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By Walter Kauenhowen

The crude-oil production of Germany without Austria during 1938 amounted to 3,864,518 bbl., representing an increase of 21.7 per cent over the 3,173,373 bbl. produced in 1937. Adding the Austrian production, the crude-oil production of the new German Reich totaled 4,259,717 bbl. during 1938, representing an increase of 25.3 per cent compared with the respective figures of the previous year. According to published official data, and using a conversion factor of 1 metric ton equaling 7 bbl., the oil production of Germany in 1938 was as shown in Table 1. A semiofficial publication1 states that the program of the crude-oil industry for the second year (1938) of the four-year plan was successfully accomplished. According to the same source, new drilling developments at the following localities were promising: Reitbrook near Hamburg, Heide in Holstein, Eicklingen-Sandlingen near Celle, Steimbke near Nienburg, Worms in the Rhine Valley, Gifhorn near Braunschweig, Mölme near Oberg, and at other places. The drilling activity for oil is illustrated by the figures in Table 2.

Jan 1, 1939

By Walter Kauenhowen

The crude-oil production of Germany without Austria during 1938 amounted to 3,864,518 bbl., representing an increase of 21.7 per cent over the 3,173,373 bbl. produced in 1937. Adding the Austrian production, the crude-oil production of the new German Reich totaled 4,259,717 bbl. during 1938, representing an increase of 25.3 per cent compared with the respective figures of the previous year. According to published official data, and using a conversion factor of 1 metric ton equaling 7 bbl., the oil production of Germany in 1938 was as shown in Table 1. A semiofficial publication1 states that the program of the crude-oil industry for the second year (1938) of the four-year plan was successfully accomplished. According to the same source, new drilling developments at the following localities were promising: Reitbrook near Hamburg, Heide in Holstein, Eicklingen-Sandlingen near Celle, Steimbke near Nienburg, Worms in the Rhine Valley, Gifhorn near Braunschweig, Mölme near Oberg, and at other places. The drilling activity for oil is illustrated by the figures in Table 2.

Jan 1, 1939

By J. D. Exner

With the introduction of rotary drilling in the Gulf Coast area, some thirty-two years ago, and its subsequent spread to other producing localities in the United States, there has been a constant change in the design of equipment. Only the general features remain, namely the rotating drill stem and the circulating mud. Only recently have the properties of mud and their behavior received attention from petroleum engineers, but circulating problems in present deep drilling demand further study and understanding. It is the purpose of this investigation to determine the relative changes in the apparent viscosity of muds with changes in temperature and to discover other physical effects due to heat. Very little information has been published regarding the effects of temperature on the viscosity of drilling muds. Maustl states: "The viscosity of most muds is decreased on heating, but the interesting thing is that the degree of flocculation is also increased on heating. There will be a greater tendency to seal off formations at high temperatures than at low temperatures." With regard to the effect of temperature on viscosity and yield point, Herrick2 states: "The variation of yield point and viscosity of mud with temperature.....is not very clearly brought out by the data available. Both appear to decrease slightly with increasing temperature up to 200' F." The experimental results presented in this paper further emphasize this point. Two types of viscosimeters are available for measuring the apparent viscosities of drilling muds: the efflux tube type as used by Herrick3 and Marsh, and the torsional type such as the McMichael or the Stormer viscosimeters. Because of its extensive use in measuring the apparent

Jan 1, 1933

By AIME AIME

MINING men in general- are a roving lot but not so Selwyn G. Blaylock. Immediately after graduation from McGill in 1899 he went to the Trail smelter and he is there today though he spent three or four years of his early professional life at other British Columbia mining centers. Either he sensed the great possibilities of the company of which he is now vice-president and general manager, or it sensed his; more probably both. Certainly the association was a happy and fortunate one.

Jan 1, 1937

By Duane N. Goens, Clifford R. Porter

A 91 kg/h (200 lb per hr) pilot plant was constructed according to "Magnex" design. A non-compliance eastern coal which would generate more than 0.85 kg of S02 per GJ (2.0 lb of SO2 per million Btu.) upon burning was brought into compliance less than 0.52 kg of SO2 per GJ (1.2 lb SO2 per million Btu) during continuous operation of the pilot plant. Approximately 85% of the pyritic sulfur was removed while recovering 90% of the Btu of the feed coal. Pilot plant operation is summarized and preliminary economics presented. Present status of the Magnex design program is reviewed.

