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By D. L. Harris, A. M. Gaudin

Observations were made of the distribution of mercaptan containing S35 between aqueous solution and mineral and between aqueous solution and the gaseous phase. Although equilibrium may not have been attained, adsorption of the reagent was shown to occur reasily from air or aqueous solution on sphalerite, zincite, and willem-ite and to correspond to flotation. Adsorption on quartz did not similarly occur. THE following results, presented here in condensed form,' were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report' of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr. Coarsely-crystallized sphalerite was handpicked, stage-crushed in the dry state, wet-screened on a 200-mesh sieve, and deslimed in water at about 5 microns. Further treatment consisted of a wash in dilute aqueous hydrogen peroxide, drying, removal of the dark-colored fraction in a Frantz magnetic separator, washing in very dilute hydrochloric acid, repeated washing in distilled and conductivity water, and drying. The last washings showed a conductivity equivalent to a few ppm NaC1, that is, much more than would be provided, theoretically, by a saturated ZnS solution. The material was stored dry in sealed bottles. Analyses were as follows: Zn, 62.3 pct; Fe, 0.43 pct; Cd, 0.44 pct; S, 31.2 pct; Mn, 0.001 pct. The specific surface (BET method) was 2000 cm2/g. Zincite from Franklin furnace of the New Jersey Zinc Co. was hand-picked, dry-crushed, wet-screened at 100 mesh, and deslimed at about 10 microns. After drying, the associated zinc, manganese, calcium, and silicate minerals were removed in a Frantz magnetic separator. The purified zincite was washed in distilled water and conductivity water to a conductance of less than 2 ppm equivalent NaC1, dried, and stored. Analyses were as follows: Zn, 75.1 pct; Fe, 0.9 pct; Mn, 2.78 pct. The specific surface (BET method) was 1740 cm 2/g. Willemite, also from Franklin furnace, was purified similarly. Analyses were as follows: Zn, 52.5 pct; Fe, 0.12 pct; SiO², 27.3 pct; loss on ignition, 0.13 pct. The specific surface was 1760 cm 2/g. Conductivity water (double-distilled) and demin-eralized-distilled water were used in most of the tests. The specific resistance was not less than 600, 000 ohms, and usually above 1,000,000. Radiosulphur-marked hexyl mercaptan (1-hexane thiol) was synthesized by Tracerlab, Inc., Boston. Two lots were secured several months apart. The last lot, consisting of about 0.5 g of the mercaptan, had a total activity of about 10 millicuries. Tracerlab Co. guaranteed only the activity; hence a quasi -vapor pressure determination (based upon an S analysis) of the mercaptan was made. The calculated value, 4.2 mm of mercury at 25.5' C, has been compared with that of a sample of Highest Purity 1-hexane thiol from Fisher Scientific Co. The latter had a vapor pressure of 4.5 mm of mercury at 2.5 C. Analytical Procedures The sample containing radiosulphur-marked mercaptan was oxidized to convert the mercaptan sulphur to sulphate, carrier barium sulphate being added to provide a suitable quantity of total barium sulphate in a filter cake. The precipitate was filtered and dried, and counting was carried out either in a streaming-gas (Q-gas) counter for high sensitivity or with an end-window G-M counter for convenience. The oxidized and precipitated mercaptan gave a radioactive count of 65 counts per minute per microgram in the end-window Geiger-Mueller counter and 1100 counts per minute per microgram in a Q-gas counter. For standardization of the mercaptan solution, 15 replicate analyses were made. The average deviation per measurement was about 1600 cpm in 65,000 cpm, the probable error in the mean being 275 cpm. It

