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By L. W. Kempf

DURING the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-ismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investi-gated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and aluminum-bismuth systems was Wright,1 who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-thal4 reported that the addition of lead distinctly lowered the solidifica-tion point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bis-muth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500° C. as compared with the conductivity of the same alloys on annealing at 300° C.

Jan 1, 1938

By P. T. Velu

Light weight aluminum alloys are the major construction materials for a number of structures in automobile and aerospace industries. Higher cost of production is the key impediment which restricts the usage of these alloys. A new electrochemical process route for the low cost production of aluminum alloys is being investigated, in which alloying elements are obtained from the dissolved compound. In the present investigation, solubility of lithium compound has been determined by measuring the EMF, when it is dissolved in the electrolyte. The solubility of Li2CO3 increased with temperature from 2.95 wt pct at 1063 K to 7.57 wt pct at 1093 K. Activities of the compound in the electrolyte were deduced using Temkin's ideal solution approach.

Jan 1, 1995

By T. Crivits

"Phase equilibria in the ‘Cu2O’-‘Fe2O3’-SiO2 system, the base slag system in copper production, were recently determined. However, the addition of MgO, commonly present in the slag, drastically changes the phase equilibria in this system. The present study focuses on the phase equilibria in the ‘Cu2O’-‘Fe2O3’-MgO-SiO2 system in equilibrium with metallic copper.Recently, an experimental procedure has been developed that resolved a number of experimental difficulties. This procedure has been successfully applied to characterise several complex industrial copper slags. It includes a high-temperature equilibration followed by rapid quenching and electron probe X-ray micro-analysis (EPMA). The methodology was adapted to the present system and used to determine the liquidus at SiO2 saturation and in contact with high-MgO phases in between 1100 and 1250 °C in Cu2Orich slags.The results indicate a maximum solubility of MgO in the system at 1200 °C of 5 wt%. The boundary line between tridymite and spinel lies 3-4 wt% closer to the SiO2 apex for every 2 wt% MgO added. These new data on the high-copper slags are important for optimisation of the direct-to blister"

Jan 1, 2014

By R. G. Reddy

Nickel solubilities in spent pickling solutions (i.e. HF-HNO3-H2O solutions ) were measured as a function of HF and HNO3 acid concentrations. The chemical analysis of the industrial pickling solutions and sludges were made. The stable phases observed in the sludges are FeF3?3H2O, and ( FeCr ) F3?3H2O. Pure Ni, and stainless steel type 316 were used in this study. The results showed that the solubility of Ni increased with increase in concentrations of HF in pickling solution at a fixed concentration of HNO3: An excellent agreement between the experimental solubility data and the theoretical data was obtained. X-ray diffraction analysis showed that the solid solubility product formed is mainly NiF2?4H2O compound.

Jan 1, 1992

By M M. Pande, M Ishfaq

The effect of aluminium on nitrogen solubility was investigated by equilibrating melt comprising master alloy of Fe-Al with pure electrolytic iron in a controlled atmosphere (pure argon) at 1873 K. Nitrogen in the samples was measured by sampling technique using inert gas fusion absorptiometry. It was found that nitrogen content decreases steadily with aluminium concentration and gradually, becomes close to 1 ppm for very high aluminium steels. Wagner’s second order interaction parameter formalism has been used to estimate the equilibrium constant and interaction parameters. Scanning electron microscopy (SEM) investigation showed, dual-phase inclusions comprising AlN phase surrounding alumina core. The 3D morphology of inclusions was studied by extracting the sample from the top and the central bottom portion of the solidified ingot. A sparse distribution of nitrogen was found for most of the inclusions which manifested the presence of almost pure alumina inclusions with different morphologies and sizes.

Jun 19, 2024

By R. M. Brick

AN increased demand for information in regard to the effect of gaseous elements in steel has accompanied the recognition of the importance of grain size. Attempts to correlate grain-size characteristics with gas con-tent, particularly oxygen in solution or in the form of included metallic oxides, have not been universally successful. Certain definite effects of dissolved gases are recognized; specifically, the role of hydrogen in causing internal cracks or "flakes" and that of nitrogen in preventing excessive grain growth of ferritic chromium steels. When irregular behavior or properties are found in a well-known steel and no definite cause for the abnormality may be assigned on the basis of chemical and metallographic tests, dissolved gases are frequently blamed as the culprits. The solubilities of hydrogen1 and nitrogen2 in pure liquid iron are known but of the ternary systems, iron-alloying element-gas, only the Fe-Si-N3 and Fe-Cr-N systems have received attention and here the study was confined to liquid alloys. Krivobok4 published a curve show-ing the solubility of nitrogen in liquid Fe-Cr alloys but gave no informa-tion on the experimental procedure employed. The considerable experimental work reported on the Cr-N binary alloys has been reviewed by Hansen.5 It is generally agreed that the nitride CrN is a stable phase although the existence of nitrides within limited temperature ranges of stability, viz., Cr3N2 and Cr2N, has been disputed, Adcock6 and others7 have reported a eutectic between Cr and CrN at 1580°C., although the supporting evidence is not complete.