Jan 2, 1979

By R. W. Raymond

The death of Privy Councilor Bruno Kerl, on March 25, 1905, terminated a distinguished and useful career. Bruno Kerl was born March 24, 1824, at St. Andreasberg in the Harz, and entered in 1840 the mining school of Claus-thal, where he studied for three years, working at the same time in the mines and stamp-mills. After an additional year of practice in the silver-reduction and iron-works of the Upper Harz, he passed his examination as a metallurgical graduate, and studied for a gear at Göttingen under Wöhler in chemistry, Hausmann in mineralogy, and eminent teachers in other branches. In 1846 he was employed at the Oker works, but very soon left this post, to become a tutor in chemistry, metallurgy, etc., at Clausthal, where he continued to labor until 1867. During this period the Clausthal school became a completely equipped Mining Academy, and Kerl was made in 1862 a full professor. Meanwhile, in addition to the work of instruction, he discharged, simultaneously or successively, the duties of many responsible official positions in the Royal Hanoverian administra-

Jan 1, 1906

Quarrying and crushing 500 tons of limestone plus burning some 240 tons of limestone per day are the two initial phases in the production of borax, soda ash, sodium sulfate and related chemicals at Stauffer Chemical Co.'s plant in Westend, Calif. These processing steps have been upgraded in recent years by the installation of new primary and secondary crushers, an 8 x 340-ft rotary kiln plus kiln feed, control and cooling components-all designed and manufactured by Traylor Engineering and Manufacturing Division of Fuller Co. As a result of this new equipment, a new product- quicklime-has been added to the West End product family and considerable reductions have been realized in fuel and manpower costs.

Jan 1, 1965

By O. W. Shimer, D. C. Helms, C. E. Brown

THE early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 334 million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20° to 90° and some are on the invert in, many sharp folds and faults. PLANNING The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been maintained. Locations of stripping areas are determined as follows: 1. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness and pitch of the beds.

Jan 1, 1944

By John V. Beall

GOING west from Denver on Route 6, the direct road to Grand Junction, one gets the first glimpse of mining a few miles east of Denver near Idaho Springs where the workings of defunct gold mines are visible on the sides of mountains along the highway. One enterprising company is turning a profit by showing tourists through the mine and mill and then selling them gold samples on the way out. We have always known that mining people are ingenious, but this proves it. About five and a half hours fast driving west from Denver brings one to Rifle, Colo., which is the site of the oil shale mine, retorting plant, and refinery of the U. S. Bureau of Mines. As you drive up to the mine, you can see a portal high on the face of the cliff in front of you where the mine surface plant literally hangs by its toenails. Below, the retorting plant and refinery gleam in the sunlight. Up at the mine, Fred Wright will show you how the oil shale is extracted in two benches (a third bench would be used for commercial mining) by the room-and-pillar method. In mining the top level, an underground crew of thirteen men have been able to produce 1500 tons of shale in each eight-hour shift. To do this, the mine is thoroughly mechanized. The mining method is de- scribed in the September issue of Mining Engineering.

Jan 1, 1949

By L. J. Buteau, R. E. Reed-Hill, W. A. Slippy

In a zirconium {1121} twins tend to have coherelzt boundaries and thus do not usually taper to a point when they intersect a grain boundary. Under the proper conditions, a (1121) twin may deform a boundary in such a manner as to clearly rcveal the twinning shear. Measurements of these grain-bounrlary rotatzons yield a value of 0.63 for the (1151) twinning shear. The magnitude of the observed shear and its shear sense are in excellent agreement with the assumption that the second undis-torted plme (K2) for this form of twinning is the basal plane (0002). The present value of the tzvinninz shear, which is approximately three limes larger than Rapperport&apos;s value? is in excellent agreement with reported results of Sokuskii and Prolsenko.5 RECENTLY westlake&apos; reported a study of the twinning modes of zirconium based on ~ap~er~ort&apos;s2 values for the twinning elements. He observed that two of the modes, (1012) and {1122), can be explained by relatively simple dislocation models. A workable model for (1121) twinning, however, proved to be very complex and questionable. Because Rapperport&apos;s second undistorted plane, (K2), for (1121) twinning has large indices, {ll2l6), it is possible that the difficulty in defining a model for (1121) twinning lies in an incorrect value for K2. A measurement of this twinning element has therefore been made, using a method based on observations of the shear displacement of grain boundaries at positions where they are intersected by (1121) twins. EXPERIMENTAL PROCEDURES The zirconium specimens were deformed in tension on an Instron machine either at the temperature of liquid nitrogen (77ºK), or prestrained at liquid nitrogen temperature and then further deformed at room temperature. Straining at 77°K was employed in order to nucleate (1 121) twins in large numbers, since simple ropm-temperature tensile deformation favors (1012) twinning. Specimens were machined from 1/2-in.-thick plate. The material was arc-melted sponge zirconium annealed to an ASTM grain size 4 and containing, in parts per million, 380 Fe, 880 0, <40 Hf, 32 N, and < 5 H. The specimen gage length and diameter were 1.25 and 0.130 in., respectively. To insure a gage section initially free of twins, the last 60 thousandths of the specimen diameter was removed by acid machining.

