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Jan 1, 1943

Jan 1, 1943

Jan 1, 1971

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By R. W. Raymond

WISH to call the attention of the Institute to a curious subject, brought to my notice last summer by Mr. Begger, the accomplished metallurgist of the smelting-works of the Boston and Colorado Company at Black Hawk, near Central City, Colorado. At these works, the richest auriferous sulphhrets of Colorado (particularly copper pyrites) are smelted in reverberatories, together with roasted tailings (iron pyrites), and the gold and silver are concentrated into a new, artificial sulphide, or copper matte, containing $1500 and upwards of the precious metals per ton, and this is shipped to Swansea. I will say in passing, that this shipment of an unrefined product, like the similar shipments from Utah and Nevada to San Francisco, Chi¬cago, St. Louis, Newark, New York, and Europe, of crude argentiferous lead or "base bullion," is not a sign of incomplete metallurgy here, but has a sound business reason. The separation of the precious metals in the West would be more expensive, to begin with ; and then it would necessitate the movement of these metals by express, at high rates and risk, to commercial centres or coining mints, while the base metals having no home market, must be shipped and sold at little or no profit. At present, the gold and silver, safely packed, as it were, in the base metals, are transported with safety as ordinary freight; and the base metals probably more than pay cost of shipment and separation. To return to the Black Hawk reverberatories. On a recent occa-

Jan 1, 1873

By R. W. Raymond

I wish to call the attention of the Institute to a curious subject, brought to my notice last summer by Mr. Begger, the accomplished metallurgist of the smelting-works of the Boston and Colorado Company at Black Hawk, near Central City, Colorado. At these works, the richest auriferous sulphurets of Colorado (particularly copper pyrites) are smelted in reverberatories, together with roasted tailings (iron pyrites), and the gold and silver are concentrated into a new, artificial sulphide, or copper matte, containing $1500 and upwards of the precious metals per ton, and this is shipped to Swansea. I will say in passing, that this shipment of an unrefined product, like the similar shipments from Utah and Nevada to San Francisco, Chicago, St. Louis, Newark, New York, and Europe, of crnde argentiferous lead or "base bullion," is not a sign of incomplete metallurgy here, but has a sound business reason. The separation of the precious metals in the West would be more expensive, to begin with ; and then it would necessitate the movement of these metals by express, . - at high rates and risk, to commercial centres or coining mints, while the base metals having no home market, must be shipped and sold at little or no profit. At present, the gold and silver, safely packed, as it were, in the base metals, are transported with safety as ordinary freight; and the base metals probably more than pay cost of shipment and separation. To return to the Black Hawk reverberatories. On a recent occa-

Jan 1, 1969

By C. W. Kempton

If New England were located in some distant and almost inaccessible region, there is no doubt that its mineral resources would have been ere this well developed and generally acknowledged, but laboring under the disadvantage of nearness, it has been neglected. Its surface, moreover, is not cut up by mountains and canons, and the remnants of many of the old ridges are extensively covered by glacial drift. Having for the past ten months been engaged in the development of a mineral district in Southeastern Maine, 1 would take this opportunity to lay before the Institute sketches of results, and try to give some idea of the formations as found. The Sullivan Mining District extends from the town of Franklin, through Hancock, Sullivan, and Gouldsborough, from northwest to southeast, about sixteen miles. A general idea of this locality may be gathered from the map accompanying. (Fig. 1). Sullivan is situated at the head of Frenchman's Bay, ten miles north from Bar Harbor, Mount Desert, twelve miles from Ellsworth,

