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By Ralph Hultgren

FEW phase diagrams of alloys composed of two transition metals have been adequately studied, probably because of the high melting points involved. Transition metals are the elements that have inner shells incompletely filled with electrons. They comprise groups IIIa to Villa of the periodic table, including more than half of all metals. We have chosen to study two systems whose comparatively low melting points allowed the alloys to be melted in a molybdenum resistance furnace. The nickel-palladium system proved to consist of a simple series of solid solutions, but iron-palladium manifested several remarkable features. The main characteristics of the latter diagram were decisively established, but lack of time prevented precise determination of phase boundaries. The gamma to alpha transformation in this system is unusual and warrants further study. Grigorjew1 determined the liquidus and solidus of the iron-palladium system by thermal methods. He found a minimum melting point, but no eutectic. He also found that palladium lowered the gamma to alpha and raised the gamma to delta transformation temperatures of iron, with a complete series of solid solutions existing between gamma iron and palladium. His measurements also indicated a compound or super-lattice near the composition FePd3. Jellinghaus2 found that annealing at 500° C. greatly increased the magnetic coercive force of an alloy of composition FePd. X-ray dif-fraction photographs showed that a tetragonal ordered phase had formed during the anneal.

Jan 1, 1939

Jan 1, 1892

By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860's. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen's and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier's principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury' in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott's difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde's equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde's equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955

By F. E. Calkins

THE following presentation of the more important accumulated facts and probabilities involved in copper ore deposition is based on my experience in examination work and study of the extensive litera-ture of the subject; to make personal mention of all sources of information would require the naming of a small army of able geologists and other investigators who have contributed to, building up the science. I have tried to present the salient features of the subject in logical order and condensed form, and to point out the relative importance of processes involved. Doubt-less many geologists could suggest some changes and many additions. ORIGINAL SOURCE The original source of all copper was in the earth's interior; it has been brought to the outer part of the earth, within reach of man, in three ways: (1) By intrusions and flows of basic igneous rocks containing copper in minute quantities, presumably as silicate or sulfide. No orebodies have been formed by this method. (2) As segregations within intrusive igneous rocks, the copper minerals having solidified at the same time as the rock itself. The few deposits known to have been formed in this manner have been of little or no importance. The oft quoted Sudbury nickel-copper deposits are now known to belong to the class following. (3) By gaseous or liquid aqueous emanations from ,large deep-seated masses of intrusive molten rock. These emanations, or mineral solutions, ascended through zones of connected openings in the earth's crust and dropped their load at points far above their source. Deposits formed in this manner were the primary source of nearly all, if not all, of the world's copper production.

Jan 10, 1923

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By R. K. Dunham, A. N. Styler

The results of two studies into the effects of undermining offshore room and pillar workings by longwall faces are presented. The first study indicated no potential instability from undermining one level of room and pillar workings. On the basis of this it was decided to undermine two levels of room and pillar workings, again monitoring pillar stability. The results showed no signs of increased instability.

Jan 1, 1982

By Hans Haalck

PRACTICAL or applied geophysics-as we designate the border region between physics and geophysics on one hand and practical geology on the other-has as its object the application of physical or geophysical methods of investigation to problems of practical geology. Its field of operation comprises all methods of physical measurement that are used in the problem of determining, from the geophysical influences of the subsoil that can be measured at the surface of the earth, the special characteristics of the association of strata, faults, etc., to detect the presence of deposits and to investigate underground structures. It therefore represents an aid, a physical method of research in practical geology, and is inseparably connected with geological studies; for this reason, it is also called geophysical prospecting. Formerly research methods of practical geology were based on observation exclusively: first, on the observation of the strata and formations at accessible tarts of the surface of the earth, especially in shafts, borings and mines if such were available; then on the observation of the tectonic conditions in so far as these were already known at places directly visible; and finally, by estimation of the importance of formations of the terrane. Later, there were added in special cases, analytical chemical crystallographical, petrographical and similar investigations of rock samples which were taken from the places under consideration. The knowledge thus obtained is of value and is expanded by hypotheses and constructions that are supported by geological theories of origin and by laws of the sequence of formations and rock systems, which are based on long experience.

