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By F. W. Bloecher

DETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and de-watering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.' During the past fifteen years a number of new surface measurement techniques have been developed. Those that are broadly applicable to materials dealt with by mineral engineers include the permeability method in which a gas or liquid is passed through the sample, and the low temperature gas adsorption methods first described by Brunauer, Emmett, and Teller."" Efforts to make surface determinations from size distribution curves have long been attempted"."." but because of the uncertainty of sub-sieve size distribution and inaccuracies in screen analyses, the method is at best only a rough approximation. The most widely used gas adsorption method utilizes nitrogen gas." Nitrogen adsorption, however, is not particularly suited as a tool for most mineral engineers because the method is not applicable for surface determinations on coarse materials, that is, materials coarser than approximately 150 to 200-mesh. Other gases have been used in mineral engineering studies, particularly ethane."' lo The use of ethane gas, however, involves .a technique that is too sensitive for most mineral engineering work. The permeability method of surface area determination has the disadvantage of not being sensitive enough to detect the surface represented by minute cracks, the so-called internal surface of a particle. The low temperature krypton adsorption method described by Beebe1 utilizes apparatus and techniques that are essentially the same as those used in the ethane adsorption method."1° The surface area is calculated by the B.E.T. method."-' The krypton adsorption technique is particularly suited to the needs of the mineral engineer because: (1) The method can be used for making surface area measurements of rather coarse materials (35 to 48-mesh), as well as extremely fine materials, such as clays or colloidal slimes with specific surface that might be as high as 20 to 30 mb er g. (2) The use of krypton gas offers the advantage of low saturation pressures (2-3 mm) at the conveniently obtained liquid nitrogen temperature. Therefore the krypton vacuum system need not be designed to measure or withstand internal gas, pressures above one atmosphere as is the case with the nitrogen gas method. (3) The krypton technique offers the safety feature of employing liquid nitrogen, as contrasted to the ethane technique in which liquid oxygen is required. Furthermore, ethane vapor pressure at liquid oxygen temperatures is low (about 10 microns), and a high sensitivity McLeod gage is required for pressure readings. (4) The measurement technique with krypton gas is much simpler and faster, and the apparatus is less elaborate than that required with either nitrogen or ethane gases. Apparatus A krypton surface measurement apparatus like that used at M.I.T. is shown in Fig. 1. It is constructed of pyrex glass. A vacuum is maintained by two mercury diffusion pumps in series backed by a mechanical vacuum pump."' The vacuum thermocouple gage is used for checking the vacuum within the system. This type of gage is quite sensitive down to a pressure of 1 micron of mercury," but may be used to indicate pressures much lower than that

Jan 1, 1952

By F. W. Bloecher

S. Mortsell and J. Svenssofi (Royal Institute of Technology, Stockholm, Sweden)—Bloecher states that the apparatus described by him should be a suitable instrument in the mineral dressing laboratories for determining the specific surface of such granular products that are generally investigated. We want to express a somewhat different opinion, as we doubt that the gas adsorption method of surface measurement really is the most suitable method in mineral dressing laboratories. It is well known that the surface area, as measured by this method, does not coincide with the surface area calculated from the size, shape, and number of particles, i.e. the superficial surface of the particles. It can be seen easily from Mr. Bloecher's own determination on ilmenite-leucoxene concentrate that the surface area measured according to this method may be several hundred times larger than the superficial surface. It is supposed that the surface of cracks, fissures, and pores within the particles also is included in the measured surface. However, this is an assumption which scarcely can be proved and certainly has not been proved. We believe that the mineral engineer could better use a method giving the superficial surface of the particles, as in most cases this surface only is of importance to him. Such is certainly the case when calculating the resistance of the fluid flow through granu- lar materials and the capillary forces of such materials, problems which are of great importance in connection with dewatering, filtration, and pelletizing'" etc. The same may also be the case when studying flotation problems, partly since the quantities of the introduced reagents usually are so small that they can only cover the most accessible surface of the particles, and partly since the molecules of at least the collecting reagents are so large that they cannot enter the smallest cracks and pores. As to the surface, which is of consequence in the application of Rittinger's law of crushing, one is inclined to believe, from theoretical reasons and from the work by Gross and Zimmerley, that the total surface here is the most important one. However, it seems as if in that case the superficial surface was as important as the total surface. Other reasons making the gas adsorption method less suitable for use in the mineral dressing laboratories are that the granular materials there very often are too coarse to be measured by this method, that the experimental technique is rather difficult, and that it takes a long time to measure the specific surface of a sample. Besides, the validity of the method must still be considered questionable. It is thus well known that with different gases one usually gets different values of the specific surface of the same sample, which values, even with such an ideal material as metal foils, can differ as much as about 50 pct.'" Still more serious

