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By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

By Edgar C. Bain

A NUMBER probably a sizable group of person with a dominant interest in metals maintain contact with the developments in ferrous metallurgy by reading week by week, as time permits, some four or five periodical devoted in considerable part to this field. It seems possible that some of these, like ourself, find it difficult to see the net results of the development day by day in clear perspective, The impression sometimes seems blurred by the uninterrupted succession of so many accounts, or out of focus from the very impact of so many reports of new things enthusiastic, well written, and understandable though they usually are. It is at times almost as though one were trying to observe, from a fastmoving vehicle, objects all too near at hand. Or perhaps this impression is merely a manifestation of our individual hyperopia ; in which case we should content ourself with an observation that it would be more satisfactory on the whole to discuss in 1941 the metallurgical advances of 1930-35 than those of

Jan 1, 1941

By Laurance S. Reid, Joe A. Porter

Gas dehydration plays an important part in the production of natural gas. Effective dehydration prevents formation of gas hydrates and the accumulation of water in transmission Systems,2,6,7 insuring uninterrupted gas deliveries at maximum efficiency under the most adverse weather conditions. At the present time, most gas companies require a maximum water vapor content of seven lb per million standard cu ft of gas. so that virtually all gas tendered for sale must he dehydrated to meet this specification. For a number of years it has been common practice to produce gas and gather it at a common point for dehydration prior to discharge into the transmission system.1,3,11,16,17 However, higher transmission line pressures, long gathering lines and relatively low ground temperatures have made it necessary to dehydrate gas at. or near. individual. wells in order to gather gas from a number of newly developed fields without unusual difficulty. Where gas has been dehydrated at pressures ranging from 300 to 800 psi in the past. future trends indicate that these processes may be operated at pressures as high as 2,000 psi. Economics of gas dehydration are of great importance, partitularly where facilities must he provided to process relatively small quantities of gas, such as the production from an individual well. Although the adsorption of water vapor from gas on a granular sorbent material such as activated bauxite, activated alumina, or one of the alumina-silica gels is highly effective and produces virtually "bone dry" gas, the cost of a small unit of this type is substantially greater than that of an absorption process which, through proper selection of the absorbing liquid, will dehydrate the gas sufficiently to meet pipe line specifications. For this reason, a great deal of emphacis has been placed on the development of small, inexpensive dehydration units8,24 and the search for more effective absorb. ent liquids has been intensified. A wide variety of methods for dehydrating gas are known' and many of these have been used in industry. Earlier applications of the absorption process employed concentrated solutions of calcium and lithium chlorides as the absorbent. The severe corrosion problems inherent in handling these solutions and the relatively small dew point depressions obtained caused early abandonment in favor of, or conversion to. diethylene glycol when it was found that aqueous solutions of this organic liquid were more hygroscopic than the brines and were non-corrosive. Processes employing diethylene glycol-water solutions are widely used for gas dehydration at pressures ranging as high as 1,200 psi.13,14,15 At nominal pressures a dew point depression of 45° to 50°F may be be and the data of Russell et al." indicate that a minimum dew point is obtained from the effluent gas at a pressure of approximately 1,200 psi when the gas is in equilibrium contact with a 95 per cent by weight diethylene glycol solution. In a number of instances the dew point depression obtained with diethylene glycol-water solutions is not sufficient to produce a specification product without cooling the inlet gas. In a recent search for a better absorhent, triethylene glycol was used in a small commercial dehydration unit and subjected to rather exhaustive field tests.' The data obtained were encouraging and indicated that, at pressures ranging from 300 to 500 psi, triethylene glycol porduced a substantially greater dew point depression than diethylene glycol. These results led to an investigation of the system natural gas-water-triethylene glycol in an effort to obtain vapor-liquid equilibrium data, to determine pressure limitations, and to develop other data pertinent to the design of gas dehydration processes. A review of the literature has failed to reveal any data which permit reasonably accurate calculation of the vapor-liquid equilibrium conditions for a solution of water and triethylene glycol in contact with natural gas at high pressure. Since these constituents form a non-ideal system, the Poynting equation18,21 or the usual combination of Raoult's and Dalton's laws19,20,22 would not be valid. Correction of Raoult's and Dalton's laws by the use of activity coefficients2' is not feasible for available data are insufficient for the prediction of the actual increase in the ratio of the activity of one component in the vapor phase to its activity in the liquid. Therefore. experi-

