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Edited by
Maurice C. Fuerstenau
Graeme Jameson
and
Roe-Hoan Yoon

Published by

Society for Mining,
Metallurgy, and Exploration, Inc.

© 2007 by the Society for Mining, Metallurgy, and Exploration.
All rights reserved. Electronic edition published 2009.

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Society for Mining, Metallurgy, and Exploration, Inc. (SME)
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and minerals professionals.

Copyright © 2007 Society for Mining, Metallurgy, and Exploration, Inc.
Electronic edition published 2009.

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Contents
CONTRIBUTORS v

PREFACE ix

PART 1 HISTORICAL ASPECTS OF FLOTATION 1
A Century of Developments in the Chemistry of Flotation
Processing 3
History of Flotation Technology 65

PART 2 FLOTATION FUNDAMENTALS 93
Some Aspects of Flotation Thermodynamics 95
The Nature of Hydrophobic Attraction Forces 133
Adsorption of Surfactants and its Influence on the
Hydrodynamics of Flotation 179
Pulp and Solution Chemistry 227
The Physics and Chemistry of Frothers 259
Surface Characterization and New Tools for Research 283
The Flotation of Fine and Coarse Particles 339

PART 3 FLOTATION CHEMISTRY 373
Flotation Reagents—A Critical Overview from an
Industry Perspective 375
Sulfide Mineral Flotation 425
Flotation Chemistry and Technology of Nonsulfide Minerals 465
Depressants in Nonsulfide Mineral Flotation 555
Flotation of Precious Metals and Their Minerals 575
Coal Flotation 611

PART 4 FLOTATION CELLS, MODELING, AND SIMULATION 635
Mechanical Froth Flotation Cells 637
Column Flotation 681
Optimal Designs for Homogeneous, Countercurrent
Flotation Processing Networks 739
Modeling and Simulation of Industrial Flotation Processes 757

PART 5 FLOTATION PLANT PRACTICE 779
Plant Practice: Sulfide Minerals and Precious Metals 781
Plant Practice: Nonsulfide Minerals 845

INDEX 869

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Contributors
N.A. Abdel-Khalek S. Chryssoulis
Central Metallurgical Research and Advanced Mineral Technology Laboratory
Development Institute (CMRDI) London, Ontario, Canada
Cairo, Egypt
Jan J.I.R. Cilliers
Hans Allenius Department of Earth Science and
Outokumpu Technology Minerals Engineering
Espoo, Finland Royal School of Mines, Imperial College
London, England, United Kingdom
Armando C. Araujo
Department of Mining Engineering William Ducker
Federal University of Minas Gerais Particulate Fluids Processing Center
Belo Horizonte, Brazil Faculty of Engineering
The University of Melbourne
Barbara J. Arnold Victoria, Australia
PrepTech Inc.
Apollo, Pennsylvania Robert C. Dunne
Newmont Australia Ltd.
Seher Ata West Perth, Western Australia
Center for Multiphase Processes
University of Newcastle A. El-Midany
Callaghan, New South Wales, Australia Central Metallurgical Research and
Development Institute (CMRDI)
Cesar I. Basilio Cairo, Egypt
Thiele Kaolin Company
Sandersville, Georgia Hassan El-Shall
Center for Particle Science and Technology
Trevor Bilney University of Florida
Kanowna Belle Gold Mine Gainesville, Florida
Boulder, Western Australia
Jan Christer Eriksson
W.J. Bruckard Department of Chemistry, Surface Chemistry
CSIRO Minerals Royal Institute of Technology
Clayton South, Victoria, Australia Stockholm, Sweden
Subhash Chander K. Fa
Department of Energy and Department of Metallurgical Engineering
Geo-Environmental Engineering University of Utah
Pennsylvania State University Salt Lake City, Utah
University Park, Pennsylvania

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Mike Fairweather Stephen Grano
M.J. Fairweather & Associates Ian Wark Research Institute
Rossland, British Columbia, Canada University of South Australia
Mawson Lakes Campus
James A. Finch South Australia
Department of Metallurgical Engineering
McGill University Michael Habner
Montreal, Quebec, Canada Kalgoorlie Consolidated Gold Mine
Kalgoorlie, Western Australia
Daniel Fornasiero
Ian Wark Research Institute Gregory J. Harbort
University of South Australia Julius Kruttschnitt Mineral Research Centre
Mawson Lakes Campus Indooroopilly, Queensland, Australia
South Australia
Martin C. Harris
Eric K.S. Forssberg Department of Chemical Engineering
Division of Mineral Technology University of Cape Town
Lulea University of Technology South Africa
Lulea, Sweden
Thomas W. Healy
Douglas W. Fuerstenau Particulate Fluids Processing Center
Department of Materials Science and Faculty of Engineering
Engineering The University of Melbourne
University of California Victoria, Australia
Berkeley, California
John A. Herbst
Maurice C. Fuerstenau Metso Minerals Optimization Services
Department of Materials Science and Colorado Springs, Colorado
Engineering
University of Nevada Ronaldo Herrera-Urbina
Reno, Nevada Chemical Engineering and Metallurgy
University of Sonora
A.R. Gerson Hermosillo, Sonora, Mexico
Ian Wark Research Institute
University of South Australia G.A. Hope
Mawson Lakes Campus Faculty of Science and Technology
South Australia Griffith University
Nathan, Queensland, Australia
Craig Goodall
Lonmin Platinum Graeme J. Jameson
Marikana, South Africa Center for Multiphase Processes
University of Newcastle
Barun K. Gorain Callaghan, New South Wales, Australia
Corporate R&D/Technical Services
Barrick Gold Corporation N.W. Johnson
Toronto, Ontario, Canada College of Engineering
University of Queensland
Brian D. Gotts Brisbane, Queensland, Australia
Potash Corporation of Saskatchewan
Allan, Saskatchewan, Canada

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Bert Knopjes D.R. Nagaraj
Lonmin Platinum Minerals Processing Chemicals Division
Marikana, South Africa Cytec Industries Inc.
Stamford, Connecticut
Janusz S. Laskowski
Mining and Mineral Processing Engineering J. Nalaskowski
University of British Columbia Department of Metallurgical Engineering
Vancouver, British Columbia, Canada University of Utah
Salt Lake City, Utah
R. Lastra
Mining and Mineral Sciences Laboratories Anh V. Nguyen
Natural Resources Canada (CANMET) Center for Multiphase Processes
Ottawa, Ontario, Canada University of Newcastle
Callaghan, New South Wales, Australia
Gerald H. Luttrell
Mining and Minerals Engineering Heikke Oravainen
Virginia Polytechnic Institute and State Outokumpu Technology Minerals
University Espoo, Finland
Blacksburg, Virginia
Richard Peaker
Alban J. Lynch Metso Minerals
Julius Kruttschnitt Mineral Research Centre York, Pennsylvania
University of Queensland
Indooroopilly, Queensland, Australia Antonio E.C. Peres
Federal University of Minas Gerais
Sharad Mathur Belo Horizonte, Brazil
Technical Center
Engelhard Corporation A.R. Pratt
Gordon, Georgia Mining and Mineral Sciences Laboratories
Natural Resources Canada (CANMET)
R. McEachern Ottawa, Ontario, Canada
Potash Corporation of Saskatchewan
Allan, Saskatchewan, Canada Robert J. Pugh
Chemical and Engineering Industries Section
Thomas P. Meloy Institute for Surface Chemistry–YKI
West Virginia University Stockholm, Sweden
Morgantown, West Virginia
Srinivasa Raghavan
J. Mielczarski Department of Materials Science and
Laboratoire Environment et Mineralurgie Engineering
Vandoeuvre-les-Nancy, France University of Arizona
Tucson, Arizona
Jan D. Miller
Department of Metallurgical Engineering John Ralston
University of Utah Ian Wark Research Institute
Salt Lake City, Utah University of South Australia
Mawson Lakes Campus
South Australia

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K.H. Rao X. Wang
Division of Mineral Processing Department of Metallurgical Engineering
Lulea University of Technology University of Utah
Lulea, Sweden Salt Lake City, Utah

S.A. Ravishankar John Watt
Minerals Processing Chemicals Division Division of Minerals
Cytec Industries Inc. CSIRO Minerals
Stamford, Connecticut Melbourne, Victoria, Australia

Geoff Senior Asa T. Weber
BHP Billiton Nickel West Dorr-Oliver Eimco
Perth, Western Australia Salt Lake City, Utah

W.M. Skinner Mark C. Williams
Ian Wark Research Institute West Virginia University
University of South Australia Morgantown, West Virginia
Mawson Lakes Campus
South Australia James T. Woodcock
CSIRO Minerals
Robert Snow Clayton South, Victoria, Australia
Beneficiation and Mining
Florida Institute of Phosphate Research Ronald Woods
Bartow, Florida School of Science
Griffith University
Ponisseril Somasundaran Nathan, Queensland, Australia
Henry Krumb School of Mines
Columbia University Juan Yianatos
New York, New York Department of Chemical Engineering
Santa Maria University
G.J. Sparrow Valparaiso, Chile
CSIRO Minerals
Clayton South, Victoria, Australia Roe-Hoan Yoon
Center for Advanced Separation Technologies
Roger StC. Smart Virginia Polytechnic Institute and
Applied Center for Structural and State University
Synchrotron Studies Blacksburg, Virginia
University of South Australia
Mawson Lakes Campus Lui Zhang
South Australia Akzo Nobel Chemicals Inc.
Dobbs Ferry, New York
G. Strathdee
Potash Corporation of Saskatchewan Patrick Zhang
Allan, Saskatchewan, Canada Beneficiation and Mining
Florida Institute of Phosphate Research
Frank P. Traczyk Bartow, Florida
Dorr-Oliver Eimco
Salt Lake City, Utah

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Preface
The year 2005 marked the 100th anniversary of Sulman and Picard’s U.S. patent award
(No. 793,808) that prescribed the use of air bubbles for flotation. 1905 was also the year
when the Potter process was introduced to flotation in the minerals industry. The produc-
tion of sphalerite concentrate at Broken Hill in Australia was the first major commercial
application of froth flotation. Following that initial application, froth flotation quickly
spread to the United States and the rest of the world, where it remains an essential separa-
tion step in the beneficiation of minerals and coal. Its scope is continually broadening to
other applications such as environmental control, bitumen extraction from tar sands, and
recycling.
Recognizing its significance, a group of flotation researchers and practitioners met in
2001 to consider ways for commemorating this important anniversary. The idea was initi-
ated by a group of individuals, including D.W. Fuerstenau from the University of California,
Berkeley; M.C. Fuerstenau from the University of Nevada, Reno; and Roe-Hoan Yoon from
Virginia Tech. They were joined by D.R. Nagaraj, Cytec Industries; J.A. Herbst, Metso
Minerals; J.-P. Franzidis, Julius Kruttschnitt Mineral Research Centre; J.A. Ralston, Ian
Wark Research Institute, University of South Australia; and G.J. Jameson, University of
Newcastle.
Two international initiatives were launched—a symposium and this commemorative
volume.
Managed by the Australasian Institute of Mining and Metallurgy, the Centenary of Flo-
tation Symposium was held in June 2005 in Brisbane, Australia. It was a great success,
attracting more than 450 delegates and 149 presentations from around the world. The con-
ference fostered in-depth discussion of recent research and up-to-date descriptions of
advanced plant practice. A CD of the conference proceedings is included with this volume.
This commemorative volume, published by Society for Mining, Metallurgy, and Explo-
ration, is a comprehensive resource detailing the state of the art of flotation. The book is the
continuation of a distinguished series published by SME. The sequence began with Froth
Flotation: 50th Anniversary Volume (1962), edited by D.W. Fuerstenau, to celebrate the first
50 years of flotation in the United States; followed by the A.M. Gaudin Memorial Volume
(1976), edited by M.C. Fuerstenau. The continuing involvement of the Fuerstenau brothers
in these important volumes over such a long time span is particularly noteworthy.
The chapters in the book are written by experts in the various disciplines and cover all
aspects of flotation, from fundamental research to industrial practice. Coverage includes the
historical aspects of flotation; flotation fundamentals; flotation chemistry; flotation cells,
modeling, and simulation; and flotation plant practice. The book is an invaluable reference
for industry practitioners, researchers, and graduate students.
Sincere appreciation is extended to all who have contributed to the various chapters.
Despite its longevity, the field of flotation is quite active and rapidly changing. The editors
and SME are fortunate to have contributions from so many leaders in the industry for this
milestone project.

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PART 1

Historical Aspects of Flotation

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A Century of Developments in the
Chemistry of Flotation Processing
Douglas W. Fuerstenau

A B S T R AC T
This chapter reviews some aspects of the significance of flotation during its early days, and partic-
ularly the development of the understanding of how flotation separations can be made by the
utilization of chemical reagents that interact with mineral surfaces. The second quarter of the
flotation century saw the development of most of the reagents and reagent schemes still used
today in flotation technology. Most of this chapter is concerned with a review of the fundamen-
tals of flotation chemistry research, particularly the surface chemistry on which flotation is based.
The first decades of fundamental flotation research were oriented toward sulfide minerals, fol-
lowed by extensive investigation of the flotation of oxide and silicate minerals, and then the spar-
ingly-soluble salt minerals. More recent application of electrochemical and surface probe
techniques brought attention again to the flotation chemistry of sulfide minerals. Topics pre-
sented here are necessarily limited to broader aspects of sulfide mineral surface chemistry and the
role of oxidation in collection processes, the interfacial chemistry of oxide and silicate mineral flo-
tation and the role of the electrical double layer and hydrocarbon chain association, and the
influence of aqueous solution chemistry on the flotation of sparingly-soluble salt minerals.

INTRODUCTION
No metallurgical process developed in the 20th century compares with that of froth flota-
tion and the profound effect it had on the mineral industry. Most of the early developments
in flotation processing originated in Australia between 1900 and 1910. In the bulk oil pro-
cesses that preceded froth flotation, generally the separation was aided by levitation of the
oil/mineral mass, either through the entrainment of air during mixing or by reduction of
pressure to generate bubbles, or by the addition of sulfuric acid to generate carbon dioxide
bubbles from carbonate minerals in the ore. Working independently as well as for Minerals
Separation Ltd., A.H. Higgins in London and G.A. Chapman at Broken Hill, Australia,
found that by reducing the oil content (oleic acid) to less than 1% and agitating the ore, the
mineral-laden bubbles rose to the surface (Rickard 1916). Modern flotation is attributed to
the resulting basic patent of Minerals Separation Ltd., where the aid of chemically generated
gas bubbles was definitively discarded in favor of air bubbles (Sulman, Picard, and Ballot
1905). The first operations in Australia simply involved bulk flotation to recover the fine
particles that were left behind in gravity concentration plants.
Froth flotation as it is known today is the process that had its beginnings 100 years ago
in Australia, but a graphite flotation process preceded it by nearly three decades. As stated
by Sutherland and Wark in 1955:
The brothers Bessel (1877) patented a true flotation process for the concentration
of graphite ores.… The modern flotation process differs little in principle from the
3
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4 HISTORICAL ASPECTS OF FLOTATION

Bessel process.… However, the work of the Bessel Brothers was forgotten, and the
modern process was evolved as the result of the work of many later investigators.
A German patent was issued to Gebrueder Bessel in Dresden, and using only 305
words, this 1877 patent outlined a process for the flotation of graphite from ores using 1%
to 10% of a nonpolar oil and listing 16 or more sources for the oil. After the ground ore was
mixed with the oil, this mass was added to water and the slurry then raised to boiling tem-
perature. According to the patent, the graphite flakes attached to bubbles, rose to the sur-
face, and were skimmed off to make the separation. From an ore containing 40% graphite,
the Bessel brothers produced a concentrate containing more than 90% graphite in an opera-
tion near Passau (Graichen et al. 1977). The market of their product was for the production
of graphite crucibles for smelting. In an attempt to reduce costs, in 1886 they patented
another gas-generating method for the process by adding acid with carbonates or metals
(Gebrueder Bessell 1886). About that same time, Ceylon graphite was discovered to be of
higher quality, which led to the demise of the Bessel graphite operation, and subsequently to
the disappearance of their process from the technical world.
In 1911, James M. Hyde installed the first flotation operation in the United States at
Basin, Montana, for the Butte and Superior Copper Company (Rickard 1916). Within 2 months,
Minerals Separation filed suit in the U.S. District Court in Montana for infringement
against Patent No. 835,120. This sparked the beginning of litigation in the early days of
modern flotation. Litigation affected the widespread adoption of flotation processing,
which is reflected in a paper by Barker (1928), who wrote:
Although flotation was known to be a successful process prior to 1912, Utah Cop-
per Co.’s ores were not entirely treated by this process until 1923. Experiments had
been conducted, of course, prior to that time, and in February, 1917, the first unit
of the Arthur plant was changed over from gravity concentration to flotation….
The reasons for the delay in adopting flotation at these plants were, first, that it was
decided to await the outcome of the litigation with the Butte & Superior Mining
Co., which began with an injunction served on the plant on Oct. 3, 1911. This lit-
igation continued for years.
After conversion of Utah Copper Co.’s operations to total flotation processing, the cut-
off grade in mining was reduced and their reserves were enormously increased.
Data gathered by the U.S. Bureau of Mines shows the growth of flotation in the United
States, this growth being related to the development of selective flotation reagents and to
the increasing demand for mineral products (Varley 1928; Merrill and Pennington 1962;
Cooper 1980). Table 1 summarizes ore tonnages treated by flotation in the United States for
some representative years. The increase in ore tonnage processed by flotation in 1923 as
compared with that processed in 1919 resulted from the introduction of chemical flotation
reagents. Similarly, the marked increase in concentration ratio resulted from the advent of
selective flotation brought about by the introduction of these new chemical reagents, as will
be discussed later. In the early years, essentially only sulfide ores were treated by flotation,
but subsequently, processing other kinds of ores resulted from the development of new
reagents and reagent schemes. The huge increase in flotation processing in the United States
by 1960 resulted not only from increased copper ore production but also from extension to
other commodities, particularly phosphate and potash ores, as shown in Table 2. By 1980
there was a very significant increase in copper ore (due to lower grade) as well as in phos-
phate and iron ore flotation.

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 5

TABLE 1 Magnitude of the flotation industry in the United States for selected years
Year Ore Treated, Mt Concentrates Produced, Mt Concentration Ratio
1919 24.08 2.82 8.6
1923 34.29 1.93 17.7
1926 46.16 3.04 15.2
1960 179.86 19.50 10.8
1980 404.34 71.93 5.6

TABLE 2 Types of ore treated by flotation and concentrates produced in the United States
(in million metric tons)
1926 1960 1980
Type of Ore Treated Concentrates Treated Concentrates Treated Concentrates
Copper 39.89 2.17 133.38 4.82 211.61 4.67
Lead-zinc 5.57 0.84 7.43 0.49 11.39 0.84
Gold-silver 0.48 0.03 0.12 0.003 0.10 0.005
Iron 1.39 0.54 37.88 21.48
Phosphate 19.03 6.37 108.70 26.63
Potash 10.87 2.83 12.93 2.99
Coal 3.73 2.54 11.70 6.86
Feldspar-mica 1.67 1.06 11.58 8.51
glass sand
Misc. industrial 0.23 0.02 2.23 0.83 0.58 0.37
minerals

In 1928, A.T. Tye wrote a landmark paper in which he described in detail not only how
selective flotation success was achieved in treating the problem ore at Cananea (Mexico) but
also the benefits to the Cananea Smelter of lowering the pyritic iron contamination in the
flotation concentrates. In 1923, with a combined gravity and bulk flotation flowsheet using
coal tar and pine oil as reagents, the grade of the concentrate was only 4.4% Cu, but by 1925
with selective flotation using xanthate, pine oil, and lime under very controlled conditions
necessitated by the soluble salts in the water, the flotation concentrates averaged 17.7% Cu.
Copper recovery by flotation increased from 87.4% to 91.2%, but overall recovery in the
smelter increased from 91% to 97% because of lower copper losses in the reduced amount of
slag. Further economic benefits resulted because much of the smelter could be shut down as
a result of the reduced tonnage of smelter feed. It is of interest that in discussion of this 1928
paper, G. Oldright suggested the promise of treating copper concentrates hydrometallurgically
instead of smelting them.
Mining geologist P. Billingsly (1928) expressed how flotation greatly expanded the role
of the exploration geologist:
The mining geologist searches for materials which the metallurgist can utilize, and
only such; and whenever an advance in metallurgy opens the gates for new materi-
als, the geologist’s problem is correspondingly modified…. The metallurgist has
been the geologist’s best friend, and the geologist in turn has been able to help con-
vert the metallurgist’s ideas into the concrete form of an increased ore supply.
Many authors of papers in Rickard’s edited classic 1916 monograph, The Flotation Pro-
cess, asked questions about and speculated on the underlying phenomena involved in the flo-
tation process. The overall objective of this chapter, therefore, is to show how many of those

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6 HISTORICAL ASPECTS OF FLOTATION

questions have been answered through research carried out during the last nine decades of
the flotation century. This chapter will primarily discuss the behavior of some typical
reagents and the surface chemistry involved in producing hydrophobic surfaces on minerals,
leaving factors that affect flotation kinetics to other presentations.

F L O TAT I O N R E A G E N T D E V E L O P M E N T
The success of any flotation separation depends on the range of chemical reagents added to
the system to control the surface behavior of minerals in the ore. Early flotation reagents for
sulfide mineral flotation were an almost unlimited range of various oils: coal tar derivatives,
crude petroleum, wood tars, and pine oils. Oleic acid could not be used where the gangue
minerals were calcareous. The coal tar derivatives contained sulfur compounds that proba-
bly possessed a certain amount of affinity for the sulfide minerals. Metallurgists were strug-
gling to make separations between lead and zinc, copper minerals and pyrite, and oxide
minerals. Flotation entered a new era in 1921 when Perkins patented the slightly-soluble
thiocarbanilid as the first nonoily chemical collector for sulfide mineral flotation. James
Bean’s (1971) recollections illustrate the significance of this to a mill operator:
Thiocarbanilid 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 triumph was demonstrated practically to me while I was flotation opera-
tor at the Arthur mill of Utah Copper Company which at the time (1922) was
using Utah Copper’s own particular concoction of Barrett Oils and sulfur stewed
up together. Late on a sleepy afternoon an operator unduly increased the “oil”
being fed, hoping to lower 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 3 or 4 inches. Years later I could still mark the area as I passed by on the highway.
Flotation reagents fall into six broad types: frothers, collectors, modifiers, activators,
depressants, and flocculants (natural and synthetic polymers). The frother is added to con-
trol bubble size and froth stability. Collectors are surface-active organic reagents that impart
hydrophobicity to minerals when they adsorb at mineral surfaces. The function of all other
reagents is to attain optimal conditions for selective separation of the minerals in an ore.
Activators are chemicals that enhance collector adsorption onto a specific mineral, whereas
depressants are reagents that prevent collector adsorption or prevent bubble attachment to
unwanted mineral surfaces. Modifiers constitute a broad range of inorganic and organic
compounds that modulate the flotation environment. Flocculants are added for assisting
dewatering of the flotation concentrates and are used in the selective flocculation/flotation
processing of nonmagnetic taconites. The great step forward that revolutionized the indus-
try came with the 1925 patent of Keller for water-soluble xanthates as sulfide mineral collec-
tors, followed by the patent of Whitworth (1926) for dithiophosphates. Table 3 provides a
brief glimpse of the amount and kinds of reagents used in the United States in two different
eras: 1925–1926 and 1980 (Varley 1928, Cooper 1980). In 1925, various oils were still used
as the collector with a large consumption of sulfuric acid to attempt selective flotation. In
1926, the change to xanthate collectors took hold, the use of oily collectors dropped sharply,

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 7

TABLE 3 Reagents used for flotation in the United States (in metric tons)
Reagent Amount
1925 1926 1980
Ore Treated 41,259,000 41,616,000 440,361,000
Frothers 2,195 2,935 12,489
Collectors
Oils 8,818 2,665 115,218
Chemicals 1,875 1,896 108,883
Modifiers
Acids 18,157 2,061 35,169
Alkalis 1,695 75,701 413,055
Other NA* NA 28,735
Activators 3,210 4,962 3,925
Depressants 754 1,104 33,389
Flocculants NA NA 18,069
*NA = Not available.

and that of alkalies dramatically increased in order to achieve the high pH necessary for
selective sulfide flotation. In 1925–1926, sulfidizing agents to treat oxidized lead and copper
ores accounted for about three-fourths of the activator consumption. By 1980, the total ton-
nage of ore treated was nearly ten times that in 1926. The application of flotation to process-
ing nonmetallic ores resulted in higher reagent consumption because of amines, soaps, and
sulfonates being used as collectors along with various depressants. Oil consumption was
again high because of its use in phosphate and coal flotation.
Along with the quest for suitable organic chemicals having the ability to collect the
desired mineral in the froth, early flotation operators also tried to find agents to aid or
inhibit mineral floatability. Their discoveries, associated with the use of inorganic com-
pounds in flotation, made possible the remarkable success achieved at present in the separa-
tion of sulfide minerals from each other, and in the concentration of oxides, silicates, and
salt-type minerals. A chronological account outlining some of these findings is presented in
Table 4, which also lists the flotation function of each chemical reagent. As this brief histor-
ical survey shows, most of the reagents used or known today were introduced during the first
half-century of flotation.
Reagent development had a great deal to do with improvement in the effectiveness of
flotation. The invention of Dow Chemical Company’s Z-200, a dialkyldithionocarbamate
by G.H. Harris and B.C. Fischback (1954), is undoubtedly the most significant sulfide flota-
tion reagent development since the invention of xanthate as a flotation collector by Keller
and dithiophosphates by Whitworth shortly thereafter. The impact of Z-200 on sulfide ore
flotation, and particularly copper ore flotation, can be illustrated with data for 1979 as an
example (Harris, personal communication). In 1979, according to Harris, 4,500,000 kg of
this reagent (and its reproduction by other producers) were sold worldwide. At a reagent
consumption of 0.01–0.02 kg/t, there is an increase in copper flotation recovery of +2 per-
centage points. With the treatment of 300 Mt of copper sulfide ores worldwide at a grade of
0.7% Cu, this means that the invention of Z-200 gave the world an additional 40 million kg
of copper in 1979 alone.

