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By E. F. Paski

Geological materials are likely the most complex and challenging substances to quantitate by ICPOES (inductively coupled plasma optical emission spectroscopy). For complex materials having widely varying compositions, spectral overlap interferences govern detection and quantitation limits attained by ICPOES based analytical methods.

Jan 1, 1993

By J. E. Hawley

Abstract Spectrographic methods for the analysis of minor constituents such as platinum-group metals, gold, silver, and silica in palladium and platinum refinery sponge are described. These involve the conversion of the sponge metals to the black form by reduction with high purity aluminum filings in either acid or alkaline media. Standards of known composition are prepared in the same manner from either refinery or spectrographically standardized sponge metals. Samples of the black metals are mounted in pellet form and a multisource spark discharge used for excitation. The range of concentrations of impurities studied are those common to refinery samples. Excellent reproducibility of intensity ratios using major constituents as internal standards, is demonstrated and two methods have noted by which the accuracy of the procedures are shown to be of the order of 3 per cent, on the basis of synthetic preparations. Introduction During the past two years an investigation has been carried out in the Spectrographic Laboratory, Queen's University, to determine the suitability of modern spectrographic techniques for the precise analysis of the platinum-group metals palladium, platinum, rhodium, iridium, and ruthenium in the form of refinery sponge analyzing about 99 per cent of the major constituent.

Jan 1, 1951

By W. L. Ott, C. L. Lewis

"AbstractA technique is described for preparation of palladium sponge and for spectrochemical analysis of the metal in this form. The precision and accuracy of the method are discussed. Analyses are compared with previous spectrochemical analyses of palladium in the black form. Good agreement was found in the two sets •of results and it is concluded that they are more reliable than wet chemical .analyses of the same material.IntroductionFOR SEVERAL YEARS the problem of platinum metal analysis by spectrochemical methods has been under investigation at the Spedtrographic Laboratory, Department of Geological Sciences, Queen's University. The problem, briefly -stated, is as follows: Samples of platinum, palladium,-rhodium, ruthenium, and iridium are received as fine metal powders, called sponge. Direct spectrographic analysis of this material has not been found satisfactory due to its heterogeneity •as regards contaminant metals, which may be present up to a total of one per •cent or more. Further-more, spectrographic standards are difficult to obtain and difficult to prepare accurately by adding weighed portions of contaminant metals to the sponge. The fact that •contaminant metals in original samples are probably alloyed with the major constituent is a further difficulty since complete fusion of these refractory metals proved impractical in the present case as a means of standard preparation. It •has, therefore, been found most satisfactory to dissolve the metals, prepare standards by addition of solutions of contaminant metals, and to reduce both standards and samples to a homogeneous form. A previous paper, by Hawley, Wark, Lewis and Ott (2) dealt with a method for spectrochemical analysis of platinum and palladium in their black form. Since completion of research on the black technique, the possibility of analyzing palladium accurately in its sponge form has• been investigated."

Jan 1, 1953

By W. L. Ott, J. E. Hawley, C. L. Lewis

"IntroductionTHE APPLICATION of spectrochemical analysis to metals of the platinum group was advocated by Harvey (3) as follows: ""The spectra of the platinum group metals have been studied less than many of the more common metals. The rarity of occurrence of these elements makes the analysis relatively unusual. Potentially, the analysis of this group is an excellent application of spectrographic methods, particularly in contrast to the tedious chemical procedure"".Wichers (8) divides platinum-metal analysis into three broad divisions as follows :( 1) The detection and estimation of these metals in other materials, e.g., ores, where the amounts present are very small.(2) The detection and estimation of impurities in the refined metals themselves ....(3) The analysis of alloys of the platinum metals .....The present paper deals with the second division: analysis of refined rhodium.Research on spectrochemical techniques for determination of trace contaminants in refined platinum metals was begun at Queen's University in 1949, under the supervision of Professor J. E. Hawley. Since 1953, the work has been continued in the Metallurgical Laboratories of Falconbridge Nickel Mines, Limited. Techniques for spectrochemical analysis of refined platinum and palladium have been published ( 4, 5). A technique for analysis of refined iridium has been developed but not yet published."