Jan 1, 1950

By Thomas T., Read

IT will be recalled that when educational instruction for the mineral industry began at Freiberg, at the beginning of the eighteenth century, the original aim was to organize and systematize the procedures previously followed by young men in gaining -familiarity with the technology then in use. There must have been many other ideas current, even then, as to just what a young man needed to learn in order to become capable of assuming 'responsibility for the supervision and direction of such technical work. The problem in Europe was decidedly different .from that in nineteenth-century America, because some of the European mines were actually owned and operated by the governing authority and the others were supervised, regulated, and taxed by it. The American problem was the e5cient performance of technical operations; the European one was regulatory supervision. It was natural, therefore, that in the development of educational processes in Europe stress was laid on those factors which conserved and protected the interests of the state. The study of mineralogy and geology, leading to correct judgments as to the workability and value of mineral deposits; assaying, which gave the means of quantitative measurements, as did surveying; chemistry, which furnished a better basis of understanding for assaying, mineralogy, and geology; and physics and mathematics, which are the bases for the understanding and efficient use of mechanical appliances, became the core of systematic instruction, for the mineral industry. It was early recognized that men could learn more than was already known about all of these subjects and education took on that dichotomy which still characterizes it; the teaching of established knowledge to the unlearned, and that of extending of the bounds of knowledge, now loosely termed research, which after two and a half centuries of work still shows

Jan 1, 1941

By Amitava Gangulee

A recent investigation has shown that solid solution hardening is almost absent in the quasibinary system SnTe-pbTe.1 The lack of solid solution hardening was attributed to the small difference of only about 3 pct between the atomic sizes of lead and tin, and to the fact that the formation of these solid solutions involved changes only in the sublattice occupied by the lead and tin atoms. The investigation reported here is concerned with the quasibinary system PbSe-PbTe which, similar to the SnTe-PbTe system, forms a continuous series of solid solutions2 and has the same NaC1-type (Bl) structure. The size difference between the selenium and tellurium atoms, however, is slightly larger than 7 pct. No indication of any ordering of the lead and tin atoms at. selected compositions had been found in the system SnTe-PbTe, which had been explained by the weak second-nearest-neighbor interactions between lead and tin atoms.' The possible occurrence of an ordering transition in the system PbSe-PbTe was also investigated in the present work. Polycrystalline specinlens of PbSel-1-xTex (x = 0, 0.20, 0.25, 0.33, 0.50, 0.67, 0.75, 0.80, and 1.0) were prepared by melting appropriate amounts of 99.999 pct pure Pb, Se, and Te j.n evacuated and sealed Vycor capsules. The capsules were quenched in water. The solidified ingots were homogenized at 800°C for 14 days. Chemical analysis of the homogenized ingots showed that the deviations from the stoichiometric compositions were less than 0.1 at. pct for each component. Part of each ingot was ground to pass through a 75 g sieve and pressed into 25.4 mm by 12.7 by 2 mm briquettes. Duplicate sets of specimens, each containing at least one briquette and part of the ingot of each composition, were sealed in evacuated Vycor capsules. Both sets were annealed at 500°C for 7 days; one set was quenced in ice-water and the other was cooled to room temperature over a period of 14 days.

