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By W. J. Verner, J. R. Lucas

Billions of tons of bulk solid materials are processed through our industrial plants each year, and the tonnage is steadily rising. It has been estimated that for every dollar spent in industry as a whole, approxinlately 30 cents is consumed in the handling of bulk solid materials. It is in this category that tremendous savings are possible through the use of improved techniques. Since World War 11, the mining, steel, chemical, and grain industries, among others have made use of increased materials-handling automation in order to gain some of these savings. However, in a chain of automatic operations, every link must be completely reliable, for if there is a single failure, the whole system immediately becomes ineffective. Only too often the weak link in the chain proves to be the flow of bulk solids from bins. To contribute to the fundamental knowledge in this area, a research study has been continuing at The Ohio State University. The principal objective of the investigation has been to study the internal stresses existing in confined bulk solids. LITERATURE SURVEY Literature studies have revealed that many outstanding people have made contributions to the field of bulk solids. For instance, C. F. Jenkin,1 suggested: a. The pressure on a bin wall is not directly proportional to the depth beneath the surface of material in the bin. b. The vertical pressure distribution on the base of a bin is not actually uniform but is a variable. c. Arches form in bins as a result of very small deformations of the material in the bin. This deformation causes a series of gaps to appear, and consequently causes the disappearance of diagonal forces that cannot act across these gaps. The removal of the diagonal forces causes horizontal forces to be introduced which seem to be the chief cause of arching. 11. A. Janssen,4 in 1895 in connection with his experiments on bins, derived a differential equation to describe both the lateral and vertical pressure in bins with vertical sides. This represents a significant contribution to bulk solid theory, and thus its solution is reproduced as follows: L = KV = RW/U' [l-e -U'KY/R] I where L is the lateral pressure of the bulk solid in psf., V is the vertical pressure of the bulk solid in psf., K is the ratio of the lateral pressure to the vertical pressure at any point, R is the hydraulic radius of the bin in feet, W is the density of the bulk solid in lbs. per cubic feet, U' is the coefficient of friction between the stored material and the bin wall, and Y is the head of material above the point in question in feet. In 1903, Jamieson,6 in an elaborate series of experiments on full sized bins measured vertical and lateral pressures by hydraulic diaphragms. He determined many values for mediums of corn, wheat, peas, and flaxseed. In 1951, Caughey, Tooles, and scheer3 measured both lateral and vertical pressure in deep bins by using strain guages on steel bands. Values were calculated for cement, gravel, sand, soy beans, shelled corn

Jan 1, 1961

By W. L. Remick

The hydrotator coal-cleaning process was developed as an economic necessity to meet the ever-increasing demand for an inexpensive method of cleaning coal down to the sizes ordinarily referred to as "dust." As the most urgent demand seemed to be in the anthracite field, all experimental work has been conducted in that territory during the past two years, with the exception of a few months during the strike of 1925-26, when some experiments were performed in the Alabama bituminous fields. The first commercial plant was constructed at the Middle Creek Colliery of the Philadelphia & Reading Coal & Iron Co.,. Pottsville, Pa. This plant is now operating. Application The field of application of the process is: 1. Cleaning anthracite fines, ordinarily described as "slush" or "silt." Slush contains all sizes from 3/32 in. down to and including I(dust." (Anthracite passing a 3/32-in. mesh is also referred to as No. 2 Barley and No. 4 Buckwheat.) 2. Cleaning sizes too fine for recovery by other methods. 3. Removal of coal from sand circulated in the Chance sand-flotation process. 4. Cleaning of bituminous sizes from % in. down to "dust." 5. As equipment for the performance of the froth flotation process. 6. Other separating, extraction and washing processes which may be considered outside the realm of coal cleaning. Principle of Operation Fig. 1 shows the method of classification practiced under the Hydrotator patent.' In coal cleaning the machines are operated as "hindered settling" classifiers, the flow of solids and liquids being so controlled that the units may be combined in series.

