Edited by B.K. Parekh and J.D. MillerSociety for Mining, Metallurgy, and Exploration, Inc. (SME) 8307 Shaffer Parkway Littleton, CO, USA 80127 (303) 973-9550 wurw.smenet.org SME advances the worldwide minerals community through information exchange and professional development. With more than 16,000 members in 50 countries, SME is the world’s largest professional association of mineral professionals. Copyright © 1999 Society for Mining, Metallurgy, and Exploration, Inc. All Rights Reserved, Printed in the United States of America Disclaimer ‘The papers contained in this proceedings volume are published as supplied by individual authors. The papers are reformatted to comply with SME's book publishing template design. The papers are proofread to ensure no errors are introduced in the design process and to correct typographical errors only. Any statement or views presented here are those of individual authors and are not necessarily those of the Society for Mining, Metallurgy, and Exploration, Inc. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. ISBN 0-87335-184-3 Library of Congress Cataloging-in-Publication Data Advance: in flotation technology. p. em, Edited by B.K. Parekh and J.D. Miller. Proceedings of a symposium held at the Annual SME Meeting, Mar. 1-3, 1999, in Denver, Colo. Includes bibliographical references and index. ISBN 0-87335-184-3 (paper) 1. Flotation-Congresses. I, Parekh, B. K. IL Miller, J. D. ‘TNS23.A35 1999 622'.752—dce21 99-12355, CIPContents ‘The Froth Flotation Century DW Fuerstenau 3 Bee wares wiatalliat P. Somasundaran and Anjing Lou_23 Internal Reflection Spectroscopy for FTIR Analysis of Carboxylate Adsorption by Semi-Soluble Salt Minerals J.D. Miller and J.J. Kellar” 45 Weak Electrolyte Collectors Single Bubble Terminal Velocity-Experiment and Modeling Yongqin Zhang and James A. Finch 83 Roe-Hoan Yoon 95 SECTION 2 __ SULFIDES AND PRECIOUS METALS 113. Richard R. Klimpel 445 Eundamentals of Sulfide Mineral Flotation SChander 129 Thiobacillus ferrooxidans Interaction with Sulfide Minerals and Selective Chalcopyrite Flotation from Pyrite P.K. Sharma, A. Das, K. Hanumantha Rao, and K.S.E. Forssberg 147 Review of Plant Practice of Flotation of Gi and Silver Ores D_Malhotra and L. Harris 467 ts PauteurImplementation and Start-Up of N,TEC Flotation atthe Lone Tree Mine Gary L. Simmons, James N. Orlich, Joel C. Lenz, and John A, Cole 183 SECTION __NONSUIFIDE MINERALS 197 sii é P a R. Bruce Tippin, H.L. Huiatt, and David Butts 199 Phosphate Rock Beneficiation Practice RL. Wiegel 213 Kaolin Flotation: Beyond the Classical Mitchell J. Willis, Sharad Mathur, and Raymond H. Young 248 Iron Ore Flotation—Historical Perspective and Future Prospects Iwao Iwasaki 231 D.R. Nagaraj, A. Day, and A. Gorken 245 Flotation Technology in Nonmineral Applications MT. Ityokumbul _ 257 SECTION __COAL CLEANING 267 ‘The Historical Development of Coal Flotation = mies Frank F. Aplan 269 Australian Coal Flotation Practice BA firth 29 M Coal Elotati x Gary F. Meenan 309 Rate and Residence Time Studies Applied to the Operation of Conventional Coal Froth Flotation Cells B.LAmold 324 Fine Coal Cleaning Using the Jameson Cell: ‘The North American Experience RQ Honaker, A. Patwardhan, M.K. Mohanty, and KU. Bhaskar 331 SECTION 5 EQUIPMENT DESIGN AND DEVELOPMENT 343 Development and Scale-Up of Large Flotation Cells Nathaniel Arbiter 345 ‘Scale-Up and Design of Large-Scale Flotation Equipment Asa Weber, Clayton Walker, Lorin Redden, Dariusz Lelinski, and Steve Ware 353 Design, Development, Application, and Operating Benefits of 100-m'+ Outokumpu TankCell Flotation Cells Adolf J. Jonaitis 371New Developments in Flotation Equipment for Water Treatment Systems Jonathan J. Owen, Dwain E. Morse, Wade 0. Morse, and Raffael Jovine 384. a f - by Horizontal Baffles T.C. Eisele, S.J. Ripke, and S.K. Kawatra 391. ‘SECTION 6 INSTRUMENTATION AND CONTROL OF FLOTATION 397 Developments in Flotation Control: One Part Evolution, ‘Two Parts Revolution John A. Herbst and William T. Pate 399 A New, Comprehensive, and Useful Model for Flotation J.-P. Franzidis and E.V. Manlapig 413 Image Analysis of Froth for Improved Flotation L.B. Hales, RA. Ynchausti, and D.F. Salmon 425 Flotation Supervisory Control at Cyprus Bagdad Don L. Jensen 433 ‘A Model-Based Approach to the Control of Incremental Ash in Coal Flotation W.T. Pate, J.A. Herbst, G.A. Adel, and GH. Luttrell 444 Is Operator Training Necessary for Optimization of Flotation Plants? Deepak Malhotra 453 INDEX 462 {NNN SNJW-160-FS7YForeword ‘The development and implementation of flotation technology during the twentieth cen- tury has been most significant in the effective utilization of our mineral resources. The ability to selectively separate fine and coarse particles by flotation is the heart of most mineral processing operations. In the United States, more than 2 million tons per day of material are processed by flotation. Even now, at the end of the twentieth century, important advances continue to be made in flotation technology, from the detailed study of interfactal chemistry to the design and construction of column and 100-m° flotation cells. Further advances in the twenty-first century can be anticipated. ‘These contributions to flotation technology, dealing with fundamentals, equipment design and development, and instrumentation and control, have impacted all mineral commodities, sulfides and precious metals, nonsulfide minerals, and coal cleaning. Developments of particular significance are presented in these proceedings of the symposium “Advances in Flotation Technology,” held at the SME Annual Meeting, March 1-3, 1999, Denver, Colorado, in honor of Professor Maurice C, Fuerstenau for his many contributions to education and research and for his professional service. Finally, the efforts of our section chairs and our authors must be recognized. The proceedings provide us with an appropriate compilation of papers that summarize the state of flotation technology at the end of the twentieth century, B.K. Parekh and J.D. Miller vilOrganizing Committee SYMPOSIUM CHAIRS B.K. Parekh Associate Director Kentucky Genter for Energy Research University of Kentucky SESSION CHAIRS Flotation Fundamentals 44. Kellar Associate Professor Metallurgical Engineering Department South Dakota School of Mines & Technology Sulfides and Precious Metals K.N. Han Distinguished Professor and Dean Metallurgical Engineering Department South Dakota School of Mines & Technology Nonsuifide Minerals B.R, Palmer Manager of Exploratory Research & Pigment Testing Kert-McGee Chemical Corp. Coal Cleaning PT. Luckie Associate Dean for Research Earth & Mineral Sciences College Pennsylvania State University Equipment Design and Development M.C. Kuhn President Western States Engineering & Construction Instrumentation and Control of Fletation G.T. Adel Professor Mining & Minerals Engineering Department Virginia Polytechnic Institute & State University vill J.D. Miller Professor Department of Metallurgical Engineering University of Utah D.W. Fuerstenau Professor in the Graduate School Materials Science & Mineral Engineering Department University of California at Berkeley E.C. Dowling Senior Vice President Cleveland Cliffs, Inc. FF Aplan Professor Emeritus Mineral Processing Section Pennsylvania State University 4.S. Laskowski Professor Department of Mining & Mineral Process Engineering, University of British Columbia D.G. Foot Director Knowledgescape Systems 4A. Herbst President J. A. Herbst & AssociatesDedication Professor Maurice C. Fuerstenau was raised in South Dakota. Many of these years were spent in the Black Hills, during which time he developed an interest in geology, rocks, and minerals. He attended the South Dakota School of Mines and Technology and graduated with a degree in geological engineering. While an undergraduate, he participated in ROTC and, later, served as an officer in the U.S. Army. He left the service at the rank of captain. After taking a course in mineral processing, he decided to pursue a career in this field and enrolled at the Massachusetts Institute of Technology (MIT), where he received his master’s degree and doctorate. When he arrived at MIT in 1955, Professor A.M. Gaudin was finishing his second edition of Flotation. He made it known that he was devoting most of his time to the book, and that he might take on a student if that person were interested in working in the area of thickening. Professor Fuerstenau quickly developed an interest in thickening and, actually, was the only graduate student working for Professor Gaudin for a year or so. Professor Fuerstenau has commented on many occasions what a rare privilege it was ta work for this giant of our profession. Although he had the opportunity to study flotation phenomena at MIT, for his dissertation research, Professor Fuerstenau studied thickening and designed instrumentation that enabled the continuous measure- ment of pulp concentration during the thickening process. Following graduation from MIT, Professor Fuerstenau went to work for BERYLCO in Reading, Penn. One of the things he looked at while working for this company was the recovery of unreacted beryl from their process by flotation. Some promising results were obtained, and he carried over this interestin beryl flotation when he joined Roshan Bhappu at the New Mexico Bureau of Mines in 1961. Dr. Bhappu had also been working on beryl flotation, and they jointly worked on this project. It was found that beryl responded to flotation with anionic collectors when grotnd in a mild steel mill but not when ground in a pebble mill. This was the advent of the extensive work of Professor Fuerstenau with metal ion hydrolysis in the activation of oxides and silicates. Professor Fuerstenau then joined the Colorado School of Mines (CSM) metallurgy faculty as an assistant professor in 1963. He developed an active research program in flotation and hydrometallurgy and assembled a large group of students. Professor Fuerstenau has been heard to comment many times on the excitement he felt personally about the accomplishments made during that period of time at CSM. Aftera short time on the metallurgy faculty atthe University of Utah, Professor Fuerstenau was extended the opportunity to head the Department of Metallurgical Engineering at the South Dakota School of Mines and Technology. Wanting to become involved inadministration, he accepted this opportunity in 1970, That department quickly increased in enrollmentand became a vibrant organization. He remained at the South Dakota School of Mines for 18 years, serving as department head and, later, as interim vice president of academic affairs. After so many years in administration, Professor Fuerstenau decided that he would like to conclude his career in teaching and research. He joined the Mackay School of Mines at the University of Nevada asthe Echo Bay Mines Distinguished Professor in 1988, However, he was not able to stay away from administration completely, as one of the subsequent years was spent as acting chair of mining engineering, and three additional years as acting chair of mechanical engineering. While at Mackay, his area of interest changed; like so many others in our field, he is now active in environmental research. Professor Fuerstenau has had the opportunity to train a large number of undergraduates during his 35 years in academe. Also, about 80 master’s degrees and doctorates have been awarded under his direct supervision. His students speak warmly of his concern and effectiveness as a teacher, and his graduate students praise his inspiration as an advisor and mentor. He was the first recipient of the Presidential Award presented by the South Dakota School of Mines and Technology annually to an outstanding professor. He was named a Foundation Professor at the University of Nevada in 1996, which is the highest research award presented by the university. Professor Fuerstenau has received many other honors and awards in his career. He is a member of the National Academy of Engineering. He was president of the Society of Mining Engineers in 1982. Professor Fuerstenau is the recipient of the Robert H. Richards Award and the Mineral Industry Education Award presented by AIME, Professor Fuerstenau, a Distinguished Member of SME, isalso the recipient of the AntoineM. Gaudin Award and the Arthur F. Taggart Award of the Society.Froth Flotation: The First Ninety Years Maurice C. Fuerstenau Flotation certainly ranks as one of the most significant technological developments in the twentieth century. The world’s natural mineral resources increased exponentially as. billions of tons of rock became ore as a result of this technology. Interestingly, Ernest Gayford (1928), Vice President of The General Engineering Company, Salt Lake City, Utah, wrote, “The flotation process is undoubtedly the most important development in the recovery of metals from ores that has taken place during the present century. No other process has effected such a great change in metallurgy in so short a time. Looked upon with suspicion by the old-time mill man, hampered by tedious and expensive patent litigation, it has nevertheless forged ahead until no one can foretell where it may lead us.” Froth flotation is approaching 100 years of age; my introduction to the field took place in the 1950s, Theadvancesthat have occurred inthe field since that time have been dramatic. Sophisticated instrumentation has enabled understanding of surface chemical phenom- ena in these systems that was previously unknown or incorrectly interpreted; very large conventional and innovative flotation cells are in common use, and process control in flotation plants is routine. It is interesting to compare the development of the technology prior to the middle of the century with the advances that have occurred since that time. Since a significant portion of my career involved research in surface chemical phenomena, Ishould like to devote this paper to that aspect of the advances in flotation. Much good work has been done, and many good papers have been published on this topic. Space limitations enable only highlighting a number of areas. Flotation had its origin in 1860, when mineral separations utilizing oil avidity were demonstrated by William Haynes. In 1877 the Bessel brothers patented a process for concentrating graphite with ail and water additions coupled with boiling of the system for gas bubble generation. This is probably the precursor to froth flotation as we know it today. They later patented the use of carbonate minerals in acid medium to generate gas bubbles. Other oil-based flotation techniques were developed and used until the discovery of froth flotation in 1905 simultaneously by A.H. Higgins in England and byG.A.Chapman in Australia. These gentlemen were both working for Minerals Separation Ltd., and this company was awarded a basic patent on the process. For the next decade or so, this company was involved in extensive litigation defending infringements on its patent. This process was introduced into the United States by James M. Hyde in 1911 at the Basin. xiReduction Company plant in Basin, Montana, Mineral Separation Led. filed suit and litigation occurred up to the U. S. Supreme Court, which upheld the patent but restricted it to “the use of less than one percent of oil.” (Hines and Vincent, 1962) In addition to the discovery of the flotation process itself, there were a number of other early benchmarks in the historical development of flotation as we know it today. Some of these were tabulated by Gaudin (1957) in his book, Flotation. Important contributions to early flotation technology (Gaudin, 1957) Year Contributor Contribution. 1860 Haynes. Bulkoill process 1877 Bessel Boiling process for graphite 1885 Bessel Chemicalgeneration gas pracess for graphite 1886 Everson Acidulated pulps desirable 1902 Froment, Potter and Belprat Gas as a buoyant medium for sulfide ores 1905 Schwarz Sodium sulfide to recover oxidized base metal minerals 1906 — Sulman, Pickard and Ballot Reduced amount of oil; introduction of gas by violent agitation 1913 Bradford Sulfur dioxide to depress sphalerite 1913 Bradford Copper sulfate as activator for sphaterite 1921 Perkins and Sayre Specific organic collectors do2a Alkaline circuits 1922 Sheridan, Griswold Cyanides to depress sphalorite and pyrite 1924 — Sulman and Edser Soaps for flotation of oxides 1925 Keller Xanthates as collectors 1929 Gaudin BH control 1929 Jeanprost Flotation of highly soluble salines. 