© 2007 by the Society for Mining, Metallurgy, and Exploration.
All rights reserved. Electronic edition published 2009.

which would be driven out to nucleate bubbles. In 1916. 2007 7:36 PM 8 HISTORICAL ASPECTS OF FLOTATION TABLE 4 Milestones in the development of flotation reagents Year Chemical Reagent Function 1901 Sulfuric acid Gas-bubble generator Salt cake (NaHSO4) Gas-bubble generator Oils Collectors for sulfide minerals 1905 Sodium sulfide Activator for oxidized heavy-metal minerals 1909 Ketones. and Rickard (1916) postulated how progress in flotation would be made: “…we know that the key to the flotation process is to be found not in the oil. and Exploration. through the years bubbles have never received the attention from flotation researchers speculated on by Rickard. Electronic edition published 2009. thereby giving rise to selective flotation. Metallurgy. Recent theories have shown that gases are of extreme importance in many instances.” As important a component as they are in the process. Fe oxide 1985 Alkoxycarbonyl adducts Collectors/modifiers for sulfides and nonsulfides B R I E F C H R O N O L O G Y O F F L O TAT I O N R E S E A R C H Many early efforts at understanding flotation were directed toward explaining differential flotation in terms of the relative occlusion of gases. . the acid. the chemical effects of dissolved gases—has received scant atten- tion.book Page 8 Tuesday. bubbles were considered to be at the heart of flotation science. bubbles usually play an inert role in flotation and merely provide a means for levitating the desired mineral particles into a froth layer. The man who understands the physics of a soap bubble has mastered the chief mystery of flotation. aldehydes Soluble frothers 1910 Alkalis Sphalerite depressants 1912 Sodium dichromate Galena depressant 1913 Sulfur dioxide Sphalerite depressant Copper sulfate Sphalerite activator 1921 Thiocarbanilid Slightly soluble chemical collector 1922 Cyanide Sphalerite and pyrite depressant 1923 Alkali sulfides Sphalerite and pyrite depressants 1924 Soluble sulfites Sphalerite depressant Soaps Collectors for nonsulfide minerals 1925 Alkali xanthates Soluble collectors for heavy-metal minerals 1926 Dithiophosphates Collectors 1928 Sodium silicate Depressant Sodium carbonate pH regulator 1931 Starch Depressant 1934 Alkyl sulfates Nonmetallic mineral collectors 1935 Amines Cationic collectors 1952 Polypropylene glycols Water-soluble frothers (polyethers) 1954 Thionocarbamates Sulfide mineral collectors (copper) 1965 Hydroxamates Chelating agent for collector of Cu. All rights reserved. January 2. © 2007 by the Society for Mining. Although industrial operators and reagent manufacturers devoted effort toward finding cheaper chemicals that might act as frothing agents and might alter froth characteristics. However. but in the bubbles. in 1934 Gaudin commented: Developments in flotation have been so rapid that one of the essential factors at play—namely.flotation0. or the apparatus. It is not unlikely that control of flotation can be exercised through con- trol of the gases.

flotation0. Oleic acid was irreversibly adsorbed on calcite and galena but not on glass and mica. In 1928. In 1917. water. The © 2007 by the Society for Mining. Anderson suggested that adsorption might play a dominant role in flotation. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 9 In a 1915 paper. and solid. He wrote that powdered sulfide minerals abstracted 90% of the thiocarbanilid in a solution and captive-bubble experiments showed the sulfide to be hydrophobic. stated: “An electric charge on an adsorbed substance probably would considerably influence the amount adsorbed. Tag- gart and Beach fairly lucidly applied these concepts directly to flotation. Metallurgy. In 1917. However.… There can be no doubt that there is a close parallelism between the angle of hysteresis of the contact angle and the ability of a mineral to float. von Reinders showed that the solid will disperse in the aqueous phase if γso > γow + γsw. . All rights reserved. Several decades would elapse before thermodynamics would become a fairly widely used tool for the analysis of flotation phenomena.… The properties of these interfacial films have been found to be greatly modified by small amounts of dissolved substances. Taggart described the results of adsorption tests on sul- fide minerals that related the structure of the adsorbate to its ability to act as a flotation col- lector. The role of interfaces in flotation had been considered by Sulman by 1912 (see Rickard 1916) when he published the results of an investigation carried out at Minerals Separation to determine the magnitude of the contact angle that various minerals needed before they were wetted and would sink when brought into contact with a water surface. and that it is the result of a certain equilibrium of interfacial tensions of air.book Page 9 Tuesday. January 2. solid–water (sw). interestingly. and this postulate was actively debated for some years before eventually being discarded (Ralston 1916).… To go into this a little farther. and solid–oil (so) interfaces. Analogous relations give conditions under which the solid will dis- perse in the oil phase or concentrate at the oil–water interface. today it is known that potential differences between bubbles and particles enter into the kinetics of bubble-particle attachment. He suggested further research with other kinds of reagents on clean mineral surfaces. von Reinders deduced how fine solid particles would be distributed between oil and water phases. Electronic edition published 2009. we ought to consider the properties of the surface layers of the sub- stances involved. using γ to represent the interfacial tensions at the oil–water (ow).” In 1920. Ralston suggested that flotation might result from the electrical attrac- tion between negatively charged air bubbles and positively charged mineral particles. and Exploration. Langmuir showed that oleic acid created large contact angles on cleaved calcite and galena but only small angles on clean glass and cleaved mica. and there always is a definite equilibrium between the two. About these phenomena. Based on Maxwell’s capillarity equations. The importance of the study of interfacial films becomes obvious. The three interfacial tensions are interrelated with contact angles by the Young equation. Ralston suggested that von Reinders’ relations might explain how interfacial tensions control flotation. For example. will suggest immediately the explanation of a contact angle. Anderson discussed the Gibbs adsorption equation in relation to frother adsorption at the air-water interface and.… One important property of this film is that it will often take up dissolved substances in different proportion from the amounts in which they are taken up in the bulk solution. The first direct application of thermodynamics to systems similar to flotation was that of von Reinders (1913). Ralston wrote in 1915 of adsorption changing contact angles and the proper- ties of interfacial films: A glance at Clerk Maxwell’s famous paper on capillarity upon which Reinders’ work is based.

January 2. These experiments led to Taggart’s formulation of the definition of the molecular structure needed for a soluble flotation collector. It would be some time before adsorption isotherms could reliably be determined quantitatively and several years until methods were developed for determin- ing specific surface area. Gaudin described their laboratory approach: It is a generally recognized scientific principle that to investigate a certain set of phenomena one variable must be allowed to vary at one time while other variables are kept strictly constant. In 1928. Electronic edition published 2009. the flotation recovery of 100 × 600 mesh galena was presented as a linear function of the fatty acid addition in pounds per ton. . NHC6H5 NHC6H5 NH2 S C O C S C NHC6H5 NHC6H5 NH2 Thiocarbanilid Carbanilid Thiourea What might be considered to be the first adsorption isotherm of a soluble flotation col- lector on a mineral are the results published by Taggart. All rights reserved. cleaned in standard fashion. that it must possess both a polar group that binds it to the surface and a nonpolar group that can orient away when adsorbed at a mineral–water interface. With these guiding principles. for spectrophotometrically measuring reagent concentrations in solution. 2007 7:36 PM 10 HISTORICAL ASPECTS OF FLOTATION adsorbed thiocarbanilid could be leached off with ethyl alcohol. With carbanilid. Gaudin. namely. Figure 1 illustrates the quality of flotation experiments conducted with carefully cleaned mineral samples and high-purity reagents (Gaudin et al. By recalculating the published results © 2007 by the Society for Mining. dedicated investigation initiated in 1926 at the University of Utah under Gaudin.book Page 10 Tuesday. to obtain consistent results in flotation research. Sulman. and the test should be run in a standard machine cleaned in standard fashion. All reagents should preferably be added in solution to eliminate the necessity for conditioning. pure minerals having a definite size should be used either by themselves or as artificial mixtures. Metallurgy. for a standard length of time after a standard preagita- tion period at a definite temperature. this early work by Gaudin and his colleagues was the beginning of the modern approach to research in flotation chemistry. and for quantitatively analyzing infrared absorption spectra. In Gaudin and colleagues’ original paper. 1928). and Knoll in 1930 for the abstraction of potassium ethyl xanthate (KEX) by ground galena as a function of reagent concentration in solution. The first systematic research that opened the way toward under- standing the chemistry of the flotation process was the extensive. Taylor. In the author’s opin- ion. These minerals should have an especially clean surface. the behavior of sulfide minerals received nearly all of the initial research attention. Distilled water should be used throughout. the founder of the scientific basis of flotation was A.M. Therefore. and Exploration. Although such early researchers as Fahrenwald. Gaudin was indeed the father of fundamental flotation research as it is known today. for radioactively marking adsorbates. and Taggart carried out a num- ber of experiments to elucidate flotation phenomena. using high-purity single minerals in a miniature flotation cell (50 g of pure 100 × 600 mesh cleaned samples) that had been developed at the Utah Engineering Experiment Station by Gates and Jacobsen (1925).flotation0. Because nearly all of the early flotation operations involved sulfide ores. there was no removal from solution. Similar experiments with thiourea (which has the same formula as thiocarbanilid but without the phenyl groups attached to the nitrogen) showed that sulfide minerals adsorb thiourea almost as much as thiocarbanilid but there is no collecting action.

In the last quarter of the flotation century. with the reagent addition in mol/t (mol wt of C11 lauric acid is 200) in terms of moles per metric ton and replotting those data in a semilogarithmic manner as shown in Figure 1. Because the carbon atom in the car- boxyl head group is not part of the alkyl chain. in that era were Taggart and Gaudin in the United States. hematite. Major headway in understanding the flotation chemistry of sulfide mineral flotation started shortly before 1930. Electronic edition published 2009. rutile. Gaudin never continued using mini-scale flotation cells in his research after he moved from the University of Utah to the Montana School of Mines.1 1. much attention was directed toward the flotation chemistry of the sparingly-soluble salt © 2007 by the Society for Mining. Flotation processing technology did not come into being as a result of an intensive fun- damental research effort. % 60 C6 40 C6 Caproic Acid C7 Enanthic Acid C8 Caprylic Acid 20 C9 Pelargonic Acid C10 Capric Acid C11 Undecanoic Acid C12 Lauric Acid 0 0. particularly quartz. Fundamental understanding of flotation resulted from careful experimentation with well-controlled systems. including thermodynamics. it was developed over the years through much empirical and intuitive work on complex ores. and silicates. All rights reserved. mol/t Adapted from Gaudin et al. and Exploration. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 11 Galena C12 C11 C10 C9 C8 C7 100 0.0 Fatty Acid Addition. January 2. the early research (1925– 1935) was mainly centered on interactions between mineral surfaces and sulfhydryl flota- tion reagents. . but. and electrochemistry.2 kg/t Terpineol 80 Flotation Recovery. later fol- lowed by a firm grounding in physicochemical principles.book Page 11 Tuesday. Metallurgy. About mid-century most of the research shifted to oxides.0 10. identification of species responsible for flotation (by Gaudin). and Wark in Australia. lauric acid (mol wt 200) is given as an 11-carbon reagent in Figure 1. chronologically. Interestingly.flotation0.01 0. Prior to about 1950. corundum. in a manner similar to the development of so much of the other technology used in the processing of raw materials. FIGURE 1 Flotation of 100 × 600 mesh galena with fatty acids of different alkyl chain lengths ranging from 7 to 12 carbon atoms. 1928. and the assessment of chemical conditions for floatability (by Wark ). The key issues were the mechanism of interac- tion between the reagent and the mineral surface (by Taggart and by Gaudin). sur- face and colloid chemistry. This systematic chain-length effect indeed substantiates the validity and care taken in their work. and that of non- metallic mineral flotation shortly before 1950. their results show the very systematic effect of the number of carbon atoms in the alkyl chain expected by the Traube rule. most of the fundamen- tal investigations were directed toward the flotation chemistry of sulfide mineral separations. The leading researchers. To achieve the desired separations from complex ores.

H.C. but they are not included here because they may not have yielded definitive results or may not have had the impact or widespread use of the seven techniques given in Table 5. particularly apatite. Mellgren). Examples of some of these techniques (and some of researchers who used them) include vacuum flotation (R. All rights reserved. Chander and D.J.F. Miller In situ J. Ottewill J. bubble-pickup (S. Woodcock and M. Taggart. Buchanan and D.R. 2007 7:36 PM 12 HISTORICAL ASPECTS OF FLOTATION TABLE 5 Selected experimental techniques that provided significant advances toward understanding flotation chemistry Major Experimental Techniques Researchers Single-mineral laboratory flotation mini-scale 50-gram scale J.A.S. These are summarized in Table 5. Trahar S. Wadsworth and A. Jones Impedance spectroscopy R.B. Laskowski S. dolomite. January 2.S. Iwasaki.M. several techniques have been widely used and have been responsible for the greatest progress. and C.S. Prakash). Iwasaki Captive-bubble contact angle determination A. Gaudin P. Williams and D. Poling J. Ewers D.C.B. Richardson minerals. film flotation (M. R. Cox R.W. Cox Rest potential J. Electronic edition published 2009. . together with the names of several of those who developed or applied these techniques to the study of chemical phenomena involved in flotation. There has been worldwide interest in surfactant adsorption behavior at solid–water interfaces in recent years. and Exploration. deBruyn.W. Yoon).K. T. Problems of energy supply gave rise to research on coal flotation and coal desulfurization.flotation0.D.M. Gaudin 5-gram scale M.E.H. Fuerstenau J.W. Cooke). Wark and A.W.M. Numerous other techniques have been devised and utilized through the years to study flotation phenomena.A.T.J. Although numerous experimental methods have been applied to investigating flotation phenomena. Choi and I.F.H. Fuerstenau H.W. major effort resumed in the last quarter of the flotation century to extensive investigation of sulfide mineral flotation phenomena. Parks P. and radiography (I. Fuerstenau Modified Hallimond tube flotation A.G. Jacobsen A. Ince I. Woods W.C.C. Cases Electrokinetics (zeta potentials) S. microcalorimetry (O.W. Sven-Nilsen. calcite.W.F.L. and G. Glembotsky. Peck Ex situ J. Wark and A.R. Gaudin A. Fuerstenau P.M.A. V.W. Gates and L. Schuhmann and B. I.D.W. Somasundaran and D. Nixon and S. resulting in many new tools having been © 2007 by the Society for Mining.N. Fuerstenau). Fuerstenau Adsorption density/isotherm A. Metallurgy. Miller Electrochemistry I. Taylor.C. Mielczarski J. Chander and D.W. Sun and A. Hallimond E. and bastnaesite. induction time measurement (I. Plaksin).B.book Page 12 Tuesday. Fuerstenau Infrared spectroscopy M.A. O’Connor D. With the advent of newer electrochemical techniques. Salamy Polarization: voltammetry J.S. Leja and G.

Miller). contact angle. such as flotation testing. or XPS (A. two-phase mineral–water inter- facial phenomena (adsorption density and zeta potential) correlate well with three-phase behavior (contact angle and flotation response). and so forth. later results for the same system at constant pH but with collector concentration as the variable are somewhat easier to explain and are therefore given in Figure 2. (The reasons for the sharp breaks in the curves that occur at hemimicelle concentration [HMC] will be dis- cussed in a later section. All of this. Here. In part. emission. flocculation. Electronic edition published 2009. contact angle measurement. determination of adsorption isotherms. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 13 used to probe the detailed nature of adsorbed surfactant and polymer films. Detailed analysis of the thermodynamic stability of minerals and reagents. Sec- ondary ion mass spectrometry. X-ray photoelectron spectroscopy. P. Almost all of the experimental investigations on flotation chemistry carried out during the first half-century involved the use of a single experimental technique. the use of zeta potential measurements in flotation surface chemistry spread rap- idly. . For example. When it became understood that any ion that strongly adsorbs at a mineral–water interface is reflected in its effect on the zeta potential. combined with application of the many new techniques for probing mineral–water interfaces at the molecular level.book Page 13 Tuesday.W. using a number of different experimental techniques to probe the behavior of the same system led to being able to make correlations among various types of interfacial phenomena in flotation systems. has recently been utilized to clearly show the nature of complexes adsorbed at mineral surfaces. particularly starting in the 1950s. Raman. Nagaraj). January 2. speciation of complexes in aqueous solution.Th. which presents the zeta potential. has been used to identify chemical species at mineral surfaces. However. to flotation systems. Somasundaran and his graduate students at Columbia University have extensively used such newer molecular-level-information-yielding techniques as absorption. and Somasundaran 1964).flotation0. adsorption density. T. Yoon. electron spin resonance. identification of surface species. this permitted direct correlation with the solution chemistry of the sys- tem. An example of such a correlation is given in Figure 2.W. and Exploration. two of the relatively simple techniques listed in Table 5 were widely adapted to the study of flotation chemistry effects.G. flotation.) Major advances.N. etc. excited state resonance. and disseminated world- wide by the generations of students that followed. Healy. J. Fuerstenau. All rights reserved. and scattering spectroscopic techniques (fluorescence. Starting in the 1950s. The modi- fied Hallimond tube permitted study of flotation response without changing the solution composition (because no material is removed as a mineral-laden froth from the device dur- ing an experiment). Buckley and R. led to much of the research in the second © 2007 by the Society for Mining. or SIMS (D.) along with adsorption.H. and this led to a more complete understanding of the surface chemical processes involved. and particularly so because of the simplicity of electrophoresis techniques. Metallurgy. this was strongly influenced by Professor J. and electrokinetic studies to gather information about the microscopic properties of the adsorbed surfactant and polymer films. The first such correlation was published in 1957 for the DAA–quartz system at constant collector concentration with pH as the vari- able. particularly electrical double-layer phenomena.R. and solubil- ity phenomena have also helped expand the understanding of different types of flotation systems. Overbeek’s year at the Massachusetts Institute of Technology (MIT) with the mineral engineering group of Gaudin. and flotation response of quartz with dodecylammonium acetate (DAA) as collector (D. were achieved through better under- standing and application of the fundamental principles of surface and colloid chemistry. Healy. Atomic force microscopy has been applied to the study of the nature of adsorbed surfactant films (R. Woods).D. magnetic resonance.

and plotted semilogarithmically.1 mol/t of mineral. a frother alone being required. nearly all of the © 2007 by the Society for Mining. but again with the xanthate additions being recalculated in terms of moles per metric ton. Metallurgy. and Somasundaran 1964. This can be ascertained by grinding pure galena par- ticles in water under anaerobic conditions.flotation0. 1928). In the sections that follow. Electronic edition published 2009. all of the early research was conducted on sulfide minerals. and pyrite. All rights reserved. and floating immediately. % Zeta Potential. and Exploration.… In practice galena particles are more or less oxidized during grinding and classification. Most of their work was conducted with xanthates and other sulfhydryl reagents as the collector. merely about 0.W. showing an extremely high affinity for the surface that is not strongly dependent on chain length if the collector has three or four carbon atoms. and zeta potentials with the flotation of quartz at pH 6–7 as a function of DAA concentration half of the flotation century being devoted to elucidating the detailed principles of mineral– reagent interactions in flotation. rather than pounds per ton. mV 3 0. Their initial research was concerned with the behavior of galena. Figure 1 illustrates the quality of their results.95 20 –80 0 10–6 10–5 10–4 10–3 DAA Concentration. (1928) for the flotation of galena with xanthates of different chain length. Fuerstenau. The amount of xanthate required for complete flotation with xanthates of two or three methyl- ene groups is extremely low. . S U L F I D E M I N E R A L F L O TAT I O N C H E M I S T R Y Because flotation was first applied to the recovery of sulfide minerals from ores.book Page 14 Tuesday. FIGURE 2 Correlation of adsorption density. unoxidized galena floats readily without the addition of a collecting agent. particularly galena. some of the major advances in understanding the flotation chemistry of various mineral systems will be briefly reviewed. chalcopyrite. and Fig- ure 3 presents the results of Gaudin et al.” For fatty acids as collector. Although no specific numbers are available.90 40 –40 1 0. Gaudin (1932) stated that “…pure. mol/t Adapted from D. μmol/m 2 Flotation Recovery.85 60 Cosine θ 0 2 0. chalcocite. requiring varying amounts of collecting agents. 2007 7:36 PM 14 HISTORICAL ASPECTS OF FLOTATION 5 Quartz Hemimicelle Concentration pH 6–7 +80 4 0. Healy. contact angles. The first systematic investigations on sulfide mineral flotation were the pure mineral flotation experiments of Gaudin and his associates at the University of Utah (Gaudin et al. January 2.80 Contact Angle 80 Adsorption Density Zeta Potential Flotation +40 Adsorption Density. sphalerite.

The results tend toward the maximum contact angle of 60°. there probably was considerable residual carboxylate left in solution. Taking one set of measurements as an illustration of their findings.0 10. and 27. Clearly. Their data given as milligrams of collector per liter have been converted to moles per liter (mol wt = 160) and are plotted in Figure 4. xanthate uptake by galena was exactly balanced by an exchange with oxidation product ions at the surface.flotation0. Assuming that most of the added xanthate was adsorbed.2 mg carbonate ions—or a total stoichiomet- ric equivalent of 57.1 mg. However. Their results for the flotation recovery of galena as a function of the percentage of monolayer coverage of ethyl xanthate are also plotted in Figure 4. and the stoichiometric equivalent of reduced sulfur-oxygen ions emitted was 13. This plot shows that about 400 μmol/kg of galena is required to achieve 90% recovery. the amount of xanthate ion abstracted was 58. These experiments show the strong affinity of a sulfhydryl collector for the surface © 2007 by the Society for Mining. Taylor and Knoll conducted a careful set of experiments to quantitatively determine the exchange process involved in the uptake of ethyl xanthate by galena.0 mg/L.1 mg sulfate ions emitted. . 1928. Wark and Cox presented some data on the contact angle of an air bubble on galena as a function of the concentration of KEX in solution.1 1.5 kg/t Sodium Carbonate 0 0. FIGURE 3 Flotation of 100 × 600 mesh galena with alkyl xanthates of different alkyl chain lengths with reagent additions expressed in mol/t (mol wt of KEX is 160) added xanthate would have been abstracted from solution.book Page 15 Tuesday. in 1957 Gaudin estimated that roughly monolayer adsorption was achieved at this ethyl xanthate addition.3 mg. using an iodometric titration technique to determine the xanthate concentration in solution. All rights reserved. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 15 100 80 Flotation Recovery. In the case of fatty acid flotation.05 kg/t Terpineol 0. Metallurgy. were recalculated in terms of micromoles per kilogram of 100 × 600 mesh galena and are also plotted in Figure 4.0 Potassium Alkyl Xanthate Addition. the oxidation products must enter into the adsorption process. Given that the surface of galena readily oxidizes. Bogdanov et al. January 2. the original con- centration of xanthate in solution was 200. together with their effect on flotation response. The 1928 results from Gaudin et al. mol/t Adapted from Gaudin et al. Electronic edition published 2009. % 60 40 Methyl Ethyl Propyl Butyl 20 0. In 1934. and Exploration. 16. In 1934. (1957) published a paper that presented a summary of extensive work conducted in Russia on the adsorption of dif- ferent reagents on various minerals using a number of radioactively marked adsorbates.8 mg. after increasing sharply to about 50° at concentrations below 20 or so micromoles per liter. in that same year.01 0. with all concen- trations being expressed as equivalent to 25 mg KEX per liter of solution.

Gaudin first published the results of his measurements of the flotation of a © 2007 by the Society for Mining. FIGURE 5 Effect of pH on the flotation of 100 × 600 mesh chalcocite and pyrite with KAX as collector of sulfide minerals and also show that experiments conducted with pure systems under con- trolled conditions can exhibit agreement among different measures of mineral-collector interaction. and Exploration. the flotation of galena as a function of the adsorption density of ethyl xanthate expressed in terms of monolayer fraction (data from Bogdanov et al. % 40 60 40 20 Flotation 20 Contact Angle Adsoprtion 0 0 0 20 40 60 80 100 Collector Addition. Electronic edition published 2009. . % monolayer FIGURE 4 Contact angle on galena as a function of the concentration of KEX expressed in mol/L (data from Wark and Cox 1934). 1957). In 1929.1] Adsorption Density. All rights reserved.015 kg/t KAX 0. January 2. [ μmol/kg galena][0.10 kg/t Terpineol 0 0 2 4 6 8 10 12 14 pH Adapted from Gaudin 1929.book Page 16 Tuesday. 1928) 100 80 Flotation Recovery. 2007 7:36 PM 16 HISTORICAL ASPECTS OF FLOTATION Contact Angle: μmol/L Solution 100 60 80 Contact Angle. Regulation of pH has been the most important method for regulating flotation chemis- try.flotation0. % 60 40 Chalcocite Pyrite 20 0. and the flotation of galena as a function ethyl xanthate addition expressed in terms of μmol/kg (data from Gaudin et al. Metallurgy. degrees Flotation Recovery.

in first refining the contact angle measurement technique of Taggart. If one considers that hydroxyl ions adsorb competitively with collector ions. essentially a year or more. Taylor. For nearly 25 years. Figure 6 presents one of their critical pH diagrams for three sulfide minerals—namely. Wark’s research group spent a prolonged effort. Electronic edition published 2009. and for collectors that do not form insoluble products © 2007 by the Society for Mining. there was spirited and ongoing debate about the mechanism of col- lection in sulfide mineral systems. the pH and collector concentration at which flotation does or does not take place. Methyl xanthate and disubstituted dithiocarbamate produced contact angles of 50°. Taggart.W. All rights reserved. galena. This was definitive work showing the depressant role of pH in the flotation of sulfide minerals. they found the contact angle of collectors having an ethyl group on the nonpolar chain to be 60° on all sulfides.10 kg/t terpineol as frother. I. by function of the reason of chemical reactions of well recognized types between the reagent and the particle affected. Figure 5 presents the flotation recovery of chalcocite and pyrite as a function of pH with 0. Diagrams such as these provide a means for predicting conditions under which flotation separations can be made. In the early 1930s at the University of Melbourne. In 1934. that the amount of collector adsorbed under conditions of incipient flo- tation is constant.” On the other hand. Gaudin on several occasions com- mented that not patenting the use of pH control for selective flotation was one of his oversights. “The mechanism by which xan- thates float other sulfides than galena may involve an adsorption of xanthate ions without further reaction. For example. either by action on the to-be-floated or on the not-to-be- floated particles affect their floatability. in flotation pulps. Gaudin was a strong proponent of adsorption as the means of collector uptake by minerals. In discussion of the 1934 Wark and Cox paper where KEX was used as the collector. mercaptan. Taggart was convinced that collectors coated mineral surfaces by chemical reaction. Wark and co-workers (Sutherland and Wark 1955) also measured contact angles of var- ious thiol collectors having a range of carbon atoms in their nonpolar groups. pyrite. and chalcopyrite—with sodium diethyldithio- phosphate as collector. January 2.015 kg/t of potassium amyl xanthate (KAX) and 0. Wark and Cox published the first of a remarkable set of papers in which they presented their classic diagrams showing the relationship between collector concentration and pH for con- ditions of incipient flotation. flotation should occur under conditions to the left of the curve. then each line in Figure 6 must be characterized by [X–]/[OH–] being constant. This included xanthate. The results clearly show that there is sharp decrease in the flo- tation of pyrite as the pH is increased above 6 and that chalcocite remains fully floatable under these conditions until the pH exceeds about 13. Gaudin (1957) interpreted the results in terms of ion exchange between adsorbed X– and OH– for surface sites. and Knoll wrote. dithiophosphate. Barsky (1934) pointed out for their experiments that [X–][H+] was constant along their critical pH curves and that the results could be interpreted as xanthic acid [HX] being constant along these curves. and for the behavior of a wide variety of modifiers and depres- sants with various collectors. and Exploration. These critical pH curves were a major contribution to early flotation theory and they show.book Page 17 Tuesday.flotation0. and also that the standard free energy of adsorption is constant. Wark (personal communica- tion) initiated an important program to understand the flotation chemistry of sulfide min- erals. “All dissolved reagents which. In 1927 he wrote. In each case. and others. . and Ince (1930) and sample preparation so that reliable and reproducible results could be obtained. Metallurgy. Taylor. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 17 variety of minerals as a function of pH. In 1930. disubstituted dithiocarbamate. for example.” Taggart’s shortcoming was his belief that the chemical theory of flotation was all-inclusive. even with regard to oils on naturally hydrophobic minerals.

“Assuming a complete or nearly complete monolayer of ‘ions’ on the mineral particles. Overall. Note that Cook’s neutral mole- cule theory is the same idea that Barsky (1934) had presented in his discussion of the critical pH curves of Wark and Cox in 1934. as will be subsequently discussed.” In 1950. galena.flotation0. Cook and Nixon were as forceful in promoting the concept that sulfide mineral flotation takes place by neutral molecule adsorption as Taggart had been in his promoting the idea of chemical reaction. counterion adsorption or exchange adsorption keeps the system electrically neutral. and chalcopyrite with sodium diethyl dithiophosphate as collector such as amines on minerals. In reality. Taggart’s chemical theory of collection is merely exchange adsorption (as was shown by Taylor and Knoll [1934]). an expert in explosives and an outstanding solution physical chemist. reaction © 2007 by the Society for Mining. Such results indicate that the chemisorption of the neutral molecule may indeed have a role in flotation in this mineral–collector system. Cook. mg/L 500 400 300 200 100 0 2 3 4 5 6 7 8 9 10 11 pH Adapted from Wark and Cox 1934. Raghavan and Fuerstenau (1975) demonstrated that the neutral hydroxamic acid molecule appears to be the active adsorbing species in the hematite–hydroxamate system. FIGURE 6 Critical pH curves for the flotation of pyrite. . Wark and Cox wrote. “Prominent theories could be recon- ciled by the electrochemical approach. Woods summarized sulfide flotation as fol- lows: “Electrochemical investigations of the interaction of the thiol collectors with sulfide minerals have demonstrated that each of the three anodic processes—chemisorption. Steininger showed that the upper pH limit for the flotation of sphalerite with a wide variety of thiol collectors was a function of their pKa values. but we are unable to decide if this is an identity. 2007 7:36 PM 18 HISTORICAL ASPECTS OF FLOTATION 700 Pyrite Galena Chalcopyrite 600 Collector Concentration. flotation ceases. did not think in terms of the electrical double layer because in all cases of ion adsorption. In 1957.book Page 18 Tuesday. “We find there is a strong connection between adsorption of xanthates and the solubility of the heavy-metal xanthates.” In 1984. and Exploration. They wrote. In 1967. All rights reserved. Nixon wrote. when a cationic amine collector hydrolyzes to the neutral molecule species with oxide minerals. January 2. Wark was another advocate of the adsorption theory of collector uptake. Electronic edition published 2009. In 1934. However. one would obtain a bulk concentrate with so much charge that it would explode with greater violence than an equal weight of nitroglycerine!” M.A. Metallurgy. There are many examples where the collector indeed appears to adsorb in its neutral molecule form.