Jan 1, 1952

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By D. R. Walker, M. C. Shaw

The laws of Kick and Rittinger are explained as functions of particle size with metal cutting theory. Comminution is shown to be basically the same process as metal grinding. The machine shop type of grinding operation is used to study mineral crushing. Evidence indicates that plastic flow occurs in comminution. THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative prop- erty largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly dependent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law. Because of its industrial importance, comminution has commanded considerable technical attention and has been the subject of continuous study for nearly a century. A number of empirical rules have been proposed to make it possible for grinding energies to be predicted. Of these so-called laws of comminution those bearing the names of Kick and Rittinger have been most widely applied and debated.

Jan 1, 1955

By Hans Allenius, R. T. Hukki

This paper describes in quantitative terms the effect of sharpness of classification on the performance of the closed grinding circuit. The analysis is based on a large number of laboratory experiments designed to simulate the two most common industrial closed grinding systems. The experimental results show quantitatively the degree of improvement achievable by more efficient classification. In an earlier paper1 the senior author has presented a trend showing qualitative analysis of mill and classifier performance in tile closed grinding circuit. According to this analysis, the master key to a major improvement appeared to be effective removal of finished fine material from the classifier sands, or in other words, improved sharpness of classification, leading simultaneously to a substantial reduction of the circulating load. One purpose of this paper is to present the results of a quantitative investigation of the closed grinding circuit. Another is to set forth the essential pertinent variables revealed by the quantitative experiments carried out by the junior author. In the two most common systems of closed-circuit grinding, (1) feed to the circuit is introduced into the grinding unit, normally the ball mill, operating in closed circuit with the classifier; or (2) feed to the grinding circuit is introduced into the primary grinding unit, normally the rod mill, discharging into the classifier in closed circuit with the secondary grinding unit, normally the ball mill. In the following discussion, these two systems are analyzed separately in the indicated order. BALL MILL - CLASSIFIER CIRCUIT The Test Apparatus and Procedure: The test appara- tus included: (1) a F 195 mm x 220 mm laboratory ball mill rotated at a speed 77% of the theoretical critical speed, and a 7-kg batch of F 20 mm-F 50 mm steel balls; (2) a conventional 65-mesh test sieve and a Ro-Tap sieve shaker serving as a classifier; and (3) a Permaran instrument manufactured by Outo-kumpu Co. for surface area determinations by the permeability method. As no continuous closed-circuit experiments could be brought about on a laboratory scale, the process was broken down into alternating grinding and sizing steps in such a way that the new feed plus the returning sands always formed a batch of 1000 gm. For each selected grinding period and for each selected sharpness of classification the basic steps were repeated six times. Steady-state conditions were then reached. Crystalline vein quartz was used as a test material. Feed to the process consisted of -10-mesh fraction of this quartz crushed in rolls. This fraction included 15% of-65-mesh material. Experimental Results: The general flowsheet is shown in Fig. 1. Table I gives the essential data obtained representing steady-state conditions under the indicated set of variables. The table is based on 110 grinding experiments, 440 screen analyses and an equal number of specific surface area determinations. Fig. 2 shows the relationship between the cumulative net energy consumption and the cumulative number of mill rotations as evaluated by separate experiments. Note that this relationship is not linear but is instead represented by a slight curve. The data given in Table I are presented in graphical form as follows: Fig. 3 shows the produced -65-mesh material in grams per minute vs. time of grinding in minutes; the sharpnesses of classification at 65 mesh were 100%, 75% and 50%. It is clearly indicated that the highest-capacity figures call for relatively short grinding times and for the sharpest possible classification. Fig. 4 presents the specific surface area on the final -65-mesh product in square centimeters per gm vs. time of grinding in minutes. In conventional mineral dressing processes, a final product characterized