1933 Nessler Flotation separation of water-soluble chemi- cal salt mixtures 1934 Chapman and Littleford Agglomeration 1934 Alkyl sulfates as collectors 1935 — Cationic collectors Itis difficult to imagine a more exciting time for research. These researchers were working shortly after the birth and during the initial development of a new technology; nearly everything that they found was new. As late as 1930, a description of collectors was provided by Taggart et al. with the generalization that they are reagents possessing both apolar group that binds them to the mineral surface and a nonpolar group that is oriented away from the surface. Most of the collectors in use taday were developed in this early era, that is, xanthate, dixanthogen, xanthogen formate, dithiophosphate, dithiocarbamate, mercaptan, mercap- tobenzothiazole, fatty acid, alkyl sulfate, sulfonate and amine. The introduction of xiixanthate asa collector in 1925 was aremarkable development in froth flotation. Probably more than any other aspect, xanthate entrenched froth flotation’s role in the utilization of the world’s natural mineral resources. In those early days, the understanding of the surface chemical phenomena occurring in flotation systems was quite limited, since the sophisticated instrumentation available today was lacking, of course. The insight of the researchers of that era was impressive, however. According to one of the notable investigators of that time, Sir lan Wark, “In the early days of the process, flotation was the happy hunting ground of the theorist, and there were almost as many ‘theories of flotation’ as there were writers on the subject. Guesses rich in intuition were made, but little experimental support was offered for the theories presented,” (Sutherland and Wark, 1955) ‘The wo principal theories of that era were the chemical theory espoused by Taggart and coworkers (Arbiter, del Guidice, Hassialis, Ince, Kellogg, Knoll and Taylor) and what might be termed a general adsorption theory espoused by Gaudin, Wark, Langmuir and others, Taggart and coworkers (1930) felt that their theory, stated below, encompassed all flotation systems. All dissolved reagents which, in flotation pulps, either by action on the to-be-floated or not-to-be-floated particles affect their floatability function by reason of chemical reactions of well recognized types between the reagent and the particle affected, These various theories were defended zealously by their proponents. Forexample, Taggart stated, “This generalization, apparently, like many pioneer structures, had for cert observers a flimsy appearance, and these, judging its stability rather by the number than by the character of its foundation posts, have attempted variously to overthrow it either by the frontal attack of gencral denial, or by the flanking movement involved in assuming that those cases in which the facts were unknown or unproved were, therefore, discordant. But as time has passed and further evidence on the question has accumulated, it has become apparent that the results of verifiable experiments add stone by stone to the substructure of the hypothesis, and that the superstructure has lost nothing to weathering.” (Taggart et al., 1934) In support of this premise, experiments had shown that sulfide minerals are oxidized during comminution, producing a surface coating of oxidized products consisting of reduced sulfur-oxides, sulfates and carbonates. After contact between collector solution and oxidized sulfide mineral, stoichiometric exchange of collector ions with mineral surface ions was shown to occur. In the case of galena, after contact with xanthate about 50-75% of the exchanged ions are carbonate and the balance sulfur-oxy ions (Taylor and Knoll, 1934). Further, it was shown that after leaching collector-coated galena particles, lead ethyl xanthate is crystallized from an alcohol solution (Taggart, 1945). Taggart and coworkers extended this theory to include activation, depression and dispersion. With his precise microcalorimetric measurements, Mellgren (1966) clearly substantiated the metathetic uptake of xanthate by galena. ‘Taggart’s shortcoming was that he believed that the chemical theory of flotation was all- inclusive, but the chemical theory had a number of flaws. A number of reagents were shown to function ascollectors even though they did not react to form insoluble products with the surface, e.g., amine on sphalerite (Gaudin ct al., 1930). An additional difficulty with this theory was the fact that large contact angles are measured on gold and platinum xiiiafter contact with xanthate (Wark and Wark, 1933). Further, flotation was shown tooccur with collector present in less than monolayer coverage. Another phenomenon that this theory could not explain is the existence of two forms of xanthate on chalcocite after con- tact with xanthate: an unleachable phase and a phase comprised of multilayers of cuprous xanthate. Xanthate in the unleachable phase was shown to be present at monolayer coverage (Gaudin and Schuhmann, 1936). In support of the adsorption theory, Gaudin (1932) stated, “Collecting agents may be classed in two varieties; those that form definite compounds by metathesis with the surface of the minerals, and those that do not seem to do so. The mode of operation of the latter type of collecting agents is not entirely clear, yet it is established that removal of the reagent from solution takes place; it is not known whether that reagent simply adheres to the surface of the minerals or is changed at the surface to a different chemical form.” ‘The first mineral to be concentrated by flotation was zinc sulfide, both in Australia and in. the United States. As early as 1911, Leslie Bradford used copper sulfate as an activator of sphalerite at the Broken Hill Proprietary mill in Australia (Ralston et al., 1930). This certainly is one of the really significant developments in flotation, and it is surprising that this discovery was not patented, especially in view of the extensive litigation that was ‘occurring at that time. He also illustrated the depressant action of sulfur dioxide on sphalerite at that time. Another important development in flotation technology was the use of cyanide to depress sphalerite and pyrite, The combination of cyanide with pH control has enabled differential flotation of complex sulfide ores, Sheridan and Griswold patented this technology in 1922, Gaudin's work in 1929 showing the control that pH exhibits in froth flotation was another giant contribution to the field. This work involved sulfides with xanthate and amine, copper carbonate with xanthate, and activation of quartz and feldspar with cupric ion in the presence of fatty acid. At that time Gaudin stated, “It appears established that H” and OH™ ion react with the mineral surfaces in some instances, and that they have much to do with the adherence of collectors on mineral surfaces in other instances.” This technology was not patented; it’s interesting to speculate on what the value of such a patent might have been. Anelegant paper was published by Gaudin in 1930 on the effect of xanthate, copper sulfate and cyanides on the flotation of sphalerite, He confirmed Roger’s experiment of 1911 in which he reported blue-black coatings on sphalerite with prolonged contact with copper sulfate solutions. He showed that unactivated sphalerite could be floated with amyl and heptyl xanthate but not with ethyl xanthate; he explained copper activation of sphalerite on the basis of the solubility products of CuS and ZnS; he showed that cyanide does not inhibit flotation of unactivated ZnS; and he demonstrated deactivation of copper- activated sphalerite with cyanide. Ina discussion of this paper, F.A. Thompson (1930) stated, “The research reported by Professor Gaudin is a splendid illustration of the way in which progress has been made and is to be made in the future in flotation fundamentals because it represents the clarification of a much befogged issue.” Perhaps the first detailed meticulous investigation of the physical chemistry of flotation was that of Wark and Cox (1934). These investigators conducted a large amount of excellent work utilizing contact angle measurements to delineate the effects of such modifiers as cyanide, hydroxyl and sulfide ion on sulfide flotation. Critical pH, cyanide xivand sulfide curves were prepared showing clearly the conditions under which bubble contact and nonbubble contact were possible. These results are still useful and have withstood the test of time. Pyrite received a rather large amount of study, as would be expected, No definitive mechanisms were delineated, however. As early as 1933, though, Gaudin and Wilkinson showed that, “Pyrite, or ferric ion derived from it by oxidation, changes xanthate to. dixanthogen; the dixanthogen can be extracted from the mineral surface provided oxidation of the dixanthogen is prevented.” This gem of an observation lay dormant for the next 35 years. In discussing some of Wark and Coy’s (1934) work, Barsky showed that the product of the xanthate ion and hydrogen ion concentrations is constant at the critical pH for bubble contact for galena and other sulfides. His suggestion was that the free xanthic acid molecule rather than xanthate ion may be responsible for flotation. The first half of the development of froth flotation was involved mainly with “how to make it happen.” After about 1950, research has been involved mainly with “how does it happen?” Great strides in understanding of these systems have been achieved since 1950. DEVELOPMENTS AFTER 1950 In 1950, Cook and Nixon published a paper in which they postulated that neutral heteropolar molecules (free acids or bases) rather than ions are responsible for the water- repellent films on collector-coated solids. Barsky’s discussion of Wark and Cox’s bubble- contact curves apparently attracted Cook’s interest in explaining the complete shape of the captive bubble curves. In this development, which became to be known as the neutral molecule theory, Cook and his colleagues (Last, Nixon, Wadsworth; 1950, 1951, 1952) assumed that ions must approach a charged surface as an ion pair. At constant ionic strength, however, the adsorption process could be merely ion exchange. Barsky (1934) showed that along the upper traces of the collector-pH captive bubble curve the total collector concentration (m,) times the hydrogen ion concentration (H"] is equal toa constant: Eme] [HT = [HXag] = Kaarsiy: where HX;qis the neutral molecule of dissolved xanthicacid. As pointed outby Wark, [H"] can be replaced by Ky./[OH"] which relationship has been used to explain results on the basis of competition between xanthate and hydroxyl ions for the surface. Assuming single-site Langmiuirian adsorption with the neutral molecule as collector, Cook and coworkers derived the relationship: _ melt “1 [H"}+K, (HX, = constant along bubble-contact curve where K, is the dissociation constant of the xanthic acid used. In basic medium under which condition the acid dissociation constant of the collector is much larger than the hydrogen ion concentration, this expression reduces to the Barsky relationship. xvAs the pH is reduced and the hydrogen concentration becomes larger, the relationship will lose linearity at some value of pH depending on the pK of the collector acid. At quite low values of pH in which the hydrogen ion concentration is much larger than the collector acid dissociation constant, the curve of collector addition will become horizontal, and the concentration of undissociated molecule will be that of the collector addition. The correlation of the critical pH curves calculated from this model compared with Wark and Cox's experimental data is remarkable (Cook and Nixon 1950). This analysis was also applied to systems in which both collector and depressants were present (Last and Cook, 1952). Other supporting evidence for this adsorption model is that provided by Steininger (1967) on sphalerite flotation with various sulfhydryl collectors. The relationship between the upper critical pH limit of flotation and the pK, of the collector acid is impressive. These data are really so striking that they are difficult to continue to ignore, Further, optimal and maximal recovery of sphalerite is obtained at about pH 3 when amyl xanthate is used as collector (Laskowski and Sobieraj, 1969; Fuerstenau et al., 1974) Two optimal pH regions are noted when chrysocolla is floated with octyl hydroxamate, the first about pH 6 and the second about pH 10, Hydroxamic acid is a very weak acid, pK of 9. At pH 6 essentially all of the collector will be neutral molecule, while hydroxamate ion will predominate at pH 10. It appears as if either species may function as the collector depending on system conditions. When the neutral molecule theory was introduced nearly a half century ago, personalities got inthe way of science, unfortunately. Over the years, acknowledgment of the existence of neutral molecules in flotation systems has been given, but the research needed to delineate the role of such neutral molecules in these systems has not been undertaken. It would appear as if it is time to reopen the cover of this book. RADIOTRACERS In the mid-century, researchers started using other technology to gain greater under- standing of surface chemical phenomena occurring in flotation. Plaksin et al. (1957) used microradiography to study the distribution of collector on mineral surfaces. Gaudin and coworkers (Bloecher, Chang, Fuerstenau, Mao, Morrow and Turkanis; 1954, 1957, 1959) utilized radiotracers to study adsorption phenomena of dodecylamine on hematite and quartz, activation/deactivation of sphalerite, and sodium and calcium ion adsorption on pyrite. Aplan and deBruyn (1963) studied the adsorption of hexanethiol on gold and confirmed that the equilibrium adsorption density of collector at the solid-gas interface exceeds that at the solid-liquid interface as predicted from the Gibbs Adsorption Equation. For the most part, work with radiotracers was confirmatory of previously established data and previously held concepts. As a result, usage of these experimental approaches was greatly curtailed after the 1950s, although periodic use of them has been made since that time when applicable. INFRARED ABSORPTION MEASUREMENTS Wadsworth and his coworkers (Eyring, Peck, Raby) were some of the first investigators to utilize infrared absorption spectroscopy as a means to study mechanisms of collector adsorption. This powerful tool provided insight into adsorption mechanisms that had not been possible previously. A very excellent paper by Eyring and Wadsworth (1956) on the xviadsorption of hexanethiol on the zinc minerals, willemite, zincite and sphalerite, showed clearly the disappearance of the -~ - X stretching of the hexanethiol and the disappear- ance of the OH” from the mineral surface. The authors indicated that either ion exchange or water formation could explain this phenomenon, Peck, Raby and Wadsworth (1964, 1966, 1967) also studied collector adsorption on oxides, silicates and semisoluble salts. Phenomena observed were: displacement of hydroxyl and water from hematite upon chemisorption of oleate and the direct relation between flotation and chemisorbed oleate on the surface; conditions under which physically adsorbed oleic acid, physically adsorbed sodium oleate and chemisorbed oleate occur on calcite; and chemisorption of oleate at monolayer coverage on phenacite (Be,Si0,) and physical adsorption of oleate on beryl, both after fluoride activation. The existence of two layers of adsorbed xanthate on galena was confirmed by Leja, Little and Poling (1963) with infrared absorption analysis. It was shown that the outer layer was composed of multilayers of lead xanthate identical in infrared pattern to bulk preci- pitated lead xanthate. After an acetone wash, this layer was removed, leaving a layer of strongly adsorbed xanthate at monolayer coverage that is not removed by any solvent. Multilayers of zinc xanthate were noted on sphalerite after contact with xanthate in the absence of activator. The multilayers exhibit the same infrared absorption characteristics as those of bulk precipitated zinc xanthate (Yamsaki and Usui, 1965; Fuerstenau et al., 1974). Kuhn (1968) also investigated other sulfide systems: chalcocite, chalcopyrite, galena and pyrite. Dixanthogen only was observed on pyrite after contact with xanthate. Precipitated zine xanthate, lead xanthate and cuprous xanthate only are formed on sphalerite, galena and chalcocite, respectively. Fourier Transform Infrared Spectroscopy was introduced in the 1980s. It has been especi- ally useful for studying surface chemical phenomena as it has enabled in situ measure- ments, quantitative calculation of adsorption density, and determination of real-time kinetics of adsorption processes as well as surfactant bonding. Mielczarski et al. (1983) and Miller and coworkers (Hu, Misra 1986) were some of the first researchers to use this technology in flotation. Mielczarski and colleagues showed chemisorption of dodecyl sulfate on fluorite. Miller and colleagues showed that elevating either the temperature or oxygen potential results in the disappearance of double bond in the hydrocarbon chain of adsorbed oleate on fluorite and in the formation of an ether linkage between the chains. THERMODYNAMICS AND THE ELECTRICAL DOUBLE LAYER In the 1950s, thermodynamics was introduced into adsorption phenomena in flotation, and concepts of the electrical double layer were also introduced. deBruyn, Overbeck and Schuhmann (1954) applied the Gibbs Adsorption