Jan 1, 1927

By H. E. Elliott, R. S. Busk, A. T. Peters

One of the problems of the fabricator of metals and alloys is the propensity of some composition rarnges toward abnoermal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, 9 per cent A1, 2 Per cent Zn, 0.2 Per cent Mn) and G alloy (Mg, 10 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other meta1s- Jeffries and Archer1 have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. Before recent developments, this phenomenon of abnormal local grain growth Was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. I) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The DOW Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germinasium since this term has been definedl as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By J. W. Downey, A. E. Dwight, R. A. Conner

THE MgCu2 type Laves phase has been observed in the thorium-osmium and thorium-iridium systems. Two alloys corresponding to ThOs2 and ThIr, were prepared by arc melting a 5-g charge in a water-cooled copper. crucible. Both alloys were very brittle. X-ray diffraction patterns were obtained using filtered Cu and Co radiation with a Straumanis-type DeBye-Scherrer camera. The a,, values as shown in Table I were obtained by a Nelson-Riley extrapolation. The structure belongs to space group Oh7-Fd3m. Relative intensities for each of these compounds were calculated on the assumption that 8 thorium atoms occupy (a) positions and 16 osmium or irid-ium atoms occupy (d) positions. The calculated intensities are the product of the Lorentz-polarization factor, the multiplicity factor and F', the structure factor, neglecting the absorption and temperature

Jan 1, 1959

By C. P. Melloy

INTRODUCTION Ventilation practice at Isa Mine has been evolving since underground mining began in 1931. Much fundamental work has been conducted and reported regarding the primary ventilation system [Mathews K.E. et a1 (1967) and Brown J.R., Fisher T.H., Gibson K.L. (1979) 1. However, ventilation networks for subsystems such as open stopes, have evolved with experience. This paper outlines current ventilation practice for open stoping. Mount Isa Mine The mine is located in semi-arid North-West Queensland, Australia, and currently produces 20 000 tonnes of copper ore and 10 000 tonnes of silver-lead-zinc ore daily in each five day working week. Mining extends over a north-south strike length of 3.5 km with a maximum width across dip approaching 1 km, and is to a depth of 960 m (Figure 1). At present approximately 90% of the mine's copper production is from the 1100 Orebody, which contains ore reserves of 121 million tonnes of 3.2% copper. Open stoping is currently the mining method employed, and is used for primary stoping and pillar recovery adjacent to cement fill walls. The development of stoping methods in the 1100 Orebody has been documented by Kirkby R.W., Blair J.R., and Hutton R.C. (19781, Hornsby B. and Sullivan B.J. (1978), and Alexander E.G. and Fabjanczyk M.W (1981). As many as thirteen open stopes may be producing concurrently in the Orebody (Figure 2). The multiple silver-lead-zinc orebodies containing reserves of 54 million tonnes of 150 g/t silver, 6.4% lead and 6.5% zinc, are mined by open stoping, and cut and fill techniques. These methods have been documented by Goddard I.A. and Bridges M.C. (1977 1, and Goddard I. A. (1981 1. Only the ventilation of the 1100 Orebody open stopes will be discussed. However, the same ventilation philosophy is employed in open stope design in the lead orebodies.

Jan 1, 1981

Map

Jan 1, 1941

By J. F. Myers, F. M. Lewis

C. G. McLACHLAN*-I have read this paper with considerable interest and wish to congratulate the authors on the care with which they carried out their experiments and for the detailed sizing data they have presented. 011 the other hand I do not feel that these data establish their contention that "with other factors the same, the work accomplished in a fine crushing rod mill is directly proportional to the rotating speed." My reason for making this statement is that their conclusion is based on the percentage of minus 65 mesh material produced at each of the speeds at which their tests were run. The rod mill is, however, not a fine grinding machine and therefore figures based on minus 65 mesh production are figures outside the range at which it operates to best advantage. Further, if rod mill performance is to be judged on the production of such material it should have been established that a rod mill will produce it as effectively as a ball mill. To check this last point I have gone over some of the rod and ball mill grind-ing figures for our Waite-Atnulet operation and find that the ball mill at that property produces more minus 65 mesh material per horsepower than the rod mill. Moreover, this comparison is even more favorable to the ball mill if it is limited to minus 100 mesh production. It therefore seems to me that the most satisfactory basis on which to try to com-pare the performance of the rod mill in the present case is by taking a weighted average of all the new surface produced per horsepower. W. H. Coghill3 has published data which can be applied to the sizing figures presented by the authors, and if this is done the units of new surface per horsepower produced in the Tennessee tests are as follows: Admittedly the increment of increase in new surface per horsepower shown in the foregoing figures is not great, but its trend is nevertheless definitely in favor of slower speed operation, for the conditions under which these particular tests were run. I also feel that some information regarding liner contour should have been given as I think it will be found that a mill which is equipped with liners which lift the rod load can be run at a slower speed than a mill in which the liners are comparatively smooth. J. F. MYERS and F. M. LEWIS (authors' reply)—The position taken by Mr. McLachlan is to be respected even though we are all aware of the faults of surface considerations. As he points out. the increment of increase is very small. It is so small in fact that for all practical purposes it does not conflict with the conclusions of the paper. The authors appreciate Mr. McLachlan's comprehensive study of the data.