Jan 1, 1969

By R. L. Wiegel

This article proposes a physical model for an idealized binary mineral system and for the process of liberation by size reduction. Based on this model, equations are derived relating the amount of each component liberated as a function of the ratio of the volumetric abundance of the two mineral components and the ratio of the mineral grain size to particle size. A definite relationship is shown to exist between the mineral concentration within a locked particle and the frequency of occurrence of such a particle. These relationships are used to obtain theoretical expressions for the concentration-recovery diagram. Physical mineral beneficiation processes are based on breaking a mineral aggregate to liberate the dissimilar mineral grains and then making use of their physical properties to separate the mixture into its components. The effectiveness of the process is therefore dependent on how well the minerals are liberated and how efficiently they are separated. Although a substantial amount of work is being done to improve our understanding of mineral separation processes, the study of mineral liberation itself has been almost completely neglected. The purpose of this theoretical study is to shed some light on the liberation phenomenon by: 1) proposing a physical model for an ideal binary mineral system, 2) treating mathematically the fracture of this system into liberated and locked particles, and 3) deriving an expression for the liberation characteristics of this system. The results of this study are useful in understanding the effect and importance of various parameters in liberation, and provide a basis for comparison with real mineral systems. 'RANDOM' MODEL It is recognized that liberation can be caused by detachment which results from fractures occurring at the mineral grain boundaries, or by size reduction which restricts the occurrence of dissimilar mineral locking to a portion of the resulting particles. The detachment effect is dependent on the relative strengths of the mineral grains and the bonds between them, and must be treated empirically for each mineral system. The size reduction effect, however, can be treated analytically if certain assumptions are made concerning the shape and geometrical arrangement of the mineral grains.

Jan 1, 1968

By O. B. Buchlen, J. W. Smith

The Coal Research Bureau of the School of Mines at West Virginia University, using an experimental flotation cell designated an airlift-cyclone was able to obtain a clean coal product containing 7.64% ash with 94% yield and 97% coal recovery. This favorable performance was obtained with the experimental flotation cell operating as a simulated three-stage unit on slurry taken from the fine coal circuit of a coal preparation plant. This experimental device, consisting of a sheet metal cyclone-like unit mounted on a U-shaped uplift pipe, uses a combined flotation and cyclone action to beneficiate the minus 14 mesh partially cleaned feed product. In addition to providing comparable analytical results, the airlift-cyclone possesses other attractive features among them being a low capital expenditure, utilization of moderate plant floor space, efficient operation on high density feed slurry, and absence of moving parts. The primary shortcoming of the experimental cell is its limited capacity. The Coal Research Bureau presently has under construction a larger unit which, it is hoped, will provide the capacity and quality to establish the airlift-cyclone as a commercially feasible unit. Froth flotation of fine coal is a practice which has only recently gained wide acceptance in this country. Various explanations can be put forth for this delayed acceptance of a very selective and efficient system of coal preparation. Among these reasons would be the advent of continuous mining machines resulting in the increased production of coal fines, the change in market patterns from domestic and rail consumers who did not want fines to a predominantly utility market which normally consumes fines, and also the imposition of legal restrictions in regard to stream pollution. However, the major detriment is probably the high cost involved both in installation and operation of the flo- tation unit and auxiliary systems. These facts assume greater emphasis when considering that froth flotation installations normally process a low quality feed product. A recent estimate' of installation costs including dryers, filters, and other auxiliary equipment for a flotation system was $5000 to $7000 per ton of capacity while the operating costs, exclusive of auxiliary equipment, were estimated at 10 to 306 per ton of feed. The Coal Research Bureau of the School of Mines at West Virginia University is currently developing a simplified froth flotation cell, designated an airlift-cyclone, which may provide considerable savings in capital and operating costs without sacrificing product quality or recovery. This experimental cell consists of three primary components: 1) a vertically mounted U-shaped pipe; 2) an air injector device; and 3) an integrally mounted cyclone-like unit (Fig. 1). A feed slurry is introduced at the top of one leg of the U-pipe while compressed air is injected near the base of the other leg. The air serves both to aerate the pulp and to cause it to flow upward into the base of the cyclone unit where the floated clean coal is separated from the reject material and unfloated coal which remains in slurry. The Coal Research Bureau's experimental airlift-cyclone is somewhat similar in principle to a flotation device developed by Russian engineers in the late 1950's. In tests upon a two-stage pilot-size device, the Russians obtained very favorable cleaning efficiencies.' However, later experience with production models demonstrated that rated capacities and acceptable product quality could not always be maintained.3 Because of these limitations, Russian engineers subsequently recommended that conventional, mechanical cells be used when cleaning difficult to float slurries. Engineers at the Coal Research Bureau felt that such a device utilizing the combined actions of a cyclone and a froth flotation machine offered numerous attractive features and merited investigation. Accordingly, a small capacity experimental airlift-cyclone was designed and, with the permission of the Christopher Coal Company Div. of Consolidation Coal Co., installed in Christopher's Humphrey preparation plant near Morgantown, West Virginia.