Jan 1, 1940

By John Chipman, Donald W. Murphy

RECENT developments in iron alloys containing nitrogen have indicated that this element may exert a considerable influence on the properties of the metal. This influence is not always in an undesirable direction and the indications are that nitrogen should be regarded as an alloying element, the amount of which should be subject to control, rather than as an inherently deleterious impurity. In controlling this element in liquid iron to the best advantage, it is necessary to have a reliable background of fundamental data pertaining to solubilities, rates of solution and chemical reactions of nitrogen in liquid iron. Obviously, the first step in such an investigation is the determination of the solubility of nitrogen in pure iron, and this has been the object of the experiments described in this paper. The solubility of nitrogen in solid iron has been measured by Zurich,1 Sieverts,2 Martin,3 and Iwasé4 and, the agreement among the first three inspires confidence in their results. No accurate determinations of its solubility in liquid iron have been recorded though several investigators have obtained approximate results. Strauss5 was able to introduce 0.03 to 0.04 per cent nitrogen into steel by the action of either ammonia or nitrogen on the liquid metal. This was accomplished by Eilender and

Jan 1, 1935

By John Chipman

RECENT developments in iron alloys containing nitrogen have indi-cated that this element may exert a considerable influence on the proper-ties of the metal. This influence is not always in an undesirable direction and the indications are that nitrogen should be regarded as an alloying element, the amount of which should be subject to control, rather than as an inherently deleterious impurity. In controlling this element in liquid iron to the best advantage, it is necessary to have a reliable background of fundamental data pertaining to solubilities, rates of solution and chemical reactions of nitrogen in liquid iron. Obviously, the first step in such an investigation is the determination of the solubility of nitrogen in pure iron, and this has been the object of the experiments described in this paper. The solubility of nitrogen in solid iron has been measured by Jurich,1 Sieverts,2 Martin,3 and Iwasé4 and the agreement among the first three inspires confidence in their results. No accurate determinations of its solubility in liquid iron have been recorded though several investigators have obtained approximate results. Strauss5 was able to introduce 0.03 to 0.04 per cent nitrogen into steel by the action of either ammonia or nitrogen on the liquid metal. This was accomplished by Eilender and

Jan 1, 1935

By Arthur Phillips, E. N. Skinner

DURING the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson1 who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.015 per cent at 1050°C. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000°C. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hewitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of minute concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicroscopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By A. U. Seybolt, C. H. Mathewson

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrence of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below.

Jan 1, 1935

By A. U. Seybolt

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrence of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except .conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below.

Jan 1, 1935

By F. N. Rhines

DESPITE the large amount of study which has been devoted to the subject our present knowledge of the copper-oxygen system remains incomplete and unsatisfactory in many respects. This applies particu-larly to those regions in which solid metallic copper exists. The primary object of the present paper is the contribution of new information relative to the solid solubility of oxygen (or cuprous oxide) in copper at atmospheric pressure, together with certain observations in the low-pressure regions of the system. It seems appropriate also to present a brief summary of the outstanding previous work on the constitution of mixtures of copper with its lowest oxide in order to show the relation between the new facts and the system as a whole. The earliest recorded investigations of the copper-oxygen system are those of M. S. Lucas (1) § and of M. Chevillot(2) in 1819 and 1820. Lucas believed that liquid copper is capable of dissolving its oxide, but neither he nor Chevillot was able to furnish convincing proof of this property. It was not until 1866 that T. Graham° definitely established the existence of such a solubility. Nine years later W. Hampe(4) measured its extent and roughly outlined the copper-rich portion of the system. The first really precise examination of the constitutional relationship between copper and cuprous oxide, however, was that of E. Heyn(5) who in 1900 published a temperature-concentration diagram covering the range from 0 to 10 per cent of cuprous oxide at atmospheric pressure. Within these limits of composition cuprous oxide was found to dissolve in liquid copper, forming at 3.4 to 3.5 per cent a eutectic which melted at 1065° C. R. E. Slade and F. D. Farrow(6) extended these studies to mixtures of higher