Equation to these systems and presented the influence of collector ions, collector precipitate formation and activation and depres- sion on surface tension. Electrical effects at interfaces, gas-solid-solution interfaces and the stability of mineral suspensions received considerable attention in books by Suther- land and Wark (1955) and by Gaudin (1957). Iwasaki and deBruyn (1958) studied the electrochemical properties of the silver sulfide-solution interface and compared experi- mental observations with calculations utilizing the Guoy-Chapman theory. Jaycock and xviOttewill (1962) studied the adsorption of ionic surface active agents on charged solids (Agl) and demonstrated optimal conditions for flotation and suggested the mode of adsorption of collector ions. deBruyn and Agar (1962) presented a summary of the surface chemistry of flotation, while Parks and deBruyn (1962) developed a model based on the dissociation of surface hydroxyl groups and adsorption of hydroxo complexes from solution on hematite. Deju and Bhappu (1966) provided a chemical interpretation of sur- face phenomena in silicate minerals. The competition and depression effects of inorganic ions on amine flotation of quartz. were presented and analyzed by the electrical double- layer theory (Onoda and Fuerstenau 1964; Hopstock and Agar 1968). Heat and entropy of adsorption and association of long-chained surfactants at the alumina-aqueous solution interface were determined by Somasundaran and Fuerstenau (1972). Cases et al. (1979, 1986) presented an adsorption model taking in account all of the potential energies in the adsorbed layer. Entropy variations during adsorption were also given. Many other excellent examples of thermodynamics and electrical double-layer theory related to flotation are given in the literature, SULFIDE FLOTATION In 1968, definitive papers on xanthate flotation of pyrite were published by Majima and ‘Takeda and Fuerstenau et al, Evidence was presented in both of these papers that dixan- thogen is the active species in xanthate flotation of pyrite. As mentioned earlier, Gaudin had presented a similar observation in 1933, but his observation was never pursued. Majima and Takeda condueted an electrochemical study with a pyrite electrode, while Fuerstenau et al. utilized infrared absorption analysis and Eh measurements. Majima and Takeda conducted polarization experiments of pyrite in basic medium and suggested electrochemical oxidation of xanthate on the pyrite surface as the mechanism of dixanthogen formation. The concept of possible electrochemical mechanisms in sulfide flotation was advanced by Salamy and Nixon in 1957; this was followed by an electrochemical study of galena and xanthate in 1964 by Tolun and Kitchener. The paper by Majima and Takeda, however, really gave impetus to the extensive study throughout the world given to electrochemical measurements of sulfides in the presence of various sulfhydryl collectors: Toperi and Tolun (1969), Woods (1971, 1972), Allison et al. (1972), Finkelstein and Goold (1972), Kowal and Pomianowski (1973), Chander and Fuerstenau (1974), and Richardson and Maust (1976). When sulfide minerals are placed in water, they develop a potential, termed the rest potential. When the rest potential of the mineral is greater than the reversible potential of the xanthate/dixanthogen couple, xanthate is oxidized to dixanthogen (Allison et al., 1972). Pyrite, arsenopyrite, pyrrhotite and chalcopyrite were found to oxidize xanthate, and dixanthogen is the collector of these minerals. On the other hand, the rest potentials of chalcocite, galena and sphalerite are below the redox potential of xanthate, and the reaction product on these three minerals is always metal xanthate. Similar experiments were conducted using dithiocarbamate as collector (Finkelstein and Goold, 1972). The greater difficulty in oxidizing dithiophosphate to its dimer, dithiophosphatogen, than xanthate to dixanthogen on pyrite provides an explanation of why pure pyrite cannot be floated with diethyl dithiophosphate above about pH 6 (Finkelstein and Goold, 1972; Wark, 1934). An excellent review of the electrochemistry of sulfide mineral flotation has been provided by Chander (1988). villMajor strides have also been made in understanding of the systems in which metal xan- thate is formed. For example, the formation of the unleachable monolayer of xanthate on galena has been shown by Woods (1976) to be due to electrochemical discharge of xan- thate on the surface. The multilayers of lead xanthate observed on the galena surface are formed by replacement of oxidized anions an the surface, namely, carbonate, sulfate and sulfur-oxy ions, For sulfides to be floated under these conditions, the mutilayers of metal- collector precipitate would have to be hydrophobic. This has been shown to be the case for lead ethyl xanthate (Finkelstein et al., 1975). Similar phenomena occur with chalcocite and sphalerite. Sphalerite is floated with short chained xanthates in the absence of activators after formation and adsorption of zine xanthate on the surface (Laskowskiand Sobieraj, 1969; Fuerstenauet al., 1974); excellent flotation is achieved with ethyl xanthate, but high additions of collector are required. The multilayers of zinc xanthate have been shown by infrared analysis to be bulk precipitated zinc xanthate (Yamasaki and Usui, 1965; Fuerstenau et al., 1974). A water rinse removes the multilayers of zinc xanthate, while an organic rinse removes the xanthate adsorbed at monolayer coverage (Plaksin and Anfimova, 1954). These phenomena reflect the greater solubility of zinc xanthate in comparison with lead xanthate. Recent significant contributions to sulfide flotation technology are the detailed thermo- dynamic calculations by Forssberg and coworkers (Palsson, Wang; 1988, 1989), the application of thermodynamics in the physico-chemical modeling of flotation reagent regimes by Abramov and coworkers (Avdokhin, Morozov, Nenadov, Shtoik; 1980, 1988) and the evaluation of chemical and operational variables in sulfide flotation of Klimpel and coworkers (Aplan, Meyer, Smar; 1983, 1994). The introduction of N-ethyl-O-isopropyl thionoearbamate (Z-200) by Harris and Fisch- back (1954) was an important development in sulfide concentration. The reagent has gained worldwide acceptance in copper sulfide flotation. The insensitivity of this reagent to pyrite in alkaline media, combined with the excellence in adsorption potential for copper sulfide minerals, has made it an effective collector. Pyrite, however, floats quite readily in neutral and acid circuits (Elarris, 1988). Chelation with surface copper ions has been suggested as a possible mechanism of copper sulfide mineral flotation (Aplan and Chander, 1988). Mechanisms involved in cyanide depression of iron-bearing sulfides have been clarified. Cyanide and iron reace to form ferrocyanide ion, Fe(CN)¢!". The iron may be abtained from the grinding media or by dissolving the iron-bearing sulfide mineral. Depression, apparently, occurs by the formation of surface ferric Ferrocyanide, a very insoluble compound (Elgillani and Fuerstenau, 1968). It is thought that the formation of this compound at the surface prevents the anodic oxidation of xanthate to dixanthogen. Natural floatability of sulfide minerals has also been clarified. The question of whether sulfide minerals possess an inherent floatability was first raised by Wark. To answer this question, Ravitz and Porter (1934) floated galena cleaned with ammonium salts in a de-oxygenated system; excellent flotation was observed. Work by Heyes and Traher (1973), Chander etal. (1975), Luttrell and Yoon (1984), Woods (1987) and Miller (1988) suggests that oxidation of surface sulfide under very mildly oxidizing conditions to ele- mental sulfur, polysulfides or a metal-deficient layer is probably responsible for this phenomenon. The fact that sulfide ion does not hydrogen bond water molecules may also xixcontribute to this phenomenon. The separation of sulfides by Eh control has now been demonstrated Hayes and Ralston (1988) and others. Molybdenite retains its natural floatability even in the presence of air, which is probably due to the weak van der Waals bonding between the electrically neutral layers of MoS;, which are obtained upon fracture (Gaudin, 1957) and to the fact that the oxidation product of molybdenite is an anion. ELECTROSTATIC ADSORPTION OF COLLECTOR IONS ‘The fact that solids are charged in water was known for many years. Some of the first work in determining the possible role that surface charge may play in flotation was that of Gaudin and Sun (1946). These authors determined the zeta potentials of a number of minerals and showed qualitatively that adsorption, floatability, activation and depression can be related to zeta potential. Sun (1943) suggested that slime coatings probably resulted from electrostatic interaction between oppositely charged particles. Modi and Fuerstenau (1960) and Iwasaki, Cooke and Colombo (1960) in their studies on corundum and goethite, respectively, showed very clearly the role that surface charge exhibits in the electrostatic adsorption of collectors on mineral surfaces. Those studies spawned many others on similar systems and the determinations of points of zero charge of many minerals. Amines and anionic collectors containing 12 carbons or less in their hydrocarbon chains generally adsorb electrostatically on mineral surfaces of opposite sign. Many studies have been conducted on a variety of minerals with a variety of collectors by many researchers. The results obtained by Laskowski and Sobieraj (1969) on chromite with sodium laurate and dodecylamine and by Moir and Stevens (1963) on beryl with dodecylsulfate as collector are typical. ‘The first real focus on electrostatic phenomena in flotation was provided by Gaudin and Fuerstenau (1955) in their study of quartz flotation with amine. The concept of hemi- micelles emerged from this work. Hemi-micelles were described by these authors as the association of collector ions at the solid-solution interface, and likened to the formation of patches of molecules in an oleic acid monolayer at an air-solution interface described by Harkins (1952), The authors based their premise on the change in sign of the zeta potential with increased concentration of amine and on calculated concentrations of amine ions at the interface from the Boltzmann relationship. Other evidence of this phenomenon was provided by the association between collector ions and frother molecules that takes place at both the air/liquid and solid/liquid inter- faces (Schulman and Leja, 1954); the change in slope of the adsorption density of amine on quartz at the same concentration as the change in sign of zeta potential occurs (deBruyn, 1954); the good agreement between flotation rate of quartz with amines of various chain lengths and calculated van der Waals cohesive free energy for hydrocarbon chain association (Fuerstenau et al., 1964); the optimal flotation of quartz with amine (pH 10) when molecular amine becomes significant in concentration (Fuerstenau, 1957); the formation of ionomolecuar complexes that form between neutral molecules and ions, especially when the surfactant ions and molecules are present at about the same concen- tration (Somasundaran, 1976); and coadsorption of long-chained alcohols with amine (Smith, 1963). RX,‘These phenomena are shown very clearly with the adsorption isotherm of dodecyl sulfonate on quartz at neutral pH (Wakamatsu and Fuerstenau, 1973). Three distinct changes in slope of the isotherm are present that describe different adsorption phenomena, At low concentration of collector, adsorption of individual ions occurs, and the zeta potential remains constant. With increasing additions of dodecyl sulfonate, hemi- micelles form, and adsorption density increases markedly and zeta potential decreases drastically with concentration. At even higher concentrations, a third change in slope occurs, which probably marks the formation of a bilayer of sulfonate ions at the interface. Allof the experiments with amine were conducted at room temperature. Since the Krafft temperature for dodecylamine is 26°C, micelles could have formed with dodecylamine (Smith, 1989; Smith and Scott, 1990). The Krafft temperature for amines with greater than 12 carbons in the hydrocarbon chain is about 56°C (Shinoda et al., 1963), and hemi- micelles could not have formed at the solid-solution interface unless different phenomena are occurring at the interface than in the bulk solution. Laskowski and coworkers (Gastro, Liu and Vurdela; 1986, 1988) have shown that the colloids of precipitated amine that form in alkaline solution are charged and have an iep at relatively high pH, e.g., dodecylamine has an iep at pH 11. They have shown that the pH region in which the amine colloids form is the same as that in which optimal flotation of quartz is obtained (Fuerstenau, 1957), These authors consider that it is the uptake of positively charged amine colloids on negatively charged quartz that is responsible for flotation under these conditions. Smith (1973) floated quartz with weak-base and strong-base amines, Precipitation of, amine colloids could very well have occurred with the primary, secondary and tertiary amines but not with a strong-base quaternary amine. Flotation with trimethyldodecylam- monium acetate was similar to the responses obtained with all of the weak-base amines, including the optimal recovery at pH 10 and the depression above about pH 13. It would be well to compare the solubility of trimethyldodecylammonium acetate with the concentration expected at the interface in basic medium to establish the roles of hemi- micelles and collector salt. ‘The association of hydrocarbon chains either as hemi-micelles or asa precipitate of collector salton the: eral surface is desirable from the standpoint of flotation. Aanthapadmanabhan and Somasundaran (1985) have stated, “If electrostatic factors are favorable for adsorption, then the surfactant concentration in the interfacial region will be higher than that in the bulk solution, The interactions that occur in the interfacial region will depend essentially on the relative concentrations of the surfactant required to form hemi-micelles and to pr the surfactant salt, If the HMC (hemi-micelle concentration) is lower, then the formation of hemi-micelles would be preferred over the salt precipitation.” OXIDE AND SILICATE FLOTATION With longer-chained homologs, Iwasaki, Cooke and Choi (1960) showed that flotation could be achieved at pH values considerably above the pze with actadecylsulfate and below the pze with octadecylamine whieh facts lent support to the hemi-micelle postulate. In other systems long-chained homologs of collector chemisorb mineral surfaces. In 1943, Taggart and Arbiter stated, “The optimum pH for soap flotation of any mineral is close to that at which the hydroxide of the corresponding metal precipitates.” Insoluble xxloxide and silicate flotation with high molecular weight anionic collector has been suggested by Fuerstenau and colleagues to occur with the following sequence of events: (1) slight mineral dissolution, (2) hydrolysis of the dissolved metal species to hydroxy complexes, (3) readsorption of the hydroxy complexes, (4) hydrolysis of the hydroxy complexes to metal hydroxide, and (4) adsorption of collector forming a precipitate of metal collectoratthe expense of themetal hydroxide. A good example of these phenomena can be seen with the chromite-oleate system (Palmer et al., 1975). Chromite is theoretically FeO.Cr,O;, but in nature Mg” is frequently substituted for Fe”’, and Al’ and Fe*‘are frequently substituted for Cr**. Since the trivalent ions are coordinated octahedrally with oxygen, and the divalent species are tetrahedrally coordinated, the divalent ions will dissolve more readily from this mineral than the trivalent species. As a result flotation of chromite is controlled by the divalent species, Mg” and Fe". Optimal flotation of chromite is obtained between pH 8-9 and pH 10-11 with oleate as collector. Ferrous ion hydrolyzes to FeOH' and Fe(OH) between pH 8-9, and Mg” hydrolyzes to MgOH' and Mg(OH), between pH 10-11. Asthe pzcof this chromite was pH 7.2, flotation was noted at pH 4 due to physically adsorbed oleate, Laskowski and Sobieraj (1969) also observed the physical adsorption of oleate on a number of samples of chromite below the pee, and they also observed the chemisorption of collector at pH 10-11. Similar phenomena are observed when pyrolusite is floated with oleate (Fuerstenau and Rice, 1968). Peck, Raby and Wadsworth (1966) showed that the flotation of hematite at pH 7.6 is directly related to chemisorbed oleate on the surface. Hydroxyl and water were displaced from the mineral surface as collector is adsorbed.. Lai and Fuerstenau (1976) in modeling positive, negative and electrically neutral sites on oxide surfaces noted that oleate adsorbs optimally near the pzc of hematite. As pointed out by Somasundaran and