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By M. Cavallini, G. Cannavale, P. P. Milella, A. Pescetelli, C. Lupi

Ni-Cd sealed and vented cells have been widely used in the last few years. The environmental hazard related to the heavy metals contained in Ni-Cd batteries is well known. Therefore, a number of scientific studies and commercial processes have been implemented in order to recycle them. Since spent batteries are a heterogeneous and complex material, any kind of recovery process needs some preliminary treatments. The proposed process described in this paper has been tested in laboratory and further developed in a pilot plant. It consists of a combination of mechanical and hydrometallurgical treatment steps, and is able to treat all type of Ni-Cd batteries. In particular, the mechanical treatments have to be done separately on vented and sealed cells, while the hydrometallurgical step is performed on a mixture of the two products obtained from mechanical steps. A fully automated dismantling line would allow the separate recovery of the plastic or metallic casing, terminals, KOH electrolyte, and electrodes to be further processed· for Ni and Cd recovery. The electrodes coming from dismantling line and sealed batteries are submitted separately to an original crushing and elutriation treatment to separate metallic and active paste in the first case and metallic, plastic and active paste in the second case. The hydrometallurgical treatment is carried out on active paste bearing product to produce Ni, Cd, and Fe comn1ercial salts through acidic leaching followed by a multi-step solvent extraction operation to obtain pure solutions.

Jan 1, 2000

By W. C. PAGE

AS the pioneer operation treating the mixed lead- zinc-iron ores from the district tributary to the Salt Lake Valley, the International Smelting Co.'s plant has offered an extremely interesting and instructive opportunity to study some phases of this problem. Basically, there were two main reason for our attempting to work out a successful operation for the separation and concentration of the values contained in the rather widespread deposits of these so- called lead-zinc ores. In the first place, the time was ripe and demanded some method of curtailing the economic waste resulting from the costs of past and present practice of smelting ores of this character, or rather, those ores which could stand the charges inherent with smelting them. Secondly, but rather primarily with us, we believe that such a solution would greatly in- crease in general the production of lead in the district tributary to the Salt Lake Valley. It is generally known that there were and are three relatively large lead smelting plants in the Salt Lake Valley and the decreasing production of correspondingly clean lead ores was not efficient to justify the existence of all three. We could not hope for better lead smelting metallurgy nor more efficient business management than was being practised, so the only prospect was to at- tempt to work out some way to increase the primary production and thus widen the scope of operations.

Jan 1, 1926

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By S. Gregory

Many gold treatment plants have sulphides and coarse particle gangue components that contain gold in their tailings (cyanide leach residues and flotation tailings). Coarse and very fine liberated gold may also be present in some tailings streams. Two issues usually govern the economics of recovering additional gold from gold occluded in sulphide and gangue particles. The liberation characteristics of the gold in the sulphide and coarse gangue (gold liberation versus grind size) is the first and most important of the two. If fine grinding can liberate a reasonable amount of the gold, then the next important issue is how effectively these two constituents can be concentrated. Flotation will achieve high sulphide recovery but is usually costly. Selectivity is also an issue because of entrainment. Continuous centrifugal gravity concentration offers a viable solution to the recovery of both sulphides and coarse gangue however selectivity is also likely to be a problem. The possibility of improving concentrate grade by using a Falcon B separator was investigated. This paper describes a program of test work carried out on a gold leach tailings using a laboratory Falcon '13' separator. The program involved three different bowl angles: 10, 12 and 14 degrees and two bowl speeds (giving 250 and 350G accelerations). A number of tests were also performed on samples that had free gold present to ascertain the size-by-size recovery of gold in these samples.

Jan 1, 2005

By P. Danson, D. A. White, S. Bashir

Composite ion exchange materials made of SnO2, TiO2 and MnO2 can be used to remove radioactive contaminants from nuclear waste streams. In several cases their selectivity and capacity are enhanced by mixing hydrous silica into the matrix. MnO2-SiO2 materials are especially useful for a number of reasons, such as their selection of heavy elements over caesium. Distribution constants and determinations of exchange capacities show that in many instances the properties of the composites are better than those of the oxides alone, while the presence of a chelating agent has been found to reduce the uptake of nuclides considerably. Methods are being developed for the bulk manufacture of the materials. Further work on sorption mechanisms is required to explain anomalous results, particularly the variation in exchange capacity for different elements and the ability of the oxides to sorb colloidal material in alkaline solution.