Jan 1, 1934

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By K. Avarmaa, P. Taskinen

"The solubilities of rhodium (Rh) in a molten silver alloy in doré-smelting conditions for treating copper refinery slime at temperatures of 1,000 to 1,300 °C were measured using a high-temperature equilibration-quenching technique and direct phase analysis by electron probe X-ray microanalysis. The results obtained indicate that the solubility of rhodium in molten silver is very limited: only 0.04 to 0.26 weight percent at 1,000 and 1,300 °C, respectively. The thermodynamic properties of rhodium in molten silver were estimated from the solubility data. The compositions of the solid rhodium alloys in equilibrium with molten silver-rich doré metal were also measured in this study. The excess rhodium in the doré alloy will precipitate during the refining as solid, greater than 99 weight percent Rh.IntroductionSilver refining is a core step of the processes of anode slime treatment and precious metals recovery in copper refineries (Hait, Jana and Sanyal, 2009; Ludvigsson and Larsson, 2003). It separates the oxidic materials, such as nickel oxide (NiO) and barium sulfate (BaSO4), from metallics after the de-coppering and de-selenation steps of the anode slime, and refines the silver bullion from the undesired elements present (Cooper, 1990; Hyvärinen, Lindroos and Yllö, 1989). Doré metal is a silver-rich alloy which after the smelting step will be refined electrolytically, and the remaining constituents of gold as well as the platinum group metals (PGM) will be subsequently recovered in their own processing stages.Because of low concentrations of PGMs in copper, they are typically soluble in the doré metal in anode slime treatment. This can be concluded from their binary phase diagram data with silver (Massalski et al., 2007). One exception is sometimes encountered in the anode slime smelting operations if the smelter feedstock is rich in rhodium, as may be the case if the raw materials contain secondary raw materials such as e-scrap. The solubility of rhodium in solid silver is less than 0.04 weight percent (Królas and Sternik, 1995), and its solubility in molten silver is highly uncertain. The only experimental information in the literature (Królas et al., 1993; Elliott, 1985) suggests that the silver-rhodium alloy system at 960 °C forms a eutectic, which locates less than 2 °C below the melting point of pure silver (Arblaster, 2015). Early observations (Rössler, 1900) propose that rhodium is insoluble in molten silver even if solid silver-rhodium solutions have been recently produced on a nanoscale (Kusada et al., 2010).The aim of this study is to measure experimentally the solubility of rhodium in molten silver at doré metal smelting and refining temperatures. The silver alloy used to mimic the doré alloy contained silver and about 1 weight percent of the alloying elements copper, gold, palladium, rhodium and tellurium. The experiments were carried out in metal-slag equilibria with nitrogen-oxygen mixtures as the atmosphere, employing an equilibration-quenching technique and using direct phase composition analysis by electron probe X-ray microanalysis (EPMA) (Jak, Hayes and Lee, 1995)."

Jan 1, 2017

By Jie Li, Shu Yang, Zhongliang Tian, Xun Hu, Yanqing Lai, Shaolong Ye

The electrolyte with high solubility for Sc2O3 is very important to realize the preparation of Al-Sc master alloy by the molten salt electrolysis. The solubility of Sc2O3 in K3AlF6- Na3AlF6-AlF3 melts is determined with an isothermal saturation method. The effects of KR (ratio of K3AlF6 to K3AlF6+Na3AlF6), the concentration of Al2O3 and the temperature on the solubility of Sc2O3 are also investigated. The results indicate that the solubility of Sc2O3 in K3AlF6-Na3AlF6-AlF3 melts increases and then decreases with KR increasing. The solubility of Sc2O3 is 8.698 wt.% in (K3AlF6-Na3AlF6)(KR25%)-18 wt.%AlF3 melts at 940℃. The effect of temperature on the solubility is little, and the values are 8.575 wt.% and 8.762 wt.% respectively when the temperatures are 930℃ and 960℃. The solubility decreases from 8.809 wt.% to 7.058 wt.% as the concentration of Al2O3 increases from 1.5 wt.% to 5.0 wt.% at 950℃.

Jan 1, 2015

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006

By P. J. M. van Heteren

The flotation system is usually distinguished from other physical chemical systems by the importance of interactions at the solid-liquid and solid-gas interfaces. In recent years, numerous quantitative studies have been made of the distribution of common collectors between the solid and aqueous solution phase. Although in flotation the main emphasis is placed on the adsorption process, chemical reactions will also take place in the bulk solution phase, These side reactions are often undesirable and will contribute towards the complex behavior of many a flotation system In sulfide flotation, the precipitation of insoluble base metal xanthates is a well-known phenomenon although the conditions under which the precipitation reaction will proceed and the magnitude of the solubility products are not known with accuracy. A knowledge of the solubility of these xanthate salts will not only be of value in flotation research, but the mill operator might be interested in knowing whether precipitation of metal xanthate can be controlled or completely prevented in the flotation circuit thereby reducing reagent consumption, For these various reasons the solubility of lead, copper, zinc, and silver ethyl xanthate was determined. The experimental techniques and results will be discussed in this paper.

Jan 1, 1958

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [(MG) l 2M +G2 = 2MG K = Ma X Pa, [I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Kl Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + SO2 = Cu2S + 2Cu20[3] K _ Cu2S X (Cu20)2 (Cu)6(Pso2)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [8 =KI = Pte, or VSO2= K2 '~/PeO, [S]]

Jan 1, 1941

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By M. D. Hassialis, Arthur F. Taggart

WARK1 observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility=product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith. The experimental work comprised. accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1946