Annanthapadmanabhan (1979), this is also the pH at which the ionomolecular species, RCOOH.RGOO , is present maximally when oleic acid is used as collector. Other minerals also respond to flotation optimally with oleate at around pH 7-8. Polkin and Najfonow (1964) showed that columbite, tantalite, garnet, ilmenite, pyrochlore, rutile, tourmaline and zircon are floated optimally at this pH. Dixit and Biswas (1969) presented similar data for ilmenite, zircon, garnet and rutile. Polkin and Najfonow stated that strong chemisorption of collector occurred on the surface followed by the formation of insoluble heavy metal oleates. ‘The use of organic chelating agents as flotation collectors was investigated by Gutzeit in 1946. The presentation and patenting of potassium octyl hyroxamate as a flotation collec- tor for chrysocolla and hematite by Fuerstenau and Peterson (1965, 1969) gave impetus worldwide to the study of chelating agents as flotation collectors (Rinelli, Marabini, Usoni; 1971, 1975, 1976; Bogdanov et al., 1973; Ragavan and Fuerstenau, 1975; Barbery and Cecile, 1977; Nagaraj and Somasundaran, 1978, 1979). A number of chelating agents have been studied with a variety of minerals. some of these collectors include salicylal- dehyde, salicylaldoxime, dimethylglyoxime, hydroxylquinoline, hydroquinone, and nitro- sophenyl hydroxylamine. The primary limitation to the use of these reagents as collectors is their cost. Of these reagents, octyl hydroxamate is used commercially as a collector, and this use occurred initially in countries with controlled economies, namely China and the Soviet Union. It is presently used in the United States to remove anatase from kaolin in clay brightening and as the active group in polymeric flocculants for red mud processing. An excellent review of the chemistry and applications of complexing agents in mineral separations has been presented by Nagaraj (1987). voxHematite is floated optimally with octyl hydroxamate at around pH 8, and chryscolla is floated optimally around pHi 6 with this collector which is the pH at which CuOH+ is present optimally and also the pH at which Cu(OH);,) forms (Peterson et al., 1965; Fuerstenau et al., 1970). Precipitates of metal-hydroxamate form on these minerals, Confirmed with infrared absorption analysis, the presence of cupric hydroxamate on chrysocollais visually apparentafter contact with octyl hydroxamate (Palmeretal., 1975). Chrysocolla turns apple green, which is the color of cupric hydroxamate, under these conditions. The presence of ferric hydroxamate on hematite has been noted from infrared absorption analysis. Ragavan and Fuerstenau (1975) showed the shift the of the pzc of hematite toward that of ferric hydroxamate with increasing levels of addition of octyl hydroxamate. Nagaraj and Somsundaran (1979) studied copper oxide flotation with salicyaldoxime. Flotation was observed from about pH 2-10, the region in which the Cu-salicylaldoxime complex is stable. ACTIVATION Metal lon Activation Tt was recognized early that pure quartz is not floated with anionic collectors, such as sulfonate or oleate. Kraeber and Boppel (1934) found, however, that quartz is activated in the presence of various metal ions at specific values of pH, e.g., Fe** from pH 3-8, Cu” from pH 6-9, and Mg** from pH 10-12. Activation was noted to occur at the same values of pH at which precipitation of the metal hydroxides occurred. Gaudin and Rizo-Patron (1934) studied Ba” activation of quartz and found thatactivation was possible in alkaline medium but notin acid medium. Schuhmann and Prakash (1950) also studied Ba** activa- tion of quartz utilizing vacuum flotation. Rogers and Sutherland (1947) found that Pb(NO;)2 activated quartz in basic medium with sodium hexadecylsulfate as collector. Fuerstenauand coworkers (Atak, Bhappu, Cummings, Elgillani, Martin, Miller, Pray, Rice; 1963, 1967, 1968) studied quartz activation in detail using oleate, sulfonate and xanthate as collectors. Activators included Fe’, Al3*, Cu", Pb?*, Zn?*, Mn?*, Mg** and Ca", and activation was found to occur at the optimal pH for the hydroxy complex, Me,OH™, formation that is very nearly the pH at which the metal hydroxide precipitates. In fact, Fuerstenau et al. (1970) found that hydroxy complexes are so surface active that they are adsorbed extensively even on a positively charged alumina surface. McKenzie (1966), in noting the change in the sign of the zeta potential of quartz from pH 2-7 in the presence of ferric additions, suggested that the adsorption of positively charged Fe(OH); colloids may be responsible for this phenomenon. In another study McKenzie and O’Brien (1969) suggested that adsorption of positively charged Ni(OH) and Co(OH)» precipitates may be responsible for the positive zeta potentials of quartz in the pH range in which these cations hydrolyze. James and Healy (1972) examined the adsorption of hydrolyzable metal ions at the oxide interface with adsorption and electrokinetic studies of cobalt on SiO, and TiO, and presented a thermodynamic model of adsorption of hydrolyzed species on these surfaces. ‘They attributed the electrokinetic phenomena to the formation of Co(OH)2,,) on the quartz. surface. These authors provided an excellent analysis of these systems in terms of com- peting energy changes as an ion approaches an interface. The attractive energy is the electrostatic free energy and any possible short-range attractive forces that might be vealinvolved, The opposing energy involves the secondary solvation energy changes as parts of the solvation sheath are rearranged or replaced, Their analysis shows that solvation energy change is much more favorable fora hydroxy complex than for a hydrated divalent ion with a solid of low dielectric, such as quartz, and, henee, the overall free energy of adsorption will be much more favorable. Studies on the adsorption of calcium species on quartz are supportive of these concepts (Clark and Cooke, 1968). Surfactant-salt precipitation is involved in these activation systems. Fuerstenau and Cummings (1967) observed activation and flotation of quartz only after precipitation of calcium laurate at pH 11.5. In fact, in some of the calcium-oleate-quartz systems in which relatively high calcium and oleate additions were made, excellent flotation occurred in systems resembling milk in appearance. Fluoride Activation of Silicates The beneficial effect that additions of hydrofluoric acid exhibits in amine flotation of aluminosilicate minerals was noted by O'Meara et al. (1939), Dean and Ambrose (1944), and Kennedy and O'Meara (1948). This action was attributed to the cleaning of the polyvalent ions and clay-like material from the mineral’s surface. Smith and Smolik (1965) and Warren and Kitchener (1972) studied this phenomenon in detail. The action of HF appears to be an attack of the surface silicic acid to form fluosilicate, adsorption of fluosilicate on an aluminum site, followed by aminium ion adsorption on the alumino- fluosilicate site. Fluoride activation of silicates was the subject of a comprehensive investigation by Manser (1975). Flotation data were obtained with minerals contained in the five groups of silicates: Orthosilicates (andalusite, beryl, tourmaline) Pyroxenes (augite, diopside, spodumene) Amphiboles (hornblende, tremolite, actinolite) ‘Sheet silicates (muscovite, biotite, chlorite) Framework silicates (quartz, feldspar, nepheline) Orthosilicates are sensitive to fluoride addition, whereas the pryoxenes and amphiboles are scarcely affected by fluoride. Sheet silicates are activated by fluoride, while framework silicates are activated to a lesser extent with the exception of quartz. Activation of Sulfides Activation of sphalerite with copper sulfate in 1911 was one of the earliest discoveries in froth flotation. The early researchers were correct when they assumed that Cu” was replacing Zn* from the sphalerite lattice, forming a copper sulfide surface on the sphalerite. Gaudin (1930) analyzed this activation phenomenon in terms of the solubility products of CuS and ZnS, Wark and Cox (1934) noted that Hg” and Ag” also function as, activators, while Wark and Wark (1936) showed that platinum, gold, bismuth, cadmium, lead, cerium, antimony and arsenic are also activators. In general, those metal ions that form relatively insoluble sulfides are effective as activators. xxiv‘The exchange of Cu" and Ag” for Zn” of the sphalerite was studied by Gaudin and coworkers (Corriveau, Fuerstenau, Mao, Morrow, Turkanis; 1954, 1957, 1959) utilizing radiotracers. With capper activation, exchange of Cu* for Zn*" is rapid for the first few layers of Zn replaced, after which parabolic diffusion occurs. Silver ion is also exchanged stoichiometrically for zinc ion, and the rate is a logarithmic function of time, Placed into asolution containing a high concentration of silver nitrate, a sphalerite particle was noted to turn completely black in about one second. Prevention of activation is important in the selective flotation of sulfides. The differences in solubility products between silver sulfide, copper sulfide and zine sulfide are so great that the only means available to reduce the activity of Ag” and Cu** in solution to prevent the activation reactions from occurring is by complexing. The cyanide complexes of silver and copper ionsare much morestable than that of zinc, and the resultant activity ratios of (Zn? ")/ (Cu?*) and (2n?*)/(Ag’)? preclude the reaction from occurring thermodynamically. Prevention of lead activation cannot be accomplished with cyanide complexing, but fortunately, the solubility products of lead sulfide and zine sulfide are fairly close in value. The equilibrium activity ratio of (2n?")/(Pb*) in solution is only about 1,000. Since sphalerite commonly resists oxidation, very little zinc dissolves from this mineral. Zinc sulfate is therefore added, and by virtue of the equilibria involving basic lead carbonate and zinc hydroxide, the activity ratio of zinc ion to lead ion in solution is greater than the equilibrium ratio, which should preclude activation from occurring. In addition to the thermodynamic considerations, there is considerable evidence which indicates that the colloids of zinc salts, formed under conditions in which preciptation occurs, function as depressants for sphalerite. The depressant role of zine hydroxide colloids was first presented by Malinovsky (1946) and confirmed by Livshitz and Idelson (2953), who demonstrated that the extent of depression of sphalerite and the coneen- tration of zinc colloids are directly related. Semi-Soluble Salts The effectiveness of fatty acids as collectors for salt-type minerals has been known since the 1920s. Gaudin and colleagues (Hansen, Martin; 1928) floated calcite, azurite, mala- chite, rhodochrosite, and siderite with fatty acids. In general, they observed that the collector requirement was reduced as the chain length of the fatty acid was increased and that increased temperature resulted in enhanced flotation. The early researchers recog- nized that chemisorption of oleate was occurring on these minerals. According to Taggart (1945), when oleate ion is abstracted by apatite, phosphate ion appears in solution, and with calcite, carbonate is released when oleate is adsorbed. Alkyl sulfates and alkyl phosphates were found by Halbich (1934) to function effectively as collectors for apatite, barite, calcite, cerussite and malachite. Xanthate flotation of the heavy metal carbonates and lead sulfate was conducted before and after sulfidization. Taggart and Arbiter (1944) and Kellogg and Vasquez-Rosas (1945) examined calcite flotation with dodecylamine. They postulated that an amine carbonate was formed at the calcite surface as amine exchanged for calcium ion. Semi-solublesalts have been shown to float by physical adsorption of collector, e.g. calcite with dodecylamine and with relatively low concentrations of dodecyl sulfate (Somasun- daran and Agar, 1967). In general, though, adsorption of anionic collectors on this group of minerals occurs by chemisorption and metal precipitate formation and adsorption. a2Chemisorption of oleate on calcite was demonstrated by Peck and Wadsworth (1964) utilizing infrared absorption spectroscopy. No evidence was found indicating that physic- ally adsorbed oleic acid was present. Fuerstenau and Miller (1967) showed with infrared studies that shorter-chained carboxylates and sulfonates, e.g., laurie acid and dodecyl sulfonate, are present as calcium carboxylate or sulfonate on the caleite surface under flotation conditions. Somasundaran (1969) observed a new phase of ealcium oleate on calcite after contact with oleate. Predali (1969) observed two types of anion collector action on dolomite and magnesite, namely, physical adsorption of collector in acid medium and chemisorption of collector in basic medium. Szczypa and Kuspit (1979) observed a strongly bound Layer of laurate with the calcite surface upon which multilayers of calcium laurate were adsorbed. Marinakis and Shergold (1985) noted the formation of metal oleate on calcite, barite and fluorite. lon composition in solution and its effect on the domains of stability of compounds, such as CaCO, Ca(Ol), and GaSiO; on calcite and fluorite, have been shown by Morozov et al. (1992). Fluorite has received considerable study. Peck and Wadsworth (1964) showed that oleic acid is physically adsorbed in acid medium, while chemisorption of oleate occurs in basic medium, Shergold (1972) showed that dodecylsulfate is chemisorbed on fluorite. Cook and Last (1950) floated a fluorite ore with oleate at two temperatures. Froth charac- teristics were very different for the systems floated at 25°C and 60°C. These authors attributed the difference in response to physical bonding of collector at room temperature and to chemisorption at elevated temperature. Hu et al. (1986) studied this phenomenon with FTIR/IRS and noted the disappearance of the C = C double bond with increased temperature or oxygen potential. Cross linking issuggested between adsorbed oleyl chains via an epoxide linkage. The enhanced floatability of fluorite with higher oxygen potentials was also noted by Plaksin (1959). Kellaret al. (1992) showed that only chemisorbed oleate appears to undergo oxidation, not precipitated calcium oleate adsorbed on the surface. Free and Miller (1996) suggest that the predominant mechanism of calcium oleate adsorption may be the formation of Ca(Ol)3 in solution followed by transportation to the fluorite surface rather than nucleation and growth at the surface. ‘The quantities of apatite and collophane concentrated by flotation are very large, and these minerals have received considerable attention as a result. Moudgil et al. (1987), Cases et al. (1988) and Rao et al. (1990) have all conducted extensive studies on the adsorption of oleate on apatite. Distinct regimes are found in the adsorption isotherm of oleate on apatite. Moudgil et al. found at low oleate concentration, physical adsorption of oleate ion occurs. With higher concentrations of oleate, chemisorption of oleate occurs. With even higher concentrations of collector, formation and adsorption of calcium oleate precipitate occurs on the surface, and with high additions of oleate, surface saturation with calcium oleate precipitate is approached. Correlation of the adsorption results with flotation response suggests that surface precipitation of calcium oleate is the mechanism predominantly responsible for flotation. An excellent review of advances in phosphate flotation has been presented by Moudgil and Somasundaran (1988). ‘The solubility produets of many of the semi-salt minerals are close in value. As. result depending on the activities of various ions in solution, metathesis of one mineral at the expense of another can occur. Probably the first example of activation in nonmetallic flotation was observed by Gaudin and Martin (1928) in which selective separation of malachite and azurite from calcite could not be effected with fatty acid even though results obtained with pure mineral systems indicated that it should be possible. Johnston and xviLeja (1978) have shown that when gypsum is contacted with a phosphate solution, metathesis of HPO,” and H)PO* for SO,* occurs. Miller and Hiskey (1972) have shown with fluorite that dissolved carbonate reacts with the surface to form a calcium carbonate compound. They have stated that this phenomenon is responsible for the pzc of fluorite at pH 10, Similar phenomena were observed by Bahr etal. (1968) and Lovell etal. (1974). Miller and Hiskey observed this same phenomenon when barite was contacted with a solution containing dissolved carbonate. In this view it is rather surprising that these minerals can be separated from each other by flotation. Bond strength of chemisorbed species on each of these minerals is different, of course. Asa result the affinity of surface calcium ion for collector ion or modifers, such as sodium silicate, is different. Modifier additions are a necessity for selective separation in most of these systems. One of the greatest challenges facing the industrial minerals community is the selective separation of dolomite from phosphate rock. Lawver et al. 