Jan 1, 1950

By A. G. Allten

EXAMINATION by metallographic and X-ray diffraction means of an austenitic steel containing 0.06 pct C, 1.26 pct Mn, 0.38 pct Si, 21.15 pct Ni, 18.72 pct Cr, 3.07 pet W, and 9.14 pet Mo indicated that a - phase, which had not been reported in the literature, existed in this steel. Both the s and car-bides of the M6 C type were present in the as-forged steel. The carbides dissolved completely in the aus-tenite at approximately 2200°F (1205°C). The s, however, was present at all temperatures up to the solidus temperature of the steel at approximately 2375°F (1300°C). Ferrite was not found in any condition of the steel. The faintness of some of the s lines in X-ray patterns obtained from samples of the steel made it desirable to isolate the s prior to verification of its entire pattern. It was found that the s phase could be separated from samples of the steel which had been water quenched from 2250°F (1230°C) by dis-

Jan 1, 1955

By F. C. Farnham

THERE has been very little, if any, uniformity in the reference datum used for magnetometer surveys. It has been the practice to choose a base station at which the magnetic field is assumed to be normal and call the difference in field strength between a given station and this base the anomaly at the given station. For small-scale surveys latitude and longitude corrections may or may not be applied, but for large-scale surveys such corrections usually are applied. The United States Coast and Geodetic Survey maps showing lines of equal magnetic intensity are commonly used to determine the normal latitude and longitude variation by scaling values from the map for given points and computing the change per mile north and the change per mile east. This method has been quite satisfactory for isolated surveys, but when two surveys originating at different base stations were extended until they joined, difficulty arose, not only because of discrepancies between base-station values, but also because of differences between the latitude and longitude correction factors used for the separate surveys. It is the purpose of this paper to describe a reference datum for magnetometer surveys which, it is believed, will eliminate most of the difficulty arising from this source. In order to be satisfactory, a general datum for magnetometer sur-veys should be as close as possible to the observed field and still he based on some assumed distribution of magnet poles, in order that the "normal" value of any component of the field for any given point may be computed to as many significant figures as desired. Such a field has been com-puted, and a comparison of the intensity of its vertical component with the average vertical intensity for the United States as shown by the U.S.C.G.S. map of lines of equal intensity for 1935 is shown in Fig. 1.

Jan 1, 1939

[A Aalseth, Earl P. (M 51) Geol, Amerada Petr. Corp., Box 1498, Billings, Mont. Abadie, Henry G. (M 43) Asst to Supvr of Oper, Long Beach Oil Dev. Co., 255 S. Santa Clara, Long Beach 7, Calif. Abbe, T. Waldo (A 56) Ass't Dist Oper Supt, Sun Oil Co., Beaumont, Tex. Abbott, J. L. (M 56) Partner, Pritchard & Abbott, 501, Century Bldg, Fort Worth, Tex. Abbott, Richard H. (J 51) Owner, Abbott & Howard, 422 W. Hermosa, San Antonio, Tex. Abbott, Seth J., Jr. (M 51) Tekoil Corp., .2;A6 Mercantile Nat'l. Bank. Dallas, Tex. Abbott,. William G. (M 50) Div Mgr, Rice Eng. & Op. Inc., Box 1142, Hobbs, N. M. Abderhalden, R. R. (J,59) Box 100, Carmi, Ill. Abel, Malcolm D., Gen Mgr, Bakke Oil Co., Midland, Tex. Abel, Raymond L. (M 28) Prof of Chem Engr, Univ. of Pittsburgh, Pittsburgh 13, Pa. Abel, Wayne K. (M 57) 1513 Patton Drive, Odessa, Tex.]