Jan 1, 1970

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

Jan 1, 1961

By Charles S. Barrett, Robert F. Mehl

It is generally understood by workers in the field of the crystal structure of metallic alloys that terminal solid solutions are of two types, the substitutional and the interstitial. In reviewing the literature, the work of Weissl on the crystal structure of the alpha copper-tin alloys was encountered, in which a new type of terminal solid solution was proposed. In brief, Weiss' findings showed that the density of the alloys calculated from the side of the unit face-centered cube on the assumption of simple substitution—that is, with four atoms to the unit face-centered cell—was much higher than the density measured directly. It was suggested that the assumption of four atoms to the unit cube is not valid for these alloys, and that each unit cube contained less than four atoms; in other words, that one tin atom replaces more than one copper atom, leaving some atomic positions unoccupied. Such a structure, if verified, would have far-reaching significance in the study of the crystal structure of metallic alloys. It would indicate a complexity in terminal solid solutions not hitherto suspected and might encourage work leading to the discovery of other alloys of the same type, and perhaps to types intermediate between it and the two recognized types. It is of importance, therefore, to reinvestigate these alloys with respect to the type of solid-solution structure obtaining therein. Materials and Experimental Method The alloys were prepared from electrolytic copper cut directly from the cathode and the high-purity tin furnished by the U. S. Bureau of Standards for the calibration of thermocouples. No analyses for impurities of these materials or of the finished alloys were made, since such impurities as might be present could have only a wholly inappreciable effect upon the data obtained and the conclusions drawn. The alloys were made by melting the weighed copper charge in a graphite crucible under a KCl-LiC1 flux with later additions of NaC1, using induction heating. When the copper was melted the weighed portions of tin were

Jan 1, 1930

By J. O. Whiteley, C. Dietz

It is difficult to give a refining outline that may be followed for any and all combinations of the platinum metals; different combinations require different methods of attack. This paper does not pretend to go into all of the reactions of the metals of the platinum group, but will outline the commercial refining of platinum scrap. Typical Platinum Scrap As a concrete case, let us take 100 oz. of miscellaneous scrap, made up of jewelry scrap, dental scrap and laboratory ware. This lot will contain some platinum, palladium, iridium, ruthenium, rhodium, gold, silver and copper. The first problem is to get all of the metals in solution. If the scrap is principally platinum, palladium and gold, a treatment with aqua regia is the course to pursue; but if the scrap contains alloys high in iridium or ruthenium, aqua regia will act too slowly. In the case in hand, we are going to presume that we have scrap high in iridium and ruthenium, and proceed accordingly. Obtaining Residue A Place the scrap, together with six times its weight of granulated test lead, in a solid carbon crucible. This crucible may be placed inside a clay graphite crucible packed with charcoal, to prevent the excessive oxidation of the carbon crucible by the furnace blast. Place a tight cover on the carbon crucible; heat gradually to a good red heat and allow it to soak in the heat for 4 or 5 hr. After the leaded mass is cool, dissolve in dilute nitric acid (1-6) on a steam plate or sand bath. This dissolves practically all of the lead and most of the palladium, silver and copper, together with seme of the platinum and rhodium, and leaves the iridium, ruthenium, gold, and most of the rhodium and platinum as a finely divided residue. Siphon off the clear solution and treat the residue with another portion of dilute nitric acid to insure the solution of the lead and copper. The second nitric acid solution is added to the first, and the residue is filtered on suction and washed thoroughly with hot

Jan 1, 1928

By Eugene Guccione

FOREWORD-At the SME-AIME meeting in Las Vegas this year, the SME Publications Board and the MINING ENGINEERING Committee decided that a fitting way of celebrating the United States' bicentennial would be to publish an article in ME covering the great men in American mining. After some discussion as to the inclusion of financiers -men such as William Randolph Hearst, J. Pierpont Morgan, etc.-the group agreed that the feature should be restricted to the "nuts-and-bolt people," e.g., mining engineers, geologists, mineral processing engineers. Thus, from the AIME All Institute Honors roll and from the SME Awards list, the group chose these 11 historical figures: Herbert Hoover, Daniel C. Jackling, Henry Krumb, James Douglas, Rossiter W. Raymond, Hal W. Hardinge, Seeley W. Mudd, Erskine Ramsay, Howard N. Eavenson, Robert A. Richards, Arthur F. Taggart. What follows is an account of each of these great miners' achievements and the problems they faced, and an assessment by some of today's mining leaders of the challenges that lie ahead.