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Fuerstenau ® The Froth Flotation Century 3 = Oxide Mineral Flotation Fundamentals 23 = Internal Reflection Spectroscopy for FTIR Analysis of Carboxylate Adsorption by Semi-Soluble Salt Minerals 45 " Weak Electrolyte Collectors 89 = Single Bubble Terminal Velocity—Experiment and Modeling 83 = Bubble-Particle Interactions in Flotation 95The Froth Flotation Century D.W. Fuerstenau” Jn mineral processing, the last century of the current millenium has been the century of froth flota- tion. The process did not result from fundamental research, but was developed aver the years by empirical methods. In mare recent years, our understanding of the fundamental principles of the ltation process have made significant strides. This paper reviews some of the historical perspectives of developments in flotation reagents, the development and application of experimental tools for delineating flotability and interfuctial phenomena, advances in flotation fundamentals, and the development of flotation kinetics, both macroscopic and microscopic subprocesses. Through the application of surface chemistry, the flotation process has permitted economic utilization of a vast array of complex ores. INTRODUCTION Froth flotation, as practiced today, had its beginnings in Australia nearly a century ago. ‘The first flotation plant in the United States, the Timber Butte Mill at Basin, Montana, began operation in 1911. By 1980 (Martin et al., 1985), 440 million tons of ore were treated in 239 flotation plants consuming 772 million kg of reagents and 6560 million kWh of energy. In 1980, 205 million tons of copper ores were concentrated to 4.2 million tons of concentrates, consuming 383 million kg of reagents. The second largest tonnage of ore treated was phosphate ore—109 million tons, from which 26.6 million tons of concentrates were produced at a reagent consumption of 227 million kg. Also, major was the flotation processing of iron ores, where 21.5 million tons of concentrates were produced from 38.9 million tons of ore at a reagent consumption of 61 million kg. Because nearly 2 billion tons of ore are treated worldwide by flotation, froth flotation is clearly one of the most important applications of surface chemistry in technology— particularly for control of the solid- liquid interface. Successful flotation separations depend on selective interaction between solid particles and gas bubbles in aqueous media. How to modify the interaction of water molecules with mineral surfaces through the judicious additions of reagents and pH control is at the very heart of making selective mineral separations from the vast tonnages of complex ores that are the source of our * Department of Materials s Calif. gineering, University of California, Berkeley,mineral raw materials, The froth flotation process did not come about as an outgrowth of fundamental research but evolved over this century by empirical developments. Much of the basic research, if virtually not all of it, has been occupied with explaining why the existing process works so well. Much of the basic research in mineral processing and process metallurgy can be characterized as post-mortem research, or as Fleming and Kitchener (1965) so nicely put it, “science in pursuit of technology.” Progress in flotation fundamentals has been based on experimental investigation in the laboratory, combined with keen insight into the meaning of the findings. Aswill be discussed, progress in understanding the details of flotation science has resulted from application of new research techniques as they have become available over the passing decades. EARLY FLOTATION RESEARCH ‘The start of modern froth flotation might be considered to be the 1904 Elmore vacuum- oil flotation patent, where dissolved air was used to levitate the oiled sulfide particles using as little as 2 kg of oil per ton of ore, as reviewed by Rickard (1916). Part of the levitating gas was carbon dioxide liberated by acidifying the pulp. Flotation, as we know it, really began with the 1905 Minerals Separation patent of Sulman, Picard and Ballot, who used an oily frothing agent together with agitation to disseminate air bubbles into the pulp. In 1906, Kirby was granted a patent that specified gentle agitation and the specific use of air, making it possible to use thin oils instead of the viscous oil required by the Elmore art, The first inventor to break away from the use of either acid or oil and to make a clear claim for air as the sole flotation agent was Norris, as outlined in his 1907 patent. However, all of this had been preceded by the successful Elmore Bulk Oil Flotation process, which in 1903, was considered to be the hope of the metallurgical world. Essentially all of the early research in flotation was directed toward patents. But there was abeginning of academic research in this field. There is some early academic research that surely could have led to the first froth flotation patent (Rickard, 1916). The November 1903 issue of the college magazine, The California Journal of Technology, contained an article by three senior students at the University of California titled, “Experiments on the Elmore Process of Oil Concentration.” In introducing their paper, they stated, The process depends upon the fact minerals with a metallic lustre, when treated in the form of a wetted pulp, adhere to oit, while earthy minerals do not. Two distinct operations are involved; first, the separation of the metaltic mineral from the gangue by means of oil; second, the extraction of the mineral from the oil. Concerned mainly with the second step, they wrote: ‘The charge may be agitated very gently, the oil being kept in a single lake, and broken up as little as possible consistent with a thorough contact of pulp and oil; or the charge may be agitated so violently as to dash oil up into a foam or froth, full of air bubbles: thus a very thorough contact of oil and pulp is obtained ... The “foam effect is produced by a violent agitation, especially in acid or salt solutions This throws the oil into a froth, which is heavily charged with air or other gases. This gas, of course, gives a greatly increased buoyant force. The oil in this condition assumesa certain load of mineral and holds it in a very stable condition. The charge does not settle and overload on standing as in the case of the lake effect. The foam effect is best adapted for light flaky minerals, such as molybdenite or graphite 4In my opinion, those three students understood how research begets new research: The work above outlined suggests many lines of further investigation, and as these come to be worked out, the process will become more valuable and of more general application. In 1915, citing that same paper (Rickard, 1916), Counsel Henry Williams stated in the case of Minerals Separation vs. Miami Capper Incidentally, the students discovered something else, and, for the first time, gave to the world the foam effect. Full disclosure as to a mode of operation which would produce an oil foam, they, for the first time in the history of the metallurgy, gave to the world. Itisremarkable that it was buried and lost, and that it took three years of litigation to unearth it. That is quite remarkable, especially that it should have been buried and lost in the University of California, which is the heart or the centre of the important mining interests on the Pacific Coast, and in the Great West. ‘The litigation surrounding the birth of froth flotation abounds in the early flotation books. In discussing concepts of bubble-particle attachment in flotation, Taggart (1945) wrote of his contempt of all these early lawsuits with his great style: This idea, conceived in ignorance and born in litigation, was fostered by selfish interest and, unfortunately, was copied into some textbooks. It never had any technical utility. Moving on to early approaches to the theory of flotation, itis of interest to note some of the early studies and discussions on flotation fundamentals—concepts familiar to modern flotation scientists (1916): The contact angle of various minerals with water was examined to find at what angle the mineral had to come in contact with a water surface before it was wetted and could sink. A glance at Clerk Maxwvell’s famous paper on capillarity will suggest immediately the explanation of contact angle, and that it is the result of a certain equilibrium of interfacial tensions of air, water and solid, There can be no doubt tha there is a close parallelism between the angle of hysteresis of the contact angle and the ability of a mineral to float Adsorption, in its most general sense, implies the unequal distribution of substances at the boundary between two heterogeneous phases: solid-gas, solid-tiquid, and liquid-gas. ... f the dissolved substance diminishes the surface tension of the solution, an excess of concentration in the surface layer diminishes the surface energy. ... We now have a new principle to apply to.a bubble, to wit: on account of adsorption, a fresh surface always has a greater surface tension than an old one; thus, ifitis stretched locally by conditions to break it, itis automatically reinforced at that point. (The author refers to Gibbs’ treatise on thermodynamics!) Inthis article, ités intended to show that there are certain molecular attractions between widely different substances which would seem to be nothing more or less than the force of cohesion acting at sensible distances. These attractions are shown 5Physical Phenomena wettability phenomena bubble/particle interactions Particle/particle interactions Flotation Science and Engineering Chemical = Mechanical Control Factors wettability bubble generation frothing particle dispersion Particle interactions macroscopic kinetics FIGURE 1A schematic representation of the three elements of flotation science and engineering For example, Ralston (Rickard, 1916) was well aware of Reinders’ 1913 classic work on the role of interfacial tensions in the liquid/liquid extraction of colloidal solid particles in oil/water systems and suggested that there would bea similar role for interfacial tensions in froth flotation. It is impressive that Reinders (1913) clearly showed how conditions for equilibrium in S/L/L systems was controlled by interfacial thermodynamics. FLOTATION SCIENCE AND ENGINEERING Clearly, flotatior far more complicated than the study of bubbles. With some early researchers having the concepts of how to approach flotation research, why was it so slow in getting under way? Perhaps the number of persons looking at the fundamentals were too few (below a eritical mass) and the process as a whole was really too complicated. ‘Successful flotation separations depend on the interrelation among the various physical, chemical, and mechanical factors in the system. This mutual interaction can be illustrated schematically with a triangular representation of these three elements of flotation science and engineering. As was recognized early on, the very basis of flotation is a physical process involving the relative interaction of three phases: one solid and two fluid. These interactions control which of the two fluids will wet the solid phase (its wettability). It is through chemical additives which modify the interfaces involved in flotation that it is possible to control wettability, particle dispersion or aggregation, bubble stability, flotation kinetics, ete. Factors involved in the processing of ores by flotation also can be represented by a triangle that shows the interrelation between the mineralogical characteristics of the ore, the chemical variables that can be used to regulate the process, and the process variables (Figure 1). The thitd part of the triangle involves flotation engineering, which broadly controls flotation kinetics.LMe DEPRESSION | ‘SULFIDIZATION (Aten (COPPER ACTIVATION, S02 DEPRESSION (Bratt) 'OLEIC ACID (oly eeteeton) (COLLECTORS 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 FIGURE 2 Historical perspective: developments ;cending mountains represent flotation reagent several sketches are presented to illustrate this century of progress in flotation fundamentals. The Historical Perspective on Reagent Development ‘The discovery of soluble collectors appears to have been the catalyst for major progress in flotation technology and for initiating fundamental research in flotation. Let us lock briefly at the development of flotation reagents in terms of the diagram given as Figure 2, which shows the ascension of the mountain of flotation reagent progress during this century. Good sources of information about early flotation developments are Sutherland and Wark (1955) and Gaudin (1957). This diagram illustrates the expansion of flotation technology with the invention of new reagents, the great leap upward occurring during the 1920s. The start wasthe oil collectors, containing creosote, fatty acids, etc., followed by aleicacid itself, There were significant early developments involving the use of inorganic modifiers,such as lime for depression and copper sulfate for activation. The discovery of water- soluble collectors was the real advance in flotation, fizst thiocarbanalid and particularly Keller's discovery of xanthates, Taggart was the person who by brilliant deduction recognized that all collectors have polar and nonpolar groups within the same molecule. Inthe 1930s, flotation was extended to the processing of nonmetallic minerals, using soap collectors with depressants, and cationic amines. Subsequently, until the 1950s there was little new in the way of reagents when Tveter developed polypropylene glycol ether frothers and Harris invented Z-200. The recollections of James Bean (1971) are particularly interesting: Thiocarbanalid for the first time gave the laboring metallurgist something that he could add which would improve the collection of the sought-for mineral without, at the same time, increasing the frothing to an uncontrollable degree. That this was no small trimph was demonstrated practically to me while I was flotation operator at the Athur mill of Utah Copper Company which at the time (1922) was using Utah Capper's own particular concoction of Barrett oils and sulphur stewed up together. Late on a sleepy afternoon an operator unduly increased the ‘oil’ being fed, hoping to lower the mill tailing, but when the rougher froth got through two cleaning steps neither the launders nor the floors could hold the resulting froth and it literally ran out of the windows over a length of perhaps 40 feet and to a depth of 3or4 inches. Years later I coutd still mark the area as I passed by on the highway. The impact of Keller’s discovery in 1925 of xanthates as sulfide mineral flotation collectors is self-evident—it was the monumental beginning of modern-day flotation technology. A brief discussion of the impact of 2-200 (a thionocarbamate) will illustrate how a new flotation collector can indeed still have major impact (Harris, 1998). In 1979, for example, 4.5 million kg of Z-200 were produced at a reagent consumption of 0.01 to 0.02 kg/t , and the increase in copper recovery when using Z-200 as collector was two percentage points (Harris, 1998). Since 300 million tons of copper ore at 0.7% copper were treated worldwide, this gave the world an additional 40 million kg of copper in that year alone! The need for new flotation technology in copper ore processing is still there, in that in 1985 the recovery of copper by flotation in the United States was still only 82.5% (Martin etal., 1987). Hopefully, at the pinnacle, we will finally have reagents that will be selective, handle all particles in the comminuted ore, and not be too costly. The Historical Perspective on the Development of Experimental Methods Because of the complexity of the interactions between minerals and reagents, basic research has made progress when working with simplified and idealized experimental systems. This has led to definite progress in understanding the fundamental basis of flotation, each step resulting from the application of more sophisticated instrumentation for probing interfaces. However, in many cases, real progress was made through the use of fairly simple techniques. Experimental techniques for assessing wetting behavior and flotation response have played their part in this process. The ascent of the next mountain in flotation (Figure 3) shows the development and application of techniques for studying flotation behavior and probing interfacial reactions. 