Jan 1, 1955

By A. G. Scobie

THE research laboratory of this Company was recently faced with the problem of determining trace amounts of tungsten in a series of classifier sands. A spectrographie survey revealed the feasibility of using this instrument in the final evaluation, but a check of the common methods in use for the isolation of tungsten (3, 4) showed these methods to give incomplete separation for trace amounts. An investigation into the possibility of modifying these procedures, or developing others, was thus indicated. ASSAY PROCEDURE Weigh 10 grams of 200-mesh ore or concentrate into a 400-ml. beaker, wet the sample well with about 20 ml. of water, and add 100 ml. of hydrochloric acid. Cover, digest at 60° to 70° C. for about 1 hour, and then boil down to approximately 25 ml. Cool, add 25 ml. of hydrochloric acid and 10 ml. of nitric acid, and again boil to former volume. Add 20-ml. portions of nitric acid with successive boiling clown until chemical action is complete. Then add 20-ml. portions of hydrochloric acid until all nitric acid is removed. Take nearly to dryness on a law-temperature hot plate, but do not bake. Take up in 10 ml. of hydrochloric acid and 20 ml. of water and heat on a law-temperature hot plate until all iron goes into solution. Dilute to 200 ml. and heat to just below boiling. Stir in pulp of about half of a No. 41 Whatman filter paper (12.5-cm.) and continue digestion on plate with occasional stirring for 15 to 20 minutes.

Jan 1, 1943

By Paul Giesecke

SINCE most modem metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. PRINCIPLES OF SPECTROCHEMICAL ANALYSIS In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1944

Spectroelectrochemical Investigation of Hydroxamate Reagents on Copper Oxide Minerals

Sep 13, 2010

By R. N. Gow

The presence of enargite (Cu3AsS4) is problematic in gold processing because it is environmentally hazardous due to its arsenic content but also because it is double refractory causing both cyanide and oxygen consumption to increase. Selective leaching and treatment of the arsenic would prove advantageous prior to applying conventional gold leaching methods. The reactivity of enargite samples from Butte, Montana and Quiruvilca, Peru were spectroelectrochemically studied under alkaline conditions, pH range of 8-13, using Raman spectroscopy and cyclic voltammetry. Raman spectra of the surface were collected during and after voltammograms were potentially cycled in order to determine and compare surface species against theoretical EH-pH diagrams determined from mass-balanced thermodynamic calculations using StabCal software. Under slightly oxidizing conditions, covellite (CuS) peaks were found in a short matter of time, above ~100mV vs SHE for pH 9-13, suggesting arsenic leaching specifically occurred. At longer conditioning times, elemental sulfur was observed and tended to passivate the surface. The presence of sulfur suggests that copper was eventually leached. By operating above pH 12, under slightly reducing conditions near -300mV vs SHE, arsenic can be selectively leached as thioarsenate (AsS43-) or thiosulfate (AsO43-) without sulfur formation.

Feb 27, 2013

By H. Huang, Y. Takasaki, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing not only because it is environmentally hazardous due to its arsenic content but also because it is refractory, causing both cyanide and oxygen consumption to increase. Selective leaching and treatment of the arsenic would prove advantageous prior to applying conventional gold leaching methods. The reactivity of enargite samples from Butte in Montana and Quiruvilca in Peru were spectroelectrochemically studied under alkaline conditions – pH range of 8-13 – using Raman spectroscopy and cyclic voltammetry. Raman spectra of the surface were collected during and after potentially cycled voltammograms in order to determine and compare surface species against theoretical EH-pH diagrams constructed from mass-balanced thermodynamic calculations using STABCAL software. Under slightly oxidizing conditions, covellite (CuS) peaks were found in a short matter of time, above ~100mV vs. SHE for pH 9-13, suggesting arsenic leaching specifically occurred. At longer conditioning times, elemental sulfur was observed and tended to passivate the surface. The presence of elemental sulfur suggests that copper was eventually leached from the surface. By operating above pH 12, under slightly reducing conditions near -300mV vs. SHE, arsenic can be selectively leached as thioarsenate (AsS4 3-) or thiosulfate (AsO4 3-) without sulfur formation.IntroductionEnvironmental limitations on the pyrometallurgical processing of ores and concentrates bearing arsenic and other hazardous elements often outweigh those in hydrometallurgical processing, particularly when minerals like enargite (Cu3AsS4) are present. The hydrometallurgical processing of enargite-bearing materials can be broken down into two categories: the co-dissolution of arsenic and copper under acidic conditions, and the selective leaching of arsenic under alkaline conditions. The selective leaching of arsenic would preferably leave behind copperrich sulfide phases, typically chalcocite (Cu2S) and covellite (CuS), which then become more amenable to conventional copper (and gold) processing. Furthermore, selective leaching often employs sulfide (S2-), bisulfide (HS-) or polysulfides (Sx 2-) to first extract the arsenic as AsS4 3- and AsS3 3- (Delfini et al., 2003; Anderson and Twidwell, 2008; Tongamp et al., 2010a,b). However, hypochlorite leaching (Viñals et al., 2003; Curreli et al., 2005; Mihajlovic et al., 2007), ammoniacal leaching (Gajam and Raghavan, 1983), and finegrinding to mechanically activate the enargite surface (Balaz and Achimovicova, 2006) have been investigated to increase the normally slow reaction kinetics. Because gold ores are becoming more refractory due to increasing arsenic contents as a result of enargite, these methods are being examined more closely by the gold-mining industry."