All rights reserved. These measurements clearly indicate that the uptake of xanthate by oxidized galena is energetically equivalent to the chemical exchange reaction forming lead ethyl xanthate from lead sulfate. and the sec- ond spectrum (b) is for a lead sulfide film that has been oxidized in the atmosphere. Washing with ether (d) removed some of the surface lead xanthate. He conducted similar studies with lead carbonate. Then he reacted xanthate with galena that had lead sulfate on its surface and again measured the heat that evolved. shows the infrared spectrum of bulk lead ethyl xanthate.110 1. showing that indeed a chemical compound is formed at the surface. pyridine. that the enthalpy is –22 kcal/mol Pb2+ in each case.300 cm–1 1. In a seminal study. First. (b) freshly evaporated PbS film after atmospheric oxidation.book Page 19 Tuesday. Little. Infrared spectroscopy has become a widely used tool to study the nature of adsorbed films in flotation systems. . January 2.014 50 A 1.110– 0 986 50 1.000 900 800 700 Adapted from Leja. but it took a strong solvent.020 1. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 19 100 1. and Poling 1962–1963. (d) after prolonged washing in ether. Mellgren also observed that © 2007 by the Society for Mining.195 50 D 990 0 1. they obtained the spectrum (c) that is virtually identical to that of lead ethyl xanthate.115 50 987 E 0 1. Leja. solid on Nujol mull. Electronic edition published 2009. The top curve (a) in Figure 7.200 1. The energetics of the interaction of xanthate with galena was carefully determined by Mellgren (1966) using microcalorimetry techniques.” New instrumentation permitted identification of species at the surface and quantifica- tion of energies involved in surface reactions. Little.110 0 1. After exposing that film to xanthate in solution. and Poling (1962–1963) applied infrared spectroscopy to demonstrate the nature of collector species at mineral surfaces.112 Absorption. % 0 1. returning the spectrum (e) back to that of a lead sulfide (oxidized) surface. Metallurgy.flotation0. Mellgren reacted lead sulfate with xanthate. and Exploration. Figure 7 presents their classic infrared spectra showing the adsorption of ethyl xanthate onto an evaporated lead sulfide (PbS) film.210 B 1. FIGURE 7 Infrared spectra showing adsorption of ethyl xanthate onto an evaporated PbS film: (a) bulk lead ethyl xanthate.100 1. taken from their work.212 1.020 1.140 50 C 1. and the formation of a dithiolate—plays a role in cre- ating hydrophobic surfaces. Mellgren’s measurements of the heat of reaction for these two cases gave identical results. (c) PbS film treated in aqueous solution of ethyl xanthate. to completely remove the xanthate. and (e) after washing in pyridine to form a metal collector compound. namely.140 1.

As suggested by Woods and Richardson (1986). about two decades elapsed before electrochemical methods were again used in flotation research for investigating mechanisms of thiol collector–sulfide mineral interaction. Wark and Cox presented a direct correlation of the potential of a copper elec- trode and the prevention of xanthate adsorption on chalcopyrite. All rights reserved. They concluded that the adsorbing species at the metal–solution interface is dixanthogen. Thus. or ferric iron derived from it by oxidation. Kuhn. showed dixanthogen to be the surface species responsible for flotation in this system. changes xanthate to dixanthogen. Fuerstenau. Metallurgy.book Page 20 Tuesday. . They have been identified as chemisorbed collector. Chander and Fuerstenau (1975) first combined this technique with the measurement of contact angles. 2007 7:36 PM 20 HISTORICAL ASPECTS OF FLOTATION at high pH. Woods and Richardson (1986). Formation of a thiol compound with a metal component of the mineral: MS + 2X – = MX 2 + S + 2e – © 2007 by the Society for Mining.flotation0. January 2. and Exploration. Electronic edition published 2009. pub- lished independently by M. Salamy and Nixon (1953) found that the concentration of xanthate determines the rest potential of the mer- cury electrode. depression in this system may also occur by a chemical reac- tion mechanism. Definitive papers on xanthate flotation of pyrite. that is.” Their observation lay dormant for the next 35 years. the reactions for the anodic oxidation of the collector can be written as follows: A. The former researchers used infrared spectroscopy and oxidation potential (Eh) measurements. and metal–collector compounds. the oxi- dation product of the xanthate ion. Numerous electrochemical investigations have been made in sulfide mineral flotation systems. As early as 1931. Oxidation of a thiol ion to the disulfide: 2X – = X 2 + 2e – C. dithiolates. galena ceases to float because basic lead compounds form on the surface in pref- erence to lead xanthate. by the formation of a surface compound that is more insoluble than the surface collector salt. However. The cathodic step usually involves the reduction of oxygen: O 2 + 2H 2 O + 4e – = 4OH – (EQ 1) and is coupled with an anodic step involving oxidation of either the collector or the mineral. Woods (1984). the dixanthogen can be extracted from the mineral surface provided oxidation of the dixantho- gen is prevented. which corresponds to the xanthate–dixanthogen reversible potential. In 1934. and Chander (1985) pre- sented thorough reviews of the electrochemistry of sulfide mineral flotation. It is interesting to note that Gaudin and Wilkinson wrote in 1933 that “Pyrite. particularly conducting linear potential sweep voltammetry for various systems. and Elgillani (1968) and by Majima and Takida (1968). The products of the anodic reaction depend on the mineral and the collector used. Charge transfer chemisorption of a thiol ion (X–): X – = X ( ads ) + e – B. and the pretreatment of the mineral surface. Kamienski measured the rest potential of a galena in xanthate solu- tion.C. and the latter conducted polarization experiments in basic medium with a pyrite electrode.

21 X2 Pyrite +0. whereas Taggart’s chemical reaction theory would be represented by the anodic process given by Reaction C. TABLE 6 Rest potential and reaction product of sulfide minerals with KEX solutions Mineral Rest Potential.15 NPI Stibnite –0. The reversible group of sul- fide minerals includes galena and chalcocite. Allison et al. He observed that metal-xanthate salts form at the surface of reversible sulfides. Similar results were reported for the diethyl dithiocarbamate–sulfide systems. V Reaction Product* Sphalerite –0. The potentials for oxidation–reduction reac- tions can be predicted if metastability of elemental sulfur is considered.13 V. In the passivated group of sulfide minerals in which Chander included pyrite.flotation0. Table 6 pre- sents a summary of their identification of surface products in ethyl xanthate–sulfide mineral systems and a correlation of those results with the rest potential of the minerals. however. Gaudin’s and Wark’s adsorption models would be equivalent to Reaction A. with the exception of covellite.13 NPI Galena +0. The surfaces of passivated sulfides are normally covered with a layer of oxidation products.book Page 21 Tuesday. The potential of such surfaces cannot be predicted thermody- namically but are so-called mixed potentials. Knowledge of the Eh of the system is therefore vital in sulfide mineral flotation. and bornite. NPI = not positively identified. © 2007 by the Society for Mining. chalcopyrite. 1972. strong oxidizing conditions would be detrimental to flotation.14 X2 Chalcopyrite +0. Metallurgy.625 mM KEX = 0. in this case) will react with thiols. In a classic paper.22 X2 Arsenopyrite +0. and Exploration. which can be a two-step reaction involving oxidation of the mineral and metathesis. forming metal tholates. the mineral will not float because surface oxi- dation may result in the formation of oxide-type materials that may not only impede elec- tron transfer from the collector to the mineral but are also extremely hydrophilic. If this compound forms at a rate that is too slow compared to the rate at which the sulfide mineral oxidizes. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 21 This mixed potential model does not actually contradict earlier theories of sulfide min- eral flotation. Electronic edition published 2009. January 2. It is possible to predict the oxidizing and reducing conditions necessary for a substance to be thermodynamically stable by constructing the appropriate Eh–pH diagram.06 MX Bornite +0. and this product is now accepted as the collecting species in these systems.16 X2 Molybdenite +0. A necessary condi- tion for sulfide mineral floatability is the thermodynamic stability of the hydrophobic entity formed at the surface. the reactions are irreversible. All rights reserved. . Chander (1985) grouped sulfide minerals into two types—reversible and passivated— based on their electrochemical behavior in aqueous solutions.06 MX NPI (MX) Chalcocite +0. Potential for X 2 + 2e – → 2X – at 0. Those sulfide minerals whose rest potentials are above this value oxidize the thiol to its disulfide. X2 = dixanthogen.22 Adapted from Allison et al. sulfide minerals that display a rest potential below the corresponding reversible potential for the oxidation of the collector to its disulfide (dixanthogen. These results clearly indicate that. Chander also pointed out that the collecting species for sulfides with sulfhydryl collectors such as xanthate can also be divided into two categories. If the species is decomposed by oxidation. *MX = metal xanthate. (1972) presented the results of a detailed study of the products resulting from the interaction of sulfide minerals with thiol collectors.

. A subsequent detailed study of the flotation of chalco- cite and pyrite using the electrochemical flotation cell.6 –0. The plots given in Figure 9 indicate that © 2007 by the Society for Mining.02 mM KEX (0. bornite. dixanthogen on pyrite because the potential at which flotation begins is that at which xanthate is oxidized to dixanthogen. In much of the early flotation literature. They found that surface hydrophobicity appears to be metal xanthates or surface analogs of metal xanthates formed by chemisorption on chalcocite and bornite.02 mM with the exception of 0. Identification of the products of the sulfide mineral–ethyl xanthate interaction was conducted by linear sweep voltammetry and ultraviolet (UV) spectroscopy. SCE) Adapted from Richardson and Walker 1985. V (vs. Richardson and Walker (1985) investigated the xanthate flotation of bornite. although this remains an area for further study. 2007 7:36 PM 22 HISTORICAL ASPECTS OF FLOTATION 100 0. At a certain reducing potential. Collection of chalcocite occurs by chemisorption.014 mM for Cu2S) pH 9. The flotation response of these sulfides.2 80 Flotation Recovery. or SCE) whereas dixanthogen is the oxidation product on passivated sulfides. Using an electrochemical microflotation cell that incorporated a packed bed of conducting sulfide particles as the working electrode to correlate interfacial electrochemical reactions with flotation response. chalcocite. and both metal xanthate and dixanthogen (at higher potentials) on chalcopyrite. FIGURE 8 Relationship between flotation recovery and conditioning potential for chalcocite.0 0. depending on the mineral.0144 mM for chalcocite (potentials given versus the standard calomel electrode.4 –0. chalcopyrite. Electronic edition published 2009. and pyrite with KEX as collector at a concentration of 0.book Page 22 Tuesday. there are discussions of how low the adsorption density of collector is for flotation. was carried out by Gebhardt and Richardson (1987).2 Potential.flotation0. % Cu2S Cu5FeS4 CuFeS2 FeS2 60 40 20 0 –0.2 0. Using in-situ electrodes in microflotation cells. flotation ceases. Gardner and Woods (1974) and Chander and Fuerstenau (1975) were the first to independently and simultaneously demon- strate that the electrochemical potential can control the flotation of sulfide minerals. Metallurgy. shown in Figure 8. January 2. together with determination of the amount of xanthate collector adsorbed. is strongly dependent on the conditioning potential and occurs only under moderately oxidizing conditions. Their results for the flotation of these two sulfides individually are plotted in Figure 9. Trahar (1984) used chemical means to control the pulp potential and observed similar behavior in the flotation of sulfide minerals. chalcopyrite. All rights reserved. and Exploration. and pyrite as a function of the electrochemical potential.

A C T I VAT I O N A N D D E P R E S S I O N O F S U L F I D E A N D OX I D I Z E D MINERALS With the exception of sphalerite and pyrrhotite (Sutherland and Wark 1955). Fifty percent recovery was achieved at an ethyl xanthate concentration in solution of 10 mM.8 –0.6 –0. whereas only 0.flotation0. pH 9.4 –0. The authors found that separation of mixtures of the two minerals by controlled potential could be achieved but under conditions different from that for the minerals alone.2 kg/t. SCE) Adapted from Gebhardt and Richardson 1987. and Exploration. Even methyl xanthate will float galena. . Most importantly. μmol/m 2 10 Flotation Recovery. reaching 100% recovery at a collector addition of 0. Chalcocite dissolution products had a deleterious effect on the chalcocite-pyrite separation by activating pyrite so that it floated below the potential at which xanthate is oxidized to dixanthogen. Flotation of pyrite does not begin until the potential for dixanthogen formation occurs. Although there is no flotation with ethyl xanthate at low concentrations. Flotation increased sharply once the necessary collector concentration was reached. Fuerstenau. Electronic edition published 2009. V (vs. sulfide miner- als respond well to flotation with short-chain xanthate collectors.C. Clifford. © 2007 by the Society for Mining. Gaudin (1930) showed that sphalerite exhibits some response with amyl xanthate and significant flotation with heptyl xanthate. Flotation response cor- relates exactly with the solubility products of the various zinc xanthate. but dissolution products from pyrite had no effect on the flotation of chalcocite. and Kuhn (1974) conducted a detailed study of the flotation of sphalerite with short-chain (C2 to C6) xanthates and found a regular relation between flotation and collector concentration in solution.2 0. All rights reserved. indicating zinc xanthate precipitation enters into the process.1 mM hexyl xanthate was necessary to achieve the same degree of flotation.2 Adsorption Density. % 60 8 Monolayer 40 6 4 20 2 0 0 –0.0 0. FIGURE 9 Flotation recovery and ethyl xanthate adsorption as a function of potential for single-component chalcocite and pyrite beds at pH 9.2 Potential. January 2. the adsorption density of xanthate is in the range of their calculated monolayer. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 23 100 Flotation Adsorption 14 Chalcocite Pyrite 12 80 –5 5 × 10 M KET. which would be the situation for any chemisorption process.05 mM when complete flotation of chalcocite occurs. and the dixanthogen coating that hydrophobizes pyrite could exceed monolayer cov- erage.book Page 23 Tuesday. M. Metallurgy. as can be seen from the plots given in Figure 3.2 in an electrochemical flotation cell at a collector concentration of 0.

sodium sulfide. Fuerstenau and Metzger (1960) investigated the adsorption of Pb(II) on sphalerite and clearly showed that the addition of zinc sulfate can prevent lead activation of sphalerite. the adsorbed copper hydroxy compounds subsequently transform to CuS and thereby activate the sphalerite. In flotation plants.book Page 24 Tuesday. has proved to be indispensable for effectively concentrating zinc sulfide ores by flotation. and their mechanism of action has been the basis for much discussion through the years (Sutherland and Wark 1955. and this early interest in deac- tivation reactions were taken up again by Mao (Gaudin. hydrolyzed cupric species form and are rapidly adsorbed. and Exploration. readily respond to flotation with thiol collectors. followed by a slow process. Salts of lead.W. with some experiments having been conducted on the reaction as far back as 1911 by Rogers. silver. Gaudin again became interested in this problem and with radioactive 64Cu showed that there indeed is a 1:1 Cu–Zn exchange. and Mao 1959). that the first two or three layers rapidly exchange. depression of the © 2007 by the Society for Mining. He correctly attributed this to slow diffusion as the copper sulfide coating thickens. Chander interpreted depressant mechanisms in terms of whether the mineral is a reversible or passivated sulfide (MS). Gaudin reported on the results of some exper- iments conducted to determine the rate of copper uptake by sphalerite and found copper uptake to be rapid initially. Wark and Wark (Sutherland and Wark 1955) examined the activation behavior of sphalerite with a wide range of metal salts. sphalerite readily responds to flotation with low additions of short-chain xanthates. In 1930. Gaudin commented that from a geological standpoint. driven by the extremely low solubility product of copper sulfide (CuS): ZnS ( s ) + Cu 2+ = CuS ( s ) + Zn 2+ (EQ 2) In his 1930 paper. Metallurgy. If copper sulfate is added under alkaline conditions. In 1930. As pointed out by Chander. the action of copper sulfate and similar salts on sphalerite had long been known. this means of enhancing the floatability of sphalerite has become the classic example of activation in flotation technology. Gaudin 1957). and that the reaction rate then continues by solid-state diffusion (Gaudin.flotation0. The coating on sphalerite was shown to be covellite. cadmium. All rights reserved. D. Mellgren and col- leagues (1973) measured the heat of adsorption of copper onto sphalerite under controlled deoxygenated conditions and found the heat of adsorption to be virtually identical to the heat of formation of CuS. and since then. Depressants include such inorganic reagents as hydroxyl ions. if the hydrophobic entity at the surface is X2. selective depression of different sul- fide minerals is desired. and mercury fall within this category. Gaudin also conducted some preliminary experi- ments on the deactivation of sphalerite with sodium cyanide. The general con- sensus on the activation of sphalerite by Cu(II) ions has been that the process involves an ion exchange mechanism in which cupric ions are exchanged for zinc ions according to the fol- lowing reaction. 2007 7:36 PM 24 HISTORICAL ASPECTS OF FLOTATION upon the addition of copper salts. Their results indicate that successful activators are salts of metals which. About 20 years later. In the flotation separation of complex sulfide ores. the oxidation of galena provides sufficient lead ions to activate sphalerite. sodium cyanide. . copper sulfate. Fuerstenau. and alkali sulfites. January 2. It is for this reason that the addi- tion of zinc sulfate became standard practice in lead-zinc flotation mills. alone or with their sulfides. This is schematically shown in Figure 10. Through contact-angle measurements and flotation experiments. Fuerstenau. who quantitatively investigated this phenomenon with 64Cu and several copper-complexing agents. the inorganic salt. In his 1985 paper. and Mao 1959). As discovered by Leslie Bradford in 1913 in Australia. Because CuS is far more stable than copper hydroxide. Electronic edition published 2009.

etc. layer MO. (b) Hydrophilic layer of mineral– (b) Hydrophilic MD layer depressant compound.0 –1. etc. Fleming (1952a) quantitatively studied the metathetical exchange of xanthate for carbonate with cerussite. Each of the sulfide mineral–collector–depressant systems can be interpreted in terms of the foregoing mechanisms. or if the depressant reacts chemically or electrochemically to form a hydrophilic coating.0 0. V 0. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 25 Reversible Sulfides Passive Sulfides 1.0022 mol/t is required.0 MS MS –1. FIGURE 10 Conditions for the flotation and depression of reversible and passivated sulfide minerals with thiol collectors passivated sulfide mineral would occur if the mineral oxidizes to form a hydrophilic oxide or hydroxide layer. Electronic edition published 2009. If MX is the hydrophobic entity. All rights reserved. He commented that because the new phase does not have much crystal-chemical resemblance to the old solid phase (cerussite). Metallurgy. the connection between the substratum and coating is fragile. MX2 X2 Depressant (a) Mineral oxidation product (a) Mineral oxidation product Species layer MO. To achieve 50% recovery of 100 × 600 mesh chalcocite with potas- sium heptyl xanthate (mol wt = 230). if MX decomposes by oxidation or by reduction.4 mol/t is required (Gaudin 1957). depression of a reversible sulfide mineral would occur if the mineral oxidizes to a hydrophilic coating. M(OH)n. Oxidized heavy-metal minerals such as anglesite (lead sulfate) and cerussite (lead car- bonate) require large quantities of sulfhydryl collectors before they respond to flotation.0 0 7 14 0 7 14 pH pH Flotation Metal/collector compounds Oxidation product of collector Species MX. To overcome the high collector consumption. namely 0. MX2 (c) Removal of surface X2 by oxidation. if MX decomposes by hydrolysis.062 mol/t for chalcocite and 11.0 1.0 X2 – X MX Eh. and Exploration. reduction. or if the depressant reacts chemically or electrochemically to form a hydrophilic metal-depressant (MD) coating. where a coating several hundreds of ions thick was formed.book Page 25 Tuesday. These huge differences show the disparity between collector adsorption on chalcocite and chemical exchange reaction on malachite. whereas for similar flotation of 100 × 600 mesh malachite. M(OH)n. a collector addition of 0. 4. The results of that same investigation permit comparison for KEX (mol wt = 160) at 20% recovery.2 mol/t for malachite. January 2.flotation0. © 2007 by the Society for Mining. Comparison of xanthate collector required for the flotation of chalcocite with that for mal- achite is quite striking. . MD (c) Removal of surface MX. V Eh. Gaudin (1957) discussed the results of a study of the uptake of amyl xanthate by cerussite conducted years earlier. or by reduction hydrolysis Adapted from Chander 1985. if the depressant decomposes X2 by reduction.

flotation0. Sulfidization is similar to copper activation of sphalerite in that. at which point the residual sulfide ions in solution again reach the concentration for depression of PbS flotation. the concentration of sulfide ions (as measured by an ion-specific electrode) in solution builds up sharply while the PbS layer on cerussite continues to thicken. Upon further addition of sodium sulfide. Thus.5 with 0. sulfidized coatings often do not adhere strongly (as noted previously by Gaudin for the collector coating). pH 9.book Page 26 Tuesday. FIGURE 11 Flotation recovery of cerussite at pH 9. Electronic edition published 2009. The effect of adding sodium sulfide to the system manifests itself in consecutive steps. A summary of their complex findings can be seen in Figure 11. M × 10 5 Residual Sulfide Number of Monolayers. who observed this to be a metathetical reaction with an equilibrium constant of about 3 × 1016. After all the dissolved lead has been precipi- tated.05 mM KAX 80 5 mM KNO3. 100 25 Cerussite 0. in industrial flotation practice. Herrera-Urbina.5 20 Flotation Monolayers Residual Sulfide. and Fuerstenau (1999) con- ducted detailed flotation and pulp potential measurements on the sulfidization reaction and flotation behavior of cerussite with KAX as collector. Sotillo. a process that converts the mineral surface to a sulfide. the residual aqueous sulfide in solution. Metallurgy. which can be accomplished by measurement of pulp potential. % 60 15 40 10 20 5 0 0 10–6 10–5 10–4 10–3 10–2 Sodium Sulfide Addition. mol/L Adapted from Herrera-Urbina. 2007 7:36 PM 26 HISTORICAL ASPECTS OF FLOTATION these oxidized minerals have long been sulfidized before adding the collector. In contrast to the Cu–ZnS (copper–zinc sulfide) system. At this point. causing a pronounced cessa- tion in flotation of the sulfidized cerussite. the addition of sodium sulfide must be closely controlled.05 mM KAX as collector. The first addition of sulfide ions precipitates the lead ions in solution as PbS particles that coagulate onto the cerussite. initially. the sulfide concentration in solution reaches that for depression of PbS flotation but is not yet high enough to initiate the metathetical exchange between carbonate and sulfide at the cerussite surface. The interaction of sodium sulfide with cerussite was investi- gated in detail by Fleming (1952b). January 2. Flotation Recovery. but at a reduced rate due to diffusion control. the sulfidization reaction begins to take place and flotation sharply increases. Sotillo. the uptake is rapid and the process then continues more slowly by diffusion as the sulfide layer increases in thickness. The surface reaction is rapid until the PbS coating reaches about 7 monolayers. and Fuerstenau 1999. All rights reserved. and Exploration. The most common activator for this purpose is sodium sulfide (Gaudin 1957). and the number of sulfide monolayers as a function of added sodium sulfide in 5 mM potassium nitrate open to the atmosphere © 2007 by the Society for Mining. .

By adding a frother (terpineol) to distilled water. particularly the effect of the oxygen in water (Plaksin 1959. In 1928. Klimpel and Hansen (1988) carried out considerable work on the effect of frother structure on the selectivity and recovery of miner- als and found that with increasing branching. Pine and eucalyptus oils repre- sent typical cyclic alcohols. and sulfur dioxide. All rights reserved. However. Klassen and Mokrousov 1963). air bubbles in industrial flotation pulps full of surface-active materials would be like bubbles in tap water and would not exhibit the rapid rise characteristic of bubbles in dis- tilled water. the main savings being reduction in sodium sulfide consumption. and fatty acids function not only as collectors but also as frothers. January 2. levitate them to the surface. oxygen. Metallurgy.book Page 27 Tuesday. He carried out extensive investigations with the common sulfide minerals plus graph- ite and sulfur using a range of gases that included air. Plaksin extensively studied the effect of nitrogen gases and dissolved gases on the flotation of various minerals.flotation0.W. Adams published the results of a detailed study conducted to ascertain whether the gas constituting the bubbles had any effect on the relative floatabilities of min- erals. This requires organic compounds (frothers) that create a surface tension gradient at the air–water interface. alkoxy-substituted paraffin-type frothers (such as triethoxy butane) contain no hydroxyl groups but gain their polarity from ether linkages. Electronic edition published 2009. the rise velocity of aged bubbles was found to slow down to that expected if they had been solid due to the surface tension gradient at the surface set up by the adsorbed frother molecules. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 27 G A S E S I N F L O TAT I O N Many people involved in flotation considered gas bubbles to be the crux of flotation (Rick- ard 1916). nitrogen. the maximum particle size that can be recov- ered decreases while at the same time selectivity increases. Previous investigations had shown that bubbles in distilled water. Typical frothers are alcohols (ROH). with the active molecule being terpineol. This retardation was similar to that observed earlier for air bubbles in tap water. KCl. Flotation in closed cells with nitrogen as the flotation gas is used industrially in the final sep- aration stage of copper-molybdenum concentrates. in a study of the effect of chemical reagents on the motion of air bubbles in water. rise faster than solids of the same specific gravity due to circulation within the bubble. including air. Long-chained sur- factants such as amines. hydrogen. is to attach to hydrophobic min- eral particles. For example. In the 1950s. nitrogen. in their extensive contact-angle inves- tigation. The primary role of gas bubbles in flotation. before they begin to distort from spherical shape. hydrogen. and Exploration. . sulfonates. and carbon dioxide. oxygen. He concluded from his experiments that the floatability of minerals depends on the nature of the gas being used. Wark and Cox (1934) were somewhat surprised to find virtually the identical con- tact angle of 60° with ethyl xanthate collector for a range of gases. Interest in frothers has increased because of overall economic factors. In more recent decades. © 2007 by the Society for Mining. For the flotation of an auriferous pyrite that oxidizes so readily that it rapidly loses its floatability. or KEX did not have any appreciable effect on the rise velocity of bubbles. 1999). solutions containing about 20 mg/L of potassium hydroxide (KOH). It was not until 1958. a nitrogen flotation system was installed at the Lone Tree mine in Nevada (Simmons et al. carbon dioxide. that D. However. either straight-chain with 6 to 9 carbon atoms or branched-chain compounds with 6 to 16 carbons. In distilled water in the absence of terpineol. Another class of frothers includes the hydroxylated polyglycol ethers (King 1982). and maintain a froth layer that lasts long enough for effective recovery of the desired mineral particles. More research is needed in this area. of course. Fuerstenau and Wayman published the first results which clearly showed that the adsorption of organic surface-active agents (frothers) retarded the velocity of bubbles.

This is the electrical double layer. and the potential at the Stern plane is ψδ. This includes such factors as the magnitude of the surface charge.flotation0. σo δ ψo Shear Region ψδ ζ 1/κ Potential Solid δ Distance NOTE: Shown are the surface potential. The electrokinetic or zeta potential. the potential drops exponentially to zero. specific adsorption of col- lectors. the adsorbed ions may lie closer to the surface at a plane called the inner Stern plane. an excess (+ or –) charge apparently fixed at the solid surface is exactly balanced by a diffuse region of ions of equal but opposite charge (termed counterions). and Stumm (1992). is called the Stern plane. and ion exchange phenomena (D. thickness of the electrical double layer. King (1982). the surface charge on an oil droplet or an air bubble may result from the adsorption of long-chained surfactant ions at the oil–water or air–water interface. and the potential decrease to zero-out into the bulk solution. 2007 7:36 PM 28 HISTORICAL ASPECTS OF FLOTATION O X I D E A N D S I L I C AT E M I N E R A L S A N D T H E E L E C T R I C A L D O U B L E L AY E R The immersion of a mineral into an aqueous solution produces a region of electrical inho- mogeneity at the solid–solution interface. Several different parameters that quantify the electrical double layer are useful in interpret- ing flotation behavior. The total double-layer potential. For example. particularly with oxides and sili- cates. This figure also shows the drop in potential across the double layer. is ψo. In the case of layer-silicate minerals (such as clays and micas). the surfaces of these crystal faces carry a constant negative charge that is independent of Stern Layer Surface Counterions. is the potential just outside the Stern plane where the diffuse layer is able to slip relative to the solid surface. with their closest distance of approach being the Stern plane © 2007 by the Society for Mining. Figure 12 is a simple model of the electrical double layer at a mineral–water interface. and Exploration. ζ. namely. . or surface potential.W. interfacial potentials. Electronic edition published 2009. The closest distance of approach of hydrated counterions to the surface. The surface charge in systems of importance to flotation may arise in a number of ways. Metallurgy. because of substitution of Al3+ for Si4+ in the silica tetrahedra and Mg2+ for Al3+ in the octahedral layer of the crystal lattice. Useful monographs that dis- cuss the electrical double layer are those of Hunter (1981). these discussions simply refer to adsorption in the Stern plane. σd Charge. All rights reserved. δ. However. the zeta potential at the slipping or shear plane. In the case of ions that directly interact with surface sites. The distance 1/κ is the center of gravity of the diffuse layer of counterions. From the Stern plane out into the bulk of the solution. particularly the selective adsorption of collectors. the point of zero charge (PZC) of the min- eral.book Page 28 Tuesday. January 2. the Stern layer potential. Fuerstenau and Healy 1972). either chemically or by some other strong spe- cific adsorption force. showing the charge on the solid surface and the counterions extending as a diffuse layer out into the aqueous phase. FIGURE 12 Simple schematic of the electrical double layer showing the surface charge on the solid and the counterions adsorbed in the diffuse layer. Electrical double-layer phenomena have a limited role in the collection of sulfide minerals but are very important in nonmetallic mineral flotation.