Jan 1, 1963

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.&apos; The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By Claus Guenter Goetzeil

(New York Meeting, February, 1937) The object of this investigation was to determine whether silver alloys could be used instead of the currently employed insert of high-expansion Average Coefficient per Deg. C. over Range 20° to 200° C. Pure aluminum..................................... 24.6 X 10-6 Cast low-expansion Si-Cu-Ni-A1 piston alloy............ 20.0 X 10-6 High-expansion austenitic Cu-Ni cast iron.............. 19.3 X 10-6 Cast steel (0.25-0.35 C, 0.40-1.0 Mn).................. 12.6 X 10-6 Cast iron (3.15 total C, 2.16 Si)....................... 12.8 X 10-6 Pure silver.......................................... 18.9 X 10-6 austenitic ferronickel alloy, to reduce the wear of ring grooves in light metal pistons. A typical example of a piston containing a ferronickel insert is shown in Fig. 1. The high coefficient of expansion of silver made it worthy of consideration, while the small size of the insert would render its use feasible in Germany as an emergency measure. The coefficients of linear expansion of several metals and ailoys are as shown in the table above. Obviously the melting point of the insert must be high enough to prevent it from melting when the light alloy is cast around it. This imposes a lower limit of about 850" C. for the solidus of the silver alloy. Pure silver melts at about 961" C., so that the tolerable depression in the solidus is rather small. To avoid deformation of the insert during use a Brinell hardness number of at least 60 appears necessary.

Jan 1, 1937

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors&apos; data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors&apos; Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors&apos; reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander&apos;s Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE D. BARRON NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1919

By William L. Fink, Kent R. Van Horn

Zinc is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd1 first established the existence of a solid solution region at the aluminum end of the diagram (-v phase) by specific volume and microscopic determinations. Bauer and Voge12 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined. The solubility was placed between 15 to 20 per cent at 60" C., 20 to 22 per cent at 140" C. and 36 to 38 per cent at 270" C. Sander and Meissner decidedly modified the limits of the -y phase field of Hanson and Gayler&apos;s diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,s utilizing dynamic hard-ness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler&apos;s at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400" to 500" C., that the solubility of zinc in aluminum at room temperature is less than 5 * Metallurgical Division, Aluminum Research Laboratories. 1 E. S. Shepherd: Aluminum-Zinc Alloys, Jnl, phys. Chem. (1905) 9, 504. 2 0. Bauer and 0. Vogel: Aluminum-Zinc Alloys, Int. Jn1. Melallog. (1916) 8, 101. 3 D. Hanson and M. V. L. Gayler: A Further Study of the Alloys of Aluminum and Zinc. Jnl. Inst. Met. (1922) 27, 267. 4 W. Sander and K. L. Meissner: ZII~ Kenntnis der Konstitution der Aluminium-Zinklegierungen. Ztsch. f. Metallkunde (1922) 14, 385. 4 T. Tanabe: Studies in the Aluminum-Zinc System, Jnl. Inst. Met. (1924) 32, 415 6 H. Nishimura: On the Age-Hardening of Aluminum-Rich Al-Zn Alloys. Mem. Kyoto Imp. Univ. (1924) 3, 133.

Jan 1, 1932

By AIME AIME

TRAINED as a mining engineer and with no little experience in the field of mining, his interests and activities later transferred to the alloying, fabrication, and physical metallurgy of nonferrous metals, principally silver, Robert H. Leach represents in his professional life both of the major phases of the fraternity of mining and metallurgical engineers. In his personal characteristics, his wide circle of true friendships, his kindly, sympathetic interest in the problems of his fellow engineers, be they the junior men of the mineral industries or the mature and experienced men, he typifies the characteristics and attitude so desirable in the professional man.

Jan 1, 1939

By D. Kramer

HASEN1 has published a phase diagram for the zirconium-nickel system. This phase diagram has been redetermined by Hayes, Roberson, and paasche2 in the range 0 to 50 at. pct Ni. Recently, Smith and Guard3 have published a tentative diagram for the

Jan 1, 1960

By AIME AIME

Award of a Gold Medal : to the Institute. The Jury of Awards of the Jamestown Ter-Centennial Exposition has conferred a gold medal, the highest distinction within its power,. on the American Institute of Mining Engineers for the excellence of its publications during the past decade. ; A half-tone photographic reproduction of both sides of the medal is given in the accompanying illustration.

Jan 7, 1908

By C. W. Sherman, John Chipman

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

Jan 1, 1953

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson&apos; measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans&apos; and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner&apos;s data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970