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By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

RUfUs J. Foster, Scranton, Pa. (communication to the Secretary*) :—In answer to one of the inquiries made of Mr. Conner, and as a matter of historical record, I beg to say that the idea of supporting the strata over worked-out areas in coalmines by flushing the openings full of culm originated and was put into actual practice by the late R. C. Luther, a former member of the Institute, at that time Chief Mining Engineer, and later General Manager, of the Philadelphia & Reading Coal & Iron Co. In the early 80's the Philadelphia & Reading Coal & Iron Co. purchased from Messrs. Hecksher & Co. the Eohinoor colliery, situated in the western part of the borough of Shenan-doah, Pa. On taking possession of the colliery the Philadelphia & Reading Coal & Iron Co. made a conlplete resurvey of the mine-workings, giving an absolutely correct map which showed not only the plan of the mine-workings, but also every improvement on the surface over the workings, and the marked features of the surface of the ground. Tidal elevations were shown at every eurvey-station in the mine and on the surface, so that, as is the case with all the maps of the company, contour-maps of either the surface or the bottom of any coal-seam, or geological cross-sections, could be constructed directly from the information on the mine-maps. In a cornparatively short time after the company took possession of the colliery, the workings which extended under the western portion of the borough of Shenandoah began to cause trouble and damage dwellings and other buildings in that section of the town. The lots in this section had been sold, in many cases, to individuals by the Gilbert & Shaefer Estate, owners of the coal-lands on which the colliery was located. In

Jan 1, 1912

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By L. P. Davidson

THE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and .operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to storage tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in. the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid-either as acid or as sulphate sulphur in the calcine-because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60° Be. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1942

By L. P. Davidson

The new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, 111., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the , equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment snd recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutid'ns can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—either as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" BC. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1944

By D. N. Stevens, D. N. Bloom, M. A. Klugman

This paper represents a portion of a larger study concerning dispersion of major, minor and trace elements in wall-rock about orebodies in part of the Colorado Mineral Belt. This phase of the work pertains to the Mg/Ca ratio variations in wall-rock adjacent to orebodies in two mines, one in the Horseshoe Mining District (Hilltop mine), and the other in the Alma Mining District (Phillips mine). The two districts lie adjacent to one another, the Horseshoe District on the south and the Alma District on the north, and are commonly referred to as one, the Alma-Horseshoe Mining District. The Alma-Horseshoe Mining District is located 80 miles southwest of Denver, Colo., (Fig. 1) in Park County, on the eastern slope of the Mosquito range. The area is typified by rugged relief with altitudes of from 10,500 to 14,000 ft. The Horseshoe District is separated from the Lead-ville Mining District by the crest of the Mosquito range, with the Leadville District to the west. The Alma-Horseshoe District has been considered as peripherial to the Leadville District, and has not received the detailed attention that the Leadville District has. These two mines were selected for this study because of their ease of access; the attitude of the workings and the drill holes to the known mineralization; the similarity of the mineralization; and because the mineralization occurs in carbonates in both mines but are of different ages. In the Hilltop mine mineralization is confined to the Leadville dolomite (Mis-issippian) and is principally lead with subordinate zinc and silver. In the Phillips mine the mineralization occurs in the Peerless dolomite and shale (Cambrian) and in the Manitou dolomite (Ordovician) and is principally zinc with subordinate lead, silver,