All rights reserved. If adsorption of counterions occurs only because of electrostatic interaction. In the case of salt-type minerals such as barite (barium sulfate). With regard to flotation behavior.059 [ pH PZC – pH ] volt (EQ 6) zF © 2007 by the Society for Mining. The surface potential is considered to be zero at the PZC.ln [ a ( H + ) ⁄ a ( H + ) PZC ] = 0. and C is the concentration of indifferent electrolyte in solu- tion. the surface charge arises from the preference of one of the lattice ions for the solid relative to the aqueous phase. Such counterions are called indifferent ions. then the diffuse layer charge. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 29 solution conditions. a. and ψδ are given for a symmetrical electrolyte with ions of valence z (where z = z+ = z–) by the Gouy– Chapman equation. and Exploration. For two of the layer-silicate minerals. T is the temperature. its value at any other pH is given by RT ψ o = -------. diffuse layer charge. R is the gas constant. and so forth. the surface of the mineral is uncharged and the solid is at its PZC. If the net adsorption density of PD ions is zero. January 2. fluorite (calcium fluoride). εo is the permittivity constant. σo. the single most important parameter that describes the electrical double layer of a mineral in water is its PZC. which is determined by a particu- lar value of the activity. The relationships among surface charge. the faces of these crystals are uncharged. Metallurgy. For oxide and silicate minerals.flotation0. Equilibrium is attained when the electro- chemical potential of these ions is constant throughout the system. as modified by Stern (Hunter 1981): σ d = – σ o = ( 8εε o RTC ) 1 ⁄ 2 sin h ( zFψ δ ⁄ 2RT ) (EQ 5) where ε is the dielectric constant of the liquid. If the adsorption of the positive PD ion exceeds that of the negative PD ion. is oppositely equal to the surface charge. hydrogen and hydroxyl ions have long been considered to be PD ions (although there remains a difference in opinion as to how pH controls the surface charge on oxides). the charge is exactly balanced within sheets that constitute the layer structure. . Electronic edition published 2009. and vice versa if the adsorption of the negative PD ion exceeds that of the positive PD ion. then the surface charge (σo) is simply given by σ o = zF ( Γ H + – Γ OH – ) (EQ 4) where F is the Faraday constant and the adsorption density (the quantity in the brack- ets) of the PD ions is in moles per square centimeters. and in the case of oxides (if the Nernst equation is assumed to be valid). This can be measured by titration of a suspension of the mineral in water and is generally a complex function of the ionic strength and the activity of PD ions (pH for oxides) in solution. argentite (silver sulfide). σd.book Page 29 Tuesday. talc and pyrophyllite. and the minerals are naturally hydrophobic. the surface of the mineral is positively charged. of the PD cation of valence z. Those particular ions that are free to pass between both phases and therefore establish the electrical double layer are called potential-determining (PD) ions. iodyrite (silver iodide). and adsorption/dissociation of surface hydroxyls is generally assumed to be the mechanism of developing a surface charge: M – OH + H + → M – OH 2+ (EQ 3) M – OH + OH – → M – O – + H 2 O If H+ and OH– are the potential-determining ions (PD+Z and express PD–Z are the PD ions of valence z in more general terms) for an oxide mineral.

W. which generally is considered to be just outside the Stern plane. zircon (ZrSiO4). particularly with concen- trated suspensions.8. The potential at the slipping or shear plane is the zeta potential.1. lead to specific adsorption. Typical values of the PZC for some of the oxide minerals are as follows (D. are such ions. and so forth. rutile (TiO2). The PZCs of silicate minerals are affected by crystal chemistry and selective leaching of metal cations or silica from the surface. as can be seen in Figure 12. cassiterite (SnO2). the liquid phase is caused to move relative to the solid phase by the application of a mechanical force (streaming potential) or by an electric field (electrophoresis).flotation0. pH 5.6. January 2. From the appropriate theory. More recently. natural hematite (Fe2O3). Fuer- stenau and Healy 1972. hydrogen bonding. pH 2. The determination of zeta potentials has been a powerful tool in delineating flotation adsorption phenomena. talc [Mg6(Si8O20)(OH)4]. The natives are mystified and admire with great awe the black box which gives the results on the dials. not everyone believed in discussing electrokinetic phenomena in terms of zeta potentials. for example. pH 2. olivine [(Mg. almandine [Fe3Al2(SiO4)3]. pH 5. A useful method for the study of adsorption phenomena in solid–liquid systems is the measurement of electrokinetic potentials that result from the interrelation of mechanical fluid dynamic forces with interfacial potentials. Such phenomena as covalent bond formation.6. pH 4. zirco- nia (ZrO2). The success of interpreting adsorption phenomena in terms and zeta potentials and all of the examples given by Hunter (1981) proved LaMer to be wrong. commented: It is for these reasons that I feel strongly that no scientific purpose is served by con- verting mobilities into zeta potentials until the more complicated connecting equa- tions have been verified. although ζ < ψδ. zeta potential is a much better advertising catch word than is electrophoretic mobility. Actually. King 1982): quartz (SiO2). pH 4. one evaluates the potential at the slipping plane. beryl [Be3Al2(Si6O18)]. pH 4. and the sign of ψδ is reversed. King 1982): kyanite (Al2SiO5). pH 2.… This above shows that much of the recent ‘hullabaloo’ about zeta potentials is meaningless. Of course if you have something to sell.6. in what is termed the inner Stern plane. indifferent and specifically adsorbed ions may lie in different planes because of ionic size and hydration. All rights reserved. spodumene [LiAl(SiO3)2]. pH 4.1. pH 5.5. the distinguished surface and colloid chemist. synthetic hematite. pH 3. ζ. Early on. .6. corundum (Al2O3).F)4]. pH 7.Fe)2SiO4]. pH 8. Stern first © 2007 by the Society for Mining. Metallurgy. Fuerstenau and Raghavan 1980.8. pH 9. Chemisorbed ions may lie closer to the surface because they are dehydrated. pH 3. and Exploration. electro- acoustophoresis has also been used to evaluate zeta potentials. These discussions will not differentiate between an inner and outer Stern plane. hydrophobic bonding. Electronic edition published 2009. solvation effects. Typical values of the PZC of some silicate minerals are as follows (D. pH 12. pH 1. In making electrokinetic measurements.8. 2007 7:36 PM 30 HISTORICAL ASPECTS OF FLOTATION The importance of the PZC is that the sign and magnitude of the surface charge has a major effect on the adsorption of all other ions.W. and orthoclase [K(AlSi3O8)]. pH 1. When counterions adsorb in the Stern plane through forces in addition to simple elec- trostatics. and particularly those charged oppositely to the surface. Because of his concern with regard to the equations connecting electrophoretic mobilities to zeta potentials. such counterions are considered to be specifically adsorbed.8.4. Flotation collectors for oxide minerals. Victor LaMer (1967).8–6. and is often assumed to approximate the Stern plane potential. ψδ.7. muscovite [K2Al4(Al2Si6O20)(OH.book Page 30 Tuesday. and magnesia (MgO). rhodonite (MnSiO3). Because of their surface activity.8. the charge in the Stern plane can exceed the sur- face charge.

The o term ΔG hpb* represents the specific adsorption phenomena through surfactant chain inter- action with a hydrophobic solid. If ions are adsorbed at the Stern plane only because of electrostatic interactions. respectively.exp ( – ΔG ads (EQ 8) 1–Φ 55. For adsorption densities less than about 30% coverage.5 is the number of moles of water in a liter. (EQ 11) where the individual terms represent changes in the standard free energy due to chemical bonding. C o ⁄ RT ) -----------. and would be absent for a hydro- philic mineral. P H Y S I S O R P T I O N O F F L O TAT I O N C O L L E C T O R S As first clearly defined by Taggart. C is the concentration of adsorbate in moles per liter. and solvation effects. There are two parts to the usual ionic collector—the charged head group and the hydrocarbon chain—and both can give rise to specific adsorption effects in the Stern layer.book Page 31 Tuesday.flotation0. These can be comprised of various contributions: o ΔG spec o = ΔG chem + ΔG ho + ΔG hpb o o + ΔG solv o + ΔG hpb* + . then the standard free energy of adsorption is given by o ΔG ads o = ΔG elec = zFψ δ (EQ 9) When an ion exhibits surface activity. such as the case for a flotation collector. such as talc or graphite. Grahame (1947) derived a Boltzmann-type relation. Electronic edition published 2009. The former type of interaction is chemisorption. r is the effective radius of the adsorbed ion. hydrogen bonding.. expressed here in terms of adsorption-free energies and adsorption densities.. hydrophobic bonding. and 55. The polar head group may react chemically with metal sites at the mineral surface or it may adsorb merely because of the sign of its electrical charge. and C has to be the bulk concentration in moles per cubic centimeter. Depending on the mechanisms involved in the interaction of the collector with the mineral surface. January 2. the molecular structure of chemical flotation collectors requires that it has a polar group and a nonpolar hydrocarbon chain. and Exploration. such as quartz. rather than in terms of charge and potentials as performed by Grahame: o ⁄ RT ) Γ δ = 2rC exp ( – ΔG ads (EQ 7) where Γδ is the adsorption density in moles per square centimeters. This approach will be used in explaining the behavior of various types of collectors on nonmetallic minerals. then the standard free energy of adsorption has additional terms: o ΔG ads o = zFψ δ + ΔG spec (EQ 10) where ΔGspeco represents the specific interaction terms. now generally called the Stern–Grahame equation. Another form of the relation expressing adsorption in the Stern plane is given as fractional coverage: Φ . the contributions to the change in adsorption free energy can be essentially zero or have a finite value.. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 31 suggested specific adsorption of counterions in terms of a Langmuir-type adsorption equa- tion. ΔGadso is the standard free energy of adsorption. Metallurgy. All rights reserved. . as exemplified © 2007 by the Society for Mining.= ---------.5 In this equation.

there are abrupt changes in the amount of aminium ions adsorbed and the zeta potential becomes sharply positive.2 (Figure 13). Based on his findings of how the adsorption of dodecylammonium ions affected the zeta potential of quartz.flotation0. whereas the latter type of interaction is one of physical adsorption. the number of ions in the micelle and the concentration at which micelles form.W. the critical micelle concentration or CMC. The charged heads orient outward to the solution so that the chains are effectively removed from water. 2007 7:36 PM 32 HISTORICAL ASPECTS OF FLOTATION by xanthates on sulfide minerals and gold. This so-called S–F isotherm can be illustrated in terms of the results obtained for the adsorption of sodium dodecylsulfonate on alumina at pH 7. in 1953 D. its electrical charge. and Exploration. If the driving force for the adsorption of physisorbing surfactants were only electrostatic. which later was shown to be a four-step isotherm when surfactant concentrations were taken above that used in flotation. conditions under which the quartz surface itself is negatively charged.book Page 32 Tuesday. and continued by Wakamatsu and Fuerstenau (1968). Nφ > zFψδ . Electronic edition published 2009.6 kcal/mol) removed from water (where k is the Boltzmann constant. Thus. the adsorbed surfactant ions come sufficiently close together that they begin to associate into two- dimensional aggregates similar to micelle formation in bulk solution. organic molecules (such as alcohols) can co-adsorb with adsorbed organic ions. all the way up to the CMC. the free energy of adsorption is given by o ΔG ads o = zFψ δ + ΔG hpb = zFψ δ + Nφ (EQ 12) where N is the number of CH2 groups in the hydrocarbon chain. Careful delineation of surfactant adsorption phenomena under controlled ionic strength was first conducted by Somasundaran and Fuerstenau (1966). and φ is the free energy change on removal of one mole of CH2 groups from water. Gaudin and Fuerstenau termed these surface aggregates hemimicelles because the charged heads would be oriented toward the mineral surface (at least until the zeta potential is reversed). depends on the number of carbon atoms in the hydrocarbon chain of the surfactant. As the adsorption density increases in the Stern plane. When surfactant ions or molecules in solution become sufficiently concentrated. clearly indicating that good flotation depends on strong collector adsorption in the Stern plane. flotation with such collectors would be limited. Combining zeta potential measurements with adsorp- tion phenomena in the alumina–sodium dodecylsulfonate system clearly showed the exist- ence of a three-step isotherm. that is. This is because the hydrophobic bonding contribution to the adsorption free energy dominates. they aggregate through association of their hydrocarbon chains into clusters containing about 50 to 80 surfactant ions called micelles. which results in a free energy decrease of about 1 kT per CH2 group (or 1 RT or 0. Through these same chain asso- ciation effects. In this case. All rights reserved. Fuerstenau first proposed that similar phenomena can take place at the mineral–water interface. . When hemimicelles begin to form. In their 1955 paper. The plots © 2007 by the Society for Mining. At about 10–4 M DAA. The driving force is as a consequence of the desire for water molecules to hydrogen-bond with themselves. and T is the absolute tem- perature). Of particular importance is the alkyl chain of the collector given that it enters into the process because of hydrophobic bonding phenomena. Metallurgy. The plots given in Figure 2 illustrate the effect of hemimicelle formation on a number of interfacial properties of quartz in aqueous solutions of DAA at pH 6–7. It is also seen that the onset of rapid flotation occurs under conditions where hemimicelles begin to form. January 2. namely. R is the gas constant. such factors as the size of the head group. and whether the head group hydrolyzes are important.

2 and on pH for dodecylsulfonate are given in the upper portion of this figure. Metallurgy. the effect of sodium dodecylsulfonate on the collector adsorption density. at which point the electrical repulsion in the Stern layer begins to act against the hydrophobic bonding forces that are responsible for continued sulfonate adsorption. and equilibrium contact angle as a function of reagent concentration. showing three distinct adsorption regions given in Figure 13 show the three regions of adsorption.001 10–5 10–4 10–3 10–2 Sodium Dodecylsulfonate Concentration. and the zeta potential is therefore constant given that excess adsorption in the Stern plane is absent. Electronic edition published 2009. In Region I. . and Exploration.book Page 33 Tuesday. Adapted from D. C for pH 7. zeta potential. Fuerstenau and Wakamatsu 1973). At the PZR. Region II is characterized by a sharp change in the zeta potential and a sharp increase in the adsorption of sulfonate ions due to hemimicelle formation through the onset of the hydrophobic bonding contribu- tion to specific adsorption. the equilibrium contact angle (virtually identical to the liquid-receding contact angle) of an air bubble on alumina is also plotted as a function of the equilibrium sulfonate concentration in solution (after the results presented by D. the dependence of the PZR on alkylsulfonate chain length at pH 7. The boundary between regions II and III occurs precisely at the concentration where the zeta potential reverses (the PZR). in all cases the contact angle reached its maximum and remained such as the concentration of sulfonate was © 2007 by the Society for Mining. degrees 1.W.2 and 2 mM ionic strength.01 0 40 Alumina 2 mM Ionic Strength pH 7. μmol/m 2 50 –20 I Zeta Potential. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 33 9 8 10 7 Carbon Atoms 12 Number of 6 pH 5 14 PZR 4 pH for C12 No. the sulfonate ions adsorb individually by elec- trostatic interaction and ion exchange with chloride ions. mV 40 0. All rights reserved. Fuerstenau and Wakamatsu 1973.W. January 2.flotation0.0 60 Adsorption Density. M NOTE: Because the maximum contact angle is reached at the PZR.0 III Contact Angle 80 II Adsorption Density Zeta Potential 70 –40 Contact Angle. FIGURE 13 For alumina at pH 7. which can be interpreted in terms of the Stern–Grahame equations.1 30 0 20 10 20 0.2 16 3 2 18 10. In Figure 13.2 0.

All rights reserved. The role of double bonds of flotation collectors has been the subject of numerous inves- tigations and that will be presented when chemisorption phenomena is discussed later in this chapter. and Somasundaran 1964.2. (1928). Healy.flotation0. Electronic edition published 2009. Fuerstenau began to develop the concept that flotation collectors which physically adsorb must function as counterions in the electrical double layer. It is interesting to note that a 4-carbon amine requires about 1 molar residual concentration for complete flo- tation of quartz. E L E C T R O S TAT I C M O D E L O F F L O TAT I O N During the period from 1953 to 1956. % 80 60 40 20 0 10–7 10–6 10–5 10–4 10–3 10–2 10–1 100 Alkylammonium Acetate Concentration. some of the surfactant ions adsorb in reverse orientation. 2007 7:36 PM 34 HISTORICAL ASPECTS OF FLOTATION C18 C16 C14 C12 C10 C8 C6 C4 100 Quartz pH 6–7 RNH3 Acetate Flotation Recovery. Figure 14 presents the flota- tion of quartz with amine collectors ranging from 4 to 18 carbon atoms. This behavior was observed for sodium dode- cylsulfonate at different pH values and also for alkylsulfonates of different chain lengths at pH 7. . Because the formation of hemimicelles depends on the length of the hydrocarbon chain.2 and for dodecylsulfonate at different pH values. given in Figure 1. Fuerstenau. FIGURE 14 Flotation recovery of quartz as a function of the concentration of alkylammonium acetates of various chain lengths at pH 6 to 7 increased. collectors having a longer hydrocarbon chain (greater N) adsorb more strongly and function effectively as flotation reagents at more dilute concentrations. the flotation of quartz with alkylammonium salts should exhibit a regular depen- dence on chain length. and that oxide mineral flotation with physisorbed anionic collectors should be © 2007 by the Society for Mining. and Exploration. which shows the concentration where the maximum contact angle (the PZR) is reached for sulfonates of dif- ferent chain lengths at pH 7. D. with continued adsorption. Because of the Nφ term. These results are summarized in the upper portion of Figure 13. similar to the well-known Traube rule. M Adapted from D. The role of the hydrocarbon chain in galena flotation with carboxylic acids is apparent by the results of Gaudin et al.W. Metallurgy. January 2.W. One interpretation is that after the PZR. This shows that the amount of collector can be reduced by increasing the alkyl chain length or by reduc- ing the pH (alumina is positively charged below pH 9). which is in sharp contrast to such strongly chemisorbing sulfhydryl collec- tors as ethyl xanthate on sulfide minerals.book Page 34 Tuesday.

Modi as part of his doctoral thesis at MIT (Modi 1956). and sodium dodecylsulfonate. . Experiments to confirm these ideas were conducted by H. % 60 40 Corundum 4 × 10–5M. showing the dependence of flotation on the PZC and the collector. The upper part of Figure 15 presents the zeta potential of corundum (synthetic sap- phire). sodium dodecylsulfate (SDS). and DAC as a function of pH. which have been termed the electrostatic model of flotation. and Exploration. Adapted from Modi 1956. are briefly summarized here. M 100 10–5 10–4 10–3 Zeta Potential.book Page 35 Tuesday. Metallurgy. Figure 15 presents the results of the very first experiments carried out to test these concepts. sodium dodecylsulfonate. All rights reserved.flotation0. Flotation experiments were conducted at a solution concentration of 4 × 10–5 M with three different high-purity collectors: dodecylammonium chloride (DAC). He determined the PZC of corun- dum by electrokinetics and conducted Hallimond tube flotation experiments with a variety of physisorbed collectors as a function of concentration and pH. The lower curve represents the flotation response of corundum with 0. All the curves intersect and cross at zero zeta potential at about pH 9. determined by streaming potential measurements as a function of pH with various additions of sodium chloride as indifferent electrolyte.04 mM SDS. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 35 150 PZC NaCl. C12 20 RNH3Cl RSO4Na RSO3Na 0 0 2 4 6 8 10 12 14 pH NOTE: The upper curve gives the zeta potential of corundum as a function of pH for a range of sodium chloride concentrations showing the PZC. mV 50 10–2 10–1 0 –50 Corundum 100 80 Flotation Recovery. The lower part of Figure 15 clearly shows that corundum responds to © 2007 by the Society for Mining.J. Modi and Fuerstenau 1960. Electronic edition published 2009. which is the PZC of this material. January 2. These concepts. which were first pre- sented in Modi’s doctoral thesis in 1956 and then published by Modi and Fuerstenau in 1960. FIGURE 15 Dependence of the flotation of corundum on surface charge appreciable only at pH values below the PZC and with cationic collectors only at pH values above the PZC.

. The pKa of dodecylamine is 10.1 Goethite pH 6. and Exploration. and Choi 1960). Two factors are involved in the electrostatic model of flotation: adsorp- tion on a surface oppositely charged to the collector and a hydrocarbon chain sufficiently long to help anchor the physisorbed collector.4 100 80 Flotation Recovery. Iwasaki and several co-workers carried out similar detailed research on the flotation of a number of iron ore minerals with high-purity reagents (Iwasaki. Experiments with sodium dodecyl xanthate showed that this reagent also functions as a physisorbed collector for corundum in a manner similar to any other anionic long-chained surfactant. given in Figure 17.W.4. Cooke. The flotation response of oxide and silicate minerals to these types of collectors is characteristically similar to that presented in Figure 15. Fuerstenau and Herrera-Urbina 1989. and Choi (1960) showed that the flotation response of hematite with 12-carbon alkyl amines and sulfates is that predicted by the PZC.4. Under these conditions. Iwasaki. In an excellent investigation of the flotation of iron oxides with 12. and Columbo 1960. the DAC in solution will be 50% aminium ions and 50% amine molecules. flotation drops sharply and ceases at pH 12. there are insufficient aminium ions to bind the collector to the surface. flotation is maximal because of coad- sorption of aminium ions and amine molecules.6 Quartz pH 2. at pH 10. as can be seen from the plots given in Figure 16.7 10–4 M Ilmenite pH 5.and 18-carbon col- lectors. Their results. 2007 7:36 PM 36 HISTORICAL ASPECTS OF FLOTATION PZC SDS DAC Corundum pH 9. Electronic edition published 2009. Cooke. show that the 18-carbon surfactants continue to function as collectors at about © 2007 by the Society for Mining. Cooke. and to the cationic collector at higher pH values where corundum is negatively charged. This upper pH limit for flotation with primary amine collectors is virtually universal.book Page 36 Tuesday. Metallurgy. January 2. % 60 40 20 0 –3 –2 –1 0 1 2 3 4 pH–pHPZC Adapted from D. Under these conditions. After returning to the University of Minnesota upon completing his doctorate at MIT in 1957. Iwasaki. which is a composite drawing showing the flota- tion response of four different oxides whose PZCs range from pH 2 to pH 9 with DAC and SDS as collectors. All rights reserved. FIGURE 16 Effect of the PZC on the flotation of several different oxide minerals with physisorbing anionic (SDS) and cationic (DAC) collectors anionic collectors at pH values below the PZC where corundum is positively charged. As the pH is raised to about 12.flotation0.6.

flotation0.book Page 37 Tuesday, January 2, 2007 7:36 PM

DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 37

+4

+2

μm/sec/V/ cm
Mobility,
0

–2
Hematite
–4

100

RNH3
RSO4
80
10–4 M
Flotation Recovery, %

C12 C12
60

40 C18 C18

20

0
0 2 4 6 8 10 12 14
pH
Adapted from Iwasaki, Cooke, and Choi 1960.

FIGURE 17 Influence of hydrocarbon chain length on the flotation of hematite as a function of
pH with alkyl sulfate and aminium collectors having 12 (open symbols) and 18 (solid symbols)
carbon atoms. The upper portion of this figure gives the electrophoretic mobility of the
hematite showing that its PZC occurs at pH 6.7

3 pH units above or below the PZC, respectively. This means that hydrophobic bonding
phenomena must be sufficient to overcome the electrical repulsion. Because each CH2
group contributes about 1.1 kT to the energy of hydrophobic bond formation, the increased
contribution to the free energy of adsorption on lengthening the alkyl chain from 12 to 18
carbons is about 6.6 RT/mol. As an approximation, the potential at the surface increases
177 mV (7 RT) when the pH is changed by 3 units. The potential in the Stern plane would
be less, but that potential is equivalent to 7 RT. Unfortunately, similar systematic flotation
studies were never conducted with intermediate chain lengths in this system.

C H E M I S O R P T I O N O F C O L L E C TO R S O N OX I D E S A N D S I L I C AT E S
If counterions are adsorbed only through such forces as electrostatic attraction and hydro-
phobic bonding (association between the hydrocarbon chains), the process is termed physi-
cal adsorption or physisorption. If the surfactant forms covalent bonds with metal atoms in
the surface, then the process is called chemical adsorption or chemisorption. As already dis-
cussed, examples of physical adsorption in mineral–water systems include alkylammonium
ions on quartz and other oxide minerals, and alkyl sulfates and sulfonates on alumina. Con-
ditions can be such that lattice ions are displaced from their lattice positions by the adsor-
bate, giving rise to surface reaction (such as the uptake of xanthate by cerussite). Examples of

© 2007 by the Society for Mining, Metallurgy, and Exploration.
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flotation0.book Page 38 Tuesday, January 2, 2007 7:36 PM

38 HISTORICAL ASPECTS OF FLOTATION

chemisorption of collectors on oxide and nonmetallic minerals include the oleate–hematite,
hydroxamate–hematite, hydroxamate–MnO2, and oleate–fluorite systems. Infrared spectro-
scopic studies have helped confirm the existence of calcium oleate, ferric oleate, ferric
hydroxamate, and Mn-hydroxamate species on the surface, indicating chemisorption by
covalent bond linkages. Chemisorption is attractive for several reasons: (1) flotation selec-
tivity should be enhanced if the collector ions/molecules bind to surface sites on a single
mineral; (2) there is reduced reagent consumption because of lower residual solution con-
centrations; and (3) fine particles should respond to flotation if the mineral surface is not
highly charged and if the collector is not adsorbed on the air bubbles because of the collec-
tor having a shorter hydrocarbon chain or to residual collector concentrations in solution
being more dilute.
In nonmetallic mineral flotation, a commonly used collector is oleic acid, which has
received considerable attention through the years. The results of an excellent and interesting
investigation of oleic acid interaction with a variety of oxide and complex silicate minerals
was presented by Polkin and Najfonow in 1964. In addition to flotation tests, they deter-
mined the amount of collector adsorbed with 14C-marked oleate, delineated chemisorption
reactions with infrared spectroscopy, conducted leaching studies to remove surface metal
ions, ascertained the effect of reagents and leaching on the zeta potentials of the minerals,
and considered various regulating or modifying reagents to increase selectivity. Figure 18
presents their results for the effect of pH on the flotation recovery of nine different minerals
with 1 kg/t of oleic acid as collector. This figure shows that the flotation response of these
minerals to oleate collector is approximately the same (except for albite, a feldspar). Experi-
ments with radioactively marked oleate showed the formation of durable multilayers on the
eight minerals that readily float. They found that pretreatment of some of the minerals with
acids provided a means for achieving selective flotation because various polyvalent metal

100
Oleic Acid
90 1kg/t
5
80

70
6,7
Flotation Recovery, %

60
1
50
2
40
5
30
6,7

20
8
9
3
10
2 9
1 3 4
0
1 2 3 4 5 6 7 8 9 10 11 12 13
pH
Adapted from Polkin and Najfonow 1964.

FIGURE 18 Similarity in the influence of pH on the flotation of a wide variety of minerals with
1 kg/t oleic acid: (1) columbite, (2) zircon, (3) tantalite, (4) ilmenite, (5) rutile, (6) garnet, (7)
tourmaline, (8) albite, and (9) perovskite

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flotation0.book Page 39 Tuesday, January 2, 2007 7:36 PM

DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 39

ions were leached or removed from the surface of some of the minerals, which thereby
removed the means by which oleate attached to the mineral. The metal ions at the mineral
surface have a major role in chemisorption of oleate collectors, which will be discussed later
in this chapter.
The role of chemisorption in the flotation of hematite has received considerable atten-
tion through the years. Reagents, such as fatty acids and soaps, chemisorb on hematite, as is
readily seen by flotation and collector adsorption occurring several pH units above a min-
eral’s PZC. Also, the shift in the zeta potential as a function of pH in the presence of soaps
clearly shows strong adsorption until the pH is 2 or 3 units above the PZC. The first
detailed study of chemisorption in the oleate–hematite system was the infrared (IR) spec-
troscopic investigation by Peck, Raby, and Wadsworth (1966). They found the appearance
of a carbonyl band with maximum absorbance between 1,520 and 1,530 cm–1 that was the
result of the formation of a surface cation–collector anion compound, with the cation
bonded to the mineral structure and the anion to the cation. They also conducted flotation
experiments as a function of pH, using 25 g of –65 mesh specular hematite with 6.3 mg
(2.2 × 10–5 mol) of oleic acid as collector in 275 mL of water, giving a starting collector con-
centration of 8 × 10–5 M (the residual solution concentration is unknown). Their results are
plotted in Figure 19 as a function of pH, the peak in absorbance is 0.30. Both the maximum
in flotation and IR absorbance occur at pH 7.9. With a titration method, Peck and col-
leagues determined the PZC of their specular hematite sample to be pH 7.7. They proposed
that the reactions of hematite with oleic acid can be expressed by the following equation:

M-OH + HOl → M-OH···HOl
(EQ 13)
M-OH···HOl → M-Ol + H 2 O

where HOl is oleic acid, M-OH are uncharged surface hydroxyls, and M-Ol are mineral sur-
face sites with chemisorbed collector.