Jan 1, 1961

By Herbert Clark Hoover, Lou Henry Hoover

As stated in the preface, the nomenclature to be adopted for weights and measures has presented great difficulty. Agricola uses, throughout, the Roman and the Romanized Greek scales, but in many cases he uses these terms merely as lingual equivalents for the .German quantities of his day. Moreover the classic language sometimes failed him, whereupon he coined new Latin terms adapted from the Roman scale, and thus added further confusion. We can, perhaps, make the matter dearer by an illustration of a case in weights. The Roman centumpondium, composed of zoo librae, the old German ceniner of 100 pfundt, and the English hundredweight of 1112 pounds can be called lingual equivalents. The first weighs about 494,600 Troy grains, the second 721,900, and the third 784,000. While the divisions of the centumpondium and the centner are the same, the Libra is divided into 12 unciae and the pfundt into 16 unizen, and in most places a summation of the units given proves that the author had in mind the Roman ratios. However, on p. 509 he makes the direct statement that the centumpondium weighs 146 librae, which would be about the correct weight if the centumpondium referred to was a ceniner. If we take an example such as " each centumpondium of lead contains one uncia of silver", and reduce it according to purely lingual equivalents, we should find that it runs 24.3 Troy ounces per short ton, on the basis of Roman values, and 18.25 ounces per short ton, on the basis of old German. If we were to translate these into English lingual equivalents of one ounce per hundredweight, then the value would be 17.9 ounces per short ton. [ ]

Jan 1, 1950

By AIME AIME

THE program of government drilling, conducted jointly by the U. S. Geological Survey and the Bureau of Mines, has demonstrated the presence in Texas and New Mexico of potash-bearing beds of considerable importance. Information regarding the ex- tent and location of the potash deposits as presented at the non-metallic sessions was of great interest to many engineers. These subjects will be covered in greater detail in later paragraphs. The first session, with about 50 in attendance, convened at 10 a.m. on Feb. 18, with Oliver Bowles, chair- man of the Committee on Non-Metallic Minerals, pre- siding. The first paper was on "Soapstone Mining In Virginia," presented by C. W. Ryan of Lynchburg, Va. The nature and extent of the soapstone deposits of Nelson County were described in some detail. In origin, the soapstone is undoubtedly related to a basic peridotite rock though its mode of formation is some- what uncertain. This main soapstone deposit occurs in three veins, the western, middle, and eastern, the middle vein being of greatest economic importance. Methods of stripping, quarrying and milling the rock were described and the uses of soapstone were enum- erated. In discussing this paper, C. P. Berkey, of Co- lumbia University strongly favored the theory of igneous origin of the soapstone and the need for further detailed geological study. J. L. Gillson of Cambridge, Mass., stated that the Vermont and New York talc deposits were always associated with characteristic minerals, such as, a chlorite of one particular variety, siderite, amphibole, magnetite, and biotite. C. H. Behre of Cincinnati, Ohio, raised the question of parallelism in the soapstone structure and Mr. Ryan stated that such parallelism was in evidence in some parts of the deposits. H. A. Wheeler of St. Louis, Mo., also took 'part in the discussion.