Jan 8, 1992

By Jean-Paul Drolet

"This paper charts, briefly, the :salient facts of international trade in minerals and their products and Canada's place in it. It also reviews inter-national agreements, economic groupings and national measures to channel and regulate production and trade in minerals. Canada's mineral industry now produces raw materials worth $3.7 billion per year, making this country a giant among mineral producers. Two-thirds of this production is exported, chiefly to the United States, accounting for about 30 per cent of Canada's merchandise exports and topping all other classes.However, several other nations are also pressing the development of their mineral resources and markets. The Soviet Bloc, China and principally Australia and Africa are becoming important suppliers of basic raw materials to some traditional markets of Canada in Europe and Japan.The outlook for Canadian mineral exports to the countries of the Common Market, Great Britain and Japan is good, although some tariff barriers remain troublesome.Concerning the United States, our most important market, Canada is seeking to have that country lift import quotas on lead and zinc, and re-cent statements by U.S. authorities give hope that this may be achieved soon. Moreover, Canada wishes to obtain easier access to the American market for several of its metals and minerals.Canada is now participating in the Kennedy Round of tariff talks under the auspices of the General Agreement on Tariffs and Trade (GATT), and is seeking to open wider doors for its exports of products.In summary, Canada has done reasonably well in some mineral commodities on world markets, but has lost ground in others. Any slackening of Canada's efforts in the development and marketing of mineral resources would soon lead to the decline of its role in the world miueral economy."

Jan 1, 1966

By V A. Chanturia, T N. Matveeva, V V. Getman, A Yu Karkeshkina

The development and application of new effective environmentally friendly reagents for the flotation of thin and ultrathin mineral components is an urgent task. The analysis of the nomenclature of chemicals, including flotation reagents and flocculants, showed that water-soluble polymers (WSP) might be used in flotation separation of fine grinding products containing non-ferrous and precious metals. Water-soluble polymers that are responsive to temperature changes are the most attractive as reagents during flotation. These are the thermo-responsive polymers or thermomorphic polymers. The presence of nitrogen and oxygen atoms in the polymer molecule contributes to the formation of a coordination bond with non-ferrous and precious metals. A research conducted at the ICEMR RAS within the framework of the scientific school of Academician of the Russian Academy of Sciences Chanturia helped to develop a method of flotation of finely ground mineral particles containing valuable components using modified thermomorphic polymers. The paper focuses on the experimental study of poly (vinyl caprolactam) (PVC) as a flotation reagent for gold recovery from finely ground mineral products. PVC is a ready-made water-soluble thermosensitive polymer that does not require complex synthesis. PVC has a high ability to form complexes in an aqueous environment when heated. According to experimental data, the polymer interacts with gold nanoparticles, contributing to the extraction of gold from fine mineral products and the tailings that makes it perspective as an additional flotation agent for the processing of gold-containing ores.

Aug 24, 2022

By J. Defreyne

CESL has developed a proprietary hydrometallurgical process for base metal concentrates, notably those of copper and nickel. The process is based on pressure oxidation (PO) of the sulphide minerals, which is done at elevated temperatures in mixed sulphate-chloride liquor at about pH 2 ? 3. The process achieves maximum oxidation of the metals whilst minimizing sulphur oxidation to sulphate. Almost all base metal sulphide minerals are efficiently treated under these conditions. In the case of copper minerals, pressure oxidation does not generally put the copper into solution, because of the relatively high pH prevailing in this process. Therefore, PO is followed by an acidic leaching stage, which specifically aims at maximum copper dissolution with minimal leaching of iron. The overall copper recovery is largely determined by the efficiency of this stage. The process has low capital and operating costs, partly because there is minimal use of acid or neutralizing agents for iron dissolution or precipitation, respectively; this is achieved by minimizing iron leaching during both the oxidation and leaching stages. Iron sulphides in the feed concentrate deport almost entirely to the solid leach residue as hematite, which has superior handling characteristics for filtering and washing. Iron minerals play a key role in the process, with pyrrhotite and pyrite having very different responses to the oxidation process. Acid management for the whole process is affected by the iron mineralogy, and the flowsheet is therefore tuned to the specific concentrate.

Jan 1, 2006

By R. C. Hubli

A chemical model has been developed to investigate the dissolution of sulphide minerals in brine solutions containing copper and iron chlorides. The model has been employed to study the dissolution .of synthetic NiS using different initial concentrations of Cu(II), Cu(I), Fe(III) and temperature. The speciation of copper with particular reference to the formation of hydroxy-chlorides as a function of total chloride and H+ has been computed. The model predictions are in agreement with experimental results. It has been found that addition of Fe(III) results in the maintenance of a high Cu(II)/Cu(I) ratio leading to enhanced rates of dissolution and suppresses the loss of Cu(II) due to the formation of hydroxyl-complexes.