100
Flotation Hematite
Infrared Absorbance Oleate
Relative Acid-Soap Concentration
Relative Infrared Absorbance

80 Flotation
Flotation Recovery, %

Acid Soap

60

40

20

0
4 5 6 7 8 9 10 11
pH

FIGURE 19 Correlation of hematite flotation recovery and infrared absorbance of adsorbed
oleate as a function of pH (data from Peck, Raby, and Wadsworth 1966) and correlation of the
flotation of hematite with the concentration of oleate acid-soap concentration (data from
Kulkarni and Somasundaran 1980)

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flotation0.book Page 40 Tuesday, January 2, 2007 7:36 PM

40 HISTORICAL ASPECTS OF FLOTATION

Noting that there is almost a universal pH at which a wide range of minerals appear to
respond to flotation with oleic acid, Kulkarni and Somasundaran (1980) proposed that it is
the acid soap which is responsible for the strong adsorption of oleic acid or oleate soap in
slightly alkaline environments. They carried out detailed analysis of the composition of oleic
acid solutions and conducted a wide variety of adsorption and flotation experiments with
hematite. Titration experiments showed the PZC of their hematite sample to be pH 7.1.
Also in Figure 19, their results for the Hallimond tube flotation of hematite with 3 × 10–5 M
potassium oleate and 8 × 10–5 M potassium nitrate are plotted together with the calculated
concentration of the acid-soap dimer. The maximum in their plot corresponds to 4.8 × 10–8
M acid-soap dimer concentration.
From the results of a series of investigations on chemisorption in nonmetallic mineral
flotation, M.C. Fuerstenau and his colleagues (M.C. Fuerstenau and Palmer 1976) found
correlations between the flotation response and the pH at which metal ions at the surface of
the mineral hydrolyze. Figure 20 presents the results obtained by Palmer, Fuerstenau, and
Aplan (1975) for influence of pH on the flotation of chromite with sodium oleate as collec-
tor. Chromite ideally is FeO·Cr2O3, but isomorphous substitution of Mg(II) for Fe(II) and
Fe(III) for Cr(III) generally occurs in nature. The chromite used by Palmer and colleagues
assayed 41.7% Cr(III), 8.0% Al2O3, 3.7% Fe(III), 7.1% Fe(II), 8.% Mg(II), plus some minor
amounts of other elements. The two flotation peaks in the vicinity of pH 8 and pH 11
match the hydrolysis peaks of FeOH and MgOH, respectively. The peak at about pH 4 is
most likely due to physisorption of oleate anions on positively charged chromite, given that
the PZC occurs at about pH 7. Cr and Al probably do not participate in the surface hydrol-
ysis reactions since Cr and Al are coordinated octahedrally, whereas the divalent cations are
coordinated tetrahedrally with oxygen.
Reaction with chemically hydrolyzed cations at the surface must differ from the chemi-
sorption concept of Peck, Raby, and Wadsworth (1966) in that the hydrolyzed cation is
probably dislodged from its lattice site before reacting with the oleate ion. Hydrolysis of the
metal ion could free the metal ion from its lattice site and make it available for surface reac-
tion. The interaction of both chrysocolla and hematite with K octylhydroxamate leads to a

100
Chromite

80
Flotation Recovery, %

60

40

20 1 × 10–4 M
5 × 10–5 M
Oleate

0
0 2 4 6 8 10 12 14
pH

Adapted from Palmer, Fuerstenau, and Aplan 1975.

FIGURE 20 Flotation of chromite as a function of pH and oleate concentration

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flotation0.book Page 41 Tuesday, January 2, 2007 7:36 PM

DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 41

change in color of the mineral surface, indicating that the surface hydroxamate product is
quite thick and suggesting that a surface reaction takes place, building up multilayers of
product. If a reagent chemisorbs, it can only reach monolayer coverage because the chemi-
sorbing species interacts with a surface site. If the adsorbing species combines with a lattice
ion, the species dislodges the ion from the lattice; this process is termed adsorption with sur-
face reaction. A surface reaction can take place by reagents reacting with hydrolyzed species,
as shown in the following reactions.

Chemisorption

M 2+ + OH – → M 2+ OH –
M 2+ + X – → M 2+ X –

Adsorption with surface reaction

M 2+ + OH – → | ( MOH ) +
M 2+ + X – → | ( MX ) +

Surface reaction

| ( MOH ) + + OH – → |M ( OH ) 2
| ( MOH ) + + X – → | ( MX ) +
| ( MX ) + + X – → |MX 2

T H E N AT U R E O F T H E H Y D R O C A R B O N C H A I N I N FAT T Y A C I D
F L O TAT I O N
The role of double bonds of flotation collectors has been the subject of numerous investiga-
tions. Probably the most detailed investigation of the nature of the hydrocarbon (other than
chain length) in flotation has, perhaps, been that of Cooke, Iwasaki, and co-workers at the
University of Minnesota for fatty acid–iron ore flotation systems. In particular, they were
concerned with the degree of unsaturation in the chain of 18-carbon fatty acid collectors
and carried out extensive investigations with elaidic, oleic, linoleic, linolenic, and stearic acid
as collectors for iron oxide minerals (Iwasaki, Cooke, and Choi 1960). For hematite, the
degree of effectiveness at room temperature followed the order: elaidic > oleic > linoleic >
linolenic. At room temperature (25°C), contact angles on hematite with 3 × 10–5 M fatty
acid at pH 6 were found to be in degrees: stearic, 81; elaidic, 90; oleic, 86; linoleic, 80; and
linolenic, 75. Because stearic acid has limited solubility at room temperature, the researchers
also measured contact angles at 70°C, where stearic acid has appreciable solubility, and
obtained the following results: stearic, 103; elaidic, 91; oleic, 88; linoleic, 81; and linolenic,
80. The greater the degree of unsaturation in the alkyl chain, the greater the degree with
which water molecules interact with the chains and, hence, the less is their surface activity.
Therefore, in a chemisorbing system, the hydrocarbon chain also plays a significant role.
A very systematic study of the double bonds in the flotation of rutile was conducted by
Purcell and Sun (1963). This included determination of zeta potentials by means of stream-
ing potential measurements and flotation response with a Hallimond tube. Because of the

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flotation0.book Page 42 Tuesday, January 2, 2007 7:36 PM

42 HISTORICAL ASPECTS OF FLOTATION

thoroughness and rigor of their measurements, Figure 21 was prepared from their results for
0.1 mM reagent concentration to illustrate how double bonds in oleate, linoleate, and lino-
lenate affected flotation and the zeta potential of rutile. The PZC of their rutile sample was
pH 6.7. Chemisorption of the soaps causes the zeta potential to become much more nega-
tive than in sodium chloride solutions. As the pH is raised, linolenate joins the sodium chlo-
ride (NaCl) zeta potential curve at about pH 8, and the linoleate and oleate curves join the
NaCl curve at still higher pH values. It is at this point that the electrical repulsion of the
charged surface overcomes the adsorption tendency of the soap ions. Linolenate with three
double bonds can interact with water molecules more frequently and hence is repelled from
the surface at a lower pH. The lower portion of Figure 21 shows that the effect of pH on flo-
tation response of rutile with these three collectors correlates exactly. Interestingly, in highly

100

Rutile
NaCl, 0.1 mM
Sodium Oleate
50 Sodium Linoleate
Sodium Linolenate
Zeta Potential, mV

0

–50

–100

100

80
Flotation Recovery, %

60

40

Rutile
20 Sodium Oleate, 0.1 mM
Sodium Linoleate
Sodium Linolenate

0
0 2 4 6 8 10 12
pH

Adapted from Purcell and Sun 1963.

FIGURE 21 Flotation of rutile in 0.1-mM sodium oleate, linoleate, and linolenate as a function
of pH to show the influence of double bonds. The upper portion shows the zeta potential of
rutile in 0.1-mM solutions of these chemisorbing collectors and also NaCl, which shows that
the PZC of this rutile sample occurs at pH 6.7.

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 43

acidic solutions, the flotation response of rutile to the three collectors is identical, with flota-
tion sharply decreasing to zero at about pH 1. The three soaps form fatty acids that behave
the same.
At this point, brief mention is made of a planned attempt to utilize hydrocarbon chain
configuration to effect flotation separations. Schulman and Smith (1953) found that a
branched-chain fatty acid collector permitted separation of a cobalt mineral from a copper
mineral, but not with a straight chain collector. Specifically, after first investigating force/
area curves for monolayers with metal salts in the substrate, they found that both chalcopy-
rite and carrolite float together with caprylic acid (a carboxylic acid with a 7-carbon alkyl
chain), whereas with 2-ethyl hexanoic acid, only chalcopyrite floats.

R O L E O F E X P E R I M E N TA L M E T H O D O L O G Y I N F L O TAT I O N
FINDINGS
Figure 20 also shows that the collector concentration used in conducting an experiment can
mask results. For example, the dual peaks in the alkaline pH region for chromite flotation
are very apparent when the collector concentration is 5 × 10–5 M, but at 1 × 10–4 M, oleate
hydrophobicity is great enough to swamp the reduced floatability at pH 10.
Figure 22 illustrates how flotation time with the Hallimond tube can lead to different
insights into the flotation behavior of a mineral. In their experiments, Iwasaki, Cooke, and
Choi (1960) floated 100 × 150 mesh hematite with 10–4 M oleic acid for 5 minutes in a
Hallimond tube. As can be seen from the plot shown in Figure 22, this long period of flota-
tion yields 100% recovery between the lower and upper pH limits. M.C. Fuerstenau,
Harper, and Miller (1970) floated 65 × 100 mesh hematite for 45 seconds in a Hallimond
tube. They investigated conditioning time and found 10-minute conditioning yielded
somewhat enhanced recovery over that obtained after 3 minutes of conditioning. Their
results for 10-minute conditioning with 10–4 M potassium oleate are also shown in Figure 22.

100

80
Flotation Recovery, %

60

40

Hematite
Oleate
20 Iwasaki
M.C. Fuerstenau
Somasundaran

0
0 2 4 6 8 10 12 14
pH

FIGURE 22 Illustration of how time for Hallimond tube flotation can accentuate or mask
various aspects of the results, based on the flotation of hematite by various investigators
(5 minutes by Iwasaki, Cooke, and Choi [1960]; 45 seconds by M.C. Fuerstenau, Harper, and
Miller [1970]; and 10 seconds by Kulkarni and Somasundaran [1980])

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44 HISTORICAL ASPECTS OF FLOTATION

By using this shorter flotation time, the decrease in hematite flotation between pH 5 and
pH 6 is very pronounced, followed by an increase again as the pH is decreased to below 5.
This second flotation region is due to the physisorption of oleate ions on the positively
charged mineral. On the other hand, Figure 22 also includes the results of Kulkarni and
Somasundaran (1980), who floated hematite with 3 × 10–5 M potassium oleate as collector
in a modified Hallimond tube for a flotation time of 10 seconds. This reduced collector
concentration and very short flotation time yields only the optimum pH for flotation. Thus,
in conducting flotation chemistry research, close attention should be given to the effect of
the range of such variables as reagent concentration, conditioning, and flotation time in
order to be certain that various effects are not masked.

C O M PA R I S O N B E T W E E N P H Y S I C A L A N D C H E M I C A L
ADSORPTION PROCESSES
In cases involving the physical adsorption of flotation collectors, one observes that flotation
is strongly controlled by the PZC of the mineral. In other words, flotation takes place when
the collector is ionic and when the mineral and collector are oppositely charged. This means
that electrokinetic measurements can quite readily delineate conditions for flotation with
physisorbing collectors. On the other hand, with chemisorbing collectors, the active species
can be an ion (as already shown for oleate) or can be a neutral molecule, as will be shown for
hydroxamic acid (a chelating agent). Moreover, when an anionic collector chemisorbs, it can
adsorb on a negatively charged mineral surface until the surface potential is made sufficiently
negative to prevent adsorption (by increasing the pH above the PZC in the case of oxides).
A detailed investigation of the behavior of manganese dioxide provides a comparison of
the complicated nature of physical and chemical adsorption in flotation processing (D.W.
Fuerstenau and Pradip 1984). The PZC of this manganese dioxide (gamma MnO2) occurs
at pH 5.6. Figure 23 (top, middle, and bottom) shows the effect of pH on the Hallimond
tube flotation response of this oxide at three concentrations of three different collectors,
namely sodium dodecylsulfonate, potassium octyl hydroxamate, and sodium oleate, respec-
tively. The results shown in Figure 23 (top) indicate that the flotation of manganese dioxide
with the anionic sulfonate behaves as expected for a physisorbing collector. Flotation only
occurs when the pH is decreased below about pH 6, which happens in conditions where the
mineral carries a positive surface charge and hence adsorbs the anionic sulfonate ions as
counterions. Lower pH values (higher positive surface charge) are necessary for initiating
flotation at lower collector concentrations.
Figure 23 (middle) shows the effect of pH on flotation with a chelating agent (hydrox-
amate), which strongly coordinates with manganese ions at the mineral surface. Although
chelating agents have been investigated as flotation reagents for 60 years or more (Gutzeit
1946; Marabini, Cases, and Barbaro 1989; Somasundaran and Nagaraj 1984; D.W. Fuer-
stenau, Herrera-Urbina and McGlashan 2000), hydroxamates have received, by far, more
attention than any other single chelating agent. Coordination of the nitrogen-oxygen atoms
to manganese takes place as shown schematically:

O C R O C R
Mn OH + Mn + H2O
HO N H O N H

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 45

100

PZC MnO2
80 10–6 M SDS
10–5
Flotation Recovery, % 10–4

60

40

20

0
100

MnO2
80
1 × 10–5 M HXm
1 × 10–4
3 × 10–4
Flotation Recovery, %

60

40

20

0
100

MnO2
Sodium Oleate
80
5 × 10–5 M
1 × 10–4
5 × 10–4
Flotation Recovery, %

60

40

20

0
0 2 4 6 8 10 12 14
pH
Adapted from D.W. Fuerstenau and Pradip 1984.

FIGURE 23 Influence of pH and collector type on the flotation of manganese dioxide at the
various reagent additions (top: physisorbing SDS; middle: chemisorbing potassium octyl
hydroxamate; bottom: chemisorbing/physisorbing sodium oleate)

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46 HISTORICAL ASPECTS OF FLOTATION

In this chemisorbing system, flotation takes place at pH values where the surface of the
mineral is highly negatively charged. The maximum in floatability occurs at about pH 9,
similar to the case for hematite, which is approximately the pKa of hydroxamic acid. Thus,
optimum flotation appears to take place where the neutral molecules and hydroxamate
anions are about equal, indicating that both coadsorption and surface hydroxylation may be
responsible for the pronounced chemisorption at pH 9. As the pH is raised above 9, flota-
tion decreases because the surface is so highly negatively charged that the hydroxamate
anions are repelled.
The flotation response of manganese dioxide with oleate collector is particularly com-
plicated, similar to the behavior of hematite, with two flotation peaks being present in this
system. The peak in the alkaline region occurs under conditions where the solid surface is
highly negatively charged (PZC = pH 5.6); therefore, strong chemical adsorption forces
must be operative, typical of oleate–mineral systems previously discussed. Under these con-
ditions, the carboxyl ion may be chemically binding to Mn surface sites or the acid-soap
dimer could be extremely surface-active. In the vicinity of pH 5, there is little flotation of
manganese dioxide with oleate. However, as the pH is lowered even more, a second flotation
maximum occurs. This must now be the result of physical adsorption of oleate anions on a
positively charged surface. Since the pKa of oleate is about pH 4.7, the actual adsorbing spe-
cies must be oleate ions together with oleic acid molecules. At pH values less than about 3,
most of the oleate has been transformed to molecular oleic acid, which is not the reactive
species, and flotation ceases (similar to the case for amines at high pH). As can be seen from
the plots for oleate in Figure 23, the total concentration of oleate in the system must be suf-
ficiently high to provide enough oleate ions for adsorption at low pH values. Liquid oleic
acid droplets form at low pH values and higher oleate concentrations, but that will not be
taken into account in this chapter.
M.C. Fuerstenau, Harper, and Miller (1970) compared the flotation of finely ground
hematitic ore using octylhydroxamate as collector with using oleic acid as collector. In a
cited example, the ore was ground to 70% minus 15 μm, and an addition of 0.2 kg/t of
hydroxamate collector resulted in a final concentrate recovery of 86% at a grade of 64% Fe.
The ability of a chelating agent such as hydroxamate to successfully float fine particles has
much to do with the fact that the bubbles will not be highly charged.

A C T I VAT I O N I N N O N M E TA L L I C M I N E R A L F L O TAT I O N
Activation in nonmetallic mineral (oxides and silicates) flotation is the result of strong
adsorption in the Stern plane of multivalent species that can reverse the sign of the zeta
potential and cause the formation of a triple layer: the first layer will be the charge on the
surface of the mineral itself; the second layer is the oppositely charged Stern layer; and the
third layer is collector counterions charged similarly to the mineral surface. Thus, activation
of a negatively charged oxide for flotation with an anionic collector requires the strong
adsorption of inorganic cations as activator. Activation in these systems does not produce a
new surface, as in the case of copper activation of sphalerite or the sulfidization of oxidized
lead or copper minerals. Industrially, calcium or magnesium salts are used for the activation
of a mineral such as quartz for oleic acid flotation. Hydrolyzed multivalent metal ions are
strongly adsorbed, and this affinity for a mineral surface has long been recognized. The
papers of James and Healy (1972) provide a method for quantification of these adsorption
processes.

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 47

In 1928, Gaudin et al. were the first to find that pH most markedly affects the flotation
of quartz activated by ferric and cupric ions when oleate is used as a collector. For quartz
activated with ferric chloride, sodium oleate as the collector, and terpineol as the frother,
they found that marked flotation occurs in the pH range of about 5 to 7. In 1934, Kraeber
and Boppel (in Sutherland and Wark 1955) found that pure quartz was not floated by a sul-
fonated castor oil but that it responded well if treated by a number of different heavy-metal
salts over specific pH ranges for each activating metal salt. Hydrolysis of the activating cat-
ion undoubtedly is important in the process. In the case of Fe(III) activation, they found a
rather wide pH range for quartz flotation for their system, pH 2 to 9. In 1966, Mackenzie
conducted a detailed investigation of the effect of ferric chloride on the zeta potential of
quartz, and for an addition of 5.7 × 10–5 M ferric chloride, he observed a marked increase in
the zeta potential at about pH 3, reaching a maximum at about pH 5, and then reversing
sign at pH 7.3. Hergt et al. (in Sutherland and Wark 1955) used contact angles to delineate
the critical bubble contact region for Fe-activated quartz with sodium hexadecylsulfate as
collector, and they observed the lower pH required for contact to be about pH 3.3 and the
pH at which contact ceased to be about 7.5. Schuhmann and Prakash (1950) presented the
results of a comprehensive investigation of activation in the soap flotation of quartz, with
vacuum flotation being their main research tool. For ferric chloride as activator and oleic
acid as collector, they found that the flotation range was between pH 3 and pH 12. Perhaps
with the vacuum flotation test procedure used by Schuhmann and Prakash, the ferric
hydroxide precipitate itself was responding to flotation and carrying with it the quartz parti-
cles. Subsequently, M.C. Fuerstenau and associates (e.g., in M.C. Fuerstenau and Palmer
1976) conducted detailed systematic investigations of hydrolyzing phenomena involved in
activation phenomena. Figure 24 presents the results of M.C. Fuerstenau and Palmer (1976)
for the flotation of quartz, with a sulfonate of mol wt 450 as collector, as a function of pH
for various activating metal ions. For clarity, only the initial flotation edge is shown in this

pH of Hydroxo Complex Formation
FeOH2+ AlOH2+ PbOH+ MnOH+ MgOH+ CaOH+
100

80
Flotation Recovery, %

60
Fe3+ Al3+ Pb2+ Mn2+ Mg2+ Ca2+

40

20

0
0 2 4 6 8 10 12 14
pH

Adapted from M.C. Fuerstenau and Palmer 1976.

FIGURE 24 Minimum flotation edges for the flotation of quartz as a function of pH with 0.1 mM
sulfonate collector and 0.1 mM metal ion activators

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48 HISTORICAL ASPECTS OF FLOTATION

figure. As can be seen, there is a distinct correlation of flotation response with the pH of the
hydroxy complex formation. However, in their work, M.C. Fuerstenau and Palmer found
both the upper and lower flotation edge to be steep, in contrast to the work previously dis-
cussed. With their system, the pH range for 90% flotation recovery with 10–4 M sulfonate
collector and 10–4 M metal salt as activator was as follows: Fe(III), pH 2.9–3.8; Al, pH 3.8–
8.4; Pb, pH 6.5–12.0; Mn(II), pH 8.5–9.4; Mg, pH 10.9–11.7; Ca, pH 12.0 and greater.
Their experimental techniques clearly delineate the activation pH for optimum floatability.
In silicate mineral flotation, activation by anions has been important. Specifically, fluo-
ride has been widely used as an activator in the cationic flotation of feldspar from quartz,
and as a depressant in the anionic flotation of beryl and spodumene (Smith 1963). By mea-
suring contact angle on quartz and microcline as a function of pH in the presence and
absence of sodium fluoride with DAC as collector, Smith showed that there is a specific pH
range in which microcline (a feldspar) is activated and quartz is depressed, as can be seen
from the results given in Figure 25. In the absence of fluoride, quartz and feldspar behave
identically with the cationic collector. Although the contact angles on quartz are not
affected by the addition of fluoride, those on microcline change significantly. The activation

Quartz Microline
60
10–2 M NaF
No NaF

4 × 10–5 M DAC

50

40
Contact Angle, degrees

30

20

10

0
0 2 4 6 8 10
pH
Adapted from Smith 1963.

FIGURE 25 Contact angles on quartz and microcline (feldspar) in aqueous dodecylamine as a
function of pH in the presence and absence of NaF, showing the activation of feldspar at low pH

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 49

of microcline can only take place through strong specific adsorption of fluoride ions on the
aluminum sites at the feldspar surface, such that the surface carries a high enough negative
charge to attract the physisorbed cationic collector ions. The high insolubility of aluminum
fluoride suggests that fluoride ions may strongly chemisorb on the aluminum sites at the sur-
face. Shergold, Prosser, and Mellgren (1968) found that inorganic anions function as activa-
tors for the flotation of hematite at pH 1.5 with 0.2 mM dodecylamine. At concentrations
greater than 3.5 mM, bubble-pickup tests showed firm bubble–particle attachment with
sodium fluoride (NaF) and NaCl but no attachment with sodium nitrate (NaNO3), sodium
thiocyanate (NaCNS), or sodium acetate (NaCH3COO), and weak attachment with
sodium sulfate (Na2SO4). Batch 1-kg flotation tests with a hematite ore and with synthetic
hematite–quartz mixtures showed excellent flotation separation with hydrochloric acid
(HCl) and also with sulfuric acid (H2SO4) at pH 1.5, with or without a small addition of
ferric chloride (FeCl3). Hematite recovery was about 90% at almost 100% hematite grade.
Evidently, a highly negative surface must be produced by adsorption of the activating anions
or surface complexes for the cationic collector to adsorb.
In the case of oxide and silicate minerals, because collector ions function as counterions
in the double layer, their adsorption density will depend on competition with any other
counterions in solution. Thus, the presence of excessive amounts of dissolved salts can
inhibit flotation because inorganic ions similarly charged to the collector can then act as a
depressant. In the case of the flotation of goethite with quaternary amine salts at pH 11,
adding 0.03 M NaCl will reduce flotation to about nil (Iwasaki, Cooke, and Colombo
1960). Onoda and Fuerstenau (1965) carried out a detailed study of the depression of
quartz flotation with DAA as collector and showed that Ba2+ and Na+ both inhibit flota-
tion, the effect being considerably greater with the divalent salt, as can be seen from the plots
given in Figure 26. Ion exchange as related to flotation would be controlled by the phenomena
involved in the Stern–Grahame equation. In the absence of specific adsorption, the

80
Quartz
100 0.1 mM DAA
pH 6.5

80 60
Flotation Recovery, %

Zeta Potential, –mV

60
40

40

20
20 Flotation ζ-Potential
NaCl
BaCl2

0 0
10–7 10–6 10–5 10–4 10–3 10–2 10–1 100
Added Salt Concentration, M

Adapted from Onoda and Fuerstenau 1965.

FIGURE 26 Effect of adding barium chloride and sodium chloride on the flotation and zeta
potential of quartz in 0.1-mM DAA solutions at pH 6.5, showing the depression of flotation by
ionic competition

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50 HISTORICAL ASPECTS OF FLOTATION

exchange is controlled directly by the ratio of their concentrations in the bulk solution. In
the case of one ion being multivalent, the valence effect given in that relation is relevant.
Most importantly, if one or both of the ions exhibit specific adsorption, then the magnitude
of the specific adsorption free energy must be taken into account. The concentration of
DAA is 0.1 mM, which is just below that at which hemimicelles begin to form. However,
barium ions can reverse the zeta potential at 0.03 M, indicating specific adsorption and
meaning that both specific adsorption and valency enter into these depression phenomena.
Onoda and Fuerstenau presented a tabulation of the experimental and calculated concentra-
tions of sodium and barium ions that would lead to depression. As an example, to reduce the
recovery to 70%, the concentration of barium chloride needed was 0.15 mM, whereas the
concentration was 6 mM for sodium chloride. The calculated concentration ratio of Na+/Ba2+
was 62 and the experimental ratio 40, which is reasonably close for such simplified calculations.

N AT U R A L F L O TA B I L I T Y
Most minerals are hydrophilic and require collectors for flotation. Because sulfide minerals
readily oxidize when exposed to air, they are hydrophilic under the usual conditions encoun-
tered in processing. In the case of oxide and silicate minerals, all but two are hydrophilic. As
for the sparingly-soluble salt minerals, all are hydrophilic because of broken ionic bonds that
form their surface. However, the silver halides exhibit some natural hydrophobicity.
The Bessel brothers in 1877 were the first to utilize natural floatability in their process
for upgrading graphite ores. It was A.M. Gaudin who, in his texts of 1932 and 1957, postu-
lated that the natural floatability or nonpolar character of certain minerals was the result of
not breaking primary bonds upon forming their surfaces. This condition would be met with
crystals held together by dispersion forces (van der Waals bonds). Examples would be
molecular crystals such as sulfur, which consists of S8 rings held in a crystal by dispersion or
van der Waals forces, as well as paraffin. Most of the nonpolar minerals are sheet crystals in
which their crystal chemistry results in individual layers that are electrically neutral, with
dispersion forces acting between the sheets to hold them together. The faces of such crystals
are nonpolar, but the edges would be polar given that primary ionic or covalent bonds are
broken in forming edge surfaces. Examples of such minerals are graphite and two of the layer
silicates, talc and pyrophyllite, which on their cleavage plane present uncharged siloxane
rings. Two sulfide minerals exhibit natural hydrophobicity, namely stibnite and molybden-
ite, also a layer mineral. As pointed out by Gaudin, boric acid (H3BO3) has a layer structure
in which all potential hydrogen-bonding OH are internally satisfied and not available for
hydrogen bonding with water molecules. It is the strong tendency of water molecules to
hydrogen-bond with each other that provides the energy for water to be displaced from
nonpolar surfaces by an air bubble or oil droplet.
Again, Taggart was at odds with Gaudin over the concept of natural floatability. In
1934, Taggart, del Guidice, and Ziehl wrote, “It may seem odd, at this date, to resurrect so
old a friend as the inherent floatability of minerals, and would be so had not a recent writer
unearthed the ancient fossil for us and dressed it up in modern appearing clothes.… Conse-
quently, we dissent vigorously and finally from any idea of inherent natural floatability.” The
fact that natural hydrophobicity occurs when the cohesive energy of water is greater than
the dispersion forces interacting between water and a solid was not known at that time. Tag-
gart went to great lengths to prove that natural floatability did not exist. It is interesting that
Fowkes and Harkins in 1940 (Harkins being an extremely meticulous surface chemist)

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 51

published their measurements of contact angles using a carefully designed tilting plate appa-
ratus rather than the captive-bubble technique. They reported contact angles for water on
the following hydrophobic solids: Ceylon graphite, 85.7°; talc, 87.8°; stibnite, 84.2°; and
paraffin, 108° to 111°. They obtained the same value of the contact angle whether the liquid
was advancing or receding before the measurement was made, and commented that, “The
‘advancing’ and ‘receding’ angles obtained by nearly all investigators other than those in this
laboratory are due to improper preparation of the surface and poor techniques in making
measurements.” The contact angles with paraffin oil were found to be zero and these solids
considered to be oleophilic by Fowkes and Harkins. The addition of such compounds as
butyl alcohol, butyl amine, butyric acid, propionic acid, and acetic acid lowered the contact
angles on paraffin and graphite.
Laskowski (1986) has reviewed fundamental aspects of the relation between natural
hydrophobicity and floatability. Using an analysis involving concepts of the work of adhe-
sion, Laskowski and Kitchener (1969) concluded that all solids would be hydrophobic if
they did not carry polar or ionic groups on their surface. It is the high cohesive energy of
water due to its hydrogen bonding that gives rise to hydrophobicity (and to the formation of
micelles in solution and hemimicelles at a mineral surface). The role of the flotation collec-
tor is to cover the polar sites on mineral surfaces that are formed by the breakage of primary
bonds to prevent hydrogen bonding of water to surface sites.
In the flotation of talc, graphite, or molybdenite, the addition of a neutral oil is used to
enhance the hydrophobicity of the mineral. In many instances, depression of these minerals
is desired, and the standard depressants are hydrophilic polymers that adsorb and inhibit
bubble attachment. The flotation of coal has become important over the last few decades,
but it is a naturally floatable material whose surface is very susceptible to oxidation that can
severely reduce its hydrophobicity.
Figure 27 is presented to illustrate the flotation response of a naturally floatable min-
eral, talc, without the addition of a collector as a function of pH. Although not shown, the
isoelectric point (IEP) of this talc sample occurs at pH 2. At pH 1, the zeta potential is
+20 mV, and in the pH range of 4 to 8, the zeta potential is about –30 mV and then becomes
more negative, to about –50 mV at pH 10 and above. The greater magnitude of the negative
zeta potential is responsible for the decrease in flotation observed above pH 10. The induc-
tion time correlates well with flotation response. Naturally floating minerals, such as talc,
graphite, and molybdenite, are depressed industrially by the addition of hydrophilic poly-
mers. Such polymers are adsorbed at the surface of a hydrophobic mineral by hydrophobic
bonding phenomena (by adsorbing, they effectively increase the hydrogen bonding of water
molecules near the interface). The adsorbed hydrophilic polymer prevents bubble attach-
ment because water molecules now can hydrogen-bond to the polymer. Figure 27 shows the
effect of 8.1 mg/L of dextrin on the flotation response of talc. Independent of pH, this small
amount of added dextrin reduces the flotation recovery to 40%.
Talc can also be depressed by hydrolyzing trivalent cations, as shown by M.C. Fuer-
stenau, Lopez-Valdivieso, and Fuerstenau (1988) in a detailed electrokinetic and flotation
study with Fe(III), Al(III), and Cr(III). As the pH is increased, the cations hydrolyze and
sharply change to reverse the sign of the zeta potential but do not affect flotation, apparently
because the hydroxo complex species adsorb onto the polar edges of the talc particles.
However, upon further increase of the pH, the metal hydroxide precipitates, the zeta poten-
tial becomes positive, and flotation ceases. As the pH is increased further, the zeta potential
of the precipitated hydroxide becomes negative again, and talc once more responds to flotation.