Jan 1, 1928

By J. B. Newkirk

Results of a Debye-Scherrer X-ray investigation are given which show that the order-disorder transformation is a first-order or heterogeneous reaction in Cu-AU alloys with compositions near CuAu. Evidence was found for conventional tie-line segregation across a usual type of two-phase field separating the ordered and disordered fields in the Cu-Au equilibrium phase diagram. The horizontal and vertical widths of the two-phase fields are about 3 atomic pct and 20°C, respectively, at 43 and 54 atomic pct Au. No evidence for the existence of an ordered structure based on a stoichiometric composition of Cu3Au2 could be found. ALTHOUGH the modern theories relating the de-Agree of order of binary alloys to temperature and composition have met with considerable success, the nature of the transformation from the disordered state to the ordered state and vice versa has never been well understood. It has been assumed by some' that this is a second-order transformation, that is, a homogeneous change of state. Others2 hold that the transformation is first-order and that the effects characteristic of heterogeneous phase transformation apply. Since this subject is discussed in detail in a recent paper,' the arguments will not be repeated here. The present paper summarizes an experiment which was designed to distinguish between these two viewpoints for the case of Cu-Au alloys near the composition CuAu. The Cu-Au system is an important one because it furnishes prototype alloys, the behavior of which has formed the basis of much of the present-day order-disorder theory. It has recently been shown- hat in alloys near Cu3Au there is a temperature range within which the ordered and disordered states coexist in equilibrium and are distinguishable as separate phases. Therefore, the transformation must be first-order for these alloys. A similar demonstration for alloys near CuAu, however, has been lacking. Experimental Method Essentially the experiment consisted of equilibrating Cu-Au samples at various temperatures, quenching them in water to retain the high temperature states, and then examining them at room temperature for the coexistence of the ordered and disordered structures. The thermal gradient method of heat treatment- as used because it was important that all temperatures over the transformation range should be represented in the test. Briefly, this method consisted of holding a wire of the desired composition, sealed under vacuum in Pyrex, in a known temperature gradient for a long enough time to allow each part of the wire to assume the crystal structure characteristic of the temperature at which it was held. The temperature gradient was produced by inserting into an ordinary wire-wound cylindrical laboratory furnace, an 18 in. length of 1/8 in. ID ceramic tube which was heavily wrapped with asbestos. The furnace power was controlled by a Tag-liabue Celectray controller and a chromel-alumel thermocouple with the junction located on the heating elements. During the equilibrating treatment the widest variation of temperature within the gradient tube was approximately 4°C at the highest temperature. The temperature at various places within the tube was determined, before inserting

Jan 1, 1954

By ERIIL SCHROEDTER

THE death, on May 6, 1908, of Dr. Hermann Wedding, Privy Mining Councilor of the Kingdom of Prussia, and Professor of the Metallurgy of Iron and Steel at the Royal Mining Academy of Berlin, was a loss keenly felt by the whole metallurgical world. Not alone in his native land, but also in foreign countries did he enjoy an esteem of which the title of honorary membership in the American Institute of Mining Engineers, the United States Association of Charcoal Iron-Workers, and the (British) Iron and Steel Institute bears eloquent testimony. Hermann Wedding was born March 9, 1834, in Berlin. At the suggestion of Dr. C. J. B. Karsten, the veteran father of Prussian metallurgy and author of the first German text-book of the metallurgy of iron, lie turned his attention, after gradu¬ating from the gymnasium, to mining and metallurgy. In 1853, he began a practical course at the Malapane iron-works, in Upper Silesia. Subsequently, he studied at the Berlin Mining Academy, and received from the University in 1859 the degree of Doctor of Philosophy. A journey which be made to England, somewhat later, led to his undertaking a German translation, with revision and additions, of John Percy's classic treatise on the metallurgy of iron and steel, the publication of which, in successive installments, stretched through many years. In 1863, lie published, as a thesis in connection with his "Assessor's examination," an essay, entitled The Results of the Bessemer Process for the Production of Steel, and Its Prospects for the Rhenish and Westphalian Iron and Steel Industry, which revealed such ability and knowledge as to secure for him a call to the chair of metallurgy in the Berlin Mining Academy.