Jan 1, 2015

By H. Huang, R. N. Gow

Acidic treatment of enargite (Cu3AsS4) dissolves both arsenic and copper from the mineral and then attempts to separate them in the leach solution. The reactivity of enargite was examined in acidic to neutral solutions, over the pH range 1-7, to determine a potential range for co-dissolution. Enargite mineral samples from Butte, MT and Quirivilca, Peru were used as working electrodes in a cyclic voltammetry corrosion cell setup, which were then cycled multiple times over -1000 to 1000 mV. Surface reactions and transitions were characterized using in-situ Raman spectroscopy, which were then compared to updated EH-pH diagrams for the copper-arsenic-sulfur-water system from a previous study done under alkaline conditions. The region of co-dissolution is limited to > 600 mV vs. SHE and pH < 1 under the proposed diagram.

Jan 1, 2014

By R. N. Gow

Acidic treatment of enargite (Cu3AsS4) dissolves both arsenic and copper from the mineral and then attempts to separate them in the leach solution. The reactivity of enargite was examined in acidic solutions, over the pH range 1-7, to determine a potential range for co-dissolution.. Enargite mineral samples from Butte, MT and Quirivilca, Peru were used as working electrodes in a cyclic voltammetry corrosion cell setup, which were then cycled multiple times over -1000 to 1000 mV. Surface reactions and transitions were characterized using in-situ Raman spectroscopy, which were then compared to updated predominance diagrams for the copper-arsenic-sulfur system from a previous study done under alkaline conditions. The region of co-dissolution is limited to > 600 mV vs. SHE and pH < 1 under the proposed diagram.

Feb 23, 2014

By H. Huang, R. N. Gow

"The reactivity of an enargite mineral electrode was investigated spectroelectrochemically under conditions typically found in alkaline sulfide leach solutions, with pH 11-13 and Na2S additions of 50 and 250 gL-1. A bulk enargite electrode was cycled between 0 and -1,000 mV for each set of solution conditions. Raman spectroscopy was used to determine and compare surface formations against species in mass-balanced EH-pH diagrams generated using STABCAL. Previously, it was determined that arsenic could be selectively leached under alkaline conditions at an average solution potential of -300mV, across the pH range 11-13. Operating under such conditions allowed for the selective leaching of arsenic with elemental sulfur formation. From several of the voltammograms obtained during this current testing, the formation of elemental sulfur appeared at increasingly reducing conditions with increasing sulfide concentration. At high concentrations, copper started to dissolve, possibly as a bisulfide complex, reducing the selectivity of the leach, unlike previous studies. However, the presence of the higher sulfide concentration is also anticipated to prevent passivation by consuming any surface formation of elemental sulfur. This study provides insight into the operating parameters of alkaline sulfide leaching in regards to the selectivity of arsenic leaching, as well as guidance for control of reagents and solution potential and, of course, the need for water treatment afterwards.IntroductionEnvironmental limitations on the pyrometallurgical processing of arsenic-bearing concentrates have forced operations to consider other solutions. Attempts to hydrometallurgically process enargite (Cu3AsS4) fall into two categories: the co-dissolution of arsenic and copper under acidic conditions, and the selective leaching of arsenic under basic conditions. The authors believe that the selective leaching of arsenic is more amenable because it produces a solid copper phase, preferably chalcocite (Cu2S) or covellite (CuS) that could then be processed using conventional methods already in place in the copper and gold industries. Potential leaching methods include alkaline sulfide leaching (Achimovicovica et al., 1999; Anderson and Twidwell, 2008a,b; Tongamp et al., 2009 and 2010), hypochlorite leaching (Vinals et al., 2003; Curreli et al., 2005; Mihaljovic et al., 2007), ammoniacal leaching (Gajam and Raghavan, 1983), and acid leaching (Gow et al., 2014b) with or without fine grinding to mechanically activate the enargite surface and increase normally slow leach reaction kinetics (Achimovicova et al., 1999; Balaz et al., 2000; Balaz and Achimovicova, 2006). In this study, the reactivity of enargite under alkaline sulfide leach conditions was examined."