Jan 1, 1929

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By C. R. Keyes

Discussion of the paper of C. R. Keyes, presented at the Chattanooga meeting, October, 190S, Bulletin No. 26, February, 1909, pp. 119 to 166. E. R. BUCKLEY, Flat River, Mo. (communication to the Secretary*) :-Some statements in the paper of Mr. Keyes relative to the nature and formation of the Ozark lead- and zinc-deposits seem to me erroneous and misleading, and I respectfully present the following criticisms, placing Mr. Keyes's original statements in quotations. Referring to the Ozark dome: (P. 127.) "It is a region that has been repeatedly upraised and planed off, until in the middle portion the oldest known' rocks only are exposed." Does he mean that the St. Francois mountains, which have always been considered as lying on the eastern flank of the Ozark dome, are the middle of the dome? Or does he mean that the Cambrian rocks of the generally-accepted middle are the oldest known rocks ? Certainly not the latter, and if the former, his idea of the middle of the dome is not in accord with that of others who are familiar with the region. (P. 138.) " . . . the ore-deposits are definitely associated with, or localized by, geologic structures of some kind that .produce in effect basins in which' the underground waters are impounded, or their flow retarded." This statement does not appear to be altogether consistent with the facts, since the ore- bodies of the Joplin district, as the rule, occur in those parts of the Mississippian formation which have a tendency to accel¬erate the flow of ground-water rather than retard it. I might name the open, breeciated ground near Joplin, Webb City, and Oronogo as especially noteworthy illustrations. The ore-bodies, everywhere, occur in positions where there must have been a free and copious circulation of dilute lead- and zinc-solutions in the presence of reducing constituents. The inequalities in the distribution of the ore-deposits are

Oct 1, 1909

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By Salinger, Herbert

WITH the large amount of metallurgical re- search work now being done and the constant effort of the engineer to effect economies of operation, I think it is a safe prediction that the next few years will see a great change in the handling of mine products. The well-managed mine, with sufficient ore reserves to warrant the necessary plants, will increasingly call upon the metallurgist and chemist for the solution of its problems. Shipping sorted ore or concentrate to the nearest smelter will not be the course followed. From ore to metal, or at least to a product directly salable to the consumer, will be the practice followed. As a consequence, mine managers will be increasingly interested in metal trade problems. By metal trade I mean the buying, selling, shipping, handling, and all the practices, forms and customs that go to make up the trade.

Jan 1, 1928

By Charles M. Cooley

A NOTED Prospector Passes-Stories of the grizzled old prospector that discovered what turned out to be a famous and highly profitable mine, only to die in poverty through the shenanigans of "the Interests," are legion. It is pleasant, therefore, to be able to report that the discoverer of one of Canada's most famous mines was more fortunate.

Jan 7, 1953

ALABAMA. Aldrich, Aldrich, W. F. Anmston, Noble, A. E Bessemen, Abbott, C E, Fergusson, V Birmingham, Aldrich, T. H, Aldrich, T. H, Jr, Bowron, J, Burbidge, T A, Collord, G L, Crockard, F H, Davis, F H, Dimmick, F. D., Hiller, E., Johnson, G R, Ludwig, C P., McCormack, G B., McCrery, Peters, R , Jr , Phillips, W B, Ramsay, E ,Shook, A. M Car bon Hall, Pill, J R Emsley, Williams, E P Gadsden, Hudson, J B , Helena, Squire, J Holt, Shook, J W. Huntnnlle, Moss Lehigh, Toulmin. Rock Run, Garvin, J. M. Sheffield, Miller, D I Tusscaloosa, McCausland, E J , Woodward, Woodward, A. H

Jan 1, 1910

By Richard P. Rothwell

In January last I published in the Engineering and Mining Journal a table giving, with a considerable degree of accuracy, the production of anthracite coal for the year 1874. At that time it mas impossible to give any correct estimate of the production of bituminous coal, for the returns I had been able to secure from such distant and scattered districts were not always forwarded punctually, and the work of .obtaining anything like a true estimate of the coal mined in districts from which I was unable to obtain official returns was both laborious and tedious. As will be seen from the detailed reports furnished herewith, I have succeeded in obtaining tolerably accurate returns of 20,093,704 tons; and upon careful revision by numerous well-informed local authorities, my first estimate of the amount of coal not officially returned to me has grown very considerably; indeed, as I get more information on the subject I find that our bituminous coal production greatly exceeds the amount we have been accustomed to hear it placed at, aggregating as it does, 26,465,704 tons. Mr. Andrew Roy, State Inspector of Mines for Ohio, has reported the production of Ohio at 4,168,445 tons, while his first estimates were but 3,820,000 tons; and similarly, in other cases, the more full the returns direct from the mines the more incorrect do I find all previous reports. I am able now to furnish, not an accurate statement, indeed, but by far the most full and reliable one that has yet been published of our coal production. The amount of labor involved in obtaining this admittedly imperfect report has been simply enormous. In the following tabular statement it will be perceived that Pennsylvania produces nearly one-half of all the bituminous coal mined

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