Jan 1, 1964

By B. H. Sage, R. T. Carter, W. N. Lacey

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

By W. N. Lacey, R. T. Carter, B. H. Sage

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

By Harold Vance

The Lafitte field, the largest oil reserve in South Louisiana, is in Jefferson Parish, some 25 miles due south of the City of New Orleans. The discovery well, The Texas Company's No. I, Louisiana Land and Exploration Co., in the southeast corner of sec. 19, T. 17 S., R. 24 E., was completed on May 15, 1935. The initial production of this well was 960 bbl. of 34.9º A.P.I, gravity oil per day, through 1/4-in. choke, with a tubing pressure of 1600 lb. per sq. in. Producing depth was 9558 to 9572 ft., the total depth being 9572 feet. The development of the field has been at the rate of three to eight new producing wells per year. Up to Jan. I, 1944, 60 producing wells and three dry holes had been drilled, while two of the original producing wells had been abandoned, Although the field is not unitized, The Texas Company was the sole operator in the field until the Lafitte Oil Co. completed its NO. I Jefferson Parish, near the center of the west line of the NW/4 sec. 20, T. I7 S., R. 24 E., on July 27, 1941. No additional wells have been drilled by the Lafitte Oil Company. Drilling and WeLl-completion Practices All drilling operations have been conducted with the steam-driven rotary equipment mounted on submersible barges. A canal is dug to the well location and the drilling unit is floated into position. The seacocks are then opened and the barge settles to the bottom. After the well is completed, seacocks are closed and water is pumped out of the barge. This procedure permits the barge, with drilling equipment still in place, to be floated and moved off the location. The conventional open-hole and the gun-perforation method of completing wells has been used in this field. Where possible, the initial completion is from the deepest 'sand and recompletions are made progressively up the hole, by plugging back with cement to the upper sand and gun-perforating opposite the new sand. The oil string usually is 7 5/8 in., 26 to 34-lb. casing. Three wells have been completed using 9 5/8-in. 44-lb casing set below 10.000 feet. Fig. I shows the completion and recom-pletion practices on one well in the field. This figure also shows the relative locations of the different producing sands as shown on the electric well log. Structure The structure is an elongated dome, cut by two north-south faults, which divides the field into three segments. The west segment is the highest structurally and contains most of the recoverable oil and gas. The center segment is less important and the east segment is of little value. Figs. 2, 4, 6, 8 and 10 are depth contour maps on top of the five main producing sands in the field. These maps show the relative size of the five reservoirs and the

Jan 1, 1945

By W. H. Blauvelt

W. H. BLAUVELT, Syracuse, N. Y. (communication to the Secretary*).-I have read Mr. Howland's paper on Calculations with Reference to the Use of Carbon in Modern American Blast Furnaces with much interest, and believe that his method of analysis of the subject will be of material assistance in our study of the action of coke in the blast furnace. Mr. Howland quotes Professor Richards' statement that from the standpoint of the generation of the maximum quantity of heat in the furnace, Grüner was right in saying that all the carbon burned in the furnace should be first oxidized at the tuyères to CO and all reduction of oxides above the tuyères should be caused by CO, which thus becomes CO2. It is clear that the maximum quantity of heat is generated in the furnace when the greatest amount of carbon is burned to CO2 irrespective of whether it is burned at the tuyères or further up the furnace. So it would appear that Grüner's theory is sound regarding the maximum production of heat only because if all the carbon is burned to CO at the tuyères the reduction of the ores will have to be effected by the further oxidation to CO2. Whereas, if the reduction of the ores is effected in part by solid carbon, part of this carbon might be oxidized only to CO, resulting in a higher percentage of CO in the escaping gases than from Grüner's "ideal conditions.? But in studying the combustion of coke in the furnace, it is clear that the production of the maximum quantity of heat is not of the first importance in blast-furnace operation, or in the utilization of the fuel charged into the furnace. To my mind the production of a high thermal head at the tuyères is of the first importance, and the best coke is that which reaches the tuyères in proper condition to produce the highest temperature at the tuyères, and in just sufficient quantity to do the amount of work required there under the conditions produced by this maximum temperature. The combustion of a much larger amount of fuel at the tuyères, under conditions that will fall short of producing the highest possible temperature, cannot produce as good results, either in fuel economy or output. If this statement is correct, does it not correspond with Mr. Howland's statement that too much wind is inimical to low coke consumption? Nothing is more fatal to obtaining the highest temperatures than an excess of air for combustion. In the blast furnace an excess of air dilutes and cools the products of combus-

Jan 10, 1916

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By J. C. Smock

The magnetic iron ores of New Jersey are found in the northern part of the State, in the Highland Mountain range, which runs from the New York line on the northeast, to the Delaware River, near Easton, at the southwest. The same range continues across Orange County to the Hudson River, and towards the southwest it is known in Pennsylvania as the South Mountain. It is more properly an elevated table-land, quite deeply furrowed by several narrow, longitudinal valleys, and shorter cross-valleys or gaps. The ridges or lines of elevation, as well as the lower valleys, conform in their general direction very closely to the general trend of the whole belt or table-land, that is, from northeast to southwest. This also agrees with the prevailing strike of the rocks. This great uniformity in the altitudes of the hills and ridges, and the direction of the lines of depression corresponding to the strike of the strata, point to an original table-land, which, through the long action of denuding agents, has been quite deeply eroded, giving rise to the present surface configuration, so that some of the former and uniform features have been partially obliterated. The very few cross-valleys or depressions are much more irregular in their course, and serve as outlets through which the drainage is carried either into the Kittatinny Valley on the northwest, or to the broad, red shale and sandstone plane bounding the highlands on the southeast. The area of this highland

