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By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By R. C. Weed

LEACHING in place at Cananea began in the 1920's on a limited scale. The first plants were small wooden boxes located underground in the Capote and Oversight mines, and output was low. Scrap iron was used as precipitant. Later several other small plants were started up. Leaching was limited entirely to underground areas, and production remained low. The Veta precipitating plant, the first on a larger scale, was put into operation in the late 1920's. After a period of intermittent service it was rebuilt in 1946 and has since been running continuously. In 1943 work on the Colorada open pit was started. This produced 40 million tons of waste, which averaged 0.20 pct capper. When these dumps had aged a few years it was decided to leach them on a large scale, and after considerable research and investigation a leaching system of pumps and pipelines was laid out and installed. At the same time the Ron-quillo precipitation plant was built to treat the copper solutions from the pit dumps. This plant started operation in March 1953. Leaching areas consist of the Colorada pit dumps and various mined out and caved underground stopes. The principal mineral, chalcocite, leaches readily in a weak sulfuric acid solution containing ferric iron. Enough pyrite is contained in the areas to produce an acid-ferric iron solution strong enough to dissolve the copper. Each area is studied to determine the best method of distributing the water over it and the best method of collecting the copper-bearing solutions after leaching has taken place. Water is generally distributed by means of ponds, ditches, and sprays. Spraying has proved the best method of spreading the water evenly; however, in a dry climate some water is lost through evaporation. After passing through the leachable material the solution is collected underground by dams and bulkheads and on surface by dams. An effort is made to give the maximum storage capacity practicable.

Jan 1, 1957

By P. S. Rudman

Laves phases, AB2, are considered as Izerrzisub-stitutional solutions m1hich are defined by a one-for-truo replacement scheme. Atomic-size tnisfit is considered in terms of deviations of the ratio 2V°b/V°A from unity, where v° = atomic volume. A simple elastic model has been used to calculated deviations from "Vegard&apos;s law of atomic vol-umes". Comparison has been made between calculated and observed atomic-volume deviations fov 222 Laves phases. Agreement is generally very good although there ave some few exceptions which appear to be excusable in terms of electronic changes that ore beyond the scope of the present model. We can consider the formation of a binary sub-stitutional solution A-B from an A solvent as one-for-one replacements of A atoms by B atoms. As the atomic-size ratio deviates from unity, the solution becomes thermodynamically less stable and hence more restricted because of atomic-misfit strain energy. In accordance with our previously presented conclusion1 that the atomic volume, v, is in general the most appropriate measure of atomic size, the ideal size ratio for a binary sub-stitutional solution is vg/vA = 1. The Laves phases have been described by Berry and Raynor2 in terms of various stacking sequences of hexagonal layers of B atoms for the three structures MgZn2(C14), MgCu2(C15), and MgNi2(C36). To form the Laves phase of ideal composition AB, we start with complete hexagonal layers of B atoms in the appropriate stacking sequence and we remove, according to an appropriate scheme for each structure, two out of every four B atoms and replace the two removed atoms by one A atom. We thus might expect to find that the ideal size ratio for the Laves phases is 2v/B/ VA= 1. From this point of view, then, we call Laves phases hemi-substitutional solutions since we employ one-for-two replacements. By analogy with substitutional solutions we can expect for Laves phases that as the ratio 2VB/Va deviates from unity the phase occurrence will be more restricted. Laves3 has plotted the distribution of Laves phases as a function of the radius ratio, ?A/rB, and found that, while the distribution extended from 1.05 < rA/B < 1.50, the

Jan 1, 1965

By Claude H. P. Lupis, John F. Elliott

WAGNERL described the thermodynamic behavior of a metallic solution consisting of the solute components 2, 3,... at very dilute concentrations in the solvent, 1, in terms of the excess partial molar free energy, or alternatively the logarithm of the activity coefficient. In the Taylor expansion of FiE, by neglecting the second- and higher-order differential terms, he obtained the excess partial molar free energy as a linear function of the composition:

Jan 1, 1965

By Richard R. Klimpel

This paper takes the liberation model recently developed by Klimpel and Austin for liberation from a binary system and reduces the over-all model form to a number of useful limiting cases. General use of the complete model form, while quite broad in utility, requires a numerical integration computer program for prediction of liberation given a specified minor component grain size distribution coupled with an optimization algorithm such as linear programming in order to back- calculate the associated grain size distribution from experimental data. In this paper, analytical solutions to the model are achieved for various assumed distributions of the minor component. These solutions are algebraic equations capable of predictive use with a hand calculator and back-calculation with very simple trial and error search procedures. The use of these special model solutions is illustrated on several sets of experimental liberation data, and the approach is shown to have practical utility.

