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By J. V. Vogel

Jan 1, 1969

By A. E. Wells, H. O. Hofman, R. P. Reynolds

A Discussion of the Paper of H. O. Hofman, R. P. Reynolds and A. E. Wells, read by title at the London Meeting, July, 1906 ; presented at the New York Meeting, April, 1907, and printed in Bi-Monthly Bulletin, No. 13, January, 1907, pp. 37 to 52. GEORGE A. PACKARD, Boston, Mass. (communication to the Secretary*) :-The very interesting results obtained by Prof. Hofman and his assistants came to my attention when I had temporarily assumed charge of the metallurgical department of the Missouri School of Mines, and had found it, pending the completion of a new building, lacking a furnace in which to roast ore preparatory to the customary lead blast-furnace run. An attempt at lime-roasting had been already determined upon, but the use of a charge which would make a slag of definite composition was a new idea. The results following were obtained by Messrs. Aubrey Fellows, J. C. Long, E. R. Wash, and Dr. T. C. Tseung, under my supervision. It is regretted that the data are not more complete; but the work was done simply incidentally to securing the desired ore for the blast-furnace, with no idea of obtaining any results of especial interest. It is submitted because of the metallic lead obtained, no notice of which has been seen elsewhere. The ore was an aggregate of several lots of concentrates, apparently from Missouri ores. The analysis follows, with that of the limestone and sandstone used, as far as made:. Ore, SiO2, 3.04; Fe, 0.77; CaO, 2.53; Pb, 68.74; Zn, 5.77; S, 13.9 per cent.; limestone, SiO2, 1.0 ; CaO, 54.35 per cent.; sandstone, SiO2, 99.8 per cent. The converter was made in the shops from a sheet of No. 14 iron riveted in the shape of a truncated cone, 20 in. in diameter at the top, 15 in. at the bottom and 22 in. high. A grate of No. 8 iron, 17 in. in diameter, with 130 s-in. holes placed at about 1.25-in. centers, was held in place by the shape of the

Jul 1, 1907

By CHARLERS R. FETTEE

A slight decrease in drilling activity occurred in the oil fields of western Pennsylvania during 1945 and a considerable decrease in the shallow-gas territory (Upper Devonian or higher). The number of deep tests (Middle Devonian or deeper) completed was two less than in 1944 and these did not open any new reserves of natural gas. Thus far, no commercial oil has been encountered in sands below the Upper Devonian in Pennsylvania. Oil production declined 8 per cent.

Jan 1, 1946

By Jack White

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the l l-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the ll-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors' reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 1% in. and a further gain of work accomplished of 2.1 pct when we went from 1 % in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951

By Jack White

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the l l-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the ll-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors' reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 1% in. and a further gain of work accomplished of 2.1 pct when we went from 1 % in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951

By AIME AIME

NO ADEQUATE salary scale, at the present time, can ignore the increase in the cost of commodities 'during the last few years or- afford to assume that this increase is merely temporary. A study of the change in prices and wages during and after the Civil War is of interest in connection with changes that have taken place from 1913 to 1919. The curves on the accompanying figure, based on reports of the War Industries Board and Department of Labor, show these changes. During the Civil War retail prices rose to 164,2 per cent. of the prices of 1860, during the next 8' or 10 years. It is interesting to note that the rise in wages during the Civil War was almost simultaneous with the rise in the prices of commodities. During the World, War, the rise in wages has lagged about a year behind the rise in prices. Furthermore, in the period immediately, following the Civil War, wages continued to rise after prices started to fall, The present price level is not considered merely temporary by such of our Government agencies as the Department of Labor and the Federal Reserve Board or by such economists as Irving Fisher' and J. S. Holden.2 Sub-

Jan 1, 1920

By H. C. Fiedler

It was recently shown with 3.3 pct Si-Fe containing 0.026 pct S and 0.06 pct Mn that the extent of secondary recrystallization to a cube-on-edge texture is determined by the cooling rate from the solution temperature of the manganese sulfide inclusions.1 With a rapid cooling rate, many small inclusions rather than a few large ones are formed, which leads to increased restraint to normal grain growth and more complete secondary recrystalliza-tion. Strip samples 12 mils thick, rolled from 1-in.-thick slabs that were cooled at 130°C per min

Jan 1, 1964

By Ziebell, Howard A.