Jun 1, 1909

By E. J. Wasp, T. C. Aude, F. B. Raymer

The following paper deals with technical aspects of terminal facilities for western coal pipelines. The information is taken from the Ohio and Black Mesa pipelines and the proposed one in Wyoming. This paper first discusses the feed terminal, the product that it must produce, and the reasons for coal cleaning. Then in the delivery terminal section, the various methods of dewatering the coal and some recent innovative ideas on bunkering the dewatered product and storing the dewatered coal in large outdoor piles are discussed.

Jan 1, 1979

Jan 1, 1930

By Thomas N. Walthier

Throughout the world, governments are placing increasingly severe restrictions on mineral exploration and mining activities. One result is that there are fewer places left where mining companies are wanted or investors are willing to go.

Jan 4, 1976

Future of State and Federal Oil Regulation. BY NORTHCUTT ELY (Trans , vol 118 2400 words) The Interstate Oil Compact, ratified by six states and Congress in 1935, replaced the petroleum code, invalidated with other codes by the Schechter decision This compact endeavors, first, to conserve reservoir energy of oil pools through substantially uniform conservation measures by the states, second, it recognizes the state rather than the Federal Government as possessing the necessary police power for that purpose, third, it establishes an interstate advisory commission, so that orderly production in one state is not penalized by uncontrolled production in another, fourth, Federal interests are recognized in the control of hot oil, regulation of imports and fact-finding forecasts of supply and demand by the Bureau of Mmes It is not as complete an instrument as proposed by the Federal Oil Conservation Board in 1932, but is workable, and will be effective in proportion to the support given it by the industry Three results may follow First, now that fear of Federal control has subsided, the industry may lose interest in the compact and let it fall to pieces, second, if vigorously supported by the industry, the compact can accomplish most of the conservation objectives sought by the Federal control measures now believed unconstitutional, third, if the Compact fails, Federal regulation is almost certain to be revived, and can probably be sustained in connection with neutrality legislation, regulation of interstate pipe lines, and coordination of Federal and state gasoline taxes Nearly every step toward governmental regulation has originated within the industry state proration, the Federal petroleum code, Federal control of imports, Federal control of hot oil are examples The Compact shows a trend toward coordination between the powers of the industry, the state government, and the Federal Government If this arrangement fails through lack of interest by the oil industry, the next step is likely to be absorption by the Federal Government of the other two factors involved in the situation

Jan 1, 1937

By Nicholas J. Grant, Italo S. Servi

Extensive data of minimum creep rates and rupture times for high purity and commercial aluminum confirm the existence of a transition range from the low temperature-type to the high temperature-type behavior. The data are analyzed in line with the suggested theories of deformation of metals. CONSIDERABLY more work has been done on the rupture and creep behavior of commercial alloys than on the less complex, high purity metals. As a result, certain fundamental behaviors are overlooked. One of the lesser known variables affecting the high temperature behavior of metals is the impurity content (or alloy content). Impurities are known to affect strongly the recrystallization temperature, electrical resistivity, and other properties of metals, but the effect on creep and other high temperature mechanical properties has been determined for very few materials. In view of these facts aluminum appears to be a fairly ideal metal, since it is available in a wide range of purity contents from 99.995+ down through the 2s (99.0 + Al) and 3s (1.2 Mn) grades in small steps. It is highly resistant to oxidation and other surface instabilities, leaving recrystallization and grain growth as virtually the only instabilities. Control of grain size is also well standardized. Limited data on the creep of aluminum have been obtained by Dushman et a1.l for high purity aluminum; by Sherby2 on 2s aluminum of variable grain size; and by Dorn and Tietz³ on cold-worked 3s aluminum. Experimental Procedure The apparatus consisted of a constant stress, creep testing unit similar to the type described by Hop-kin.' The specimens were held at temperature for 30 min before loading. The loading time was less than 2 min. Factors affecting the accuracy of the data were: 1-—the temperature gradient and control, ± 3°F; 2-the stress determinations, ± 1.5 pct; and 3—elongation measurements (1 in. gage), ? 0.001 in. Three grades of aluminum were tested: 1— high purity (99.995 pct Al), 2—2s (99.3 pct Al), and 3—3s (98.2 pct Al). The spectrographic analyses of these materials are reported in Table I. The specimens were annealed then electropolished in a perchloric-acetic mixture before testing. Data on heat treatments and grain size obtained appear in Table 11. The entire creep curve was determined for almost all of the tests. A few tests were interrupted after the beginning of the third stage of creep, and in these cases the rupture time was estimated. Experimental Results Constant stress creep-rupture testing gives a much longer, more accurately measurable second stage of creep than constant load testing. This behavior is in agreement with the results obtained by Andrade for lead (see Fig. 1). If the test is run to completion, the third stage of creep appears as soon as stress intensification occurs. In the case of specimens which fail in a ductile manner, the stress intensification begins when the sample starts "necking". This differs from the "high temperature brittle" specimens in which the stress intensification is caused by intercrystalline cracking. These specimens