Jan 7, 1976

Jan 1, 1960

By Francis T. Havard

A Reply to the Discussion by Mr. Francis T. Havard of the Paper by Mr. Henry W. Edwards, which was read at the Atlantic City Meeting, February, 1.904. (Annual Meeting, February, 1905.) MR. HENRY W. EDWARDS, Grand Junction, Colo. (communication to the Secretary) :* Effect of Heat. It should be remembered that the coefficient of expansion of concrete is nearly that of iron; therefore in constructing flues the design must take account of this important detail. The cracking of flues, mentioned by Mr. Havard as having occurred at a temperature of 100° C. and above, . were possibly caused by neglecting to appreciate the extent of the expansion and contraction of the concrete. Effect of Atmospheric Moisture.-The moisture present in the atmosphere is exceedingly injurious to flues of any material, and those made of concrete are no more susceptible than of brick. My experience with flues of the Monier construction, having walls from 1.5 to 2.5 in. thick plastered upon a net-work of iron rods, was unsatisfactory from the standpoint of dura¬bility.

Mar 1, 1905

By Richard E. Chism

Jan 1, 1902

Jan 1, 1963

By C. H. Burgess

ON June 5, 1947, Secretary of State George C. Marshall in a speech at Harvard University outlined a plan for the economic recovery of Europe. The plan contemplated that the United States should provide assistance which would enable the European nations better to help themselves and to help each other to reconstitute from their war-torn lands conditions which would make possible decent standards of living.

Jan 1, 1950

By J. L. Rodda

A large amount of time has been devoted to the microscopical study of the copper-zinc alloys, emphasis naturally being placed upon the commercially important alloys of the system. Suitable methods are available for microscopically recognizing the two phases richest in copper, Per cent,by weight FIG. 1.-COPPER-ZINC EQUILIBRIUM DIAGRAM. (Frond National Metals Handbook, 1933.) but none appear to have been developed for the positive identification of the other phases. This is, however, accomplished, for the phases normally encountered, by an electrolytic method described in the following pages. Five phases of the copper-zinc diagram (Fig. 1) are considered for the purpose of this paper: the solid solution of zinc in copper, alpha (a); the intermediate phases, beta (ß), gamma (y), and epsilon (e); and the solid solution of copper in zinc, eta (n). Beta prime is not considered a separate

Jan 1, 1936

By Charles H. Fulton

CHARLES H. FULTON, chairman, presided at the first session of the Mineral Industry Education Division on Wednesday morning. Reporting for the program committee, Edward Steidle, its chairman, pointed out that its function was not to arrange programs for meetings but to plan a program for the Division to follow in the development of its activities. This was appropriately followed by presentation and discussion of his paper, "Basic Trends in Mineral Industries Education," which, being available in printed form, was only presented in oral abstract. Jay A. Carpenter submitted interesting written discussion that was read, in his absence, by A. M. Smith. Most of the morning was devoted to the discussion of the paper, which was too extensive and ranged too widely to attempt to report in much detail. H. T. Mann, H. P. Hammond, Cadwallader Evans, C. H. Fulton, T. T. Read, D. F. McFarland and P. B. Bucky joined in the discussion, Mr. Hammond making a plea for more unification in mineral industry education, saying that in the study he made for the Society for Promotion of Engineering Education about 35 different curricula preparatory to work in the mineral industry were discovered to exist. He felt that most of the needs of the mining industry could he met by men who had had four years of engineering training of good enough basic quality to permit them to advance along special lines. However, there was apparently a growing demand, as reflected by the increasing number of candidates for the Master's degree in engineering, for men with more thorough training in the fundamentals.