Jan 1, 1984

By L. W. Pommier, F. B. Brien, A. K. Bhasin

The diflerential movement of solid particles through solid-liquid suspensions is very important to many branches of engineering. The flow of suspensions around immersed bodies is mainly of a turbulent nature. Problems are encountered when attempts are made, as is the general practice, to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. The conventional velocity and resistance relationships for turbulent flow in fluids when applied to suspensions, do not take into consideration the two very important variables: suspension particle size and solid volume fraction. A study of the effect of suspension particle size (dgb) on the velocity of falling balls leads to the concept of a critical particle size (dgc) at which the suspensions will be Newtonian. This leads to the classification of static suspensions into two types: suspensions consisting of particle of diameter dgh > dgt, and those with dgh, < dgr. Separate velocity and resistance equations for these two types of suspensions have been proposed, taking into account both the solid particle size and solid volume fraction. The agreement between the velocities predicted from the proposed equations and the measured velocities, confirms their validity. The resistance force offered by suspensions to the movement of immersed bodies has been calculated from the proposed equations, and the effects of suspension particle size and solid volume fraction on the resistance force and velocity have been examined. The movement of immersed bodies in solid-liquid suspensions is of great importance in many areas of engineering such as minerals processing, oil well drilling, suspension flow in pipelines, and hydrometallurgy. A number of mineral dressing processes deal essentially with the movement of solids in suspensions—in particular, classification, thickening, filtration, ore washing, and gravity concentration—thus a study of the fluid characteristics of suspensions is of theoretical and practical interest.&apos; A rigorous analysis of the mechanisms of momentum transport of a solid-liquid system is complex indeed. The rheological properties of the suspensions deviate from those of liquids, varying, for example, with density, solid volume fraction, size and shape of the solid phase of the suspension, and with the density and viscosity of the liquid phase. The flow of suspensions around immersed bodies is mainly of a turbulent nature and hence studies of the turbulent flow characteristics of suspensions are of par- ticular importance. Problems are encountered when attempts are made to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. Due to the numerous variables present in a suspension, certain limitations and assumptions become necessary in order to produce quantitative relationships for predicting their effects. The solid particle size and the solid volume fraction are two of the more important variables. By comparing the measured and calculated Newtonian velocities of falling balls in simple static suspensions, the existing velocity and resistance relationships have been modified to take these variables into account. In order to keep the study less complex, all other variables such as the characteristics of suspending liquid and shape of the particle are maintained constant. Objective The objective of the present investigation is to modify the Newtonian velocity and resistance equations in order to take into account the suspension particle size and solid volume fraction. Theory Liquids are classified on the basis of viscosity, which may be defined as the relationship between applied shear stress and resulting rate of shear.&apos; pure single-phase fluids composed of small light molecules behave as Newtonian liquids, having a single viscosity pa-

