, Pa..:.Oct., &apos;72.. 1 25 7. Boston, Mass Feb., &apos;73.. 1 28 8 Philadelphia, Pa.&apos; May, &apos;73.. 2 3 9. Easton, a Oct., &apos;73.. 2 7 10. New York, N. Y Feb., &apos;74.. 2 11 11. St. Louis, Mo.* May, &apos;74.. 3 3 12. Hazleton. Pa Oct.. &apos;74.. 38 13. New Haven, Conn Feb., &apos;75.. 3 15 14. Dover, N. J.&apos; May, &apos;75.. 4 3 16. Cleveland, 0 Oct., &apos;75.. 4 9] [ ]

Jan 1, 1925

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country&apos;s war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country&apos;s war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By C. D. Broadbent

INTRODUCTION The slope stability research plan at Kennecott was developed to serve the specific needs of large, open pit mines; primarily those developed in faulted and highly-fractured intrusive deposits. The program emphasis is on applied research; being defined in this case as research into the engineering mechanics of discontinuous rock and into the related rock property survey and slope design techniques. The program has been developed in phases, with each phase organized to explore more thoroughly the most significant findings of previous work and to improve on techniques found to be applicable. The current work is based on principles developed early in the program and that show promise of having engineering and economic value. A brief summary of the conceptual principles of the program is given to put our current work in context. This is followed by a review of the two cooperative programs done with the U. S. Bureau of Mines. Most recent work is described and interpreted in terms of practical slope design. Although failure-free slopes are a desirable goal, it is recognized that some failures will occur when overall slope designs approach a calculated safety factor of one. A discussion of failure control research is therefore offered. BACKGROUND In 1965 Kennecott management specified that a slope stability technology must be used to achieve optimum development of ore resources. The subject was carefully explored and by 1960 it had been established that there was no technology readily applicable to open pit slope design. Therefore, in 1962, Kennecott Copper Corporation and the U. S. Bureau of Mines agreed upon a cooperative research program having the objective of developing a mine slope stability science. One of the first decisions made by the cooperating groups was that the research must be conducted primarily in the field and not in the unrealistic environments of a laboratory. Accordingly, the Kimbley Pit, an abandoned mine once operated by Kennecott&apos;s Nevada Mines Division in Nevada, was selected for the full-scale research. Fortunately, there was near-universal agreement on the basic stability parameters and thus on the areas to be investigated. These parameters were acknowledged to be: (1) anisotropy (generally due to faults or joints), (2) stress, and (3) water; in that order of importance.

Jan 1, 1972

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

Jan 1, 1955