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52 HISTORICAL ASPECTS OF FLOTATION

100 0

Talc
0.002 M KNO3
40
80

80
Flotation Recovery, %

Induction Time, μsec
60

120

40

160

20
Flotation Without Collector 200
Induction Time Without Collector
Flotation with Dextrin

0 240
0 2 4 6 8 10 12 14
pH
Adapted from D.W. Fuerstenau and Huang 2003.

FIGURE 27 Influence of pH on the flotation of talc and induction time in 2 mM potassium
nitrate without the addition of a collector, and the depression of talc by the addition of 8.1 mg/L
dextrin

Depression is due to heterocoagulation of the hydroxide onto the nonpolar face of the talc
particles. The driving force for this must be the displacement of water molecules from the
talc face, thereby allowing water molecules that were at the interface to resume hydrogen
bonding with each other and with the hydroxide coating on the talc. Once the zeta potential
of the hydroxide particles becomes negative again, the hydroxide particles redisperse, once
more providing a nonpolar talc face.

S PA R I N G LY - S O L U B L E S A LT M I N E R A L S
The first systematic research on the flotation of salt-type minerals was conducted by Gaudin
and Martin (1928) on a wide range of carbonates, namely, calcite, magnesite, rhodochrosite,
siderite, malachite, and azurite. They found that aliphatic fatty acids are effective collectors
for these minerals and that there is a pronounced systematic chain-length effect. In general,
the carboxylic acid needed to have at least 7 carbon atoms (heptylic acid), although chains
as short as propionic collected azurite and malachite. The industrial workhorse collector for
salt-type minerals is oleic acid, which interacts with the mineral surface by chemical
exchange. Gaudin and Martin (1928) conducted experiments at higher temperatures with
longer-chained fatty acids and found marked increase in flotation by raising the temperature
from 25°C to 70°C. An increase with rising temperature is a direct indication of activated
chemical reaction taking place—the chemical exchange reaction of carboxylate with carbon-
ate ions in the crystal lattice. More recent measurements of flotation and zeta potentials by
Somasundaran and Agar (1967) showed that DAC and SDS are physically adsorbed by cal-
cite, at least until solubility products are exceeded, as evidenced by plots similar to those
shown in Figure 16.
The flotation of sparingly-soluble salt minerals such as apatite, barite, calcite, and fluorite
appears to be controlled by chemical interaction of the carboxylate collector with mineral

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 53

cations, and collector interaction appears to be controlled by solubility criteria. Many
researchers have conducted IR spectroscopy studies on all of these salt-type minerals, and
the results generally show the expected metal–carboxylate bond from chemical exchange,
chemical reaction, or chemisorption when oleate is used as the collector. Some physical
adsorption has been observed at lower pH values. However, with these types of systems, var-
ious researchers have found that collector uptake may go far beyond a monolayer and that a
new soap phase may form at the surface. Thus, the collection process perhaps should be con-
sidered as one of surface reaction rather than one of adsorption. In fact, Kitchener (1984)
wrote the following about the flotation of salt-type minerals:
The main problem over soaps is to identify the form of the product, which, in this
case, seems very unlikely to conform to the naïve monolayer model. There is no
doubt that, given a chance, calcium minerals, for example, would go on reacting
with sodium oleate almost indefinitely. This is not reversible physical adsorption;
Atademin has shown that supposed ‘adsorption isotherms’ for such systems are
almost certainly abstraction-by-precipitation curves.
Industrial processes for the recovery of salt-type minerals from oxide and silicate
gangue minerals are quite straightforward. However, separating salt-type minerals from
each other is complex and difficult. For example, several are calcium salts that interact quite
similarly with the collector, or they have slightly different solubilities such that dissolved
anions (or cations) can react with the surface of the less soluble mineral, causing a surface
transformation that leads to reduced selectivity. Flotation separations of these minerals are
effected by utilizing a number of modifying agents that make insoluble inorganic com-
pounds with the alkaline-earth cations in the minerals, including silicate, fluoride, phos-
phate, and dichromate, or by the addition of organic molecules such as tannins and starches
that coat the surface with a hydrophilic layer of material.
Pugh and Stenius (1985) presented results of a detailed study of the electrokinetic
behavior, solubility, and flotation of fluorapatite, calcite, and fluorite with sodium oleate.
Figure 28 presents their results for the flotation of these three minerals as a function of
sodium oleate concentration at pH 10. This figure shows that the amount of oleate required
as collector follows the order fluorite < apatite < calcite. Fa et al. (2003) also determined the
flotation response of fluorite and calcite as a function of sodium oleate concentration and
obtained fairly similar results, namely, to obtain 50% flotation recovery of fluorite, 3 × 10–6 M
oleate was required and 4 × 10–5 M oleate for calcite. Using molecular modeling, Pradip and
Rai (2002) carried out computations to model the interactions of oleic acid with calcium
minerals and calculated the interaction energies for oleic acid with these calcium mineral
surfaces to be –52.6, –46.8, and –40.2 kcal/mol for fluorite, fluorapatite, and calcite, respec-
tively. They also calculated the interaction energies for water with these minerals, which is
lower in each case, indicating that oleic acid will replace water at the mineral surfaces. Their
calculated interaction energies give the same order as the observed flotation response. Fa and
colleagues suggest that the lower floatability of calcite is due to the low density of calcium
sites at the carbonate surface.
Aqueous solutions of these three minerals are complex, because all of the ions involved
are subject to hydrolysis, depending on pH. Fa et al. (2003) listed the solubility products of
these three minerals as follows: fluorapatite [Ca10(PO4)6F2], 6.3 × 10–137; fluorite (CaF2),
5.0 × 10–11; and calcite (CaCO3), 4.6 × 01–9. Their measured solubilities of calcium ions in
solution after 15 minutes were 2.5 × 10–5, 1.3 × 10–4, and 1.5 × 10–4 M for fluorapatite,

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54 HISTORICAL ASPECTS OF FLOTATION

Interaction Energy Calculation Fluorite Apatite Calcite
by Molecular Modeling: –52.6 kcal/mol –46.8 kcal/mol –40.2 kcal/mol
100
Fluorite
Apatite
Calcite
pH 10
80
Flotation Recovery, %

60

40

20

0
10–6 10–5 10–4 10–3
Sodium Oleate Concentration, mol/L

Adapted from Pugh and Stenius 1985; Pradip and Rai 2002, 2003.

FIGURE 28 Flotation recovery of fluorite, apatite, and calcite as a function of the
concentration of sodium oleate at pH 10

fluorite, and calcite, respectively. Fa and colleagues report high adsorption densities of ole-
ate on these minerals, the amount being related to their rate of dissolution and solubility,
namely 11, 100, and 300 μmol/m2 for apatite, fluorite, and calcite, respectively. Because
monolayer coverage is 6 μmol/m2, any oleate uptake above that amount cannot be chemi-
sorption but must be the calcium oleate soap resulting from surface reaction.
The solubility product of calcium oleate is 3 × 10–16, which indicates that calcium soap
will be precipitated on addition of sodium oleate in alkaline solutions. Free and Miller
(1996) investigated the precipitation and transport of precipitated calcium oleate soap to
the fluorite surface. Because the fluorite surface would have a coating of chemisorbed oleate,
this process is one of coagulation and not really heterocoagulation, with hydrophobic bond-
ing phenomena playing a significant role. In their paper, Fa et al. (2003) showed that colloi-
dal particles of calcium oleate soap coagulate onto the surface of fluorite and make it readily
floatable. A higher concentration of calcium oleate colloids was required to initiate calcite
flotation.
In flotation systems involving slightly soluble salt minerals, a major complication is that
of the conversion of the surface of a mineral to that of another mineral or compound. As an
illustration of surface conversion, consider the use of soda ash on the surface properties of
barite. Equilibrium is controlled by the following reaction:

BaSO 4 + HCO 3–( aq ) = BaCO 3 ( s ) + H (+aq ) + SO 42–( aq ) (EQ 14)

There are several ways to demonstrate that the surface of barite behaves as barium car-
bonate (BaCO3) rather than barium sulfate (BaSO4) in the presence of sodium carbonate
(Pradip and Fuerstenau 1991). Figure 29 shows that the addition of sodium carbonate for
pH regulation in a flotation separation involving barite and calcite causes barite to behave as

© 2007 by the Society for Mining, Metallurgy, and Exploration.
All rights reserved. Electronic edition published 2009.

Metallurgy. All rights reserved. but they found that no separation from cal- cite could be achieved. Sutherland and Wark (1955) stated that this is probably one of the first examples of cross-activation to be found in nonsulfides.book Page 55 Tuesday. two minerals which are very similar in chemical composition. as shown by zeta potential measurements and solution equilibrium pH though it were BaCO3. as indicated by the electrokinetic behavior of the mineral. . January 2. and malachite. Electronic edition published 2009. mol/L Adapted from Pradip and Fuerstenau 1991. This sur- face transformation is controlled by bulk thermodynamics. When working with single minerals of calcite. as would be expected when any of these processes are a surface chemical reaction. μm/sec per V/cm (Barite) 1 BaCO3 (Powder) 0 –1 –2 –3 24 Hours Equilibration 11 10 BaCO3 Equilibrium pH 9 Ba Na2CO3 SO 4 +[ Solution HC 8 O – 3] =〈 Ba CO 3〉 +[ H+ ]+ 7 [SO = 4] BaSO4 6 10–6 10–5 10–4 10–3 10–2 10–1 Initial Sodium Carbonate Concentration. FIGURE 29 Surface transformation of barite to barium carbonate by the addition of sodium carbonate. the results of Gaudin and Martin (1928) suggest that it should be possible to separate the copper minerals from calcite with heptylic acid as the collector. Gaudin and Martin aptly com- mented: “It is indeed very remarkable that azurite and malachite. and Exploration. and crystallographically. azurite. can be separated by flotation © 2007 by the Society for Mining.flotation0. Finally. in this system. 2007 7:36 PM DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 55 3 Reaction Onset 2 BaSO4 to BaCO3 BaSO4 Electrophoretic Mobility. the flotation response of the barite under these conditions must be that of a carbonate.

conditions were such that little cal- cite would have dissolved during the experiments. calcite (closed and open to the atmosphere).book Page 56 Tuesday. For this system. Electronic edition published 2009. in a complex mixture of salt-type minerals such as calcite and apatite. This figure shows that supernatants of apatite and even that of calcite depressed the flotation of calcite in the pH region of about 6 to 13. partic- ularly when the mineral is in equilibrium with the solution before the collector is added. carbonate. calcium ions can precipitate the collector if the solubility of the calcium soap is exceeded (the KSP of calcium oleate is 10–15. and Exploration. phosphate. and also calcium oleate. be separated from calcite. In the case of calcite flotation in water. depression results from the bulk precipitation of the collector as calcium 100 100 90 80 Turbidity. Any condition where the concentration of Ca2+ exceeds that of calcium oleate can cause collector precipitation and hence depression.” Similar to the foregoing statement. by this same reagent. Metallurgy.6). Anathapad- manabhan and Somasundaran (1984) constructed a diagram showing the amount of Ca2+ in solution from apatite. January 2. and fluoride ions into solution—ions that can all chemisorb onto the different minerals and compete with the collector. Likewise. and calcite supernatants. All rights reserved. Using the known equilibria of the various species that would be involved with apatite and calcite in water. 2007 7:36 PM 56 HISTORICAL ASPECTS OF FLOTATION with one of the lower fatty acids. and with added nitrate.flotation0. FIGURE 30 Effect of apatite and calcite supernatants on the flotation of calcite with potassium oleate as collector and also the turbidity of the supernatants upon the addition of oleate at various pH values showing collector depletion by bulk calcium oleate precipitation © 2007 by the Society for Mining. Fig- ure 30 presents their results for the oleate flotation of calcite in water and in supernatants of calcite and apatite. by any means now known. Turbidity measurements after the addition of oleate to the supernatants. in their supernatants. . % Turbidity 80 0. Added calcium nitrate depressed calcite flotation similar to that shown in Figure 30 for the effect of supernatants. and phosphate salts. while the carbonates of copper cannot.1 mM Potassium Oleate 60 Apatite Supernatant Calcite Supernatant 70 40 Calcite Flotation 0.2 mM Potassium Oleate 20 mM Potassium Nitrate Water 60 20 Apatite Supernatant Calcite Supernatant 0 50 0 2 4 6 8 10 12 14 pH Adapted from Ananthapadmanabhan and Somasundaran 1984. but at slightly lower oleate concentration without added potassium nitrate. dissolution of the minerals can put carbonate. % transmittance Flotation Recovery. are also given in Figure 30 and show the precipitation of calcium oleate from these solutions. The researchers also conducted detailed experiments on the flotation of apatite and calcite in water. apatite.

flotation0.book Page 57 Tuesday, January 2, 2007 7:36 PM

DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 57

oleate, probably before any appreciable amount adsorbed onto the mineral surface. By
increasing the oleate concentration, flotation was fully restored.
The standard, yet rather inefficient, process for the flotation of bastnaesite ore involves
six stages of conditioning with steam, soda ash, sodium fluosilicate, sodium lignin sulfonate,
and tall oil from carbonate and sulfate gangue, producing a low-grade concentrate. In an
attempt to improve the separation of bastnaesite, (La,Ce)CO3F, from barite and calcite,
conditions were found under which bastnaesite can be floated quite effectively with hydrox-
amate as the collector (Pradip and Fuerstenau 1983, 1991). This appears to result because
hydroxamate chelates more strongly with rare-earth ions than with Ba2+ and Ca2+. From
their results, the collector interaction with barite is probably one of adsorption, reaching
only a close-packed monolayer. In the case of calcite, uptake initially appears to be that of
adsorption but eventually changes to multilayer uptake. On the other hand, the rare-earth
chelates with hydroxamate are so stable that a surface layer which is equivalent to 5 or 6
monolayers is formed. Again, this can no longer be considered an adsorption process, but
must be one of surface reaction, where ions are pulled from lattice sites and form multilayers
of a metal hydroxamate compound at the surface. If the rate of metal dissolution and diffu-
sion through the boundary layer is faster than diffusion of the collector to the surface, bulk
precipitation may occur. As previously discussed, hydroxylation of the cations in the mineral
surface may assist surface reaction phenomena by first providing some surface atom move-
ment. Readsorption of hydrolyzed species may participate in surface reactions. Flotation
experiments conducted with potassium octyl hydroxamate as collector at pH 9–9.5 showed
that 50% flotation recovery for bastnaesite, calcite, and barite is achieved at the respective
initial collector concentrations of 0.12 mM, 0.30 mM, and 0.80 mM (Pradip and Fuer-
stenau 1991). Recent computations by Pradip and Rai (2003) show that the interaction
energies for hydroxamate with bastnaesite and barite are –66 and –33 kcal/mol, respectively,
in accordance with the strong uptake of hydroxamate by the rare-earth mineral.

S O M E E X A M P L E S O F P R A C T I C A L M I N E R A L S E PA R AT I O N S
The recovery of copper, lead, and zinc from a complex sulfide ore can be achieved in various
ways. For an ore that might contain galena, sphalerite, and chalcopyrite with such gangue
minerals as pyrite, carbonates, and quartz/silicates, the first step involves the joint flotation
of chalcopyrite and galena at pH 6–7 with xanthate collector and a small amount of sodium
cyanide to depress pyrite and zinc sulfate to depress any sphalerite activated by heavy-metal
ions in solution. Copper sulfate is then added to the tailings from this first step to activate
the sphalerite, and sodium cyanide and lime are added to bring the pH to 10.5 to ensure
depression of the pyrite. With the addition of more xanthate, sphalerite is then floated. If
the pyrite contains gold, for example, it could subsequently be recovered from the tailings.
Separation of galena and chalcopyrite in the bulk concentrate can be achieved by depressing
galena with sulfur dioxide (SO2) or with sodium dichromate at weakly acidic pH values.
Another procedure is to float the galena after depressing the copper sulfides with sodium
cyanide at pH 8–9.
As an example of oxide mineral flotation, with iron ores, the usual problem is separation
of hematite (PZC, pH 7) from quartz (PZC, pH 2). Hematite can be floated away from
quartz with a sulfonate at pH 2–4, or with sodium oleate at pH 6–8. Quartz can be floated
away from hematite with an amine at pH 6–7, or at pH 11–12 with sodium oleate as collec-
tor after activating the quartz with calcium ions and depressing the hematite with starch.

© 2007 by the Society for Mining, Metallurgy, and Exploration.
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58 HISTORICAL ASPECTS OF FLOTATION

Although not used industrially in iron ore processing, hematite can be floated away from
quartz with hydroxamate at pH 8.5, or with an amine at pH 1.5 in the presence of hydro-
chloric or sulfuric acid as a hematite activator.
In the case of a pegmatite containing spodumene (PZC, pH 2), muscovite (IEP, pH 1),
iron-bearing oxide/silicates (PZC, pH 6), feldspar (PZC, pH 2), and quartz (PZC, pH 2),
separations can be made sequentially by utilizing differences in silicate mineral surface
chemistry and crystal chemistry. First, spodumene is floated at pH 7.6 with oleic acid as col-
lector through chemisorption on aluminum surface sites. Then by adding an amine collec-
tor at pH 2–2.5, the layer-silicate mineral muscovite is floated by making use of its fixed
negative surface charge. After that, the iron silicate impurities are floated at pH 3 with a sul-
fonate as collector. Finally, with hydrofluoric acid (HF) as an activator, the feldspar can be
floated with an amine at pH 3, leaving a marketable pure quartz as the tailing.
The simplest large-tonnage separation of a sparingly-soluble salt mineral is exemplified
by the flotation of apatite from quartz. In a typical Florida phosphate plant, both anionic
and cationic flotation are used to produce an acceptable product. After desliming, the phos-
phate mineral is floated at pH 9–9.5 with fatty acid and fuel oil extender. Subsequently, the
concentrate is acid-blunged to remove the collector coating and then refloated with an
amine at pH 7–8 to remove silica impurities. A major challenge is the increased dolomite
content of phosphate ores, namely, to effectively prevent the dolomite (Ca,Mg)CO3 from
floating with the apatite.

S U M M A RY
Basic flotation research conducted over the last several decades has answered questions
posed by Rickard in 1916 as to why minerals float. By simultaneously using more than one
technique to study the surface chemistry and flotation response of pure minerals with puri-
fied chemical reagent systems, the fundamental mechanisms by which sulfide, oxide, silicate,
naturally-floatable, and even sparingly-soluble salt minerals respond to flotation is now
fairly well understood. As outlined in this review, some systems are better understood than
others. Because collector–mineral interactions appear to be more interesting, more research
has been directed toward the behavior of collectors than depressants. How activators and
inorganic depressants function is fairly well understood, but fundamental knowledge of
how and why such organic depressants as quebracho, starch, gum guars, and so forth, attach
to mineral surfaces is lacking. Systems involving mixtures of sparingly-soluble salt minerals
are subject to complex solution chemistry where species from one mineral may dissolve and
adsorb/precipitate onto the surface of another mineral. Furthermore, minerals made up of
ions, such as carbonates, phosphates, sulfates, and sulfides, appear to react with collectors,
consuming reagent and forming precipitates that may adsorb (coat) more than one mineral,
lowering grade. The chemistry of frothers and the role of frothers in determining selectivity
have not received adequate attention.
Real ores do not behave as pure minerals. Mineral grains may have different chemical
compositions (trace elements and locked particles), surfaces smeared with coatings of a
softer mineral in the ore, and highly active surfaces (that may change with time) due to flaws
produced during comminution. More research should be directed toward the study of mineral
mixtures and the behavior of actual ores—but conducted with an aim toward quantifying
what is going on and not just ore testing.

© 2007 by the Society for Mining, Metallurgy, and Exploration.
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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 59

As speculated by Kitchener (1984), hypothetically, there should be a systematic way to
plan the flotation processing of an ore by establishing the surface chemistry of all the con-
stituent minerals along with their responses to the reagents relevant to the process, then by
determining the likely interferences between the various species, and, finally, by planning
the best conditions for securing a large difference in hydrophobicity between the reagent-
treated minerals. Many of the reagents and reagent schemes that have been successfully used
before and after the invention of chemical collectors were found by trial and error, and often
with great ingenuity. However, with decreasing grade, decreasing grain size, and increasing
complexity of ores with the passage of time, there is an ongoing need for more selective and
effective flotation reagents and reagent schemes. In some cases, finding reagents that adsorb
rather than react with a mineral may lead to reduced reagent consumption. The rational
design of new reagents may result from understanding the selectivity of interaction of flota-
tion reagents with interfaces in terms of identifying the underlying molecular recognition
mechanisms.

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Mellgren, O. 1966. Heat of adsorption and surface reactions of potassium ethyl xanthate on galena.
Trans. AIME 235:46.
Mellgren, O., R.J. Gochin, H.L. Shergold, and J.A. Kitchener. 1973. Thermochemical measurements
in flotation research. Page 451 in Proceedings of the 10th International Mineral Processing
Congress. London: The Institution of Mining and Metallurgy.
Merrill, C.W., and J.W. Pennington. 1962. The magnitude and significance of flotation in the mineral
industries of the United States. Page 55 in Froth Flotation—50th Anniversary Volume. Edited by
D.W. Fuerstenau. New York: American Institute of Mining, Metallurgical, and Petroleum Engineers.
Modi, H.J. 1956. Electrokinetic properties and flotation behavior of corundum. Sc.D. thesis,
Massachusetts Institute of Technology.
Modi, H.J., and D.W. Fuerstenau. 1960. The flotation of corundum—an electrochemical
interpretation. Trans. AIME 217:381.
Nixon, J.C. 1957. Discussion. Page 369 in Proceedings of the 2nd International Congress on Surface
Activity. Volume 3. Edited by J.H. Schulman. London: Butterworths.
Onoda, G.Y., and D.W. Fuerstenau. 1965. Amine flotation of quartz in the presence of inorganic
electrolytes. Pages 301–306 in Proceedings of the 7th International Mineral Processing Congress.
New York: Gordon and Breach Scientific Publishers.
Palmer, B.R., M.C. Fuerstenau, and F.F. Aplan. 1975. Mechanisms involved in the flotation of oxides
and silicates with anionic collectors. Part II. Trans. AIME 258:261.
Peck, A.S., L.H. Raby, and M.E. Wadsworth. 1966. An infrared study of the flotation of hematite with
oleic acid and sodium oleate. Trans. AIME 235:301.
Perkins, C.L. 1921. U.S. Patent 1,364,304.
Plaksin, I. 1959. Interaction of minerals with gas and reagents in flotation. Min. Eng. 11:319.
Polkin, S.I., and T.V. Najfonow. 1964. Concerning the mechanism of collector and regulator
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International Mineral Processing Congress. New York: American Institute of Mining,
Metallurgical, and Petroleum Engineers.
Pradip, and D.W. Fuerstenau. 1983. The adsorption of hydroxamate on semi-salt minerals. Part I.
Adsorption on barite, calcite, and bastnaesite. Colloids Surf. 8:103.
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molecular modeling approach. Colloids Surf. A 205:139.
———. 2003. Molecular modeling and rational design of flotation reagents. Int. J. Miner. Process. 72:95.

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DEVELOPMENTS IN THE CHEMISTRY OF FLOTATION PROCESSING 63

Pugh, R., and P. Stenius. 1985. Solution chemistry studies and flotation behavior of apatite, calcite
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Purcell, G., and S.C. Sun. 1963. Significance of double bonds in fatty acid flotation—an electrokinetic
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Raghavan, S., and D.W. Fuerstenau. 1975. The adsorption of aqueous octylhydroxamate on ferric
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Schulman, J.H., and T.D. Smith. 1953. Selective flotation of metals and minerals. Pages 393–413 in
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Simmons, G.L., J.N. Orlich, J.C. Lenz, and J.A. Cole. 1999. Implementation and start-up of N2TEC
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64 HISTORICAL ASPECTS OF FLOTATION

Tye, A.T. 1928. Effect of preferential flotation at Cananea mill and smelter. Page 151 in Flotation
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Whitworth, F.T. 1926. U.S. Patent 1,553,232.
Woods, R. 1984. Electrochemistry of sulfide flotation. Pages 91–115 in Principles of Flotation—the
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The Australasian Institute of Mining and Metallurgy.
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Page 154 in Advances in Mineral Processing. Edited by P. Somasundaran. Littleton, CO: SME.

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History of Flotation Technology
A.J. Lynch, J.S. Watt, J.A. Finch, and G.E. Harbort

A B S T R AC T
The development of flotation as a major industrial process occurred during three main time
periods. During 1860 to 1900, small-scale attempts were made in industry to float or agglomer-
ate the valuable minerals in ores and wash away the waste minerals. From 1900 to 1925, the
economic necessity to concentrate fine sulfide particles led to immense research efforts for floating
zinc and lead minerals at Broken Hill, Australia (1901 to 1915), and copper minerals at the
huge mines in the western United States (1911 to 1925). During this time, flotation became an
industrial technology and provided much of the copper that made the widespread distribution of
electricity possible. Two major advances occured after 1960. X-ray and radioisotope on-stream
analysis systems were developed, which gave rapid information about assays of process streams
and made accurate process control possible, and new flotation machines were introduced. There
were high-volume columns in which the pulp and air bubbles moved in countercurrent flow,
and high-energy cells in which the pulp was aerated with very small bubbles prior to separation.
The high-energy cells provide much higher flotation rates than the columns. This chapter pre-
sents developments in flotation technology that occurred during these periods.

THE NEED FOR A NEW PROCESS
“A new metallurgical process never springs fully developed from the brain of one person, but
is the result of patient investigation, application, and improvement by many minds, during
many years” (Hoover 1914, p. 2). Flotation did not happen in isolation; it was one of many
inventions in the second half of the 19th century that brought a seminal change to mining
and mineral processing technology and greatly increased mineral production. This was an
exciting period in the mineral industry as the Industrial Revolution was gaining momentum
and was causing rapid increases in the consumption of minerals and metals (see Table 1).
In 1850 the mineral industry had been technically stagnant for more than 200 years,
the last major innovations being the use of water power to drive crushing and grinding
machinery in the 16th century and the amalgamation process and blasting by black pow-
der in the 17th century. The industry was ill-equipped then to handle the problems pre-
sented by the rising demands for minerals and metals, but it was transformed by new
technology during 1850–1900 and moved from the era of black powder, hand carts, stamp

TABLE 1 World production of copper, lead, zinc, and coal, 1850–1900
Commodity 1850 1875 1900
Copper, kt 55 130 525
Lead, kt 130 320 850
Zinc, kt 65 165 480
Coal, Mt 75 233 660
Source: Habashi 1994.