Jan 1, 1879

Jan 1, 1966

By B. N. Das, P. A. Beck

THE o phases have a complex tetragonal structure with Lo/ao = 0.52 and 30 atoms per unit cell.1 A large number of such phases are now known to occur in various binary systems of the transition elements and they exhibit the following typical features: 2,3 The composition of binary o phases is variable, ranging from approximately A4B to ABI. With only a few exceptions, in the o phases the A-ele-ment comes from the V- or Cr- group of the periodic table, while the B-elements are from the Mn-, Fe-, Co-, or Ni- group. In the first long period the corresponding o phases of the V- and Cr-series have approximately the same compositions. However, as the B-element changes from Mn to Fe to Co to Ni, the mean composition shifts monotonously toward higher A-contents.2-4 For example, if the mean compositions of the various o phases with vanadium are compared with each other, the composition shift mentioned above becomes plainly visible: V 30Mn0 80 Vo.45Feo..,, Vo .,Coo. 45 and Vo.5Nio.3. Similiar composition shifts, although not the same composition values, were observed in u phases formed by second and by third long-period transition elements.3'4 This behavior, very characteristic of o phases, is in rather sharp contrast to the usually quite well-behaved stoichi-ometry of the Laves phases. In the latter, the AB2 stoichiometry predominates, with A the large atom and B the small atom.= The p phase occurs in the four binary systems of Mo or W with Fe or Co. On the basis of their crystal structure determination, Arnfelt and westgren6 ascribed to the p phase in the Co-W system the ideal composition W,Co7. Since all four binary pphases have nearly the same composition, it would seem quite plausible that some definite stoichiometry such as A6B7, might be characteristic of this phase, as AB2 is of the Laves phases. On the other hand, it has been noted,7 that the phases occur at average electron concentrations near to those at which the various cr phases are found. Also, it has been pointed out by Shoemaker and associates8 that structurally the a phases and the p phases are somewhat related to each other; both of these structures may be described in terms of suitable stackings of quasi-hexagonal layers'of atoms. By studying a suitably chosen ter- nary phase diagram, one might expect to be able to find out which one of the two conditions, the analogy with the o phase or the constant ratio between the number of large atoms and the number of small atoms in effect governs the behavior of the p phase. Several isothermal sections of ternary systems containing o phases have been investigated. In all cases where two binary o phases occur, these were found to be connected b a more or less straight ternary o phase field.7' '10 Such elongated o phase fields were also found in ternary systems in which only one of the limiting binaries is known to contain o phase. In this manner a latent o forming tendency could be detected and the virtual composition of a "binary o phase", which does not actually occur as such was approximately determined by extrapolation. The behavior of the phases, including their composition shift, is analogous to that of the classical electron compounds, as described by Hume-Rothery.11 In order to decide whether the p phase is essentially a "size compound" like the Laves phases, where a fixed stoichiometric ratio is quite generally maintained between the "large atoms" and the "small atoms", or whether the p phase is typically an "electron compound" in the same sense as ois, it was decided to investigate an isothermal section of the Mo-Mn-Co system. The Mo-Co system12 and the Mo-Mn system13 each are known to have a binary o phase. It could be therefore expected that a ternary o phase field will connect these two binary cr-phase fields. The p phase is known to occur in the Mo-Co system. If the p phase should turn out to form an elongated phase field extending deep into the ternary system, the following considerations mighto apply. The atomic radius of manganese (1.314for C.N.12) is between the va,lues for Mo (1.40Afor C.N.12) and for Co (1.26Afor C.N.12). If it is assumed that p is a "size compound", and that Mn is substituting for the smaller Co atoms in the p-structure in the ternary system, the y-phase field might be expected to extend parallel to the Mn-Co binary line. If Mn is substituting for the large Mo atoms in the p-structure, the p-phase field may be expected to extend parallel to the Mn-Mo binary line. On the other hand, if the p-phase turns out to be an "electron compound" like o, the ternary p-phase field should extend parallel to the ternary o -phase field connecting (Mo,Mn)owith (Mo, Co) a

Jan 1, 1961

By GEO M. FOWLER

AN appraisal of the activities of the mining geologists during 1936 clearly indicates the ever in- creasing utilization of geology in the search for ore. Few men with geo- logic training are idle at present; this is particularly true regarding recent graduates. Many have accepted employment in distant fields, such as the Philippines and South America, and greatly increased mineral production from these places reflects their activities. In North America, regions of intense mineralization formerly important are being restudied in greater de- tail and with better understanding; as a result, new mineral wealth is being found in many such districts. Much is being done by private companies and individuals, and it is to be hoped that mining companies will increasingly make available the purely scientific results of such studies by permitting their geologists to publish. On such generosity to a large extent will future advances in ore finding depend.