Jan 1, 1933

By D. C. Seidel, E. F. Fitzhugh

The cementation of nickel from acidic solutions by metallic iron is discussed. The cementation is carried out in pressure vessels at temperatures above 100°C. The results from bench scale studies on variables such as retention time, temperature, and solution pH are presented. A continuous processing flowsheet is proposed. Cementation is one of the oldest known hydrometal-lurgical reactions. The cementation of copper on iron was recorded by 'Paracelsus the Great' in about 1500,1 and by 1600 the technique was being used to recover copper at the Rio Tinto operations in Spain.2 At least one early author felt that cementation may have been one of the primary reasons for the alchemists' belief in the transmutation of metals.' The early writings state that when iron was placed in the clear waters from some mountain springs, the iron disappears and copper is found in its place. To the alchemists this may well have been one of the most convincing proofs that transmutation could and did occur. Since these early times the recovery of copper from acidic solutions by cementation has been practiced in plants throughout the world. Probably the cementation technique in some form has been common to more copper mining and milling operations than any other single recovery process. During current hydrometallurgical extraction studies, which were sponsored by the Republic Steel Corp. at the Colorado School of Mines Research Foundation, Inc., it was found that under the proper conditions, metallic nickel could be cemented from acidic solutions by powdered iron. The reactions are apparently similar to those that occur during the cementation of copper, but the nickel cementation had not been anticipated because iron and nickel are nearly adjacent in the electromotive series. The potential difference between iron and copper is approximately 0.78 v, while the potential difference between iron and nickel is less than 0.21 v. The cementation of nickel with iron at room temperature is almost negligible, but when the reaction is carried out in a closed vessel at temperatures in excess of 100°C, the nickel can be cemented almost quantitatively. The part played by this discovery in a practical method of nickel recovery is set forth in a separate paper.3 The following paragraphs are a discussion of experimental studies that were made to investigate this cementation reaction. The technique has been designated the HTC or High Temperature Cementation procedure. The cementation work was part of a study on hydrometallurgical techniques for the extraction of nickel from the garnierite or silicate type nickel ores. A hydrothermal extraction procedure had been developed, and this technique produced an acidic pulp or solution that contained both nickel and appreciable amounts of magnesium.3 Small quantities of ferric and ferrous iron were also present along with cobalt, manganese, and chromium. The potential for recovering the nickel from these acidic solutions by ion exchange or solvent extraction did not appear to be promising because of the relatively high magnesium content. The Ni ++ and Mg++ have nearly identical ionic dimensions and tend to be co-absorbed or extracted during ion exchange or solvent extraction treatments. Preliminary tests indicated that the nickel could be precipitated as a sulfide when using the high pressure H2S precipitation technique developed for the Moa Bay operations of the Freeport Nickel CO.4 This technique gave good recoveries, but the nickel sulfide product requires considerable additional processing before a marketable form of nickel is realized. The process also requires clarified feed solutions, and the solids-liquid separations on the garnierite residues are difficult. A program was initiated to investigate alternate procedures that might shorten the route to a marketable nickel product, and hopefully also permit bypassing the difficult solids-liquid separation steps required for the H2S precipitation technique. It was during these studies that the nickel cementation reaction with iron was encountered. EXPERIMENTAL EQUIPMENT AND PROCEDURES The bench scale precipitation tests which were conducted during this experimental program were made in 2-liter stirred autoclaves.* A photograph showing the form and arrangement of the autoclave

Jan 1, 1968

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam's path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By Robert F. Winkle

A detailed breakdown of mining costs, available to management on monthly and year-to-date bases, is mandatory for a controlled and efficient mining operation. A simple lump sum reporting of costs may indicate a profit or loss differential, but it does not allow an effective search for areas of possible cost reduction. Moreover, functional reporting is necessary on a timely basis so as to note trends of increasing costs In specific areas, which in turn allow possible preventive action by management. Definitive cost information helps to eliminate the tendency to overlook areas where cost Improvements can be made. A good cost control system points out salient operational weaknesses by: ( 1 ) allowing comparison of functional costs with similar costs of other mines and (2) pinpointing sudden increases over unit empirical costs within the organization. In general, the cost accounting structure is relatively uniform within large open pit mines, but surprisingly some systems will overlook the need for detailed breakout in comparatively high cost areas. In some other systems, unrelated costs will be lumped together, preventing careful analysis of cost accrual.

Jan 1, 1979