Jan 1, 1964

By S. M. Wu, R. L. Stone, T. D. Tiemann

The dissolution of silica from quartz in sodium hydroxide solutions was investigated by statistical methods. A second-order predicting equation was developed with 28 experiments expressing the dissolution of silica as a function of the variables quartz size, time, temperature and sodium hydroxide concentration. With this equation a comprehensive picture of the dissolution reaction was gained which included the effect on extraction of each variable and their interactions, fractional extractions, reaction rates and activation energies. A previous investigation of the extraction of silica from low grade siliceous iron ore by digestion in sodium hydroxide solutions presented the extraction as a function of time, temperature and sodium hydroxide concentration.' The present paper is an outgrowth of the previous work and develops by a mathematical analysis the functional relationship between the extraction of silica and time, temperature, sodium hydroxide concentration and particle size. Relatively pure quartz was used in this study in order that the basic quartz-sodium hydroxide reaction could be studied without the influence of other constituents that are commonly found in iron ores. The functional relationship between the dissolution

Jan 1, 1965

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By A. M. Gaudin

Activation of sphalerite with silver ions results from the exchange of two Ag ions for one Zn ion in the sphalerite lattice. The exchange is proportional to the logarithm of time and proceeds until either of the reactants is consumed. Sodium cyanide prevents the activation of sphalerite by controlling the ratio [Zn++]/[Ag+]' in solution. If sphalerite has already been activated with excess silver, cyanide ions can deactivate sphalerite provided oxygen is present. SOLUBLE: silver salts are effective activators for flotation of sphalerite with potassium ethyl xan-thate as collector.* Since sphalerite takes up large quantities of silver ions rapidly,2-4 investigation of this system appeared fruitful for studying the mechanism of sphalerite activation and deactivation. Experimental data presented here comprise studies of the mechanism and rates of activation and deactivation of sphalerite with silver and cyanide ions. A 20-lb sample of sphalerite from Ottawa County, Oklahoma, was handpicked, crushed, screened, hy-drosized to produce a 65/100-mesh fraction, and purified by electrostatic separation. The sphalerite was then leached with benzene and absolute ethyl alcohol to remove possible organic contaminants and with 0.1 M NaCN to remove any copper that might have been picked up during screening. The benzene had been specially purified by grinding with fine sphalerite for 12 hr to remove trace impurities that might have had a specific affinity for sphalerite. Ii'inally, the mineral was washed, dried in flowing nitrogen, and stored in large ground-glass stoppered weighing bottles under a small nitrogen pressure. The specific surface of two samples from the 65/100-mesh sphalerite stock, measured by krypton gas adsorption," was 420 cm2 per g. Compared with spheres of the same size and specific gravity, the prepared mineral had five times as much surface. Results of a wet chemical analysis and of a spectro-graphic study are given in Table I. Manganese, nickel, tin, indium, thallium, cobalt, and magnesium were not detected spectrographically. All solutions were preparid by -adding reagent-grade chemicals to conductivitv water. which had been previously saturated with the desired gases. Nitrogen and oxygen were purified, but no attempt was made to purify the laboratory air. Radioanalysis was carried out with prepurified Ag110 tracer obtained from the Oak Ridge National Laboratory. The complete decay scheme for Ae is complex. Its primary emissions are 0.09 and 0.55 mev ß rays and 1.48 mev y raysB and its half-life is believed to be 270 days. In preparation of solutions of AgNO3, the amount of Ag110 added was negligible compared to that of the inert silver. Abstraction of silver from solution by sphalerite was measured after agitation of 1.5 g sphalerite with 20 ml of solution in 50-ml pyrex flasks. All sample preparations were carried out in a dry box so that the proper atmosphere could be maintained. After the mineral had been agitated in the silver nitrate solution, an aliquot of the solution and a sample of the wet mineral were transferred to separate counting vials and weighed. The solid sample was dried and re-weighed and the activity in both vials measured by means of a scintillation counter. With scintillation counting it is possible to count y radiation from the solid and liquid, a distinct advantage over the older ß-ray counting techdiques.4 All measurements of silver activity were made using a sodium-iodide well-type scintillation counter. The amount of zinc in solution was measured colorimet-rically by the monocolor method of Sandell.7 Activation Studies Exchange Between Zinc Ions and Silver Ions During Activation: The increase of Zn++ in solution during activation with Ag+ is shown in Table 11. These data indicate a replacement of one Zn++ by two Ag+. Analysis of a separate two-month agitation test indicated that the replacement of Zn++ by Ag+ was, as expected, in the molar ratio of 2.0.