Jan 1, 1937

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy's spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,' was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969

By W. M. Peirce

COAL'S importance in the metallurgy of zinc may be gauged by the fact that approximately a million and a half tons is so employed annually in the United States. This brief paper will show in what way the various steps in the treatment of zinc ores utilize this fuel, either in its primary form or as coke or gas, and to what extent. The first step in zinc metallurgy that requires the use of fuel is roasting the sulphide ore, which is the type of ore in which zinc commonly occurs. Since the roasting is nearly or completely autogenous, however, this use of fuel is too minor to warrant further attention. Concentration of zinc ores is usually carried out by conventional milling methods, but a pyrometallurgical method, the Waelz process, is used to concentrate certain low-grade ores, and to recover the zinc content of certain residues in concentrate form. The Waelz process uses a continuous rotary kiln in which a mixture of coal and zinc-bearing material is heated to a

Jan 1, 1948

Jan 1, 1968

By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after it has been pulverized to pigmentary size. The current world production of iron oxide pig¬ments is estimated by the author to be between 450,000 and 550,000 tons based on 1969 data. The fact that highly colored natural deposits of iron ore are found throughout the world ac¬counts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments pro¬duced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970). Nomenclature With the increasing importance of the syn¬thetic iron oxides it is necessary to make a distinction between the natural or mineral pig¬ments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a com¬mercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pig¬ments. Natural pigment ore sources are se¬lected for their special physical-chemical prop¬erties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pig¬mentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments.

Jan 1, 1975

By J. Jones-Parra, R. S. Reytor

The porosities of fractured limestone reservoirs can be divided into two broad types in accordance with their effects on fluid distribution and fluid flow. In the coarse porosity, gravity segregation lakes place freely and the resistance to fluid flow is very small. In the fine porosity there is no segregation and a high resistance to flow, and it has relative permeability characteristics similar to tight sandstones. By analyzing the affect of the two porosities it is concluded that in some cases to recover the maximum amount of oil it is necessary to remove large quantities of gas from the reservoir by producing at high gas-oil ratios. In this manner the fine porosity is drained of its oil and the gas-oil contact drops slowly permitting higher production rates from the oil leg. Since this conclusion is contrary to widely accepted principles of conservation, a mathematical model (Fig. I) was constructed to duplicate the conditions desired. The behavior of the model indicates that under certain conditions it is possible to recover more oil by producing at high gas-oil ratios than by production at low gas-oil ratios, and that the rate of production is affected more by gas shut-offs than by the decrease in pressure (Figs. 2, 3, 4 and 5). INTRODUCTION It has been noted that certain limestone reservoirs behave in such a way as to indicate that there are two distinct types of porous spaces available for fluid storage and fluid flow. Regardless of the nature of these porous spaces the distinguishing characteristic is that in one type of porous space there is definite gravity segregation between the oil and the gas; while in the other, the gas evolved tends to remain distributed equally throughout the reservoir. For the sake of simplicity the porosity in which gravity segregation takes place at a fast enough rate to affect the behavior will be called "coarse po- rosity", while that in which this is not so will be termed "fine porosity". The behavior of a reservoir of this type would be different than that of a sandstone reservoir, especially if most of the oil is in the fine porosity. It has been observed that fluid flow to the wells takes place mostly through the coarse porosity. The large fractures which

Executive SCOTT TURNER, Chairman FREDERICK M. BECKET JOHN A. MATHEWS H. A. GUESS WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL D. MERICA ROBERT E. TALLY Admissions JOHN M. LovEJOY, Chairman GEORGE D. BARRON ERLE V. DAVELER WILLIAM H. BASSETT W. D. B. MOTTER, JR. Alternates HENRY B. FERNALD F. JULIUS Polls AMOR F. KEENE

Jan 1, 1932

By Carl Henrich

Jan 1, 1893