Jan 1, 1997

By C. C. Walden, D. W. Duncan, P. C. Trussell

Thiobacillus ferrooxidans released copper from -400-mesh chalcopyrite at a rate of 54 mg/I/hr. Any flotation chemicals remaining on the concentrate did not inhibit the leach rate. Zinc rougher tailings were also leachable. With bacteria, 75 per cent of the zinc and 68 per cent of the copper came into solution. In the sterile controls, only 16 per cent of the zinc and 10 per cent of the copper were released; 100 per cent of the copper and 36 per cent of the zinc were leached from pyrite cinders through the action of bacteria, and 17 per cent of the copper and 10 per cent of the zinc were solubilized in the sterile controls. Less than 0.027 per cent of ~he iron came into solution. The majority of the copper in a converter slag was acid-soluble, but a reverberatory slag responded to microbiological leaching. About 62 per cent of the copper came into solution, compared to 12 per cent in the sterile control. The various factors influencing the rate and extent of microbiological leaching are discussed.

Jan 1, 1966

By T. Mahlangu Mahlangu, T. Fungene, K. C. Sole

"Although oxygen is widely employed as the oxidant of choice in gold leaching by cyanide, its low aqueous solubility presents some drawbacks in practical application; hydrogen peroxide has therefore been considered as a possible alternative. The aim of this investigation was to study the catalytic decomposition of hydrogen peroxide, which generates an oxidizing intermediate species, and to understand its effect on cyanide destruction. Operating conditions that facilitated the effective decomposition of hydrogen peroxide were established by varying the pH and catalyst type and concentration. The oxidizing intermediate, detected using an indirect technique, was found to be the hydroxyl radical (OH?). OH? is commonly generated in acidic solutions, but this work demonstrated that it is also produced at the alkaline pH values necessary for cyanide gold leaching. The effects of free and complexed iron and copper catalysts on the oxidation and consumption of hydrogen peroxide and cyanide were also investigated. It was shown that the cyano complexes of Fe(II) and Cu(I) are also effective as decomposition catalysts. Hydrogen peroxide concentrations above 0.01 M decreased the free cyanide concentration, which was attributed to the probable formation of the cyanate anion (CNO-). Although cyanide consumption increased due to its oxidation in the presence of OH?, excessive cyanide consumption in the presence of copper was attributed primarily to its complexation by the unstable copper(I) cyanide species. Rate constants for the decompositions of H2O2 and cyanide by ferrocyanide and copper cyanide were calculated; the latter was identified as being a better catalyst. IntroductionLeaching of gold from its ores using cyanide has been employed for well over a century (Habashi, 2016). Addition of cyanide converts the gold into a cyanide complex (Au(CN)2 -) that is soluble in water (Wang and Forssberg, 1990). The leaching reaction can be represented as Equation [1]:"

Dec 1, 2018

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By John Brown

Let’s talk about things that you, the driIl boss, the pit boss and the driller can do to eliminate the trend in drilling related accidents that have come to plague our industry in recent years. My paper will focus on reaI issues, problems and solutions that will affect our everyday outlook and attitudes about our jobs and lives. There are some real hard facts we must address if we are going to reverse this terrible killing trend.

Jan 1, 2000

By O. Leuangthong, E. Schnetzler

"The McMurray formation in the Athabasca oil sands deposits of northern Alberta is part of the world’s second largest proven crude oil reserves. The formation is characterized by stratigraphic layers that correspond to three different depositional environments: Marine, Estuarine, and Fluvial facies. Resource estimation for oil sands has traditionally relied on polygonal and inverse distance schemes. These techniques are simple and straightforward in practice, but they do not permit reliable uncertainty assessment. This paper describes the modelling of the McMurray formation using modern geostatistical techniques.Geostatistical modelling should be performed within homogeneous geological facies. The methodology for geostatistical simulation within each of the identified facies involves: 1) assessing the most appropriate stratigraphic transformation for optimization of the correlation structure; 2) determining representative distributions with declustering and debiasing techniques; 3) modelling spatial continuity of the bitumen grade, fines grade, water saturation, and other petrophysical variables; 4) performing estimation and cross validation as checks against simulation results; 5) performing simulation for uncertainty quantification of bitumen and fines grade; and 6) model checking of simulation results against the input data, and comparisons against the kriged models. These steps are described in detail. The application of these models for uncertainty quantification in support of resource classification is also discussed."