Jan 1, 1958

By G. W. Mao, A. M. Gaudin, D. W. Fuerstenau

Jan 1, 1960

By R. W. Smith

It is well known that certain silicates such as the feldspars and beryl can be readily floated from quartz at a low pH value using a long chain cationic collector in the presence of a fluoride.1-3 However, the mechanism whereby the fluoride activates feldspars and beryl is not known. Indeed, only a few authors have even speculated about possible mechanisms.1,3,4 As a first approach to the problem, it is perhaps best to look closely at the interesting character of hydrofluoric acid and how it dissolves silica and silicic acid. Hydrofluoric acid, unlike hydrochloric acid, is a weak acid with a dissociation constant of about 3.53 x 10-4 at 25°C.5 The reason for the weak acidic character of HF lies in the very small size of the fluoride ion.6 The pKa value is 3.45 which means that at pH 3.45 half the HF is present in molecular form and half in ionic form. The anion present is probably HF2.-6 At pH values below the pKa value, molecular concentration increases rapidly at the expense of the HF2- anion. It is known that HF readily attacks glass, silicates, quartz and silicic acid. The equation usually cited pertaining to the first step in HF attack of silica is6-'

Jan 1, 1965

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By S. R. Balajee, I. Iwasaki

The adsorption mechanism of corn starch and its derivatives at mineral-solution interfaces was investigated by the adsorption of cationic starch, unmodified corn starch, British Gum 9084, and anionic starch on quartz and hematite. The adsorption of these starches, which decreases in the order mentioned, is dependent on the balance between the magnitude of the electrostatic interaction and the magnitude of the hydrogen bonding. There exists a critical starch concentration for both optimum flotation and flocculation conditions of iron ores, which corresponds to a point where the starch adsorption reaches a saturation coverage. Flocculation occurs due to the adsorption of starch via electrostatic and hydrogen-bonding forces and by interparticle bridging as a result of the conformation of starch molecules at the interface. The depressant property of starches and starch derivatives in flotation' and their flocculation char: acteristics in clarification and filtration2.3 have long been recognized on a wide variety of ores. The effectiveness of a starch as a depressant for iron minerals has been the subject of much investigation in recent years both in the amine flotation of siliceous gangue and in the anionic flotation of activated silica from iron ores. It has been reported that the depressant activity of starches and dextrins in the cationic flotation of quartz from hematite increases with molecular weight, branching, and number of hydroxyl groups, 1 and that the selectivity is affected by changing the configuration of starch molecules and the composition of its polar groups.4 ,5 The manner in which starches are solubilized was shown to exert a significant influence as a depressant in the anionic silica flotation, and a series of articles covering the practical aspects of flotation and flocculation have already been reported.618 Chemical modification of the starch structure, the pulp pH, the calcium ion, and the residual starch concentration were identified as some of the more important variables affecting the flotation behavior. In the flocculation of iron ores, it was noted that most starches flocculated suspensions of hematite in water but did not flocculate similar suspensions of quartz,9 and that an excessive use of starch restabilized the suspensions due presumably to protective action. 6 An admirable application of such an observation to practice may be cited in the selective flocculation and desliming in the anionic silica flotation of iron ores, which resulted in superior metallurgy and lower reagent cost. 10 From detailed adsorption measurements, Schulz'and Cooke4 established that the adsorption of starches and their derivatives depended on the types of minerals and of starches, pH, and electrolytes present. Their adsorption data and the foregoing flotation and flocculation observations suggested that an electrical interaction between starches and charged mineral surfaces might be playing a role in their adsorption process. Adsorption of organic polymers, particularly of synthetic origin, at solid-liquid interfaces has been extensively studied in recent years,' and it is realized that their adsorption mechanism is considerably more complex than that of simple ions or molecules. A polymer molecule possesses a number of functional groups, and the adsorption at a point may restrict the adsorbability of adjacent groups. The mechanism may be further complicated by the conformation