65
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66 HISTORICAL ASPECTS OF FLOTATION

TABLE 2 Production rates and profits at Broken Hill Proprietary Company, 1886–1902
Mining, profits 1886 1888 1890 1892 1894 1896 1898 1900 1902
Kilotons mined 10 80 170 300 590 440 400 520 660
Dividends and bonuses, 50 370 1,000 800 580 420 280 180 110
$A × 1,000
Source: Lynch 1987.

TABLE 3 Typical milling statement, Broken Hill, 1900
Assay Proportion
Product Ton Pb, % Ag, oz Zn, % Pb, % Ag, % Zn, %
Lead concentrate 11,141 60.6 19.6 10.4 69.2 49.8 12.8
Tailing 37,936 7.8 5.8 20.8 30.8 50.2 87.2
Crude ore 49,077 19.9 8.9 18.5 100.0 100.0 100.0
Source: Woodward 1965.

TABLE 4 Recoveries of copper by gravity concentration in mills processing porphyry
copper ores
Milling Utah* Chino† Ray‡ Nevada§
Year 1913 1915 1915 1915
Tons milled per day 25,000 7,357 7,805 8,442
Average copper in ore, % 1.25 2.16 1.67 1.54
Average copper in concentrate, % 17.31 21.55 19.29 7.77
Copper recovery, % 63.95 66.59 64.11 70.18
Source: Hines and Vincent 1962.
*Utah Copper Company, Utah.
†Chino Copper Corporation, New Mexico.
‡Ray Consolidated Copper Company, Arizona.
§Nevada Consolidation Copper Company, Nevada.

mills, and sluices to the era of dynamite, steam shovels, ball mills, and Wilfley tables. Even
with all the improvements, there was still a serious problem—fine particles could not be
concentrated efficiently by gravity machines, and fine-grained ores were replacing coarse-grained
ores as the source of many metals. The problem can be illustrated by referring to what hap-
pened at the Broken Hill Proprietary Company (BHP) in Australia. Table 2 shows how div-
idends and bonuses at BHP declined per ton of mined ore from 1896.
BHP started operating at Broken Hill in 1886, and, initially, profits were very high
because miners extracted the surface ore that was rich in coarse-grained silver and lead min-
erals, but earnings plummeted when this ore was exhausted, and the fine-grained primary
sulfides had to be mined. This was a problem because there were high losses of silver and
lead when the fine particles from the mills were concentrated in gravity machines, and zinc
was lost almost entirely. Table 3 shows a typical milling statement in 1900.
By 1900 the early years of prosperity had given way to pessimism, and employment had
fallen by 30%. The economics were simple—find a new process or abandon the mines.
Heavy investments were made in magnetic separation and in the unproven flotation process,
and it was flotation that provided the answer. The growth of flotation from ideas described
in patents into a remarkable industrial process was described as “…one of the outstanding
achievements in twentieth century technology…” (Klassen and Mokrousov 1963, p. xiv).
The same problem occurred with porphyry copper ores some years later in the western
United States. There were high metal losses using gravity concentration, as shown in Table 4,

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HISTORY OF FLOTATION TECHNOLOGY 67

and a process had to be found to reduce these losses and increase copper recovery by 20%.
Again, flotation was the answer.
The research and development programs that established flotation as the major concen-
tration process at Broken Hill and in the western United States overlapped, the main activ-
ity at Broken Hill occurring from about 1900 to 1915 and in the western United States
from about 1911 to 1920. Minerals Separation Company (MSC), which was active in both
areas, ensured that there was transfer of technology, although at the cost of bitter patent lawsuits.
At Broken Hill the major results of the program were as follows:
• Froth flotation, which was developed as an industrial process for concentrating sul-
fides and was used to extract zinc from millions of tons of slime tailings. By 1907, the
annual production of zinc concentrate had risen to 236,251 tons.
• Differential froth flotation, which was developed during 1910–1915 for making
separate lead and zinc sulfides
Progress must have seemed slow to investors in the Broken Hill mines, but metallurgists
had to find out how to float minerals on water and how to control the many variables that
made the process successful. It was not an easy task. “The propensity of minerals to float was
a valuable discovery, but scores of more elusive and more important discoveries had to be
made before the process could earn a profit. ‘It is to manipulation, learned empirically in the
laboratory and mill, that the flotation process owes its metallurgic success,’ wrote T.A. Rick-
ard” (Blainey 1968, p. 70; Rickard 1932).
In the United States, froth flotation was first used in a zinc mill in Montana in 1911,
and its success gave companies the incentive to investigate the process for the concentration
of copper sulfides. Its potential to improve the economics of copper milling was realized in
1915 when a 15,000-tons-per-day flotation plant was built at the Inspiration Company, and
the recovery of copper was increased to 80%. Not surprisingly, flotation circuits swept the
copper industry within a few years. How flotation developed as a great industrial process
will be discussed in this chapter. It is necessarily brief, and more information about the early
years of flotation is given in the bibliography, in particular, Hoover (1914), members of
the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy (1930),
Hines and Vincent (1962), Crabtree and Vincent (1962), Fuerstenau (1999), and Megraw
(1918).

E A R LY I D E A S , 1 8 6 0 – 1 9 0 0
The first hint that differences in surface properties could be used to separate minerals
appeared in a patent awarded to William Haynes (Haynes 1860). The process claimed that
sulfides in a powdered ore could be agglomerated by oil and the nonsulfides could be
removed by washing. There is no evidence that the idea was tested in a plant.
The first commercial flotation plant was built by the Bessel brothers in Dresden, Ger-
many, in 1877 to clean graphite ore (Graichen et al. 1977). Adolph Bessel graduated from
the University of Gottingen in 1855 and joined a factory that made refractories and cruci-
bles in Grobalmerode. In 1864 this factory was moved to Dresden, close to the Polytecnic
and the Bergakademie Freiberg. Adolph and his brother became its owners in 1866. Because
the quality of the graphite used in the crucibles was poor, they developed a process for clean-
ing it that involved mixing graphite ore with a small amount of oil, adding water, and boiling
the mixture to float the graphite to the surface of the pulp. Their process yielded a concen-
trate containing 90% graphite from 40% graphite in the feed. Bessel patents of July 2, 1877,

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68 HISTORICAL ASPECTS OF FLOTATION

and May 12, 1886, contained all the essential features of froth flotation including the use of
nonpolar oils to enhance process kinetics (Bessel 1877, 1886). The first patent referred to
bubbles being generated by boiling and the second to CO2 bubbles being generated by the
reaction of lime with acid. In 1878 the Wohler Gold Medal was awarded to Adolph Bessel
for the invention patented in 1877.
The first flotation plant to process sulfide ores was based on Carrie Everson’s work,
although it was not a commercial success as was Bessel’s plant. The circumstances were
unusual. Everson was born in 1842 in Massachusetts and studied medicine before marrying
Dr. W. Everson in 1864. He invested in mining shares which failed, and this led to Carrie
taking an interest in mineralogy so she could understand the reason for the failure. About
1878 she started to experiment with ways to concentrate sulfide minerals and eventually
patented a process in 1885 for separating sulfides from gangue by mixing powdered ore with
a small amount of oil in an acid solution and floating the sulfides in a scum (Everson 1885).
Flotation must have been due to entrained air. The myth is that Everson’s patent originated
in observations made while washing geologists’ sample bags; the less romantic reality is that
she was a good scientist who would carry out experiments in a laboratory and was prepared
to test the results in practice. Everson’s process was successful in small plants but not on a
larger scale (Megraw 1918), perhaps because the ores were unsuitable—sulfide flotation did
not reveal its secrets easily. Unfortunately, she did not have the financial resources to con-
tinue her research, and she became a teacher to earn a living. Later assessments of Everson’s
work were “…if the invention had been a less startling innovation, it would probably have
received more attention from engineers and metallurgists, and the application of the idea
would probably in that case have taken place many years before it did,” (Hoover 1914 p. 6)
and “as a metallurgist she was a quarter of a century in advance of her profession” (Megraw
1918 p. 7).
The year 1885 was important in the history of flotation because of the patents by the
Bessel brothers and Carrie Everson. The same year, a patent was awarded to Hezekiah
Bradford in the United States for a film flotation process in which powdered sulfide ore was
placed gently onto the surface of water and the sulfides adhered to the surface while other
minerals sank (Bradford 1885). It is likely that these inventors made their discoveries inde-
pendently, and although their efforts had little immediate technical impact, their patents
showed that the potential significance of flotation-type processes was becoming recognized.
In 1898 Francis Elmore patented a process for concentrating sulfide minerals by adding
oil to pulverized ore in water, agglomerating the sulfides and buoying them to the surface of
the water, and washing away the gangue particles (Elmore 1898). He proved its value at
the Glasdir mine in Wales, and his work was discussed at an Institution of Mining and Met-
allurgy meeting in London in 1900 (Hoover 1914). The process was widely applied and can
be regarded as the first successful process for floating sulfides, although it was not froth flo-
tation as it is currently known. Entrained air was an unrecognized but important factor. By
1900 it seems that only the Bessel brothers had deliberately used gas bubbles to accelerate
flotation rates, but in 1901 an engineer in Italy, Alcide Froment, patented the use of gas bubbles
to float sulfide particles (Froment 1902). Froment also used sulfuric acid and limestone to gen-
erate bubbles although he recognized that gas of any kind would be suitable (Hoover 1914).
This is the background to the events that occurred at Broken Hill during 1901–1915.
Engineers there would have known of the process in which sulfides could be agglomerated
by oil and gangue washed away, so it is not surprising that they became interested in the
technique.

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HISTORY OF FLOTATION TECHNOLOGY 69

F R O M A S TA R T L I N G I N N OVAT I O N T O A N I N D U S T R I A L
PROCESS, 1901–1925

Zinc and Lead at Broken Hill, 1901–1915
In 1901 the immediate problem at Broken Hill was how to extract zinc from the dumps. As
a measure of their size and potential, in 1904 the dumps contained more than 7 million tons
of tailings that assayed at about 4% lead, 140 g/ton silver, and 15% zinc. A process to extract
zinc would revive the mines and restore prosperity. The zinc problem at Broken Hill was,
therefore, the question of the hour. From 1901 engineers at Broken Hill worked on several
flotation processes and machines (Woodward 1965).
• Froth flotation was independently investigated by Guillaume Delprat, general man-
ager of BHP, and by Charles Potter, who was a brewer in Melbourne. They each pat-
ented a process in which the zinc mineral in gravity plant tailings was floated by
carbon dioxide generated by adding acid to hot pulps that contained carbonate min-
erals (Potter 1902; Delprat 1902). Neither used oil; probably the tailings contained a
sufficient amount to make flotation occur. Potter’s process had a short life, but the
BHP process worked on gravity plant tailings from 1902 to 1923, the acid consump-
tion being 26 lb per ton and the pulp temperature being 82°–88°C (180°–190°F).
About 90,000 tons of zinc concentrate was made annually from 300,000 tons of tailings.
• A film flotation process that was similar to Bradford’s 1886 invention was patented
by Auguste de Bavay in 1904. In this process a pulp that had been deslimed, acidified,
and oiled flowed down a corrugated cone dipped at an angle into water. The hydro-
phobic sulfides floated on the water, whereas other particles were wetted and sank. It
worked at Broken Hill from 1905 to 1917, and at its peak produced 80,000 tons of
zinc concentrate annually from 300,000 tons of tailings.
• Vacuum flotation, a form of froth flotation, was patented by Francis Elmore in 1904
and was used in the Zinc Corporation plant for 6 years. In this process, a small
amount of oil was added to an acidified tailings pulp, and the sulfide particles were
floated with bubbles generated by applying a vacuum of 600 mm of mercury to the
pulp and precipitating the dissolved air. At its peak, it produced 80,000 tons of con-
centrates annually from 250,000 tons of tailings.
• The Minerals Separation Company, which had been formed in England in 1903 to
specialize in ore dressing problems, came to Broken Hill in 1904 to test a process pat-
ented by Arthur Cattermole (1902) for which it had purchased the rights. In this
process, a small amount of oil—insufficient to give a buoyant effect—caused the sul-
fides to agglomerate and sink, and other minerals were washed away. This process
was a failure because the granules of sulfides that still required further concentration
tended to break on the concentrating tables. Another test proved successful, how-
ever, wherein an even smaller amount of oil was added and the pulp was violently agi-
tated to entrain air because the sulfides were carried into a froth and removed in a
spitzkasten. Staff at MSC and the Central Mine at Broken Hill developed this con-
cept into stirred flotation cells that were used in series.
• Sketches of early flotation cells are shown in Figures 1 and 2. All the concentrates
made by flotation at Broken Hill contained 47%–49% Zn; recoveries were more
than 80%, and working costs varied only by 10%. A measure of the success of flotation

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70 HISTORICAL ASPECTS OF FLOTATION

To Vacuum Pump
Acid Separating
Cone
9 ft
Worm-wheel
Feed

Oil Acid
Froth Feed
Launder

Mixer
15 ft Baffles

Tailing

Tailing Concentrate

Potter-Delprat Cell Elmore Vacuum Cell

Feed
Corrugated Cone
Water Level
Regulating Wheel
for Discharge Valve Overflow
Launder

Agitation Froth
Box Launder

Water Level

Feed Frothing
Chamber
Discharge Tailing

Minerals Separation Cell De Bavay Cone

Source: Truscott 1923.

FIGURE 1 Flotation cells at Broken Hill, 1902–1910

Feed

Concentrate

a

f
e
k
a — Thickener h
b — Feed tank c d
c — Pump Impellor
d — Separating cone
e, f, g — Pipe and valves for air and frother g l
Air Inlet
k, l — Concentrate, tailings outlets

Lyster Cell Owen Cell
Source: Hoover 1914.

FIGURE 2 Cells built for differential flotation at Broken Hill, 1911–1913

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HISTORY OF FLOTATION TECHNOLOGY 71

was that in 1913, 10 years after the start of investigations, more than 11 Mt of mate-
rial had been floated, and 3 Mt of zinc concentrate produced (Woodward 1965;
Hoover 1914).
While these cells were being developed and used at Broken Hill, a flotation cell was pat-
ented in 1903 by H.L. Sulman and H.F.K. Picard of London, in which particles were floated
by air bubbles formed in the cell by compressed air flowing through holes in an immersed,
perforated tube (Sulman and Picard 1903). It would be some years before pneumatic cells
were used in plants. By 1908 bulk flotation of zinc concentrates was working well, and it was
time to develop a differential flotation process for primary sulfides. Three approaches were
investigated (Woodward 1965):
1. In 1910, E.J. Horwood of BHP roasted to 400°–500°C a concentrate made by bulk
flotation to “deaden” galena by oxidizing its surface to lead sulfate. The blende was
unaltered and was refloated to make salable concentrate.
2. In 1912, F.J. Lyster, mill superintendent at the Zinc Corporation, observed that the
natural flotation rates of galena and blende were different and devised a process to
make separate concentrates. Galena was collected during gentle flotation of an alka-
line pulp to which eucalyptus oil had been added as a frother; blende was then
floated from the deleaded pulp. Lyster recognized the importance of air control and
devised a cell in which air was added to a pulp, and the mixture was passed through
a pump before entering a tank in which the froth separated. Differential flotation
was achieved by controlling the air flow rate. A subaeration cell was developed by
T.M. Owen at Broken Hill South in 1913 for the same purpose, and in an improved
form, it became the standard cell.
3. Leslie Bradford at BHP activated and depressed minerals selectively by adding
chemicals to the pulp. In 1913 he patented his discoveries: that copper sulfate acti-
vated sulfide minerals and that sulfur dioxide depressed blende during galena flota-
tion. Some months later, John Myers in the United States independently discovered
that copper sulfate was an effective activator.
These discoveries, in particular the selective activation and depression of minerals,
changed flotation from an inflexible bulk process into a process that could be used for the
production of individual mineral concentrates. By 1916 the urgent problem of finding a
new concentration process for the Broken Hill ore had been solved; the prosperity of the
town was ensured, and the turbulence and excitement associated with testing new ideas
diminished, at least for a time.

Copper in the United States, 1911–1920
Film flotation was the first flotation process used successfully in the United States.
Machines designed by Arthur Macquisten in Scotland were used in Nevada in 1906 and in
Idaho in 1911. The principle of operation was that deslimed and oiled sands flowed through
a rotating drum designed to continually lift the particles and gently present them to the sur-
face of the pulp (Figure 3). Sulfides adhered to the pulp surface and were collected. Mac-
quisten cells worked well on sands; the Nevada plant produced a 20% copper concentrate
from a 2.5% copper feed, and the Idaho plant, which operated for 10 years, produced a 45%
zinc concentrate and a high-grade lead concentrate (Truscott 1923; Crabtree and Vincent
1962).

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72 HISTORICAL ASPECTS OF FLOTATION

6 ft Water Level
Feed

Concentrate
Roller

Tailing

Source: Truscott 1923.

FIGURE 3 Macquisten film flotation cell

In 1911 froth flotation was used in the United States for the first time (Hines and Vin-
cent 1962). “James M. Hyde installed the first froth flotation plant in the U.S., about August
1, 1911, at the Basin Reduction Company plant, Basin, Montana, which was then under
lease to the Butte and Superior Copper Company (Hines and Vincent 1962, p. 11). …It
would have been difficult however to pick an ore as suitable as the Black Rock ore for treat-
ment by froth flotation with the knowledge available in 1911. The ore contained only 1%
pyrite, 1.1% Pb as galena with which the silver was associated, 17–20% Zn, and 0.25% Cu
(p. 19).” The events relating to this plant have been fully described by Hines and Vincent
(1962); suffice it to say that an important technical innovation was the use of rougher and
cleaner cells in closed circuit with cleaner tailing returning to the rougher. James Hyde
clearly understood the importance of cleaning concentrates to remove entrained gangue
particles although the 50-ton mill at Basin was his first experience with froth flotation. Dur-
ing the next year, the company built mills with capacities of 200 and then 1,200 tons per day
to verify that flotation would work, and with their success, flotation was poised to take off.
The Basin ore was a good ore to start with, but the real prize would be the copper ores.
Growth in the use of copper in the United States during the late 1800s and early 1900s was
5.8% annually, and even the rich deposits in Upper Michigan, Montana, and Arizona could
not support this indefinitely. Lower-grade deposits had to be mined eventually. Daniel Jackling
set the pattern in 1903 when he was given the task to build a 300-metric-tons-per-day mill
to process 2% copper ore and persuaded the owners to mine 5,000 metric tons per day,
which required a total change in the mining and milling systems. The new mill was ready for
operation in 1907, and even at 60% recovery, it made large profits on 1% ore. Its capacity
was soon doubled and redoubled. Others followed his lead, and large mills were built in
Nevada and Arizona to process low-grade ores that were also very profitable at high copper
prices although the recoveries were low.
The Inspiration Company was a leader in developing flotation for porphyry copper
ores. In 1911 it owned part of a huge deposit in Arizona, but this ore gave poor results with
simple gravity concentration. The investment required to make it profitable could not be
made by its backer, W.B. Thompson, and it was purchased by the Anaconda Company. Dr.
Louis Ricketts became consulting engineer. “He did not think the mill Thompson’s engi-
neers had planned would recover enough of the copper. To the horror of the stockholders,
he threw away one million dollars’ worth of mill construction and spent a year and another
million dollars experimenting. Then, he built the first mill that used the new flotation pro-
cess. The result of Dr. Rickett’s delay was that this company caught the high copper price of
1915 with the most successful mill that had ever been built” ( Joralemon 1973, p. 243). In

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HISTORY OF FLOTATION TECHNOLOGY 73

Feed Overflow Lip
9 ft Float

Water Porous Feed Tailing
Level Canvas Mat Concentrate

Air Box Inclination 1:20 Air Mat
Air at 4.5 lb
Tailing

Cross Section Complete Cell

Source: Truscott 1923.

FIGURE 4 Pneumatic Callow cell modified by Inspiration Copper

late 1912, Dr. Ricketts carried out flotation tests in the MSC laboratory and obtained 87%
recovery of copper in a 15% concentrate from a 2% ore. Then he built a 50-tons-per-day mill
in early 1913 and a 600-tons-per-day mill in early 1914 to verify the results. His testwork
was comprehensive and included studies of different flowsheets and flotation machines,
new reagents, and the effect of fine grinding. In 1915 a 15,000-tons-per-day mill was built,
and 80% of the copper in the feed was recovered. It was the first mill in which flotation was
applied to ore instead of gravity tailings.
Two of the innovations in the new mill were ball mill–classifier circuits for grinding the
ore directly to flotation feed size and flotation machines that used compressed air. Both of
these had an effect on the control of the process: the closed grinding circuits controlled
particle size and minimized the production of coarse, composite particles; and the com-
pressed air cells controlled bubble size. The cells built by J.M. Callow (see Figure 4) were
chosen by the Inspiration Company in preference to subaeration cells, and their success led
to their wide use in concentrators for many years. “Flotation spread at a rapid rate; by 1914,
42 mining companies were operating or experimenting with the flotation process. The list
increased in 1915 to include most of the principal copper and lead mines” (Hines and Vincent
1962, p. 29), and in 1918, 25 million short tons of copper ore were concentrated by flotation.
A spin-off from the new technology was a growing business in flotation chemicals for
enhancing or retarding the flotation rates of specific minerals, and by 1916 many companies
were making reagents. By 1925 thousands of patents had been awarded for flotation chemi-
cals, the most important being to Cornelius Keller and Carle Lewis in 1923 of MSC for the
use of xanthates as collectors for sulfides. Xanthates took much of the guesswork out of sul-
fide flotation because they increased flotation rates of sulfides considerably; they were solu-
ble in water, and their addition rates could be controlled. It is not known how Keller and
Lewis came to discover the collecting properties for sulfides; perhaps it was because sodium
ethyl xanthate was used in making rubber and as a defoliant and herbicide, or the initial tests
might have been conducted because a bottle of xanthate was readily available on the shelf.
The result of their discovery was that xanthate-lime-pine oil circuits were soon in common
use, and by 1925 xanthate had transformed flotation into a process that was stable and reli-
able because it could be added in controllable amounts.
With the success of copper flotation, the “startling innovation” proposed by Carrie
Everson had become a reality. Because she lived until 1914, she saw the start of large-scale
flotation and would have known that her remarkable, but unrewarded, efforts during 1885–
1892 had not been in vain.

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74 HISTORICAL ASPECTS OF FLOTATION

Zinc and Lead at Cominco in Canada, 1917–1922*
Flotation started in Canada in 1917 at the Sullivan mine of Consolidated Mining and
Smelting Company (Cominco). The metallurgist responsible was Ralph Diamond who had
joined the Anaconda Company in Anaconda upon graduation from the University of Tor-
onto in 1913. In May 1914 he was invited to lead a project to study a new “secret” process.
The first flotation plant in North America had been built at the Superior Mill in Butte,
Montana, and arrangements were made for Diamond to learn laboratory flotation testing
there. The Superior Mill used the Hyde process on ore from the Black Rock mine. Follow-
ing this assignment, Diamond commenced testwork on Anaconda slimes under the direc-
tion of George Chapman of MSC. Chapman had been one of the pioneers in froth flotation
in Australia between 1904 and 1906. Later, in 1914, Diamond worked under J.M. Callow at
the Inspiration Test Mill in Miami, Arizona, on MS cells in which ore was being treated at a
rate of about 16,000 tons per day. It is interesting that the Anaconda plant used the experi-
mental Callow pneumatic cell. The Anaconda slimes flotation plant started operation using
standard Hardinge mills—likely an association that resulted in the use of Hardinge mills at
Sullivan in 1922. The Anaconda Company had taken out a license under MSC.
The processes used for copper slimes and copper sands and zinc ore had been developed
by MSC, largely under the direction of George Chapman. Diamond remained in charge of
flotation research for Anaconda until February 1917. At that time, Diamond went to Utah
to install and operate a flotation plant for the Ohio Copper Company near Bingham, Utah,
for the treatment of a partially oxidized copper ore. While in Utah, Diamond was contacted
by Selwyn Blaylock, assistant general manager of the Cominco, regarding work in the devel-
opment of the electrolytic treatment of zinc ores. This proposal was declined but resulted in
a proposition to instigate testwork on the application of the froth flotation process to the
refractory ore from the Sullivan deposit. The Sullivan deposit presented two new challenges
to existing froth flotation practice. These were, firstly, a remarkably fine association between
the valuable galena and blende minerals and the gangue iron sulfide present. Secondly, the
ratio of iron sulfide, mainly pyrrhotite together with a small amount of pyrite, to the lead
and zinc sulfide minerals was significantly higher than in ores previously studied. A sample
of ore was sent to Diamond in Utah for preliminary testing. This work was sufficiently
encouraging that Diamond joined the Consolidated company in June of 1917 and contin-
ued flotation work on the Sullivan ore at Trail. By the end of 1918, a successful three-stage
differential flotation process had been demonstrated on a 600-tons-per-day test mill. The
1918 annual report of the company includes the following statement: “Important improve-
ments in metallurgical practice in regard to treatment of the complex ores of the Sullivan
Mine have added many years to the life of that property and have made it one of the most
valuable mineral deposits in America if not in the whole world.”
Cominco had taken out an MSC license in 1917. This was imperative despite the high
royalty rates as MSC controlled most of the important patents. Furthermore, much of the
general flotation knowledge that prevailed among millmen in those early days stemmed
from the MSC reservoir of knowledge although MSC’s work on Sullivan ore was negative
throughout. MSC never had an employee stationed in Trail to work on the Sullivan deposit
problems, not even for a few days. MSC had a laboratory in San Francisco, but trained men
were at a premium, and at that time, and for the next few years, they were simply deluged
with ore samples for testing, requests for information, and help in the field. They had just

*This section was written by Mike Fairweather.

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HISTORY OF FLOTATION TECHNOLOGY 75

three or four and occasionally five men at any time who were available for all laboratory and
fieldwork. Most of the ores submitted were simple and reacted favorably to the existing acid
or neutral circuit flotation configurations. Some of these represented great reserves, poten-
tial large operations, and large royalty producers. With many, major construction was soon
under way. All ores as received were simply subjected to certain standard tests, and those
presenting difficulties were set aside. There were plenty of simple ores to fully occupy their
time. The Sullivan was a very complex ore and did not react to standard tests. Moreover,
MSC knew little at that time of the potential of the Sullivan ore body, and Cominco, as a
company, did not occupy a prominent place in the mining world. In those early years, MSC
was not impressed with the possibilities of copper sulfate, and this reagent was not included
in testwork in 1916. It was around 1920 that they became aware of its importance. Sullivan
ore was a special problem, and copper sulfate meant more to its successful treatment than
was the case with 99 out of 100 ores.

Coal in Europe
“It was not until 1920 that the experimental work of Bury, Broadbridge and Hutchinson
directed attention to the possibilities of the use of froth flotation for coal cleaning. The first
froth flotation plants for coal cleaning were erected the same year in Spain and in France.
The first British plant was erected in 1922, and during the following year, plants were
erected in Germany and in Belgium” (Chapman and Mott 1928, p. 385). Flotation was the
only process available in 1920 to clean the fine fraction (–0.5 mm) of coking coal. Labora-
tory studies of coal flotation had started in the United States in 1915, and it was found to be
very effective, but there was little incentive to use the process because coal was mined from
thick seams, and relatively few fines were made during mining and transport. The high cost
of dewatering coal concentrate was also a deterrent.
In Europe, coal mining was mainly carried out in thin seams underground, and mecha-
nized mining was used, which generated a high proportion of fines, so there was a higher
incentive to use flotation. Consequently, coal flotation was first used there in 1920, and by
1925, flotation was cleaning about 1 Mt of coal annually. In 1927, 36 plants were using
MSC cells, 14 being in Spain and 12 in Germany. Coal flotation took much longer to
become popular than sulfide flotation because it could be used to clean only a small part of
the mined coal, and its product was low in value. It did grow, however, and in 1933, there
were about 60 coal flotation plants in Europe and 1 in the United States (Aplan 1999). It is
interesting that the Elmore vacuum process, which had only limited success on sulfide ores,
was widely used in England for many years to float minus-1/8-in. coal because the power
required was low, the froth was easy to dewater, and coarse particles were floated.

Technology Transfer and Litigation
The growing interest in flotation was reflected by the fact that the Engineering and Mining
Journal published 3 articles about the process in 1901, 10 articles in 1902, and 32 in 1903
(Hoover 1914). There were many inventions and patents, and inevitably, there was litigation
between inventors who developed virtually identical processes at different mines and who
wished to claim damages for breach of patents. An important issue was license fees. These
encouraged the sale and transfer of technology if they were reasonable but often led to
piracy and secrecy if they were excessive. At Broken Hill the royalty cost in flotation was up
to 30% of the operating cost, so it is not surprising that companies sought to make changes
in the process to avoid paying royalties. Litigation often continued for years and must have

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76 HISTORICAL ASPECTS OF FLOTATION

rewarded many lawyers with high incomes. Whether litigation helped or hindered flotation
is debatable, but there is no doubt that the expensive court cases are a reminder that legal
action should be a last resort in metallurgical disputes.
To close this section on the formative years of flotation, a comment should be made on
the contribution of MSC. It was formed in London to apply oil agglomeration processes to
the Broken Hill ore to concentrate sulfides, but by 1904, it had found that floating sulfides
in a scum with a little oil gave better results than agglomerating them with excess oil. So the
company turned to flotation. Then came stirred cells, froth flotation, and eventually xan-
thates—the company was involved in all three processes. The company employed skilled
and experienced engineers who successfully promoted the flotation process and sold MSC
flotation cells in many countries. Not surprisingly, MSC became involved in many lawsuits
as staff left the company and worked on flotation as consultants or employees for other com-
panies. There is no doubt that staff of MSC contributed much to the growth of flotation
and that the rather aggressive tactics of the company helped the transfer of the new flotation
technology considerably.