Jan 1, 1952

By V. R. Garfias

Even before the arrival of Cortes in 1519, the history of Mexico was closely linked to that of its mineral production; the mining activities of the Aztecs being thus described by Clavigero, one of the early historians: In the mountains of Anahuac there abound in veins all kinds of metals, and infinite variety of other fossiliferous products. The Aztecs obtained gold from the countries of the Cohuijques, of the Mixtecas, of the Zapotecas and from various other places. They gathered that precious metal usually in gain, from the sands of the rivers, keeping a certain portion for the crown. They obtained silver from the mines of Taxco, of Tzumpango and others; however, this metal was not as esteemed by them as by other neighboring nations. They had two kinds of copper; one hard, which they used instead of iron to make sickles, lancea and all kinds of rural and military instruments and another, soft, with which they made kettles, goblets and other receptacles. This metal abounds mainly in the province of Zacatula and in that of Cohuijques, which at present is in the kingdom of Michoacan. They obtained tin from the mines of Taxco and lead from those of Izmiquilpan, located in the country of the Otomies. From the tin they made money, and the lead, we know they sold in the market places, but we ignore the uses to which they applied it. They also had mines of iron in Tlaxcala, in Taxco and in other places; but they either had not discovered them, or did not know how to make use of the metal they contained. In Chilapa there were mines of mercury, and in other places there were mines of sulphur, alum, vitriol, cinnabar, cohre and of a white earth which they esteemed highly. As regards mercury and vitriol, we do not know of what use they were to them; the other metals they used in paintings and dyes. There were then great abundance of amber and asphalt—bitumen of Judea—on the coast of the seas and many cities of that territory paid tribute of one and the other to the kingdom of Mexico. They mounted the amber in gold, and it was only used as ornament and display by them. With the asphalt they made certain perfumes. The following extracts dealing with pre-Colonial gold are taken from the famous " Cartas de RelaciÓn " to Charles V, in which Cortes described the progress of the Conquest: . . . here there came two chiefs who owned lands in the valley; one four leagues down the valley and the other two leagues up the valley and they gave me some gold necklaces of little value and seven or eight girls. . . . . . . that day I left the City of Churultecal and traveled four leagues to some villages of the City of Cuasucingo where the natives received me very well and gave me women and pieces of gold. . . .

Jan 1, 1937

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

Jan 1, 1942

By H. E. Sadler, Prof. Silliman

The research here recorded was undertaken early in the present year, and has been prosecuted steadily for about eight months. While the work has been under my constant supervision and advice, the labor has all been performed by Mr. Sadler, to whom is chiefly due the development of the successive steps which have led to the final result. The process is better than I dared to hope, and we are able to place at the command of chemists and engineers interested in the matter an apparatus of continuous and uninterrupted action, and methods of analysis by which the daily averages of the two variable and inconstant factors of illuminating gas, ammonia and sulphur, may be determined with all needful accuracy, even by those little skilled in chemical manipulation, and with very little loss of time. This research has been carried out in the laboratory of the New Haven Gaslight Company.

Jan 1, 1957