Jan 1, 1971

By M. B. Bever, A. M. Reti, A. K. Jena

The results of this investigation show that in the system SnTe-PbTe l) the solid solutions have small exothermic heats of formation relative to the binary compounds, 2) solid-solution hardening is almost absent, 3) the tin and lead atoms are .randomly distributed on the sublattice occupied by them and do not undergo an ordering transition during a thermal treatment designed to promote such a transition, and 4) the lattice parameter changes linearly with composition. These findings suggest that the solid solutions of tin telluride and lead telluride approach ideal behavior. THE binary compounds SnTe and PbTe form a continuous series of solid solutions.&apos; Information on several physical properties of these solid-solution alloys has been published.1"3 In the work reported here, the heats of formation, microhardness, and lattice parameters of these alloys have been measured and the possibility of an order-disorder transition has been investigated. Order-disorder transitions occur in some solid solutions of binary compounds. In the system Bi2Te3-BizSes, for example, the electropositive bismuth atoms and the electronegative tellurium and selenium atoms always occupy separate layers. In the disordered alloy Bi2Te2Se, the tellurium and selenium atoms are randomly distributed on the layers occupied by them, while in the ordered alloy they occupy distinct layers.4 The NaC1-type (Bl) structure of SnTe-PbTe alloys consists of two sublattices, one of which is occupied by the electropositive tin and lead atoms and the other by the electronegative tellurium atoms; any ordering would be expected to occur in the sublattice occupied by the tin and lead atoms. PREPARATION OF SPECIMENS Polycrystalline specimens of PbTe and Sn1-xPbxTe (x = 0.25, 0.50, and 0.75) were prepared by melting stoichiometric amounts of lead (99.999 pct), tin (99.98 pct), and tellurium (99.999 pct) in evacuated and sealed Vycor tubes. Because of the deviation of tin telluride from the stoichiometric composition5 this compound was prepared by melting 49.8 at. pct Sn and 50.2 pct Te. The tubes containing the melts were quenched into water; the solidified ingots were removed from the tubes and annealed for 2 weeks in vacuum (PbTe approximately 100°C below its melting point, the three alloys 100°C below their solidus tem-

Jan 1, 1969

By D. D. Todd, W. A. Oates

THERMODYNAMIC data for solutions are best derived from a combination of equilibrium and calorimetric studies. However, the accurate measurement of heats of mixing of metallic solutions at high temperatures presents considerable experimental difficulties, simple calorimeters1-3 giving

Jan 1, 1964

By Wendell E. Dunn

INTRODUCTION The early history of the chloride process has been recorded in a chapter of a Bureau of Mines bulletin (9 by one of the inventors of a chloride process, Stewart Croasdale, who is famous for the Pohle- Croasdale Process. The earliest use of chlorine in metallurgy was in 1557 by Bartholome Medina. But apparently even earlier there was knowledge that salt could be used in gold and silver extraction because a treatise, de la Pyrotechnica, published in 1540 in Venice, asserted that silver could be obtained from its ores by a wet salt process. In 1609 a priest, Alonzo Barba, invented a process using a copper vessel and boiling a solution of salt to extract silver chloride ores. The copper vessel was, of course, one of the reactants. This led to the Kronke process introduced in Chile in 1860 which substituted cuprous chloride for the kettle. A major step was taken in Europe in the late 1700&apos;s to chloridize roasted silver ores in combination with amalgamation using iron to reduce the silver chloride. By 1843 the Augustan process was introduced. Ores were roasted with salt and leached with a saturated salt solution. The silver chlorides passed into solution from which silver was precipitated by copper. In 1848 sodium or calcium thiosulfate solution of silver chloride was suggested by Dr. John Percy, and the idea was applied in 1856 by Von Patera in Bohemia.

Jan 1, 1983

By N. J. Olson, G. W. Toop

A regular solution is characterized by a finite molar heat of mixing and entropy due only to ideal or random mixing. The thermodynamic properties of binary regular solutions which exhibit constant atomic coordination number and constant atom-atom intefac-

Jan 1, 1967

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By F. R. Conley, D. A. Shock

Solution Mining or In Situ Mining has received increasing attention in the past few years because the method offers many attractive possibilities in improving the environmental impact of mining as well as making feasible the extraction of deeper, low value mineral reserves. This paper will present a brief discussion of the state-of- the-art in total solution, slurry removal and leach mining. As a specific example of utilizing the method, the uranium deposits of South Texas are a type of deposit which have been considered as being amenable to in situ leach mining. The parameters required to ascertain the amenability of such a deposit for in situ leaching will be presented. The hydrological factors which influence the production of the soluble uranium solutions and their displacement will be discussed. Mathematical models for various well configurations have been made and graphic representation will be presented to illustrate various production methods and the resultant hydrological consequences.