of the polymer molecules which may exist as coiled spheres, helices, or extended chains as a result of intramolecular interactions among functional groups as well as intermolecular interactions with solvent molecules. The object of the present investigation was to examine the effect of the chemical modification on the adsorption characteristics of starches and starch products on quartz and hematite at several pH values, so that by correlating this information with flocculation and flotation results, adsorption mechanism of starches on mineral-solution interface may be elucidated. EXPERIMENTAL MATERIALS Quartz: St. Peter sand was screened at 35 mesh and the undersize was scrubbed and deslimed at a Fagergren cell. The deslimed sand was cleaned with 0.1 N hot hydrochloric acid and washed repeatedly with distilled water, For anuscript, measurementsl the -200-mesh fraction of the sand was ground dry in a porcelain mill for 3 hr. The specific surface of the finely ground quartz was

Jan 1, 1970

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By D. L. Harris, A. M. Gaudin

Observations were made of the distribution of mercaptan containing S35 between aqueous solution and mineral and between aqueous solution and the gaseous phase. Although equilibrium may not have been attained, adsorption of the reagent was shown to occur reasily from air or aqueous solution on sphalerite, zincite, and willem-ite and to correspond to flotation. Adsorption on quartz did not similarly occur. THE following results, presented here in condensed form,' were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report' of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr. Coarsely-crystallized sphalerite was handpicked, stage-crushed in the dry state, wet-screened on a 200-mesh sieve, and deslimed in water at about 5 microns. Further treatment consisted of a wash in dilute aqueous hydrogen peroxide, drying, removal of the dark-colored fraction in a Frantz magnetic separator, washing in very dilute hydrochloric acid, repeated washing in distilled and conductivity water, and drying. The last washings showed a conductivity equivalent to a few ppm NaC1, that is, much more than would be provided, theoretically, by a saturated ZnS solution. The material was stored dry in sealed bottles. Analyses were as follows: Zn, 62.3 pct; Fe, 0.43 pct; Cd, 0.44 pct; S, 31.2 pct; Mn, 0.001 pct. The specific surface (BET method) was 2000 cm2/g. Zincite from Franklin furnace of the New Jersey Zinc Co. was hand-picked, dry-crushed, wet-screened at 100 mesh, and deslimed at about 10 microns. After drying, the associated zinc, manganese, calcium, and silicate minerals were removed in a Frantz magnetic separator. The purified zincite was washed in distilled water and conductivity water to a conductance of less than 2 ppm equivalent NaC1, dried, and stored. Analyses were as follows: Zn, 75.1 pct; Fe, 0.9 pct; Mn, 2.78 pct. The specific surface (BET method) was 1740 cm 2/g. Willemite, also from Franklin furnace, was purified similarly. Analyses were as follows: Zn, 52.5 pct; Fe, 0.12 pct; SiO², 27.3 pct; loss on ignition, 0.13 pct. The specific surface was 1760 cm 2/g. Conductivity water (double-distilled) and demin-eralized-distilled water were used in most of the tests. The specific resistance was not less than 600, 000 ohms, and usually above 1,000,000. Radiosulphur-marked hexyl mercaptan (1-hexane thiol) was synthesized by Tracerlab, Inc., Boston. Two lots were secured several months apart. The last lot, consisting of about 0.5 g of the mercaptan, had a total activity of about 10 millicuries. Tracerlab Co. guaranteed only the activity; hence a quasi -vapor pressure determination (based upon an S analysis) of the mercaptan was made. The calculated value, 4.2 mm of mercury at 25.5' C, has been compared with that of a sample of Highest Purity 1-hexane thiol from Fisher Scientific Co. The latter had a vapor pressure of 4.5 mm of mercury at 2.5 C. Analytical Procedures The sample containing radiosulphur-marked mercaptan was oxidized to convert the mercaptan sulphur to sulphate, carrier barium sulphate being added to provide a suitable quantity of total barium sulphate in a filter cake. The precipitate was filtered and dried, and counting was carried out either in a streaming-gas (Q-gas) counter for high sensitivity or with an end-window G-M counter for convenience. The oxidized and precipitated mercaptan gave a radioactive count of 65 counts per minute per microgram in the end-window Geiger-Mueller counter and 1100 counts per minute per microgram in a Q-gas counter. For standardization of the mercaptan solution, 15 replicate analyses were made. The average deviation per measurement was about 1600 cpm in 65,000 cpm, the probable error in the mean being 275 cpm. It