Jan 1, 2015

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By A. G. Scobie

A spectrographic method for the determination of small amounts of gold and the platinum metals in ores has been developed. By means of this method, an assay of 0.001 ounce per ton on one assay ton samples is possible, and by seecrrographic adjustments the sensitivity may be increased to 0.0001 ounce per ton. All the prec10us metals may be determined from one spectrographic arcing with an accuracy of about 5 per cent average deviation from absolute values, and the complete analysis of an ore or similar product may be reported five or six hours after receipt of sample.

Jan 1, 1945

By J. E. Hawley

"IntroductionA STUDY of the trace elements in the ash •of coals from nine seams in the Sydney coalfield, Nova Scotia, was undertaken at the suggestion of Dr. W. A. Bell, Geological Survey of Canada, as a part of a larger study of these and other Nova Scotia coals being made by the Geological Survey and the Nova Scotia Department of Mines under the direction of Dr. P. A. Hacquebard.The main purpose of this investigation has been to •determine if a knowledge of the trace element distribution might be of assistance in the recognition of individual seams, the distinction of which is not always easy or positive in folded and faulted strata by ordinary stratigraphic and structural means.The study has been so conducted as to afford information on the variation of trace elements in individual petrographic intervals or divisions in each of the seams examined, intervals determined by Dr. Hacquebard on the basis of their banded ingredients, vitrain, clarain, durain, fusain, etc, as observed under the microscope in polished sections. The results, as well, indicate the trace element composition of the coals of the area as a whole, and quantitative data for fifteen elements are given, along with concentrations of thirteen other elements, stated in terms of intensity ratios. Data on distribution of germanium, though considered here along with other elements, are dealt with elsewhere*."

Jan 1, 1955

The ultraviolet spectrum of isopropyl ethylthionocarbamate (the principal constituent of Dow flotation collector Z-200) in water and of Z-200 itself in water was found to have an absorption peak at 242 nanometers(nm). The height of this peak was found to be directly proportional to isopropyl ethylthionocarbamate concentrations up to 15 p.p.m. Z-200 contains about 90 per cent isopropyl ethylthionocarbamate and the heightof the peak was proportionately lower, but obeyed the straight line relationship up to 15 p.p.m. This showed the potential value of spectrophotometric measurements for the determination of Z-200 residuals in flotation liquors.Methyl ethyldithiocarbamate (an impurity in Z-200) increased the peak height slightly, but other impurities in Z-200, xanthates, and most inorganic salts present in flotation liquors do not interfere. However nitrate ion and thiosulphate ion have absorption peaks which overlap the isopropyl ethylthionocarbamate peak.The simplest general method to overcome this effect is to extract the isopropyl ethylthionocarbamate into cyclohexane and to measure the absorbance of the extract.The maximum absorbance of the cydohexane extract was at 247 nm and the peak height at this wavelength was found to be directly proportional to the isopropyl ethylthionocarbamate or Z-200 concentration in the original aqueous solution. An alternative method is to measure the spectrum of the original aqueous solution using the aqueous raffinate from extraction as a reference solution. This gives the spectrum due to isopropyl ethylthionocarbamate alone and measurement of the absorbance at 242 nm gives the concentration in the original aqueous solution. Both methods give the same value for the concentration of isopropyl ethylthionocarbamate in the original solution.