Jan 1, 1974

By R. H. Doremus

From measurements of carbide precipitation rates in a iron it was concluded that the carbides nucleated on dislocations in both strained and unstrained samples, except for the latter at lower temperatures and higher carbon concentrations, where there were more muclei than could form on the dislocations. The equation of Cottrell and Bilby for the segregation of atoms to dislocations was found to be inapplicable to this system. No satisfactory theory for the growth process is available. A study of the rate at which a second phase separates from solid solution can frequently reveal much about the mechanism of separation. There are still many features of the precipitation of carbon from a iron that are not understood, although this system has been examined extensively. To provide more insight into the mechanism of carbide precipitation in a iron, rates of this process were measured at different temperatures, carbon concentrations, and densities of dislocations in the iron. The concentra- tion of carbon in solution was followed from the height of the internal-friction peak; this height is directly proportional to the amount of carbon in solution and is not affected by the growing carbide particles. In this paper these rates are compared with those found by earlier investigators, and the mechanism of precipitation is discussed in light of these results as well as two earlier studies1, 2 and the electron microscopic work reported in the preceding paper. EXPERIMENTAL The amount of carbon in solution was followed by

Jan 1, 1961

By Herman F. Kaiser, Charles S. Barrett, Robert F. Mehl

The copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possibility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previously the structures in this system are unique in their origin, for one terminal solid solution will precipitate the other, and vice versa. In most of the other systems for which crystallographic data on the precipitation (or transformation) process arc available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system&apos; is 779" C. At this temperature copper dissolves 4.3 atomic per cent (7.0 weight per cent) of silver in solid solution; this solid solubility decreases to zero at room temperature.² Silver at the eutectic temperature rctains 14.0

Jan 1, 1935

By Charles S. Barrett, Herman F. Kaiser, Robert F. Mehl

The copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possibility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previously the structures in this system are unique in their origin, for one terminal solid solution will precipitate the other, and vice versa. In most of the other systems for which crystallographic data on the precipitation (or transformation) process arc available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system&apos; is 779" C. At this temperature copper dissolves 4.3 atomic per cent (7.0 weight per cent) of silver in solid solution; this solid solubility decreases to zero at room temperature.² Silver at the eutectic temperature rctains 14.0

Jan 1, 1935

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O&apos;Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

By W. M. Weigel

Economic deposits of barite occur in Missouri in two main districts. The most important, the Southeastern or Washington County district, is in the southeastern part of the state, mostly in Washington County with a small extension into the northeastern part of St. Francois County. Roughly, it embraces nine townships or about 200,000 acres and accounts for from 80 to 90 per cent. of the state production. The Central district, is in the central part of the state, includes most of Morgan and Miller counties, and parts of Camden; Benton, Moniteau and Cole counties. The area embraced is much larger than the Washington County district, but the deposits are more infrequent. The location and general area covered by the two districts is shown in Fig. 1. There is another small area in southern Franklin County but so far its production has been of small consequence. It might be considered as a northward extension of the Washington County field. An, area in the central part of Hickory County has also produced a small amount. The outline of the districts as shown indicates the general area in which deposits have been found. The total area covered by deposits of barite is only a small part of this, as, in the Central district especially, there may be miles of supposedly barren areas between ore-bearing areas of an acre or two in extent. The date when barite was first mined in Missouri cannot be definit stated, but the industry probably dates back to about 1860. The occurrence of barite was known long before this, as it was encountered in the lead mines in Washington County and mentioned by several earlier writers." Missouri is reported as producing 8000 tons in 1882 so it is evident the industry was well under way in the seventies in order to have arrived at this substantial production. By 1893 Missouri production had increased so that it ranked with that of Virginia, then the largest producer it increased until in 1914 Missouri accounted for about 65 per cent. of the total United States output.

Jan 1, 1929

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,&apos; 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.&apos; 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&apos; 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&apos; 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&apos;s law for the solvent and to Henry&apos;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&apos;s are the corresponding partial molal quantities and the N&apos;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

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By F. C. Blake

The best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld&apos;schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide.7 It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results

Jan 1, 1881