Jan 1, 1955

By Homer Staley

THE casting alloy 88 copper, 10 tin, 2 zinc, commonly known in England as Admiralty metal and in this country as Government bronze, gun metal, or Naval Department composition G, has, at its best, many valuable properties. However, its physical properties are known to vary widely with slight changes in method of manufacture of the castings, such as slight variations in composition, variation in pouring temperature, kind of mold used, method of pouring and gating of molds, size and shape of castings, amount and kind of heat treatment., and so forth.1 The microstructure of castings made from this alloy is influenced by slight variations of composition, rate of cooling, and kind and length of heat treatment. This is best understood by reference to the equilibrium diagram. The part of the diagram in which we are interested and the effect of the thermal equilibrium relations on the physical properties of the alloy 88 copper, 10 tin, 2 zinc, have been discussed by Hoyt, Camp-bell, Primrose, and Rawdon.2 In Fig. 1 is given the equilibrium diagram of the copper-tin alloys. Briefly stated, the relations of composition and temperature changes are as follows. Compositions between A and a consist of but one constituent-the a bronze, which is a, solid solution of copper and tin, rich in copper. On cooling from the molten state these compositions gradually crystallize, at temperatures above 790°, into a mass of interwoven tree-like crystals or dendrites. The cores of the dendrites are rich in copper and the percentage of tin gradually increases as the surfaces are approached. As cooling progresses, after all the metal has crystallized, no further changes occur, in the crystals other than diffusion within the crys-

Jan 9, 1919

By C. P. Proctor, J. B. Morrow

With numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sampling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1936

By C. P. Proctor, J. B. Morrow

With numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sampling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1936

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

By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

By W. R. Ingalls

THE paramount subject of interest and concern at the present time is the readjustment in economic conditions following the cataclysmic disturbance produced by the war and the misconceptions leading to an orgy of extravagance that prevailed during two years following the armistice he, time is too short for me to undertake to review the nature and extent of the upheavals occurring between August, 1914, and October, 1920. Bulky volumes will be written about them. . But I shall have to refer to some of the results in order to outline a prognosis. It is the future, not the past;' that is of most interest to us. Let me be so bold as to say, without further preface, that I am not optimistic as to the near future. .We shall, indeed, have revivals in trade, but they will be delusive if their nature be not 'understood. We shall build hopes and expectations upon political maneuvers and events, only to find in the end that they were folly. In the meanwhile fundamental economic influences will continue to exert their steady and irresistible pressure. The new administratiow at Washington has no magic wand with which to kindle the fires in our idle steel furnaces, or create a million new houses for the people; nor can the premiers of Europe put into motion the spindles of the cotton and woolen mills, or by any incantations compel the people of the Orient to buy goods. The people of the Orient, and of, Europe, and of the two Americas are in the grip of the same economic forces. The readjustment has proceeded further in some parts of the world than in others. In the United States I do not think we, have gone more than over the threshold. I shall tell you why 1 think thus, but in telling you I shall be limited, in view of the immensity of the subject, to a series of bald statements, without much elucidation.

Jan 1, 1921

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By Lo-Ching Chang, Kenneth M. Goldman

INTRODUCTION THE kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was simple. A graphite crucible 1 5/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an induction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature [ ] for 3-5 min., after which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 min. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the temperature of the furnace in 1 to 1 1/ 2 min. Slag

Jan 1, 1948

By Lo-Ching Chang, K. M. Goldman

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By K. M. Goldman, Lo-Ching Chang

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By J. J. Taber, I. S. K. Kamath, R. L. Reed

Alcohol floods of consolidated sandstone cores have shown the process to be strongly dependent on the phase behavior of the particular alcobol-oil-water system used. This means that in many cases the mechanism does not conform to the idea of a piston-like displacement. Instead, it is found that by changing the alcohol it is possible to change the relative velocities of the oil and water and, in fact, the entire mechanism of the process. The effects of rate, viscosity, initial saturation, distance travelled and hysteresis of relative permeability on the alcohol flooding mechanism are discussed. INTRODUCTION Reasons for interest in the use of alcohol to miscibly displace oil and water from a porous medium appear in the existing literature.l-7 The mechanism of the displacement has been considered and the apparent implications formulated into a theory which presumably would enable one to predict the essential features of the process.6 Unfortunately, most of the reported experiments have been performed with unconsolidated or artificially consolidated sands. With these systems some of the noteworthy facets of the process are obscured and resulting data appear uncertain. It is the purpose of this paper to show how the use of consolidated sandstones has led to revision of the mechanism and, hence, the theory of alcohol flooding. The practical result is increased pessimism toward the possibilities of commercial application of the simplest form of the alcohol-slug process. However, elucidation of the mechanism has made it possible to define the essential characteristics of a system of slugs which will behave in a nearly piston-like fashion and, thus, yield the best possible result. EQUILIBRIUM PHASE BEHAVIOR Fig. 1 is a diagram of the ternary system isopropyl alcohol (IPA)-Soltrol-calcium chloride brine. Brine was used to prevent plugging of the core and calcium chloride was used because sodium-chloride brine exhibits a solid phase with Soltrol and IPA. If alcohol is added in increments to the immiscible mixture of water and oil represented by Point A, the path followed by the successively equilibrated samples will be on the Line ABC and pass from the immiscible region to the miscible region by crossing the binodal curve at B. Consider the intersection D of this path with the tie Line EF. The quantity of oleic phase is proportional to the Segment ED and the quantity of the aqueous phase is proportional to DF. Compositions of the two phases are specified by Points E and F. It is clear that in the case shown the oleic phase is diminishing and entirely disappears when miscibility is achieved. Such will