0at WETTING FLA THICK. (E HALLIMOND TUBE (exer. (Chander) usec) 'VOLTANMETAY (woods) cartive BUBBLES GTEADY-STATE POLARZATION ont NS, 'NIGROCALORIMETRY (wesgre) INFRARED SPEGTROSCOPY (wadsmoty) SURFACE TITRATION (eetray) REST POTENTIALS (Satay & Nao) WET CHEMICAL ANALYSIS 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 FIGURES Historical perspective: development of experimental tools for delineating flatability and interfacial phenomena Progress was first made in understanding flotation behavior by Gaudin and his coworkers through study of the flotation of pure minerals using miniature flotation machines. Starting with the captive-bubble device of Taggart, Wark worked out the detailed flotability response of sulfide minerals. It was Wark and his colleagues who developed the technique to reliable accuracy. (Wark stated that contact angle data published before 1931 were unreliable.) In the late 1940s and 1950s, Gaudin and his coworkers extensively utilized radioactive tracer techniques to determine adsorption isotherms of flotation collectors and activators on purified minerals. In the early 1950s, several micro-flotation devices were developed and used for studying small-scale flotation: bubble pick-up, induction-time measurement devices, the modified Hallimond tube, etc. Electrokinetic measurements (zeta potentials) were found to be a very useful tool in flotation surface chemistry. In the early 1970s, electrochemical flotation devices were conceived of for ating the electrochemical aspects of sulfide mineral flotation.(a) Ralston and Allon's 1916 ‘estubes for flotation (©) Ewers’ 1952 modification of ‘the Halimond flotation tube rows LAYER = ==-+ PATHOF FLOATED PARTICLES ‘oROUNO JOHNT ‘CONCENTRATE. te MAGNETIC STIRRING BAR Pomous FrIT couecteo, —oAsmET CONCENTRATE. rrorcim MAGNETIC | STIRRER FIGURE 4 (a) Test-tube devices used by Ralston and Allen In 1916 (Rickard, 1916), (b) the Hallimond flotation tube as modified by Ewers in 1952 (Sutherland and Wark, 1957), and (c) the Hallimond flotation tube as modified by Fuerstenau in 1955 (D. W. Fuerstenau et al., 1957) Parallel to this, but offset by about two decades, has been the application of techniques for measuring directly the interaetion of reagents with mineral surfaces and for probing the structure of adsorbed films at the interface, exsitu and insitu. The modified Hallimond tube has provided a widely used means for delineating correlations of surface chemical conditions with flotation response in pure systems. Although not shown here, the apparatus that Hallimond (a mineralogist) constructed in 194410 separate mineral grains by their differences in flotability almost had its beginnings some 80 years ago, as can be seen in Figure 4(a), which shows tubes for testing flotation response published by Ralston and Allen in 1916 (Rickard, 1916). In 1952, Ewers (Sutherland and Wark, 1955) in Australia modified the Hallimond tube so that it could beused for experimentation in flotation systems [Figure 4(b)]. Fuerstenau (1957) further modified the Hallimond tube so that it could easily be operated reproducibly under closely controlled aeration and agitation conditions [Figure 4(¢)]. Because the floating mineral particles are not removed from the flotation medium in Hallimond tube flotation tests, the physical chemistry of flotation can be delineated ifthe experiments are conducted with 121 t ouantz eee oer %p 40/-0.60 © GON. ANGLE o- x & ie otwe = | & tera ror * duos g 0 norsrion E 2 3 solos Bool 5 g 5 z 3 z - Loe g 1,8 E 2 3 5 8 aol o008 go, @ 8 e z 2 b 2 |e 3 4-208 c Eid 20 3 3 = 7-80 Oe or 10" 10-* 1o-* o> CONCENTRATION OF 044, MOLE/UITER FIGURE 5 Correlation af contact angle, adsorption density, zeta potential, and flotation response for quartz at neutral pH with dodecylammonlum acetate as collector (after Fuerstenau ot al., 1964) high-purity samples and reagents (Fuerstenau, 1957). Figure § illustrates the precise correlation of the Hallimond tube flotation response of quartz with dodecylammonium acetate collector with the adsorption isotherm, the zeta potential, and the contact angle. It is through this type of experimentation that significant progress was made in working out the physical chemistry of flotation during the last 40 years. The Historical Perspective on the Developments in Flotation Fundamentals The third ascent of the historical flotation mountain (Figure 6) illustrates how progress has been made toward understanding flotation fundamentals, that is the fundamentals of reagent-mineral interactions, which really started only after 1920. However, in 1914, Ralston and others proposed what was termed “the electrical theory of flotation.” Of this, Ralston wrote (Rickard, 1916: Icis a scientific fact that when a solid particle is suspended in water, the water will form around the particle a contact film that generally possesses an electric charge, the amount and polarity of which will depend upon the nature of the particle surface and theelectrolyte in which itis suspended. ... thas been demonstrated that flotable particles have charges of one polarity (positive) and that nonflotable particles have charges of opposite polarity (negative), and that the froth is charged negatively and so attracts the positively charged or flotable minerals (such as galena and sphalerite) and repels the negatively charged or nonflotable ones such as silica or limestone.Renee er er, BINS Sire ALorATON (enn Poo nara ie EGET a Pan ReTeROSORG NOSE Ba LEO-POTENTAL MOD ee) LEG POSTAy KODE. OF GOL own HEE BGbate Ute WFLBE tonmnonn Pana OKtORTION (say lo Wiha MOLECULE HOSEL 4900 1910 1920 1930 1940 1950 1960 1970 1880 1990 2000 FIGURE 6 Historical perspective: ascending mountains represent advances in flotation chemistry fundamentals In 1927, Gaudin even commented that, “This theory, unfortunately, was not developed as fully as it seems desirable.” Interestingly, modern theories of bubble/particle interaction contain elements of these ideas. Periods of marked progress in understanding the surface chemistry of collector adsorption were made in the 1930s (mostly toward delineating sulfide flotation behavior), in the 1950s (mostly in understanding oxide flotation behavior) and in the 1970s and 1980s (where much attention was readdressed toward delineating the electrochemical nature of sulfide mineral flotation). This same period has seen real progress made in the flotation of fine particles and in understanding the complex surface reactions involved in the flotation of sparingly soluble salt minerals. The broad period of the 1930s decade was one of pronounced advancement in flotation fundamentals and particularly in delineating the chemical aspects of flotation, largely through the seminal contributions of Gaudin, Wark, and Taggart. The period starting in the 1950s was another one of major advancement, characterized by the application of the fundamental principles of surface and colloid 146 I ‘conuNouM 4 ouapre PIC t 4 ° ZETA POTENTIAL, mv é FLOTATION RECOVERY, PERCENT FIGURE 7 Correlation of the zeta potential as a function of pH for quartz and corundum (alumina) with flotation recovery with 4 x 10-° M dodecylammonium chloride and sodium dodecylsulfonate and as collector (from Fuerstenau and Herrera-Urbina, 1989) chemistry to flotation systems. In part, this was strongly influenced by Professor J. Th. G. Overbeek’s year at M.L'T. with the mineral engineering group of Gaudin. Pethaps the systems that are best understood today invalve the flotation of oxides with ionic surfactants. The behavior of oxide and silicate mineral systems depend on the char- acteristics of the electrical double at the mineral/water interface, adsorption phenomena, water/hydrocarbon-chain interactions, and solution chemistry. Flotation collectors that physically adsorb on oxides (such as alkyl sulfonates or alkyl ammonium salts) function as counter ions in the electrical double layer at the mineral/water interface. That is, the collector ions adsorb when they are charged oppositely to the surface itself ({t should be recalled that the charge on oxide surfaces are determined by the adsorption/reaction of hydrogen ions with surficial lattice sites), and separations then depend on the pH at which the surface of the different mineralsis uncharged (the point of zero charge, or PZC). Figure 7 (after Fuerstenau and Herrera-Urbina, 1989) combines results from Modi and Fuer- stenau for corundum (alumina) with those of Iwasaki for quartz (silica) to illustrate the effect of pH on the zeta potential and flotation response of these two minerals with a5FLOTATION RECOVERY, % é 8 8 x Ss “03-02 -Ol ° Cr a a} POTENTIAL vs SHE, V FIGURE 9 Relationship between flotation recovery and conditioning potential for chalcacite, bornite, chalcopyrite, and pyrite. Ethyl xanthate concentration of 0.0144 mM for ehalcocite and 0.02 mM for the other minerals (Richardson and Walker, 1985). Cook and Nixon (1950). “Assuming a complete or nearly complete monolayer of ions’ on the mineral particles, one would obtain a bulk concentrate with so much charge that it would explode with greater violence than an equal weight of nitroglycerine!” From this evolved Cook's neutral molecule theory of flotation collection, whichis the same idea that Barsky presented in his 1934 discussion of the critical pH curves of Wark and Cox (1934), namely, “The data reported may be used to substantiate the view that the contact angle measured was that of a xanthicacid film.” Itshould be pointed out that Cook clearly did not consider ionic adsorption in terms of the electrical double layer. Nixon (1957). “Prominent theories could be reconciled by the electrochemical approach.” Woods (1984). “Electrochemical investigations of the interaction of thiol collectors with sulfide minerals have demonstrated that each of the three anodic processes~chemisorption, reaction to form a metal collector compound, and the formation of a dithiolate—plays a role in creating hydrophobic surfaces.” ‘There is no doubt that electrochemical reactions have a significant role in the flotation of sulfide minerals with xanthate collectors. Richardson and Walker (1985) clearly showed the dependence of the floatability of a number of sulfide minerals (Figure 9) with ethyl xanthate on the oxidation potential, going from reducing to oxidizing conditions. The electrochemical potential can be regulated either with a potentiostat or chemically. In the case of pyrite, the adsorbed collector is readily oxidized to dixanthogen, which is then the species that imparts hydrophobicity to pyrite. In the case of the copper minerals, the potentials are below that for the formation of dixanthogen and the hydrophobicity results from the formation (chemisorption) of cuprous xanthate at the surface. Fuerstenau and aq100 2 © 80 o 3 c S ° 60 oi = a 40 a < © CHRYSOCOLLA 5 Sx 10" WH HM S20 = © CHALCOCITE 107? HEM 600 av (SHED pH FIGURE 10 The offect of pH on the flotation response chrysocolla and ehalcocite with potassium octyl hydroxamate as collector. The potential for the chalcocite system Is slightly ‘oxidizing. Hanson conducted a detailed electrochemical investgation of chalcocite with a collector that does not oxidize, namely a chelating compound, potassium octyl hydroxamate (Fuerstenau, 1988). Figure 10 shows the pH dependence of the floatability of chrysocolla (a hydrous copper silicate) and that of chalcocite. The flotation response of chrysocolla shows essentially two peaks, the lower one under the conditions where copper ions hydrolyze (about pH 6) and the second where the hydroxamate hydrolyzes to hydroxamic acid (about pH 9). In the case of chalcocite, under reducing potential conditions, ther no flotation of chalcacite with hydroxamate as collector. But under oxidizing conditions, the lattice copper ions become available to chelate with hydroxamate and the behavior is now somewhat similar to that with chrysocolla. During the last three decades, there has great interest in the processing of fine particles, as exemplified by the selective flocculation/flotation operation of the Tilden Mine of Cleveland Clifis, Laboratory experimentation has included not only selective flocculation, but also floc flotation, shear flocculation, and chelating flotation reagents, and the fine- particle investigations continue today. Again, the 1934 foresight of Gaudin is intriguing, in that we say the same today: One of the outstanding problems in need of solution for the impravernent in metallurgical efficiency is that of treatment of particles of colloidal or near-colloidal size. ... Since a major part of the present-day losses isin the form of near-colloidal or colloidal material, the problem assumes enhanced importance.POPULAT. BALANCE (uaa) FUNCT. DISTRIB, (Woodburn) DISTRIB. RATE (rmaizur, novo} Y BUBBLE PARTICLE FILM THINNING (Fase) 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 FIGURE 11 Historical perspective: ascending mountains represent development of flotation kinetics, both macroscopic and microscopic subprocesses The Historical Perspective on the Concepts of Flotation Kinetics ‘The final depiction (Figure 11) of the ascent of flotation fundamentals illustrates the development of flotation kinetics, both macroscopic and microscopic models. It is the interfacial interaction of collectors with minerals that determines whether or not a separation can be made by flotation. On the macroscopic scale, kinetic studies are concerned with rate of removal of floatable material from flotation machines; on the microscopic scale, the unit event is the formation of the bubble/particle aggregate, with the kinetics of the subprocesses determining the overall kinetics. The microprocesses depend on the surface chemistry and physies of the system. Research at the most funda- mental level in kinetics would certainly be to develop an absolute flotation-rate theory, that is to formulate a model for the microprocesses, to develop kinetic equations on the basis of the model, and to subject these to appropriate experimental tests. The earliest attempt to develop a theoretical basis of flotation microprocesses was by T. S. Mika, who unfortunately never published his work but presented it at an Engineering Foundation 19Nixon, J.C., 1957. Discussion, in Proceedings of the 2nd International Congress on Surface Activity, ed. J, H, Schulman, Butterworths, London. 3: 369. Queneau, P.E., 1973, Modern practice and technological innovation in the nonferrous industries. Journal of Metals, 15-18, von Reinders, W., 1913. Die Verteilung eines suspendierten Pulvers oder eines Kolloid gelosten Stoffes zwischen zwei Losungsmitteln. Koloid-Zeitschrift, 13: 235. Richardson, P.E., and Walker, G.W., 1985. The flotation of chaleocite, bornite, chalcopyrite, and pyritein an electrochemical flotation cell. XV International Mineral Processing Congress, Cannes, GEDIM, St-Etienne. Il: 198-210. Rickard, T.A., 1916, The Flotation Process. Mining and Scientific Press, San Francisco, 364 pp. Sutherland, KL. and Wark, LW., 1985, Principles of Flotation. Australasian Institute of Mining and Metallurgy, Melbourne, 489 pp. ‘Taggart, A.F., Taylor, T.C., and Knoll, A.F., 1930. Chemical reaetions in flotation. Trans. AIME. 8 17-260. Taggart, A.F., 1945. Handbook of Mineral Dressing. Wiley, New York, p. 12-52. Wark, L.W., and Cox, A.B., 1934, Principles of flotation, I-an experimental study of the effect of xanthates on contact angles at mineral surfaces, Trans, AIME, 112; 189-244, Wark, LW., 1938. Principles of Flotation. Australasian Inst. of Mining and Metallurgy, Melbourne. Woods, R., 1984. Electrochemistry of sulfide flotation. In Principles of Flotation—The Wark Symposium, ed. M. H. Jones and J. T. Woodcock. Symposia Series No. 40, The Australasian Institute of Mining and Metallurgy, Parkville. 91-115.Oxide Mineral Flotation Fundamentals P. Somasundaran” and Anjing Lou" Flotation of axide minerals is controtled by a number of factors, such as surface potential and Solubility of the mineral, concentration and type of various inorganics, properties of the callector, pH, ionic strength and temperature, The role these factors play depends on the mechanisms of ‘adsorption of the collector inorganics or polymer additives. The major mechanisms include electrostatic interactions, chemical adsorption, chain-chain interaction between adsorbed collector species and modifications of the surface by inorganics. In real systems, flotation is, however, markedly affected by various other processes, including aging of the minerals, surface precipitation ‘of the collector on the mineral and associative interactions between various collector species leading to highly surface active, for example, ionomolecular complexes. These effects are reviewed here with selected examples. INTRODUCTION Oxides and their combinations are the most abundant minerals in the earth's crust. Their flotation behavior is significant both because of their inherent value and their common occurrence as gangue minerals in ores. In this paper the oxide mineral flotation with collectors that adsorb mainly by physical interactions, such as electrostatic and hydro- carbon chain interactions, will be discussed. Because of similarities with many of the nonmetallic minerals, detailed knowledge of the surface chemistry of these minerals is required to optimize flotation selectivity. For collectors that adsorb by physical inter- actions, such factors as surface charge, reactivity with modifying agents and crystal chemistry of the minerals must be taken into account to design flotation separations. OXIDE MINERAL FLOTATION Awide range of methods exist for separating oxide minerals by flotation. Generally, there are two different schemes used for the separation of certain oxide-type minerals and oxidized sulfide minerals': 1. Flotation with fatty acids or amines as collectors (without intentional activation). * Langmuir Center for Colloids and Interfaces, Columbia University, New York, N.Y. 232. Activation, for example, using sodium sulfide to convert the oxide surface to sulfide (a treatment referred to as sulfidization) followed by flotation with thio collectors such as xanthates. The first technique, flotation with fatty acids, is not very selective and can be applied to only a few ores with relatively insoluble minerals. If soluble minerals are present, the metallic ions released into the solution can create undesirable activation of the gangue minerals. Also, for fatty acid flotation, the gangue minerals should not contain pyrite or pyrrhotite (which float readily with fatty acids) and should be acidic in character. The second procedure, that of controlled sulfidization followed by xanthate flotation, is more selective and efficient. Inthe case of iron ores, the usual problem is to separate hematite from quartz. Six different procedures have been developed, the first four of which have been put into industrial practice*: 2. Flotation of hematite using sulfonates as the collector at pH 2 to 4. 