THE Washington magnesite deposits, located in the hilly and mountainous northeastern part of Washington, occur as massive lenses in a sedimentary series made up of dolomite, shale, and quartzite, into which basic dikes have intruded. The ore pattern resembles a series of disconnected chain links extending approximately 25 miles in a south-west direction. Magnesite in this district is all crystalline and closely associated with dolomite, talc, serpentine, and basic dike rock. All deposits which have been developed are near the surface so that quarry-bench mining has been possible. For over twenty years hand sorting magnesite ore at the quarry face was standard practice. Ore cars were hand trammed on 30-lb rail systems which led from the face to ore passes or raises for the magnesite ore and to the waste dumps for disposal of the rejected waste material. This system was somewhat modified by the use of Dempster Dumpster trucks. The ore was, however, still sorted by hand from the calcium and silica bearing waste rock. Power equipment. consisting of one 3/4-yd electric shovel, was

Jan 1, 1949

By Warden A. Moller

(Pittsburg Meeting, March, 1910.) THE Fushun coal-field, now being opened up by the South Manchurian Railway Co., is connected with the main line by a branch, 30 miles long, from Sui Chia Tun, 10 miles south of Mukden, the capital of Manchuria. The coal-field, which lies on the southern bank of the Hun river, 25 miles east of Mukden, consists of a long narrow valley,. running east and west between hills composed of granitic and volcanic rocks. At the foot of the northern hills, the Hun river flows westward towards the Liao river, which drains the greater part of South Manchuria. At the foot of the southern hills, resting immediately upon volcanic rocks, and overlain by 20 ft. of alluvial, is a thick layer of Tertiary shales, carrying near the base two coal-seams. In many places the lower of these two seams is in immediate contact with volcanic lauds and basalts, the flows of which were evidently both prior and subsequent to the formation of the coal-seams. This contact has practically destroyed the lower seam for commercial purposes. The value of the field lies in the upper seam, which, for a length of nearly 8 miles, varies from 100 to 130 ft. thick. Of this seam, 85 per cent is good coal. The seam dips to the north conformably with the shales, at angles of from 25° to 30°, and appears to have an uninterrupted dip for about 1.5 miles before being possibly cut o$' by the northern hills. The coal-bearing shales extend east and west for a length of about 20 miles, but towards the east the continuity of the seams is broken by intrusive rocks. The coal is of the sub-bituminous variety, low in ash, bright in appearance, and breaks with a conchoidal fracture. It has the usual qualities of Tertiary coal-quick steam-raising and poor stacking-qualities. Pieces of resin, varying in size from

Apr 1, 1910

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike's Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

By COREY C. BRAYTON

PACIFIC COAST steel and iron industries can now take care of all the western and export demands except for heavy structural shapes, thick plates, rails, alloy tool steels, and a few other items. In. 1902 all of our steel came from St. Louis and Milwaukee and points still farther east. A small quantity at that time came from foreign countries. Early mining in the West was, broadly speaking, prior to the steel age. 'Wood for structures and iron for castings were almost exclusively used. Forgings were made of rolled iron that came from the East and foreign countries. San Francisco was, from the early days of mining, the manufacturing center for mining and milling machinery of all types and held that position until the .nineties, when eastern competition began to be felt. Even today in the old mining camps of the West, and many abroad, you will find machines and equipment with familiar San Francisco manufacturers' names. ..Iron, either rolled or cast, entered into their manufacture, for steel castings did not come into general use :until the nineties.

Jan 1, 1929

By Ralph H. Sweetser

OF SPECIAL importance in the design and construction of an iron blast-furnace plant are tile raw materials to be employed. Obviously the iron must come from some ore of that metal, but the many kinds available lead to important differences in plant arrangement, and in the design of furnaces and accessory equipment. For instance, the bulk of the gangue in the ore is subject to wide variation as is that of the ash in the fuel. A gradual increase in the bulk of raw material necessary to produce a ton of pig iron has been noted, but this has been more than offset, so far as costs of operation are concerned, by improvements in the machinery used for handling large quantities of ore. coal limestone, and slag. The mechanization of coal and iron-ore mining. the building of big ore boats and limestone carriers, of ore docks for fast loading and unloading, and the general use of heavy railroad equipment have all contributed to greatly reducing the number of man- hours required to mine, transport, and manufacture the raw materials into a ton of pig iron. This looks like a big saving and it is. If it were not for these big labor saving machines it would be impossible to produce the tonnage of iron and steel that is made each year in this country. On the other hand, the total capital investment necessary to bring down the man-hours per ton of pig iron to a 2.3 hours average at the blast furnace and to a total of only 12 man-hours from ore to metal (see Table 1) is so great that even the present high price of pig iron is probably not far above the true cost of manufacture when all the fixed charges are properly included.

Jan 1, 1939

By H.E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By H. E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By C. C. Harris

This article presents a general equation describing the xYt surface in batch grinding. This equation contains as special cases most of the relationships which have been deduced from kinetic studies. In an earlier paper an analytical solution of the integro-differential equation of batch grinding was proposed1 as a first approximation of the xYt surface.' A more general equation will be presented here, which appears to combine in a single statement many conclusions reached by experiment. A possible underlying mechanism is that the changing product fineness leads to changes in the particle crushing strength and in the probability of encounter with the crushing media.

Jan 1, 1969

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis' and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations' that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963