By Nathaniel Herz

The formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D'Arey, as follows: D = cV w1l Where, D = the volume of compressed air delivered in cubic feet per minute, at the final pressure. c = an experimental coefficient determined for the various sizes of pipe, d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. p, = the initial gauge-pressure in pounds per square inch, p2 = the final gauge-preesure in pounds per square inch. w1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p1. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, cd5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the density of the air, w1, and often, for convenience, a table giving the values of the expressions p1-p2 and c J I hare constructed a graphic chart, Fig. 1, for the solution of

Jan 1, 1913

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,' a pure metal and its vapor,' and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By M. R. J. Wyllie, H. W. Patnode

In the quantitative interpretation of electric log data it is essential to know the formation factor, defined as the ratio of the resistivity of the formation 100 per cent saturated with brine to the resistivity of the brine.' This concept implies that the formation factor for any given rock is constant irrespective of the resistivity of the brine or solution with which it is saturated. It is apparent that this can be true only when the rock matrix is wholly non-conductive. As reservoir rocks may contain clay or shale having an appreciable conductance one may expect these constituents to influence the determination of true formation factor. The formation factor may be theoretically derived from log data by dividing the resistivity of the mud filtrate invaded formation by the resistivity of the mud filtrate. Such a method of calculntion has implicit in it the assumption that the fluids in the invaded formation are wholly replaced by mud filtrate. that the solid matrix is non-conducting, and that the formation factor of the invaded zone is identical with the formation factor of the uninvaded zone. Since the validity of the first two basic assumptions regarding the insulating character of porous matrices and the displacement of the interstitial fluids in porous media do not appear to be fully established, the formation factors of a number of cores and clay slurries have been measured under conditions suitable for verifying the assumptions and the extent of any errors inherent in them. CORE STUDIES Apparatus and Procedure Resistivity measurements were made on short cylindrical permeable cores which had been previously mounted in lucite.2 The cores were clamped by means of insulated bolts between brass plates about 5 cm square and 1 cm in thickness. The plates were provided with a ring seal to prevent leakage between them and the core mount, and had a centrally located orifice so that fluids could be flowed through the mounted core. The brass mounting plates were used as electrodes and any current flow between them necessarily passed only through the constituents of the intervening core. Fluid saturation of the core, and fluid flow through the core, were effected by a centrifugal pump connected to the outflow end of the core, thus providing a differential pressure across the core of approximately one atmosphere. The procedure used was first to evacuate each core by means of the pump and then to saturate the core with an aqueous sodium chloride solution of known resistivity. The resistance of the core was measured and flow of the solution through the core continued for sufficient time to establish a constant resistance reading. After equilibrium had been reached with one solution, another sodium chloride solution of a different resistivity was flowed through the core and the flow continued until a constant resistance reading was again obtained. This procedure was continued until resistance measurements of the core had been made with a series of solutions within a salinity range from 1.0N NaCl to distilled water. The data obtained enabled the apparent formation factor of given porous rocks when saturated with fluids of different resistivity to be computed and also provided information regarding the ability of an invading fluid to displace interstitial water from a core. Results Berea Sandstone — The first core examined was a specimen of Berea sandstone." This core had been cut essentially parallel to the bedding for permeability studies. The core was clamped in the core holder and saturated with 1.0N NaCl solution and the resistance determined. It was subsequently flushed and the resistance measured when saturated in turn with 0.1N, 0.025N, 0.01N, .005N sodium chloride solutions and finally with distilled water. In flushing the core with each