2. Flotation of hematite with fatty acids as the collector at pH 6 to 8. 3. Flotation of quartz with amines as the collector at pH 6 to 7. 4, Flotation of quartz activated with calcium ions at pH 11 to 12, using soaps.as the collector together with starch to depress the hematite, 5. Flotation of hematite with amines as the collector at pH 1.5 in the presence of hydrochloric acid or sulphuric acid, 6. Flotation of hematite with hydroxamates as the collector at pH 8.5 and methyliso- butylearbinol as the frother. Briefly, the flotation of hematite with sulfonate results from the adsorption of the anionic collector on positively charged hematite at pH 2 to 4; quartz, being negatively charged at this pH, does not adsorb sulfonate. In the second process, the fatty acid chemisorbs on the hematite but does not adsorb on quartz. In the third process, the cationic amine adsorbs on the highly negatively charged quartz but not on the essentially uncharged hematite. In the fourth process, the flotation of hematite is prevented with the hydrophilic starch macromolecules that chemisorb on the hematite through their carboxyl groups. Without the starch, the hematite would also float under these conditions. For concentrating non- magnetic taconites, a method that involves the selective flocculation of fine hematite, followed by the flotation of the coarser quartz particles by procedure 3 or 4, has been put into industrial practice. In the case of quartz, because its solubility is very limited and because the only cation comprising the mineral is silicon, flotation is obtained only after metal ions are added to the system ina pH range in which hydrolysis of the ions to hydroxy complexes occur, The flotation edges shown in Figure 1 outline minimum values of pH at which flotation is obtained with 1 x 10~* mol/I sulfonate and 1 x 10 mol/I of various metal ions. The pH range in which flotation is obtained in the presence of some of these activators is shown in Figure 2. The absence of flotation above the upper flotation edge and below the lower flotation edge is attributed to insufficient amounts of hydroxy complex that is required for flotation. The pH ranges in which flotation is obtained in the presence of various metal salts are listed in Table 1. Flotation response at pH 11.5 at variousconcentrations in the presence of calcium chloride and laurie acid is presented in Figure 3.° Concentrations of laureate at which calcium 24TABLE 2 Point of zero charge (p2c) of several oxides and salt-type minerals Mineral pzc References Anatase 5 5 Barite 95, 7 Calcite 810.8 72 Cassiterite 45 73 ‘Chromite 567.2 20 ‘Corundum 99.4 74 ‘Cuprite 1-95 o1 Dolomite 7.0 76 Fluoroapatite 46 92 Fluoroapatite (syn) 5.2 76 Goethite 67 7 Hematite 48-67 980 Kaolinite 5-6 88,89 Quartz 233.7 83 Rutile 6.0 83 Talc 35 84 Tenorite 95 85 Zircon 5.8 86 adsorption of the surfactants at the interface, as well asits effect on the flotation efficiency, is essential for optimizing the flotation selectivity. SURFACE CHARGE AND PRETREATMENT EFFECTS Surface Charge Surface charge can be generated by a number of mechanisms, namely, specific chemical interaction, preferential dissolution of surface ions, or lattice substitution. For oxides, specifiechemical interactionsis the most important mechanism involved in surface-charge generation. For example, hematite, silica and alumina are considered to acquire their charge by hydrolysis and pH-dependent dissolution. The process can be represented by the following reactions: MOH = MO” + H* H’ + MOH = MOH,” Where M represents the metal atom, Itis clear from these equations that the oxide surface will be positive at low pH and negative at high pH values. The pH at which the surface is neutral is referred to as point of zero charge or pzc of the mineral, The pzc(s) of major oxide and salt-type minerals are listed in Table 2,'° 27TABLE 3. Characteristics of the major types of collectors ‘Type Formutar* Ton Tonization Fatty acid ep ROG ‘Weak nace So... wae Allyiphosphate RPO; Weak Alkyisultate ° RSO,- Strong i O—S—0...Na* I @ Alkyisulfonate ° RSO;- Weak I R—S—O" Nat I ° Primary amine salt H RNH,* Weak 1 RON I H ‘Secondary amine salt A Weak I a= Ney or a Tertiary amine salt R RNR(R') Ht Weak | A-N—H..or | R Quaternary amine salt R RNR'),* Strong Alkyl xanthates Rocs;- Strong RY —O—C—S"...Nat *R, long-chain alkyl g/oup containing eight or more carbon atoms: R’', a short allyl chain, usually & ‘methyl group; R. normally ethyl or amyl group. a4REGION! NO AGGREGATION REGION II NUMBER OF AGGREGATES INCREASES. ~120-130 MOLECULES PER AGGREGATE REGION II SIZE OF AGGREGATES INCREASES >160 MOLECULES PER AGGREGATE FIGURE 11 Schematic representation of evolution of surface aggregates at different regions of the adsorption isotherm shown in Figure 107° Adsorption of fatty acids on calcite and barite has been proposed by several investigators to occur by chemisorption.***7 In examining the chemical forces involved, a major factor thatis often ignored isthe change in the active chemical form of the surfactant with change in pH. This has often forced researchers to adopt chemisorption as the mechanism of adsorption. For example, flotation maximum at pH 8 for the hematite-oleate system has been proposed to be due to covalent bonding between the surfactant species and the mineral surface (Figure 12). Oleate itself, however, has been found to exhibit maximum. surface tension lowering at pH 8, suggesting formation of highly surface active complexes inthis pH region.°®*° fon molecular complexes that can form between oleicacid and oleate in this pH range can be expected to give rise to a flotation maximum. Indeed, the surface activity of the acid-soap oleate complex for hematite flotation exhibits a maximum at the same pH (Figure 12). Surface Precipitation An important factor that has to be taken into account in this regard is the possibility of the precipitation of the surfactant on the particle surface. Because the concentration of an ionic surfactant at an oppositely charged surface is higher than that in bulk, precipitation 35100 80 quart: DDACI 10> M 60 (a) 40 8 FLOATED 20 100 O85 sec Oi0sec 80 DODEGYLAMINE HYDROCHLORIDE 60 Sx10°M (b) % FLOATED 40 20 pH FIGURE 45 _Halllmond cell flotation of quartz as a function of pH at (a) 5 x 10° M amine and (b) 10 M amine flotation maximum can be correlated solely tothe formation of the ion-molecular complex. Similar correlations between collector association and flotation have also been observed for the oleate-hematite system.*! Modifying Agents. In addition to surfactants that function primarily as collectors and frothers, other chemi- cals are used as depressants, deactivators, activators, pH modifiers, and dispersants in most flotation systems. Depressants act by retarding or inhibiting the flotation of the solid selected. Polymers such as starch and tanin are common depressants, Interestingly, depression of flotation does not always take place, due to inhibition of collector adsorp- tion. For example, flotation of quartz using amine is depressed by a cationic polymer even 39QUARTZ/SULFONATE/PAMA, 100 ‘SULFONATE (kmolim*) 460% 10% 01.2% 104 pH=65 80 60 Etoct of Polymor an Suifonate Adsorption (G=2 x 10 kmotin’) Pomel = [= mon [=| Qo 1 10 100 POLYMER CONCENTRATION, mg/kg % FLOATED 40 FIGURE 17 Activation of flotation of quartz dodecylsutfonate by the cationic polymer PAMA at natural pH. Adsorption of sulfonate In the presence and absence of polymer Is shown In the inset. and chemical interactions between the surfactants and the oxides as well as the polymers, is needed to reveal the mechanisms involved. ACKNOWLEDGMENTS ‘The authors wish to acknowledge the support of the National Science Foundation (CTS- 9632479, EEC-9804618 and INT-9415417). REFERENCES 1, Jan Leja, Surface Chemistry of Froth Flotation, Plenum Press, New York, p. 35, 1982 2. Fuerstenau, D.W., and Healy, T.W., in Adsorptive Bubble Separation Techniques, edit. R. Lemlich, Academic Press, New York, Chap. 6, 1972 3, Fuerstenau, M.C., and Palmer, B.R., Anionic flotation of oxides and silicates, Flotation \(uerstenau, M.C. ed.), AIME, New York, p. 148, 1976 4. Fuerstenau, M.G,, Role of metal ion hydrolysis in oxide and silicate flotation systems, AILCHE Symp. Series, No, 150, 71, p. 16, 1975 5. Fuerstenau, M.C., and Cummins, W-F., The role of basic aqueous complexes in anionic flotation of quartz, Trans, AIME, 238, p. 196, 1967 6. Gaudin, A.W., and Rizo-Patron, A., The mechanism of activation in flotation, Trans, AIME, 153, p.462, 1942 7. Cooke, S.R.B., and Digre, M., Studies on activation of quartz with calciumion. Min. Engng, 1 (Min. Trans, AIME, 184) p. 299-305, 1949 8, Fuerstenau, M.C,, and Elgillani, D.A., Calcium activation in sulfonate and oleate flotation of quartz, Trans, AIME, 235, 9405, 1966 4413. 14. 15. 16. 7. 18, 19. 20. 21. 22, 23, 24, 25. 26. 27. 28, 29. 30. 31. 32, 33. 34. 35. 36. 37. 38. 39. 41. 42. 43, Somasundaran, P., and Agar, G.E., J. Colloid and Interf. Sci., 24, p. 433, 1967 Berube, Y.G., and de Bruyn, P.L., J. Colloid and Interf, Sci., 27, p. 305, 1968 Kulkarni, R.D., and Somasundaran, P., Inter. J. Mineral Process., 4, p. 89, 1974 Harkins, W.D., The physical chemistry of surface films, Reinhold, New York, 1952 Somasundaran, P., and Ananthapadmanabhan, K.P., Solution chemistry of surfactants and the role of it in adsorption and froth flotation of mineral-water systems, Solution chemistry of surfactants (Mittal, K.L. ed.). Plenum, New York, p. 777. 1979 Mukerjee, P., and Mysels, K.J., Critical micelle concentrations of aqueous surfactant systems. Natl. Bur. Standards, NSRDS_NBS 36, 1971 DuRietz, C., Chemisorption of collectors in surface chemistry, proceedings XI Intl. Min. Process. Congr., Calgary, p. 376, 1975 Amankonah, 0.J., Somasundaran, P., and Ananthapadmanabhan, K. at the 114th Annual AIME Meeting, New York, 1985 Amankonah, 0.J., and Somasundaran, P., Colliods Sutf., 15: p. 335-353, 1985 Amankonah, 0.J., Somasundaran, P., and Ananthapadmanabhan, KP., Colliods Sutf., 15: p- 295-307, 1985 Modi, H.J., and Fuerstenau, D.W., Trans, AIME, 217, p. 381, 1960 Modi, H.J., and Fuerstenau, D.W., J. Phys. Chem., 61, p. 640, 1957 Somasundaran, P., Trans, AIME, 255, p. 64, 1974 Choi, H.S., and K.U. Wang, Korean Chem. Soc., 7, p. 91, 1963 Choi, H.S,, and KU, Wang, Trans. Can. Ins. Min, Metall., 66, p. 242, 1963 Iwasaki, I, Cooke, $.R.B., and Kim, Y.S., Trans, AIME, 223, p. 113, 1962 Fuerstenau, M.C., Rice, D.A., Somasundaran, P., and Fuerstenau, D.W., Trans IMM (London), 73, p. 381, 1965 Fuerstenau, M.C., Martin, C.C., and Bhappu, R.B., Trans, AIME, 226, p. 449, 1963 Saleeb, F.Z., and Hanna, H.S.,.J. Chem, UAR, 12 (2), p. 237, 1969 Chandar, P., Somasundaran, P., Kenneth Waterman and Turro, N.J., J. Phys Chem, French, R.O., J. Phys Chem., 58: 80J, 1954 Peck, A.S., and Wadsworth, M.E. Proc. 7th Int. Min. Proc. Cong. (Arbiter, N.ed.), Gordon and Breach, New York, p. 259, 1965 Bhar, A., Clement, M., and Surmatz, H., Proc. 8th Int. Minl. Proc. Congr., Leningrad, Paper $-11, 1968 Blissing, U., Dissertation, Bergakademie Frieberg, Ger-Text, 1969 Shergold, H.L,, Trans. IMM. 81(3): C148, 1972 ‘Somasundaran, P., Ananthapadmanabhan, K.P., and Ivanov, 1.B.,,J. Colloid Interface Sci., 99(1):128, 1984 Ananthapadmanabhan, K.P., Ph.D. thesis, Columbia University, 1981 Ananthapadmanabhan, K.P., and Somasundaran, P., Colloids Surf., 13:65-72 Somasundaran, P., and Ananthapadmanabhan, K.P., in Selutien Chemistry of Surfactants (Mittal, K.L., ed.). Plenum, New York, 1979 Mukerjee, P., J. Phys Chem., 62:1404, 1958 Somasundaran, P., and Cleverdon, J., Colloids Surf., 13(1):73-85, 1985 Paper presentedTABLE 1 Synthetic single-crystal IREs that are useful for flotation studies internal Useful ‘Average Reflection Transmission Refractive Element (IRE) Range (cm) Index, SiO, 50000-4000 144 AL,O5 33000-2800 75 Mgo 20000-1700 1.68 CaF, 66000-1300 1.40 NaCl 25000-900 15 Kel 2000-700 147 As,S3 12500-1300 24 2nS 14000-1000 2.22 TiO, 20000-2000 2.6; 2.9 210, 25000-1800 2.45 Beginning in the late 1980s, researchers demonstrated the utility of fabricating the desired substrate into a reactive IRE and directly studying surface reactions in-situ at the IRE sur- face. Sperline et al. (1987) first used this approach to quantitatively monitor the adsorption density of the surfactant cetylpyridinium chloride onto a zine selenide IRE. Of course, this method is limited to systems where IR-transparent IRE crystals are available, and appropri- ate care must be taken to avoid and/or correct for any impurity contamination of the sys- tem. Synthetically grown single-crystal IREs that are readily available and useful from a flotation standpoint are listed in Table 1. Also listed in Table 1 is the useful transmission range of each IRE. Since the initial investigation by Miller and Kellar (1989), numerous IREs have been used to describe adsorption processes associated with flotation chemistry. The use of natural mineral crystals as IREs was first postulated by Harrick over 30 years ago and now has been developed for flotation chemistry studies (Hartick, 1979; Hartick Scientific, 1988). In the case of semi-soluble salt-type minerals, fluorite, calcite, and fluoroapatite crystals have been used as reactive IREs (Miller and Kellar, 1989; Kellar et al, 1990; Lu et al., 1998; Young and Miller 1998). ‘The focus of this paper is a review of the FTIRVIRS technique for the analysis of carboxy- late adsorption in the flotation chemistry of semi-soluble salt minerals, using these same minerals as reactive IREs. ADSORPTION DENSITY In the first demonstrated use of reactive IREs for in-situ flotation chemistry research, Miller and Kellar (1989) and Kellar et al. (1989) showed that the adsorption density of oleate at the surface of a fluorite IRE could be calculated from in-situ spectral data. Sub. sequently, this approach was refined by Free et al. (1994). The general utility of the FTIR/ IRS adsorption density equation for reactive IREs has now been established. A/N-2G,d, 10008(24,/d,) 471000 ox 100-05 1.00605 L.00E-04 1.00603 1.008-02 Equilibrium Oleate Goncentration (ta) FIGURE 3 Comparison of oleate adsorption isotherms at apatite, fluorite, and calcite ‘surfaces at about pH 9.5 and a temperature of 20°C to 25°C (Lu et al., 1998) & S = £ fro a 3 4 s 6 7 x 9 10 PF fromm fsotherm (umalim® } FIGURE 4 Adsorption density values for transferred LB monolayers of fatty acids calculated by the FTIR/IRS adsorption density equation vs. those determined from the 7-A isotherms (ang and Miller, 1993) 49TABLE 3 Comparison of the measured heats of adsorption of oleate at the fluorite/water interface with isosteric heats of adsorption for different levels of surface coverage (Miller et al., 1989) Heats of adsorption of oleate (keal mol") Measured by Calculated from adsorption microcalorimetry isotherm data Ghemisorption (monolayer coverage) 2.36 277 Surface precipitation (above monolayer coverage) -5.31* -6.60 "At oleate Surface coverage 0, = 0.59 (i.e, 0= 1.59). region it appears that the adsorption is mainly due to surface precipitation of calcium dioleate or heterocoagulation of calcium dioleate collector colloids. Therefore, itis reason- able to relate adsorption density to the extent and kinetics of calcium ion release to solution as has been discussed in the literature (Young and Miller, 1998; Free and Miller, 1997). In this regard, itshould be noted that the adsorption isotherm is quite sensitive to the level of dissolved calcium, particularly region one, the chemisorbed layer. If even a modest amount of calcium is present in solution