Jan 1, 2006

By K. R. Koch

Although some of the platinum(II/IV) and rhodium(III) chemistry is considered ?old? and well-known, the application of modern multinuclear NMR spectroscopic methods to this chemistry in solution reveals new details about their rich and relevant solution chemistry. In this paper we will briefly illustrate that the highly-sensitive 195Pt NMR shielding is an excellent probe to explore aspects such as solvation, ion-pairing, and the hydrolysis chemistry of inter alia [PtCl6-n(H2O)n]n-2 (n=0-5). Moreover the novel use of 35Cl/37Cl and 18O isotopes effects as unique NMR ?fingerprints? leading to a new and unambiguous method of chemical speciation of the numerous possible PtII/IV and RhIII complexes present in halide-rich aqueous solutions. In the case of Rh(III) chemistry a new, direct speciation distribution diagram has been established for [RhCln(H2O)6-n]3-n complexes (n = 3-6) in HCl solution at 292 K with these methods.

Jan 1, 2012

By R. C. Gabler

Effective recycling or disposal of flue dusts is a continuing problem, particularly for secondary smelters treating low-grade Cu scrap. The Bureau of Mines investigated a variety of flue dust treatment approaches and demonstrated the technical feasibility of a bench-scale alkaline method that includes leaching, cementation, precipitation, and roasting. Flue dust was leached at room temperature with an alkaline solution of (NH4)2C03 and NHpH to solubilize ZnO and Zn metal. Some copper, lead, tin, and most of the zinc were dissolved in the leach step. Copper, lead, and tin were recovered in the cement product. The Zn in the flltrate was precipitated by pH adjustment to neutral using CO2 injection. The Zn salt was flltered from solution and roasted to give high-purity ZnO. The leach residue, enriched from 4.3 to lOA pct Sn, could find a ready market; the metallic cement product can be recycled back to the copper converter; and the high-purity ZnO product can be sold in several markets, leaving no material for disposal. The possibility for recycling of reagents, lower energy demand, and low environmental impact make this method economically and environmentally attractive for recycling secondary copper smelter flue dusts.

Jan 1, 1988

By Alan P. Prosser

The heap leaching of gold ores by cyanide solution was simulated by computer program. The program uses only basic m1neralogical and chemical data; no process testwork data, such as column leach results, are required. The simulation can be used to forecast the consequences of various changes before and during the testwork, design and operation stages of a particular ore-process system. Also, data about the state of different parts of the heap at various times help create an understanding of what is happening. The effects of mineralogical and process variables on the overall performance of the ?heap leaching process are illustrated. Comparisons are made to column leach tests and production data. The potential of the simulation strategy is discussed for making better use of operating experience and for suggesting specific research objectives. It has become clear that more attention should be paid to other metals that dissolve in the solution.

Jan 1, 1989

By B. A. Hancock

New permit discharge standards instituted at Hecla Limited?s Lucky Friday Mine required installation of water treatment plants to manage water quality at two outfalls to the South Fork of the Coeur d?Alene River. The 002 Outfall Water Treatment Plant (WTP) is a clarification-filtration plant for treating the combined mill and underground discharge water flows. Process optimization efforts were a significant challenge until the negative impact the exploration diamond drilling products had on the clarification process was identified and resolved. The products were being wasted directly to the mine water discharge system which was pumped to the surface WTP. Anionic soluble oil and polyacrylamide based products were causing TSS particle hydrophobicity and dispersion that greatly affected coagulation and flocculation response, resulting in excessive chemical usage and treatment control issues. This paper details how problems associated with the drill products negatively impacted the 002 WTP and how system changes, alternative product usage and treatment at the source resulted in more consistent plant performance.

Jan 1, 2011

By David Schlain

The galvanic corrosion properties of titanium in contact with commercially pure aluminum, copper, or type 302 stainless steel in some of the common organic acids were investigated. Acids used in these experiments were 10 percent formic, acetic, lactic, citric; 1 percent oxalic and tartaric; and 9 percent oxalic. Electrode-potential measurements and several types of galvanic couple experiments were carried out. Solutions were aerated by three methods: Flow of air, flow of helium, and natural aeration. Work was done at 35° C. with couples consisting of equal areas of the 2 metals. Titanium was resistant to corrosion in most of the organic acids studied, whether alone or in contact with a dissimilar metal. However, titanium coupled with aluminum did corrode in 1- and 9-percent oxalic acid solutions. Contact with titanium usually caused aluminum to corrode by galvanic action. Copper was subject to galvanic attack in 10-percent acetic acid with a flow of air. Contact with aluminum to some solutions in which titanium is ordinarily inert and noble with respect to aluminum caused titanium to corrode

Jan 1, 1956

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969