Jan 1, 1950

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By Jesse O. Betterton

Recently some experimental work was conducted by the author in connection with the direct leaching of certain zinc ores with sulfuric acid with the object of subsequently recovering the zinc by electrolysis. The ores contained relatively large quantities of soluble silica, making it necessary to evolve special methods for handling the silicate solutions resulting from a leach of the ore, and also for the final removal of the silica before electrolysis. The problem was complicated by the presence of vanadium in the ore, the commercial recovery of which was very desirable. This paper, however, deals only with the silica phase of the problem. The zinc in the ore occurs in the form of a silicate (hemimorphite) and, to a very small extent, as the phosphate (hopeite) and carbonate (calamine); the vanadium is found as descloizite and vanadinite but mainly as descloizite. The experimental work was done in a plant producing 50 lb. of zinc = daily, in which the complete cycle of operations, including the final electrodeposition of the zinc, was performed continuously for one year. Some of the conclusions given here are the result of the operations in -this plant; the others are from laboratory tests inaugurated both as a guide to the plant operations and, in certain cases especially, to determine the limits in question. The practice in the 50-lb. zinc plant was to direct leach the ore crushed to pass 40 mesh, with spent electrolyte from the cells containing approximately 3 per cent. zinc and 10 per cent. free acid. This resulted in an acid leach solution and an ore residue. The acid leach solution was ' subjected to a special treatment for subsequent removal of vanadium; then the silica and vanadium in solution were precipitated together and removed as a "silica residue" by pressing through an ordinary plate and frame press. The next step was to treat the filtrate from the silica residue with zinc dust as a final purification step before it went to

Jan 1, 1923

By Lawrence B. Wright

The occurrence of gold, gold-silver, silver-lead-zinc ores in the post-Cambrian sediments in the Black Hills of South Dakota, and their genetic relationship to the Tertiary intrusives, is well known and accepted, but the occurrence of gold in the pre-Cambrian rocks at the Homestake mine, which underlie this Tertiary gold mineralization, has given rise to differences of opinion as to the period of major gold introduction into the older rocks. Fig. 1 illustrates the distribution of mineralization along the axis of the Tertiary uplift in both pre-Cambrian and post-Cambrian rocks. The following possibilities have been presented: 1. The Homestake gold deposit was formed in pre-Cambrian time and the deposits in the overlying Cambrian sediments formed during Tertiary time. 2. The Homestake lode existed at the beginning of Cambrian time, but was enriched by the passage of Tertiary auriferous solutions. 3. The Homestake lode was represented by pre-Cambrian quartz-chlorite sulfide mineralization, very low in gold content and the gold superimposed on the older nearly barren mineralization during the Tertiary metallogenic epoch. 4. The sulfides and sulfarsenides as well as gold were deposited in both pre-Cambrian and post-Cambrian rocks during the Tertiary period. Those favoring the first proposition feel that the question is pretty well settled, while the proponents of the second theory are more flexible in their view, feeling that the amount of gold introduced in either period is still an open question. The third and fourth theories, with some modifications, are supported by the proponents of the Tertiary theory, who feel that the evidence strongly favors that period. The following pages are intended to present the evidence and to give the reaction of various observers with my own comments and conclusions; also, the accumulated facts of observation gathered over a period of close association with the area under discussion, beginning in 1919.

Jan 1, 1937

By Jesse O. Betterton

Recently some experimental work was conducted by the author in connection with the direct leaching of certain zinc ores with sulfuric acid with the object of subsequently recovering the zinc by electrolysis. The ores contained relatively large quantities of soluble silica, making it necessary to evolve special methods for handling the silicate solutions resulting from a leach of the ore, and also for the final removal of the silica before electrolysis. The problem was complicated by the presence of vanadium in the ore, the commercial recovery of which was very desirable. This paper, however, deals only with the silica phase of the problem. The zinc in the ore occurs in the form of a silicate (hemimorphite) and, to a very small extent, as the phosphate (hopeite) and carbonate (calamine); the vanadium is found as descloizite and vanadinite but mainly as descloizite. The experimental work was done in a plant producing 50 lb. of zinc = daily, in which the complete cycle of operations, including the final electrodeposition of the zinc, was performed continuously for one year. Some of the conclusions given here are the result of the operations in -this plant; the others are from laboratory tests inaugurated both as a guide to the plant operations and, in certain cases especially, to determine the limits in question. The practice in the 50-lb. zinc plant was to direct leach the ore crushed to pass 40 mesh, with spent electrolyte from the cells containing approximately 3 per cent. zinc and 10 per cent. free acid. This resulted in an acid leach solution and an ore residue. The acid leach solution was ' subjected to a special treatment for subsequent removal of vanadium; then the silica and vanadium in solution were precipitated together and removed as a "silica residue" by pressing through an ordinary plate and frame press. The next step was to treat the filtrate from the silica residue with zinc dust as a final purification step before it went to

Jan 1, 1923