Jan 1, 1969

By P. L. Sibrell

Three different refractory carbonaceous gold ores from the Carlin operation in northeastern Nevada were investigated to characterize the effect of passivation treatments on the nature of the carbonaceous material. The carbonaceous material was chemically isolated from the ores and passivated residues, and examined by FTIR spectroscopy, elemental analysis, and gold adsorption capacity. The main component of the carbonaceous material in these ores was found to be a naturally occurring activated carbon-type compound. Hydro-carbons were detected on rare occasions, but no evidence was seen for humic acids. Ore samples were passivated by autoclaving, or by treatment with sodium hypochlorite or gaseous Chlorine. In some of the passivation tests, a new peak was observed in the IR spectra of the isolated carbonaceous material, that was due to carbonyl functionalities. However, all of the passivation treatments tested decreased preg robbing significantly. This suggested that the appearance of the carbonyl peak was due to the severity of the conditions during passivation, rather than the method used.

Jan 1, 1990

By S. R. Sankaranarayanan, T. Sowmya

Slags and fluxes used in metallurgical processes are typically made up of oxides (especially silicates), with additions of fluoride and carbonaceous matter. Despite the efforts made towards understanding the role of slags in various processes, little information is available on the structure of these slags. Tools such as X-ray diffraction, spectroscopy, and electron microscopy could be used for this purpose. This paper is based on an ongoing spectroscopic and structural investigation of slags and related materials. Spectroscopic studies of various commercial slags (predominantly ferrous), ores, glass and related materials, covering a wide range of compositions, have been carried out to understand the structure. The infrared spectra were recorded, predominantly, using FTIR spectrometer (Bruker IFS 66U) spanning 4000 to 100 cm-1using the KBr pellet method. The resolution was typically 4 cm-1. The spectral outputs have been compiled in terms of bands present (corresponding to different bonds) and then compared with the typical bands expected for such bonds. Efforts are in progress to identify the trends with respect to the chemical composition?for example, the effects of SiO2, Al2O3, and non-bridging oxygens. Data obtained so far indicate some trends such as (i) a shift in the Si-O band (969 to 1099 cm-1) towards a higher wave number with increasing silica content (almost 2 to 92 weight percentage) and (ii) further strong shifts as a function of the alumina content. These are being further investigated structurally and in terms of chemical composition/parameters. Keywords: slags, silicates, structure, spectroscopic analysis, shifting of bands

Jan 1, 2004

By G. C. Allen

Selective flocculation is used for the purification of clay minerals. Here we present data from a surface spectroscopic investigation into the polyacrylamides mediated selective flocculation of kaolin from an impure matrix. Use of X-ray photoelectron spectroscopy (XPS) was shown to offer a useful approach for investigating the observed selective separations. In particular, a new small area XPS technique was used to characterize, in situ, the differential competitive, f1occulant adsorption onto mixed kaolin/gangue systems.

Jan 1, 1998

By A. G. Jackson, S. J. P. Laube

"Control of thin films during the growth process is dependent on several parameters that are difficult to monitor, including flux of film material, pressure, substrate temperature, composition, and thickness. One means for easing this difficulty is to take advantage of emission spectra associated with the process and the film. For pulsed laser deposition (PLD), the ion cloud generated by the laser has characteristic emission spectra that can be used to control the flux and, hence, the film. For chemical vapor deposition, the species present can be determined using mass spectroscopy and specific peaks can be used to control the deposition. Raman spectroscopy affords the possibility of real-time control by sensing characteristic peaks associated with film composition and thickness. These spectroscopic methods offer a real-time alternative to process control that is very attractive, because of the ability to accurately control films to achieve the engineered structures and properties sought. Examples are presented to illustrate the capabilities of these methods for thin film preparation.IntroductionThe drive to reduce costs and improve efficiencies of operation sets the tone for much of research, basic or applied. Basic research is limited by the ability of sensors and associated instrumentation to measure parameters accurately and reproducibly. Applied research has the same limitations and also the added constraints of time and costs. Hence, there are strong incentives to explore means for refining existing sensors with respect to performance and cost, as well as finding new sensors and techniques for more accurately and rapidly measuring quantities of interest in experiments and in various processes."

Jan 1, 1997