Jan 1, 1955

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By A. M. Gaudin, J. G. Morrow

FLOTATION requires the existence of a definite contact angle. This contact angle, the surface tension of the solution, and adsorption at the solid-fluid interface are quantitatively related. Adsorption of dodecylammonium acetate on hematite was measured for a wide range of concentrations of reagent in solution. Similar measurements for quartz have already been made. Contact angle measurements were then made on polished surfaces of hematite and of quartz immersed in aqueous dodecylammonium acetate solutions, and a functional relationship was sought between adsorption density at the mineral-solution interface and the contact angle. Finally, the surface tension of the aqueous amine acetate solutions was measured. These data were combined to give an evaluation of the work of adhesion for the three-phase system. Specular hematite was crushed and then ground dry in a laboratory porcelain mill, with flint pebbles, to pass a 200-mesh screen. The ground product was sized in a Haultain infrasizer, and one of the granular sizes (cone No. 3) was used in all adsorption tests. A hand magnet was used to remove magnetite and abraded iron. Quartz was removed in a Frantz isodynamic magnetic separator. The purified hematite was leached in aqua regia, washed with distilled water until the washings appeared free of electrolyte by conductance measurement, dried in a low-temperature oven, and stored in a pyrex container. The specific surface of the closely sized hematite was determined by the krypton gas adsorption method.' Three measurements gave an average value of 1350 sq cm per g. Chemical analysis showed Fe -69.37 pct, insol = 0.72 pct. The quartz used in the flotation tests had been prepared by Chang" for an earlier investigation. Demineralized distilled water was used for all test solutions. Dissolved salt content was of the order of 0.03 ppm, expressed in terms of sodium chloride, as estimated from conductance measurements. Dodecylammonium acetate was obtained from Armour & CO. in two forms, the unmarked compound and a preparation marked by carbon 14 in the hydrocarbon chain of the aminium ion. Specific activity of the active salt was 0.134 millicurie per g. The important physico-chemical constants for the primary amine salt have been reviewed by de Bruyn. The calculated effect of hydrolysis of amine salt on pH of aqueous solutions and the effect of pH on the distribution ratio of the alkylammonium ion to free amine are of particular interest. All other chemicals used in this investigation were of analytical reagent grade. A column method' was used for adsorption work. Attainment of equilibrium distribution in the adsorption column depends on the solid-solution contact time, hence upon the volume of solution passed. It was assumed that contact time required for equilibrium would be a maximum for the lowest reagent concentrations. On this premise it was demonstrated experimentally that the passage of 500 ml of solution through the mineral bed was adequate. An aliquot (1 to 5 cc) of the solution to be analyzed was transferred to a small pyrex cup and allowed to evaporate to dryness at room temperature; 4 or 5 mg of unmarked amine acetate were added to the dried sample and the cup and its contents were transferred to the combustion system for analysis. Evaporation at room temperature must be emphasized, as even slightly elevated temperatures result in loss of reagent. A laboratory model G Beckman pH meter equipped with a glass electrode was used to measure pH of amine acetate solutions. The technique of internal gas counting of radioactive carbon dioxide in a Geiger-Muller counter was used. Developed originally by Brown and Miller,- his method was adapted to the analysis of carbon-14 marked flotation reagents by Chang, de Bruyn, and Bloecher. nalytica1 method and procedures have been described in detail by Bloecher.' Contact angles were measured by the captive-bubble technique." The mineral specimens were carefully selected to avoid cracks and inclusions of other minerals. All specimens were mounted in plastic and polished to produce a smooth surface. The final polishing and contact-angle measuring