By R. C. Rastogi, F. F. Aplan

The goal of this study is to evaluate the coal flotation process and the interaction of the chemical (reagent) and hydrodynamic (machine, operational) variables as they affect yield, flotation of various sized particles, and sulfur and ash rejection. Coal flotation is found to follow a first order process with the coal floating much faster than either pyrite or ash. This circumstance may be used to achieve gangue rejection during flotation. When floated with MZBC, cresol, or pine oil frothers, coal floats in the size sequence: 108 pm ( - 65 mesh), 589 x 808 pm (88 x 65 mesh), and 1.17 mm x: 589 pm (14 x 18 mesh). However with a substantial amount of fuel oil collector, all particles tend to float roughly in proportion to their content in the feed. An increasing aeration rate was found to be the most important variable in increasing the coal flotation rate. This increase in flotation rate, unfortunately, is also accompanied by an increase in the flotation rate of the pyrite. The rejection of pyrite during coal flotation is best accomplished at low aeration rates, low frother concentrations, and low impeller speeds.

Jan 1, 1986

By Franklin H. Sharp, Kenneth L. Clifford

During the last few years the New Lead Belt of Southeastern Missouri has become the main source of lead in the United States. It also produces significant amounts of zinc, copper and silver. The mines are located on a narrow, mineralized trend extending southward from Viburnum, MG. for about 35 miles. The ore occurs as replacement deposits in the Bonneterre lime- stone formation which is about 1000 ft below the surface. In most of the mines, enough water is produced to supply the milling requirements without any reuse. There are dry areas, however, and at least two mills must rely on water reclaimed from their tailings lake to augment the mine water. These mills have no choice but to utilize recycled mill water.

Jan 7, 1973

By John A. THOMPSON, Pazcl D. Torrey, Frank Breayster

DISCOVERY of natural gas in the Dundee field of New York in February, 1930, and the subsequent discovery in Tioga in September of that year, focused the attention of the natural-gas industry on the enormous possibilities of production and distribution in - the most populous area of the United States-New York and New England. Prior to 1926 the natural-gas industry in New York State had settled into a definite and limited policy, with the distributing companies controlling the output from its discovery to the ultimate consumer. Production amounted to between G and 7 thousand mil- lion cubic feet a year, with another 10,000 million feet imported from Pennsylvania for distribution in New York State. This gas was primarily from the Medina sand stone in. the western part of the state.

Jan 1, 1932

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By Kenneth K. Humphreys, F. R. Zachar, A. G. Gilbert