prior to oleate addition, the precipitation event can over- whelm chemisorption and the plateau, so characteristic of the chemisorbed monolayer, can be eliminated as demonstrated for the fluorite system by Free and Miller (1997). ‘The two regions of oleate adsorption (chemisorption and surface precipitation) are also revealed from thermochemistry studies of the fluorite/oleate system (Miller et al., 1989). As shown in Table 3, adsorption at low equilibrium oleate concentrations reveals an endo- thermic reaction of oleate at the fluorite surface, whereas at high equilibrium oleate concentrations, an exothermic reaction associated with multilayer adsorption by surface precipitation of calcium dioleate is observed. Similar results that indicate an endothermic chemisorption reaction of oleate ata calcite surface have been reported (Young and Miller, 1998). In summary, based on these adsorption density and thermochemistry considerations, chemisorption predominates at low equilibrium concentrations (low adsorption densi- ties) and a precipitated calcium dioleate predominates at higher adsorption densities. In the case of fluorite, a close-packed monolayer of oleate forms during the chemisorption reaction, creating a strong hydrophobic state at the fluorite surface. On the other hand, in the case of calcite and apatite, monolayer formation is incomplete during chemisorp- tion and, at best, a weak hydrophobic state is created at these surfaces. ADSORPTION KINETICS Detailed studies of adsorption kinetics ate relatively uncommon in the flotation literature. ‘There are numerous reasons for the dearth of such data, including lack of instrumentation capable of giving real-time results. Furthermore, most kinetic studies have been performed ex-situ. An exception to this occurred in 1997, when Free and Miller (1997) examined the adsorption kinetics of oleate and linoleate in-situ using a reactive fluorite IRE. Itwas found that the adsorption process was not controlled by convective diffusion or mass transport but rather by the reaction of the collector molecules at the fluorite IRE substrate. Another sig- nificant finding from this analysis was that, once oleate chemisorbed at the fluorite surface, 54TABLE 4 Band positions (em) of chemisorbed and surtace-precipitated oleate at fluorite, apatite, and calcite surfaces from selected references (Young and Miller, 1998) Band Positions: (cm) Reference Mineral Chemisorb __Precipitate Detection Method Fluorite (CaF) Kellar et al. (1991) synthetic, 1549 1573, 1535 In-situ FTIR/IRS Jang and Miller (1994) synthetic 1550 - LB FTIR/IRS, Bahr et al. (1978) naturat 1560 1575, 1538 KBr transmission Sivamohan et al. (1990) natural 1565 1575, 1540 Diffuse reflection Rao and Forssberg (1991) synthetic, 1965 1576, 1540 Diffusion reflection Peck and Wadsworth (1965) natural 1555 1877, 1543 Nujol Mull Hu et al, (1986) synthetic, 1587 1577, 1540 KBr transmission ‘Apatite (Ca,(P0,)3X] Gong et al (2992) X= 0H 1560 1574, 1593 Diffuse reflection Antti and Forssberg (1983) x=F 1550 1577, 1541 Diffusion reflection Lu and Miller (1998) X=F 1954 1575, 1540 Exsity FTIR/IRS Calcite (CaCO,) Peck (1963) naturat 1562 - KBr transmission Antti and Forsberg (1989) natural unable unable Diffuse reflection ‘Young and Miller (1998) naturat 1562 1969, 1534 Exsitu FTIR/IRS Not all researchers agree with this position. The above analysis touched off significant debate in subsequent publications (Miller et al., 1995). Complete understanding of the phenomena that cause the formation of a singlet and doublet was not fully resolved until the IRS work of Lu and Miller (1998) with fluorite showed that the 1550 cm singlet and the doublet at 1540 and 1575 cm could be explained in terms of the coordination strue- ture of carboxylate groups with calcium ions. (For example, splitting of the asymmetrical stretch is not observed for magnesium and barium carboxylates, and in fact, such splitting reveals the unique multiple coordination states, characteristic of calcium in such aqueous systems.) In this analysis it was shown that constrained calcium carboxylate groups in a chemisorbed state at the surface (monolayer coverage) give rise to the singlet, whereas carboxylate groups associated with calcium ions in three-dimensional seven- or eight-fold coordination (multilayer coverage) give rise to the doubler. It is now clear that the singlet peak is indicative of the chemisorbed oleate when it is constrained at the surface and ited in coordination with calcium. This is true even if a calcium dicarboxylate is formed in such a constrained state (Lu and Miller, 1998). In view of the adsorption density observed for monolayer coverage at a fluorite surface and the calcium surface site density (Table 2), the bridging structure for the chemisorbed oleate (Figure 5) is justified by the carboxylate singlet position observed at ~1550 cm”. Such close packing of the oleate monolayer and the ordered arrangement (see next section) account for the great stability of oleate at fluorite surfaces and the excellent hydrophobicity observed (Jang et al., 1995). 53FIGURE 8 Examples of trans (left) and gauche (right) butylene linkages. The asterisk Indicates the gauche bond (Kellar et al., 1993). four-carbon subchain are on the same side (gauche) or opposite sides (trans) of the plane of the middle carbon/carbon bond. Typically, if the sample has a predominantly gauche population, the band location will occurat higher wavenumbers than when the population is predominantly of the trans conformation. Such analyses have been performed by researchers studying surfactant chemistry (Kellar et al., 1990). For example, when the sur- factant is predominantly in the monomer form, the alkyl band position occurs at higher wavenumbers than when the micellar form of the surfactant prevails. Kellar et al. (1993) used this concept to better understand the conformational behavior of adsorbed oleate on a fluorite IRE. It was found that at very low adsorption densities, the oleate molecules adsorbed initially in predominantly the gauche conformation, and as the adsorption density approached monolayer coverage, the trans conformation pre- dominated. These results, together with more recent results, are shown in Figure 9 (Drelich et al., 1997). Also, it should be noted that Jang and Miller (1995) used polarized- light FTIR/IRS experiments to analyze the conformational behavior of self-assembled (SA) and Langmuir-Blodgett (LB) layers of stearate molecules at the surface of a fluorite IRE, They found that for both the SA and LB monolayers, the predominant conformation was the trans state, Finally, with respect to orientation, Jang and Miller (1995) determined the orientation angle (relative to surface normal) from the same FTIR/IRS polarization experiments. It was found that this angle was 21° to 22° for the SA layer and from 9° to 16° for the LB layer. ‘These orientation/conformation results complement the previous adsorption density and speciation results and demonstrate, in the case of fluorite, that a well-ordered/organized, tightly packed, chemisorbed monolayer layer forms at low oleate concentrations. CONCLUSIONS A Fourier transform infrared spectroscopic technique has been developed that has allowed for the acquisition of fundamental information concerning carboxylate collector adsorp- tion in semi-soluble salt flotation systems. The technique allows for in-situ measurements on both synthetic and naturally occurring minerals. In general, the in-situ measurements, which include adsorption density, kinetic, speciation, and orientation/conformation stud- ies, have provided additional information that was not available with other spectroscopic 552916 +—+-—+ + + : tf —+- | 0 2 4 6 40 Adsorption Density [ umol/n } FIGURE 9 Peak frequency change of the asymmetric C-H stretching mode of the -CH,- group with increasing adsorption density of oleate at a fluorite surface (Drellch et al., 1997) techniques. Specifically, the spectroscopic evidence and thermochemical data show that, in the absence of dissolved calcium, chemisorption predominates at low equilibrium oleate concentrations (low adsorption densities) and a precipitated calcium dioleate predomi- nates at higher adsorption densities. In the case of fluorite, a close-packed monolayer of oleate forms during the chemisorption reaction, creating a strong hydrophobic state at the fluorite surface. On the other hand, in the case of calcite and apatite, monolayer formation is incomplete during chemisorption and a weak hydrophobic state is created at these sur- faces. At high equilibrium oleate concentrations, a surface precipitation reaction occurs that leads to multilayer calcium dioleate coverage in the case of fluorite and caleite. ACKNOWLEDGMENT This research has been supported by DOE Office of Basic Energy Sciences, most recently by DOE Grant No. 93-ER14315 REFERENCES Antti, BM, and E, Forsberg, 1989, “Pulp chemistry in industrial mineral flotation: Studies of surface complex on calcite and apatite surfaces using FTIR spectroscopy.” Miner. Eng. 2:217-227. Bahr, A.M. Clement, and H. Luther, 1968, “Effect of some electrolytes on the flotation of fluorspar with sodium oleate.” Z, Erz. Metall. 21:1-8. Drelich, J., W.E. Jang, and J.D. Miller, 1997, “Examination of adsorbed oleate layers at a fluorite surface by contact angle measurements and FTIR/IRS spectroscopy.” Langmuir 13:1345-1351. Free, M.L., W.H, Jang, and J.D. Miller, 1994, “Quantitative Fourier transform-infrared internal reflection spectroscopy (FTIR/IRS) for adsorption density measurements." Colloids and Surfaces 93:127-135. Free, M.L., and J.D. Miller, 1996, “The significance of collector colloid adsorption phenomena in the fluorite/oleate flotation system as revealed by FTIR/IRS and solution chemistry analysis.” JMP 48:197-216. 56Free, M.L., and J.D. Miller, 1997, “Kinetics of 18-carbon carboxylate adsorption at the fluorite surface.” Langmuir 13:4377-4382. Gong, W.Q., A. Parentich, L.H. Little, and L.J. Warren, 1992, “Adsorption of oleate on apatite studied by diffuse reflectance infrared Fourier-transform spectroscopy.” Langmuir 8:118-124, Hartick, N.J., 1979, Internal Reflection Spectroscopy, 2nd ed. Ossining, New York: Harrick Scientific Corp. Hartick Scientific Corp., 1988, Crystals for Optical Spectroscopy. 3. Ossining, New York: Harrick Scientific Corp. Hu, J.S., M. Misra, and J.D. Miller, 1986, “Characterization of adsorbed oleate species at the fluorite surface by FTIR spectroscopy.” Int. J. Miner. Process. 18:73-84. Jang, W.H.,J. Drelich, and J.D. Miller, 1995, “Wetting characteristics and stability of Langmuir- Blodgett carboxylate monolayers at the surfaces of calcite and fluorite.” Langmuir 11:3491-3499. Jang, W.H., and J.D. Miller, 1993, “Verification of the IRS adsorption density equation by FTIR analysis of transferred Langmuir-Blodgett films.” Langmuir 9:3159-3165. Jang, W.H,, and J.D, Miller, 1995, “Molecular orientation of Langmuir-Blodgett and self- assembled monolayers of stearate species at a fluorite surface as described by linear dichroism theory.” J. Phys. Chem. 99:10272-10279. Kellar, J.J., W.M. Cross, and J.D. Miller, 1989, “Adsorption density calculations from in-situ FTIRVIRS data at dilute surfactant concentrations.” Applied Spectroscopy 43(8):1456-1459. Kellar, J.J., W.M. Cross, and J.D. Miller, 1990, “In-situ near-infrared internal reflection spectroscopy for surfactant adsorption reactions using reactive internal reflection element \pplied Spectroscopy 40(9):1508-1512. Kellar, J.J., W.M. Cross, M-R. Yalamanchili, C.A. Young, and J.D. Miller, 1993, “Surface phase transitions of adsorbed collector molecules as revealed by in-situ FTIR/IRS spectroscopy.” Minerals and Metallurgical Processing 10(2):75-80. Kellar, J.J., C.A. Young, K. Knutson, and J.D. Miller, 1991, “Thermotropic phase transitions of adsorbed oleate species at a fluorite surface by in-situ FTIR/IRS spectroscopy.” J. Colloid and Int, Sci. 144(2):381-389, Kellar, J.J., CA. Young, and J.D. Miller, 1992, “In-situ FTIR/IRS investigation of double-bond reactions of adsorbed oleate at a fluorite surface.” MP 35:239-251. Lu, Y.Q.,J. Drelich, and J.D. Miller, 1998, “Oleate adsorption at an apatite surface studied by ex-situ FTIR internal reflection spectroscopy.” J. Coll. Int. Sci. 202:462-476. Lu, Y.Q., and J.D. Miller, 1998, “Caraboxylate stretching vibrations of spontaneously adsorbed and LB transferred calcium carboxylates as determined by FTIR internal reflection spectroscopy. Submitted for publication to Langmuir. Miller, J.D., and J.B. Hiskey, 1972, “Electrokinetic behavior of fluorite as influenced by surface carbonation.” J. Coll. Int. Sci. 44(3):567-573. Miller, J.D., J.S. Hu, and R. Jin, 1989, “Thermochemistry of oleate adsorption at the fluorite/ water interface.” Colloids and Surfaces 42:71-84. Miller, J.D.,W.H. Jang, and J.J. Kellar, 1995, “Comments on nature and structure of adsorption layer on apatite contacted with aleate solution.” Langmuir 11:3272-3274. Miller, J.D. and J.J. Kellar, 1989, “Quantitative in-situ analysis of collector adso: by FTIR internal reflection spectroscopy.” In Challenges in Mineral Processing. Edited by K.V. Sastry and M.C. Fuerstenau, 109-129. Littleton, Colorado: AIME/SME. Miller, J.D., JJ. Kellar, and W.M. Cross, 190, “Infrared spectroscopy for in-situ characterization of surface reactions.” In Advances in Coal and Mineral Processing. Edited by S. Chander, 33-44. Littleton, Colorado: SME/AIME. Peck, A.S, 1963, “Infrared studies of oleic acid and sodium oleate adsorption on fluorite, barite, and calcite.” U.S. Bureau of Mines Report of Investigation No. 6202. 87Weak Electrolyte Collectors Janusz S. Laskowski" Studies carried out over the last 10 years reveal that precipitating particles which may appear in alkaline solutions of long-chain amines and in acidic solutions of fatty acids exhibit clear isoelectric points around pH 10.6-11 for dodecylamine and around pH 2.5-3 for fatty acids, These colloidal species can accumulate at solid/liquid and liquid/gas interfaces and affect flotation. While the pre- RCOOH aq) a [RCQO"}1H"} a “ [RCOOM,aq)] pK, = 4.7 £0.5 is usually used for fatty acids (Fuerstenau, 1982). For laurie acid, we use the dissociation constant value quoted by Predali (1969), pK, = 5.9, and the laurie acid solubility C, = 1.2 x 10° M (Fuerstenau,, 1982). The CMC of sodium laurate solution was found to vary with pH: it is 2x10"? M at pH 9, and 7 x 10M at pH 7 (Dai and Laskowski, 1991b). 62Micellization 3 & 2. , 2 4 © W'p-------- “ ” Bo HH, z 10 Pi Q 107 Oleic acid | 6 {-------- Solubility timit ] 10° pH FIGURE 5 Domain diagram for lauric acid and oleic acid The concentration of the ionized form according to eqs. 1, 2 and 3 is given by: log [RCOO"] = log K, + pH + log [RCOOH] cy At the pH,, the pH of precipitation, the concentration of the neutral species (RCOOH) is exactly the solubility limit C,, and the concentration of (RCOO’) is equal to the difference between the total concentration of acid originally added, Cr, and the solubility, C,. Hence (Fuerstenau, 1982): = pK, ~ logC, + log (Cy ~ C,) (5) The values of pH, calculated for lauricacid are shown in the form of a domain diagram in Figure 5. The zone on the right-hand side of the pH, borderline denotes a zone of a true solution, The precipitation appears when the pH is lower than that of pH,. Figure § also shows domain diagram for oleic acid (Laskowski, 1993). For the solubility of oleic acid, in many publications (e.g., Morgan et al., 1986) the following equil constant is quoted after Jung's unpublished thesis (Jung, 1976): HO oi) = HOliag) ) PK (ot) = 7.6 a The value of 2.5 x 10° M was substituted for C, in Eq. 5 to construct the domain diagram for oleic acid. The critical micelle concentration (CMC) for potassium oleate was given by Klevens (1953) to be 8 x 10 M, while Zimmels and Lin (1974) gave a value of 2.1 10° M for sodium oleate. The latter is used in this work. 633 1x10” MC, ,Hj;COONa Fy | my = 4x10 MC\3Hy,COOH Be 22 0 = + 3 ——1x10” MCyHgCOOH E32 48 Bz 3 4 Z 4 ’ 2x10 M C,jH3yCOONa’ gl ‘ \ \ 2 4 6 8 pH FIGURE 6 Effect of pH on electrophoretic mobility of the colloidal precipitate In aqueous solutions of fatty acids (Vurdela and Laskowski, 1987) Asseen from Figure 6, the colloidal precipitate that appears in the acidic solutions of fatty acids, depending on pH, can be either negatively or postively charged (Vurdela and Laskowski, 1987). The i.e.p. for the precipitate is situated around pH 2.5-3.5. According to Drzymala (1990), the ie.p. of oleic acid droplets is situated around pH 2. To sum up, as these results reveal, the colloidal species that may appear in aqueous solu- tions of weak electrolyte anionic surfactants, depending on pH, are either positively or negatively charged. Amines Amines ionize in an aqueous solution according to the following reaction: RNH(aq) + HzO ¢ RNH,+ + OH” ® with the dissociation constant: __ (RNH,"}10* > = - © [RNHp (qq) HLH") For dodecylamine, Ky, ~ 4.3 x 10 and pK, 3.37 (pK, = 14 ~ pKy,= 10.6) In saturated solutions: RNHy¢5) > RNA (aq) (10) 64