Jan 1, 1955

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

The adsorption density of ethyl xanthate on pyrite was determined as a function of xanthate concentration. Surface preparation of the mineral appears to have asafunctionsome effect on the subsequent adsorption process, A monolayer of xanthate on the surface is exceeded only in presence of oxygen. The effect of OH- , HS- (and x and CN- S=)and on the amount of xanthate adsorbed was investigated. Competition between OH- and X- (xanthate) ions for specific adsorption sites is indicated over a wide pH range. IN the flotation of sulfide ores, xanthates are most commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite.2 In the work on chal-cocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh.9 ut the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5;4 at neutrality, a contact angle of 60" is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants. In this study of pyrite collection the writers have sought to relate measured xanthate adsorption to the method used in preparing pyrite, to the presence or absence of oxygen, to concentration of hydroxyl, hydrosulfide, sulfide, and cyanide ions. The principal experimental tool has been radioanalysis," " using xanthatcx marked with sulfur 35. Experimental Materials Pyrite: Unlike most sulfides, pyrite is a poly-sulfide. The structure given by Bragg7 resembles that of sodium chloride, the iron atoms corresponding to the position of sodium and pairs of sulfur atoms corresponding to the position of chlorine. The edge of the unit cell in pyrite is 5.40 A and in halite 5.63 A. The S-S distance in pyrite is 2.10 A; the Fe-S distance, 3.50 A: and the Fe-Fe distance, 3.82 A. Natural pyrite from Park City, Utah, was used in this investigation. Pyrite 1 was obtained by hand picking pure crystals. Pyrite 2 and Pyrite 3 were obtained from finer textured crystalline material containing inclusions of silicates. The same cleaning technique was utilized for the preparation of Pyrite 2 and Pyrite 3, whereas a different cleaning technique was used for Pyrite 1. Pyrite 1 was prepared as follows: The crystals were ground in a porcelain ball mill and the 200/400 mesh fraction was separated by wet screening with distilled water, followed by washing for 1 hr with deoxygenated distilled water acidified with sulfuric acid to pH 1.5. The acid was removed by rinsing with deoxygenated distilled water on a filter until a pH of 6.0 was reached in the effluent. This filtration was carried out under nitrogen. The sample was then dried in a desiccator under nitrogen. The period of time for which this pyrite sample was in contact with water containing oxygen was about 4 hr. The specific surface as determined by the BET gas adsorption method was 582 cm2 per g. Final material assayed 53.12 pct sulfur and 46.5 pct iron (theoretical, for FeS,: S, 53.45 pct; Fe, 46.55 pct). After crushing, Pyrite 2 and Pyrite 3 were washed with 1 M HCl. rinsed, and fed to a laboratory shakinq table to remove the small amount of silicates. The concentrate obtained was ground in a laboratory steel ball mill. The 200/400 mesh fraction was separated by classification in a Richards hindered settling tube. This fraction was then given a final wash with 0.1 M HCl and deoxygenated water was filtered through the sample. The final effluent showed a conductivity equivalent to that of a solution having a salt concentration of 0.3 ppm. Aqueous hydrogen sulfide solution was then added to the sampln (about 100 ml saturated H,S solution to about 1000 g pyrite under a few hundred milliliters of water) which was stored wet under nitrogen. The sample stored in this manner showed no indication of formation of iron oxides, whereas iron oxides appeared

Jan 1, 1957