INTRODUCTION by F. R. ZACHAR and A. G. GILBERT Coal producers are not only faced with the problems of mining coal, but must also decide to what extent they can invest capital and what operating and maintenance expense they can afford, after mining, to market their product in sufficient volume and at a reasonable profit. Regardless of whether the operator is contemplating a new operation or merely considering expanding present facilities, market requirements, ability to make a product meeting requirements, probable costs and possible future changes in raw coal or finished product must be considered. In addition, such items as flow sheet, structural designs, storage facilities, etc, must be examined individually and collectively. In estimating preparation costs to meet predetermined market specifications, the operator must calculate the economics of present preparation practices to anticipate the increase to total production which results when the quality of the finished product is increased. The consumers of coal are continually seeking to obtain the best and most adaptable product for their money. Regardless of whether coal is used for coking, industrial requirements, electric power generation, domestic fuel or for other purposes, it will be scrutinized from such standpoints as delivered cost, suitability for utilization in certain equipment, ease of ash disposal, adaptability to material handling system plans and its potential for generating dust problems. Utilities, due to large capacity volume requirements, are generally in a position to select coal that will result in the lowest over-all cost per million Btu. Freight costs, paid by the utility, are important and are given utmost consideration when a coal is under consideration. Steel companies, whether producing or purchasing coking coal, are continually seeking coal that will result in lowering the cost of pig iron production. Since it is usually necessary to clean to lower specific gravities, say 1.40, to turn out a product meeting metallurgical requirements, it follows that a high ash "middling" product is created. These low quality middlings do not command a good price. Therefore, unless the metallurgical coal can command sufficient realization to carry or subsidize the middlings, the operator may be ahead economically to prepare steam coal at a higher specific gravity. While the "unit-train" rate reductions have been helpful to the economy of the coal industry, the establishment of these rates has made mandatory the installation of storage and rapid car loading facilities at mines and plants shipping utility coal (see Chapter 15). A study of the economics

Jan 1, 1968

The American Museum of Safety has installed a large collection of exhibits at 18 West 24th St., New York City, and extends a cordial invitation to the members of the Institute to visit this exhibition. The Museum is open daily from 9 am. until 5 p.m., and special arrangements will be made for the admission of a large party in the evening. The exhibition covers all phases of industrial and general safety, and also the important questions of sanitation and hygiene.

Jan 2, 1917

By W. G. Matteson

The origin of the salt domes of the Gulf coastal plain has been investigated by many of the most able geologists, but the problem cannot be said to have been satisfactorily solved. Since 1860, numerous theories have been presented, only to be discarded, at least in part, as more complete infomation revealed their fundamental weakness. Real progress toward solution dates from 1902, when Hill1 advanced the theory of secondary deposition of the domal materials from saturated solutions of hot saline waters ascending from great depths under hydrostatic head along structural lines of weakness. Shortly thereafter, Harris,² using Hill's hypothesis as a basis, explained the doming and pronounced uplift associated with these salt cores as the result of forces exerted by growing salt crystals. This was a marked advance over the ideas of Coste3 and Hager,4 since no evidence of igneous intrusives, as they assumed to explain the uplifts, had been found associated with the domes. Harris5 developed his theory until it offered such apparently plausible explanations of so many details of dome phenomena that his hypothesis and conclusions received widespread acceptance, despite some serious objections, and today his theory, somewhat modified, is considered by many able investigators to be the best explanation of the origin of these domes. The immense production of oil per acre, the recognition of the high lubricating quality of the oil, the development and recognition of the efficiency and advantages of oil-burning vessels, with the subsequent exceptional demand for fuel oil, and the resultant advance in the price of coastal crude, have been responsible for a prospecting and develop- 1 Robert T. Hill: Beaumont Oil Field with Notes on Other Oil Fields of the Texas Region. Jnl. Franklin Inst. (1902) 164, 143. 2Gilbert D. Harris: Rock Salt in Louisiana. Louisiana Geol. Survey Bull. 7 (1907) 76. ³E. Coste: Volcanic Origin of Natural Gas and Petroleum. Jnl. Canadian Min. Inst. (1903) 6, 73. 4Lee Hager: Mounds of the Southern Oil Fields. Eng. & Min. Jnl. (July 28, 1904) 78,137, 180. 6Gilbert D. Harris: Geologicel Occurrence of Rock Salt in Louisiana and East Texas. Econ. Geol. (1909) 4, 12.

Jan 1, 1921

By Robert H. Richards

While yet in correspondence with the heads of the several mining schools for the purpose of bringing the details of my Address into the best form for publication, a severe illness overtook me, and before I had recovered sufficiently to turn my attention to matters of this character the Address had been printed in its imperfect form for volume xv. of our Transactions, and the type had been distributed. The incorporation of the later corrections, in the form of a Supplement, became a necessity. To simplify the corrections as much as possible to the reader, every paragraph which has been revised in any way is here reprinted in full.

Jan 1, 1887