Y E A R S O F C O N S O L I D AT I O N , 1 9 2 5 – 1 9 6 0
By 1925 efficient subaeration cells were available, and chemicals were being used for the
selective activation and depression of minerals. This was just as well, given that technical
progress was slow during the next 25 years, which were dominated by economic depression
and war. But the demand for minerals produced by flotation continued to increase. The
scope of flotation also expanded during this time, two examples being an oil flotation pro-
cess that was patented in 1928 to recover phosphates from previously discarded fines and a
process that was developed in 1937 to recover potash from salt-saturated brines.
To meet the increased demand for flotation, plant sizes increased. But caution was the
order of the day in plant design, and large plant capacities were obtained by use of many
small units that were known to be reliable rather than by use of new large units that promised
economy of scale but were untested. One example was the Morenci concentrator built in
1942, which had 432 cells, each with 2.2 m3 of volume to float 45,000 tons per day of ore.
A by-product of the early years of flotation was the interest of many senior engineers in
research because they had seen the immense rewards that it could bring. The result was that
companies established research units in several universities in the 1920s to work on flotation
fundamentals, and these contributed much to the understanding of flotation. Particular
mention is made of the groups led by A.F. Taggart at Columbia University (New York),
A.M. Gaudin at the Massachusetts Institute of Technology (MIT), and I.W. Wark at the
University of Melbourne (Victoria).

A D VA N C E S I N F L O TAT I O N T E C H N O L O G Y, 1 9 6 0 – 2 0 0 0
The production of minerals by flotation increased rapidly from 1950, as shown in Table 5
for copper and zinc, and during this time there were many improvements in the process. The
focus was on reagents, flotation machines, and the control of circuits. Discussion in this sec-
tion will be limited to flotation machines and to on-line analysis of pulp streams, which is
necessary for accurate control.
The most commonly used flotation machines can be divided into three groups based on
flotation rates:

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HISTORY OF FLOTATION TECHNOLOGY 77

TABLE 5 World mine production of copper and zinc, 1950–2000
Metal 1950 1960 1970 1980 1990 2000
Copper, Mt 2.3 4.1 6.3 7.6 9.0 11.0
Zinc, Mt 2.0 2.8 5.7 6.1 7.0 8.9
Source: International Zinc Association 2003; International Copper Study Group 2004.

1. Flotation columns in which feed pulp enters the collection zone at the top of a col-
umn, flows downward, and contacts air bubbles that have been generated by sparg-
ers at the base of the column. The column tank itself is both the primary collection
zone and the disengagement zone. Columns are considered to be low-intensity
machines, and the flotation rate constants are low.
2. Mechanically agitated flotation machines in which a rotating mechanism is used to
keep solids in suspension and to create bubbles by shearing air that is either applied
to the machine under pressure or induced. They are considered to be medium-
intensity devices with flotation rate constants 1.2 to 1.5 times that of a column.
3. High-intensity flotation machines that consist of an external aeration/contacting
mechanism by which pulp is brought into intense contact with fine bubbles. The
external contactor can use either pressurized air or air entrained into a fluid jet. The
contactor is the primary collection zone, and the tank is the disengagement zone.
These machines have flotation rate constants 2 to 4 times greater than that of the
mechanical flotation cells.
Only mechanically agitated machines were used until the 1960s, after which columns
were introduced, followed by high-intensity machines. These type of machines will be dis-
cussed in the following sections.

Mechanical Cells
Mechanical flotation cells have changed little in their principle of operation since they were
invented in 1912, although many aspects of their operation have been improved. Significant
literature is available on their design and development, with excellent recent reviews by
Arbiter (1999), Weber et al. (1999), and Yianatos (2003). Their maximum size has been
increased greatly during the last 35 years to reduce the capital cost of equipment and the
floor area required per metric ton of ore floated in high-capacity plants. Increase in maxi-
mum cell volume from 1960 to 2004 is shown in Table 6.

Pneumatic Flotation
These machines introduce air through diffusers or aerators (or, as a general term, spargers)
rather than by mechanical dispersion. Flotation columns are the current principal represen-
tatives of this class. Their history contains the colorful characters, claims, and counterclaims
that have marked flotation from the earliest days.
The first machine with obvious column geometry, tall relative to its side dimensions,
appears to have been invented by Norris (1907; Figure 5a). The novelty, however, seemed
less to do with geometry and more with introducing air using pressurized water to overcome
the limitations of vacuum release flotation at high altitude. Towne and Flinn (1919) pat-
ented a column depicting a countercurrent-flow slurry descending against a rising swarm of
bubbles (Figure 5b). Towne and Flinn made some prescient observations: that the addition

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78 HISTORICAL ASPECTS OF FLOTATION

TABLE 6 Maximum size of Outokumpu mechanical flotation cells (m3), 1950–2000
1970 1976 1980 1995 1997 2002 2004
16 38 60 100 160 200 300
Source: S. Ronkainen, personal communication.

Wash Water
1

2
2
2 1
1 – Feed
2 – Concentrate
3 – Tailing 1
4 – Air

4 4
3
3
4 3

A. 1907 Norris column B. 1919 Towne and Flinn C. 1963 Boutin and Tremblay
(Norris 1907). Air column (Taggart 1927; column (Boutin and Tremblay
injected into pulp. Rubenstein 1995). Air 1963; Rubenstein 1995). An
Not tested in plants. entered through porous air sparger and wash water
medium. Unsuccessful in were used—a simple and
plants because of sanding. successful column.

FIGURE 5 Evolution of flotation columns

of oil increased “bubble-forming capacity” and that attached “oil-jacketed” particles stabi-
lized froth. They also noted that particles not attached to bubbles in the froth “settle back
towards the water or pulp column”; that is, they were describing entrainment and dropback.
Depending on the perspective, either of these candidates represents the “first” flotation col-
umn (Figure 5c; Rubenstein 1995; Jameson 2002).
Initially, interest in pneumatic flotation was short-lived and not revived until the sec-
ond half of the 20th century. The problems that developed, which were articulated in the
patent issued to Hollingsworth (1968), included sanding of coarse particles in the absence
of mechanical agitation, plugging of porous diffusers, and channeling in scaled-up versions.
It was not so much solving these problems (many still exist, in fact) that prompted the rapid
commercial expansion after about 1980 but rather the use and control of wash water into
the froth—the “key feature which permits high upgrading” (Finch and Dobby 1990, p. 3).
If wash water is the “key,” it is of interest as to who first claimed this innovation. Search-
ing column patents has identified four that incorporated wash water: Bennett and Dell
(1963), Boutin and Tremblay (1964), Hukki (1967), and Hollingsworth (1968). For
wash-water use, the patents reference Bennett and Dell back to 1958, Boutin and Tremblay
to 1963, Hukki to 1965, and Hollingsworth to 1965. Therefore, the honor of first mention
appears to go to Bennett and Dell.
The use of water sprays was already known to increase grade by washing away of gangue
particles, which are mechanically entrained into the froth (Klassen and Mokrousov 1963).
But application was fitful. Why was it more successfully exploited in columns? It was cer-
tainly not because wash water “can kill the froth” in mechanical cells (Fuerstenau and Han
2003, p. 297). Column geometry, small cross-section to volume compared to most mechan-
ical cells, does economize on wash water. But, most importantly, column operators learned
how much to add. Column Flotation of Canada Ltd. (the first column flotation company,

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HISTORY OF FLOTATION TECHNOLOGY 79

founded to develop and market the invention of Boutin and Tremblay) promoted the addi-
tion of sufficient wash water to generate a so-called “positive bias,” that is, a net flow of water
downward across the froth–pulp interface, which could be controlled by maintaining a tails
flow higher than the feed flow (ideally, this refers to flow of water, but in reality, it is usually
flow of slurry). Operating with a positive bias helped ensure that entrainment was countered.
Wheeler (1983), president of the company after 1963, openly discussed this strategy during
a column seminar at McGill University in Montreal and within days, one of the attendees,
Roger Amelunxen, was back at Gibraltar Mines successfully operating a “homemade” column.
Many column designs have been proposed in the West and in Russia (Rubenstein
1995), but the one that survived is that of Boutin and Tremblay. The deciding factors were
probably the simple design, basically an open vessel, coupled with the positive bias strategy.
The invention germinated in trials using columns for a solvent-in-pulp process (P. Boutin,
personal communication). Entrainment of slurry in the rising droplet wake was solved by
the addition of clear aqueous phase just below the interface. The inventors were quick to
realize that flotation offered more potential. Given the role of “oil” in the early history of flo-
tation, it is interesting to see it as a source of inspiration here. The inspiration continues with
a recent proposal to combine flotation and solvent extraction (Chen et al. 2003).
The commercial road was not smooth. Some 17 years after founding Column Flotation
of Canada Ltd., the first industrial installation was recorded at Les Mines Gaspé (Cienski
and Coffin 1981). This may seem a long gestation period but is about the norm for the min-
erals business (Napier-Munn 1997). After 1981, progress was rapid. A scale-up methodol-
ogy was developed (Dobby and Finch 1986) that was first used to design the columns at
Mount Isa Mines (Espinosa-Gomez et al. 1989). By the early 1990s, three additional compa-
nies were marketing flotation columns based on the Boutin–Tremblay design, which was
becoming known as the conventional or Canadian column. The main suppliers today (in no
particular order) are MinnovEX, CPT, Dorr-Oliver-Eimco, Cisa, Control International,
Multotech, RIF, Metso, and Dual Extraction. One estimate is that there are some 3,000 col-
umns installed worldwide, about 30%–40% being homemade, ranging from the minerals
industry to the offshore oil industry (the flotation capacity in the oil industry may actually
exceed that in the minerals industry).
The success of columns helped usher in other novel developments in flotation machines
(Finch 1995). Some were aimed at overcoming the well-known problem of pneumatic
cells—reliable gas injection. Jet-type spargers is one outcome. Dispersing air into slurry and
injecting the mix into the column is another. The patent of Hollingsworth (1968) ventured
this possibility, the Microcel being a commercial version (Yoon, Adel, and Luttrell 1992).
The high retention time in some columns (tens of minutes on occasion) is eliminated in the
Jameson cell, which exploits air dispersion/slurry contacting in a downcomer where reten-
tion time is just seconds ( Jameson 1988). The Voith Sulzer cell developed for de-inking
recycled paper shares some design features (Finch and Hardie 1999). Research focused on
understanding mechanisms has also led to a range of sensors finding application in mechan-
ical cells (Gomez and Finch 2002), such as optimizing gas distribution to banks of cells
(Cooper et al. 2004).
The conventional cell manufacturers were not idle during this period. From the “virtual
columns” of the early 1990s (Finch 1995), a range of competing tank cell designs is now
available, which, when viewed from a certain angle, reveal their inspiration.

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80 HISTORICAL ASPECTS OF FLOTATION

Tank Air
Feed

Flotation
Jet Chamber Tank
Nozzle Body
Baffle Tailing

Deaeration Zone

Source: Cusack 1968.

FIGURE 6 Davcra flotation cell FIGURE 7 XPM-series flotation machine

Flotation columns have taken their place among the options in cell selection. Overused
in the initial flurry perhaps, they have retained a place in many circuits for most mineral
commodities.

High-Intensity Flotation Cells
High-intensity cells use very small bubbles produced by forced air (e.g., Davcra, Bahr, and
Microcel cells) or induced air (e.g., Jameson and XPM cells). The Bahr cell, which was
invented in 1974, was a column fed by a high-pressure air–pulp mixture, and this cell started
a trend to combine the best ideas of columns and high-intensity cells into single machines.
The first reported high-intensity cell was the Davcra cell (shown in Figure 6) devised by
Bill Davis at the Zinc Corporation in Broken Hill and tested there in 1966. The principle
was that most particle–bubble interactions are time independent, and recovery depended
mainly on the characteristics of the intensely mixed zone (Davis 1966). The cell worked by
air and feed slurry being injected into the tank through a dispersion nozzle, with energy
being dissipated via collision with a vertical baffle, as shown in Figure 6 (Cusack 1968). The
Davcra cell was used for some years in plants for floating sulfide minerals and coal.
In China, Professor Daiwei Wu and colleagues developed jet flotation cells and started
using them in an industrial plant in 1967. The XPM flotation machine is similar to a
mechanical flotation machine, but the rotating mechanisms are replaced by jets of pulp and
air that form “aeration-agitation” zones. Part of the pulp within each cell is drawn along with
air into a circulating pump, and the mixture is pressurized and squirted from a conical jet, as
shown in Figure 7. Froth forms rapidly and is removed by scrapers. These cells are used in 14
Chinese coal-preparation plants (Wu and Ma 1998). The largest cells are now 23 m3.
For the past 30 years, extensive development of high-intensity flotation machines has
been conducted in Germany with much of the original work undertaken by Professor Bahr
at the Technical University of Clausthal. The Bahr cell shown in Figure 8 was one of the initial
flotation devices developed from this work. The Bahr cell uses aerator units in which compressed
air flows through small openings via channels into the pulp. The aerator units were located
beneath the main flotation tank and entered the tank vertically (Cordes 1997). Since its
development, many derivations and variations of the Bahr cell have been produced under a
variety of names including Ekoflot, Pneuflot, Allflot, and Imhoflot.
The Jameson cell, shown in Figure 9, was developed by Graeme Jameson of the University
of Newcastle (Australia) and the technology was developed for commercial application by

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HISTORY OF FLOTATION TECHNOLOGY 81

Air

Air
Feed
Tailing Concentrate
Feed

General arrangement. The Typical feed pipe showing
tank contains several feed the aeration zone.
pipes with their aeration zones.

Source: Truscott 1923.

FIGURE 8 Bahr cell

Pulp Feed Downcomer

Induced Air Nozzle

Free Jet

Plunging Jet

Recirculating Eddy Mixing Zone
Submerged Jet

Pipe Flow Zone

Concentrate

Disengagement Zone
Pulp Mixture

Cell Tailings

FIGURE 9 Jameson cell

Mount Isa Mines Limited. Its principles of operation have been discussed by numerous authors
including Jameson (1988); Jameson et al. (1988); and Evans, Atkinson, and Jameson (1995).
The high-intensity contacting zone is the downcomer. Feed pulp is pumped into the
downcomer through an orifice plate, creating a high-pressure jet. The plunging jet of liquid
shears and then entrains air, which has been naturally aspirated. Because of a high mixing
velocity and a large interfacial area, there is rapid contact and collection of particles. One
unique feature of the Jameson cell is the operation of the downcomer under a vacuum,
which results in a high-intensity contact residence time that varies from 1 to 10 seconds.
Since its invention in 1986, there have been 225 Jameson cells installed in variety of coal,
metalliferous, and industrial mineral applications.
The Microcel was developed by Yoon, Adel, and Luttrell (1992) at the Virginia Poly-
technic Institute. In the Microcel flotation machine, the slurry is mixed with small bubbles in
the microbubble generator, which is outside the column, and separation occurs inside the column.

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82 HISTORICAL ASPECTS OF FLOTATION

Wash Water
Distributor

Froth Product Wash Water Inlet
Slurry
Air Feed Inlet Pressure Transducer
Frother Inlet
Slurry Manifold
Inlet from Pump
Bubble
Generators
Tailing Outlet

Control Valve
Outlet to Pump
Microbubble
Suspension

Source: Yoon, Adel, and Luttrell 1992.

FIGURE 10 Microcel

The microbubble generator is a high-intensity bubble-contacting zone formed by a
static in-line mixer; slurry is drawn from the base of the column and pumped through the
generator; pressurized air is injected into the mixers, and the high resultant shear forces create
fine bubbles (see Figure 10). The operation of the Microcel has been described in several
publications, for example, Phillips et al. (1997) and Brake (1998). There are more than 100
installations in mineral and coal plants worldwide.

O N - S T R E A M A N A LY S I S
A seminal change in flotation technology occurred when on-stream analysis (OSA) systems
were developed. These enabled the metal contents of streams to be measured on-line and
circuit grades and recoveries to be calculated every few minutes. In the days before OSA, flo-
tation was an art, and results depended on the operator’s skills in observing the froth, using
the panning dish, and controlling air and reagents manually. After OSA became available,
flotation could be monitored accurately and controlled. Its development in the 1960s was
timely; cell size was about to grow rapidly, and there was no alternative sensor for process
control. OSA by itself was not enough. In the early 1960s, digital computers became avail-
able, and it was the OSA–computer link that changed flotation into an advanced technology.

Setting the Scene
The problem with flotation for many years was that there was a long delay between taking
samples from circuits and obtaining the assays, so the results were of historical value only
and were not useful for circuit control. Better control could only be achieved if the delay was
reduced to minutes, but rapid analysis of elements such as lead and copper in circuit streams
was not possible until particles could be analyzed in the pulps rather than by sampling, dry-
ing, and use of conventional wet methods.
In the 1950s, it was realized that X-ray techniques offered the most promising
approach, and there seemed to be only one likely candidate: X-ray fluorescence (XRF) anal-
ysis by wavelength dispersive methods based on X-ray tube and (Bragg) crystal spectrome-
ter. In the 1960s, an alternative approach was developed of using radioisotope X-ray
techniques based on gamma-ray preferential absorption, or XRA, and energy dispersive
(XRF) analysis.

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HISTORY OF FLOTATION TECHNOLOGY 83

Developments Required
In 1960 the X-ray and radioisotope approaches required completely different developments
before a practical OSA system could be realized.
• The X-ray tube and crystal spectrometer system was relatively complex and expensive
but was known to give accurate results because the wavelength dispersive system
could resolve fluorescent X-rays from adjacent atomic number elements. The equipment
had to be mounted in a central location of the plant, where it would sequentially
analyze continuous samples taken from each process stream. This involved accurate
sampling of each process stream, long runs of pipelines to the central analyzer, pump-
ing, sample splitting, constant head tanks, and flow cells.
• The radioisotope techniques of analysis involved the use of relatively inexpensive
source-detector systems. Hence, one or more head units could be placed near each
plant process stream, with only a short sample by-line between process stream and
analysis system being required so that construction problems were simpler. The two
radioisotope techniques were at different stages of development:
1. XRA techniques: These were suitable for high atomic number elements such as
lead, uranium, tungsten, and bismuth. The problem was that there were only a few
radioisotope sources emitting gamma rays of suitable energy, and even fewer were
commercially available.
2. XRF techniques: These were essential for medium atomic number elements such
as iron, nickel, copper, zinc, and tin. The problem in this case was that the detec-
tors that were available could not resolve fluorescent X-rays from adjacent atomic
number elements.

X-ray Tube Systems
Plant tests were carried out in the late 1950s using laboratory X-ray tube systems for off-line
measurement of dry plant samples and on-line measurement of plant pulps. The systems
worked well. The first on-line system was tested during 1959–1960 in the 36,000-tons-per-
day concentrator of the Anaconda Copper Corporation in Butte, Montana. The X-ray sys-
tem was satisfactory, but problems occurred with sample handling and presentation, which
took months to solve. For example, “Sufficient wood is present to completely stop all flow
through the X-ray head. Various types of screens were tried before finding a satisfactory
solution. This was typical of the type of mechanical problem that plagued and delayed the
final process control by X-ray analysis” (Lucy, Fulmore, and Holderreed 1963, p. 682). The
system presented assays of 13 streams every 20 minutes. Another system was built in 1962
by the Research and Instrumentation Division of Rhoanglo Mine Services Ltd. in Northern
Rhodesia (now Zambia). It was installed in the Bancroft concentrator and presented copper
assays of 6 streams every 8 minutes (Barlin and Keys 1963).
In 1962 the Outokumpu Group in Finland started what became a successful program
of X-ray tube on-stream analyzers. In that year, the company established an Institute of
Physics and brought the Pyhasalmi multimetal mine into operation. The mine became a
large-scale laboratory in which instruments developed by the institute were tested, and this
was an important factor in the success of the program. The objectives of the institute were to
develop electromagnetic and XRF technology, and Professor Pekka Rautala became its
director. Ore from the Pyhasalmi mine was floated to produce lead, copper, zinc, and pyrite
concentrates, so there was a broad scope for experimentation.

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84 HISTORICAL ASPECTS OF FLOTATION

The institute developed a 14-stream, wavelength dispersive X-ray analyzer, which was
installed in the Pyhasalmi plant in 1968, and its success led to the installation of a second
analyzer in 1970 (Lahteenmaki, Miettunen, and Saloheimo 1999). Assays of each stream
were available to the operators every 6–7 minutes; the cost per assay was about 2 cents, and
the analyzers had a high availability that was usually more than 99%. Using this analyzer,
Outokumpu developed its own process control and management system and installed the
first at the Kotalahti nickel concentrator in Finland in 1973. The analyzers have been con-
tinually improved, and current models can be installed in the process area instead of in a sep-
arate room. By 2004 more than 400 Outokumpu X-ray tube analyzers had been sold for use
in mineral concentrators worldwide (M. Kongas, personal communication).

Radioisotope Systems
Radioisotope systems offered the possibility of simpler and less expensive OSA compared
with the X-ray tube systems. The plant system could be built up in stages as needs arose.
Short sample by-lines would reduce the problems of pipe blockage caused by coarse particles
and wood chips, and wear on detector windows would also be reduced. The critical link
between the mineral industry and expertise in radioisotope X-ray techniques was estab-
lished in 1962 when North Broken Hill Ltd. (NBH) approached the Australian Atomic
Energy Commission (AAEC) with their requirements for OSA. The approach by Conzinc
Riotinto of Australia (CRA) to the AAEC in 1965 resulted in the highly productive collab-
oration between physicists at the AAEC led by John Watt and metallurgists at CRA led by
Bruce Rawling.

Gamma-ray Transmission for High Atomic Number Elements
Gamma-ray transmission was the first technique developed for OSA using radioisotopes. In
1957 the AAEC was investigating a reactor system based on uranium powder suspended in
liquid sodium, and the suspension was simulated by tungsten powder in water which was
pumped around a 25-mm cross-sectional loop. The concentrations of tungsten over a cross
section of pipe were determined by scanning the gamma-ray beam (thulium 170, 84 keV
gamma rays) over the pipe cross-section. This was the first radioisotope OSA system of slur-
ries (Watt and Lawther 1958).
In 1962 NBH asked the AAEC whether it was possible to continuously determine the
lead concentration of their flotation feed slurry on-line in a 150-mm-diameter steel pipe.
Calculations showed that this should be possible by combining measurements of gamma-ray
transmission at two different gamma-ray energies, about 200 and 662 keV. The AAEC over-
came the lack of a suitable 200-keV radioisotope by developing a novel source based on
Compton scattering of higher-energy gamma rays yielding an output of about 225-keV. This
dual-energy gamma-ray transmission technique was successfully tested in the NBH plant in
1964 and 1966 (Ellis et al. 1967). The radioisotope system was installed on-line at the NBH
concentrator in 1968. This was the world’s first permanent installation of a radioisotope
OSA system in a mineral concentrator.
In December 1965, Bruce Rawling asked John Watt about measuring both lead and
zinc in sample by-lines from various process streams in a CRA concentrator at Broken Hill.
Watt’s response was that lead in flotation feed would be accurately determined by dual-
energy gamma-ray transmission based on radioisotopes Gd-153 (100 keV) and Cs-137
(662 keV). For tailings, a correction would have to be made for matrix variations by a further
transmission measurement with gamma rays of suitable energy. These predictions were later

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HISTORY OF FLOTATION TECHNOLOGY 85

confirmed by calculation and experiments on samples of solids taken from plant streams
(Watt 1967; Ellis et al. 1969). Philips Industries Pty. Ltd. provided laboratory equipment to
CRA for sample by-line trials, and in 1968 CRA staff proved that lead could be determined
accurately in a sample by-line from the main flotation feed stream (Hinckfuss and Rawling 1968).

XRF for Medium Atomic Number Elements
The discussions between Rawling and Watt in 1965 crystallized thoughts on the urgency of
developing radioisotope XRF techniques for OSA for medium atomic number elements
such as copper and zinc. Australian mineral companies had to be contacted to obtain com-
prehensive information about their requirements, and samples had to be collected over
extended periods of time from various process streams in several concentrators so that the
AAEC could determine whether the techniques provided sufficient accuracy to meet these
requirements. The AAEC contracted Australian Mineral Development Laboratories
(Amdel) in 1966 to undertake the survey of mineral company requirements for OSA, and
this was completed in mid-1967. Over the period from 1966 to 1968, mineral companies
supplied the AAEC with suites of about 25 samples from each of several process streams in
their plants that were taken over a period of at least 6 weeks.
During 1966–1968 the AAEC undertook extensive development of radioisotope XRF
assemblies and techniques (Watt and Gravitis 1973; Watt 1983). In 1966, XRF measure-
ments were made on samples of lead/zinc ore, taken from widespread locations throughout
the CRA mine, with excellent results of zinc in the range 0–34 wt % being determined to
0.6 wt % (1σ) (Watt 1967). Measurements on the samples taken from several streams in
each of six concentrators also gave promising results (Ellis et al. 1969) with one exception:
copper in the iron-rich tailings from Tennant Creek, which was later solved with the devel-
opment of the detector-radiator assembly (Watt 1972). The success of laboratory measure-
ments on samples was followed up with on-stream trials of radioisotope XRF systems at five
mineral concentrators, undertaken during 1968–1971 by AAEC, Amdel, and plant staff
(Fookes et al. 1971). Overall, these trials were very successful and led to improvements in
radioisotope X-ray assemblies and techniques.
During 1967 Douglas Hinckfuss of CRA proposed replacing XRF measurements on a
sample by-line with measurements by probes directly immersed into the plant process
stream (Hinckfuss 1972). The probe was a casing containing the radioisotope source and
detector assembly. The immersion probe, shown in Figure 11, was a key development to the
radioisotope OSA system because it overcame the need for use of sample by-lines and dra-
matically reduced window wear (Fookes et al. 1973). There was now a complete contrast in
approaches to OSA by the radioisotope and the X-ray tube systems. Joint CRA–AAEC trials

Density Probe

Pb Probe Pulp In

Zn Probe

To Adjacent
Flotation Cells
Existing Slurry
Vessel
Source: Cutmore et al. 1993.

FIGURE 11 Radioisotope probes immersed in a plant mineral slurry

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86 HISTORICAL ASPECTS OF FLOTATION

at Broken Hill using immersion probes demonstrated excellent results for lead and zinc
determined in plant process streams (Fookes et al. 1973). Stump and Roberts (1974) dem-
onstrated better control of grinding and flotation at the New Broken Hill Consolidated
concentrator based on using radioisotope probes and computer control, as well as excellent
accuracies of the OSA for lead and zinc in actual plant installations.
From 1967 the AAEC also used silicon solid-state detectors for laboratory XRF mea-
surements on mineral samples from plants. These detectors had good X-ray energy resolu-
tion and proved to be very suitable for the analysis of samples from process streams
(Gravitis, Greig, and Watt 1974). These detectors were then not sufficiently stable for use in
industrial plants. In the early 1980s, Amdel incorporated these detectors into immersion
probes for plant use in tailing streams.

Commercial System
The radioisotope XRF and XRA assemblies developed by the AAEC, incorporated into the
casing of the immersion probe developed by CRA, became the basis of the commercial OSA
system. Philips Industries Ltd. was selected as the licensee to design and manufacture the
commercial system hardware, and Amdel was selected to undertake the feasibility studies,
installation, and calibration. Amdel installed the first three plant-analysis systems in concen-
trators in 1973. The development of the radioisotope on-stream analysis system had been a
productive 10-year project that contributed much to flotation technology.
Amdel took over the system manufacture in 1978. Thermo Electron Corporation took
over the Amdel Instrumentation Division, including staff, in 1999 and continues to manufac-
ture the radioisotope OSA system in Australia and market it worldwide. By 2003 about 170
radioisotope X-ray systems had been sold worldwide for mineral processing operations.

Automatic Control of Flotation Circuits
By 1975 the problem of long delays between taking samples in plants and receiving assays
had been solved; flotation circuit performance could be assessed every few minutes, and
automatic control systems could be developed for flotation circuits that would take into
account changes in mineral contents and floatabilities. Multistream X-ray tube systems and
radioisotope systems were being used to monitor and control flotation circuits in several
concentrators.
The objective of automatic control was and still is to operate each flotation circuit at
the point on its optimum grade-recovery curve that gave the best economic results. Some of
the approaches tried in early control systems were
• Controlling reagents by the feed grade and/or the concentrate grade
• Automatic raising and lowering of concentrate diverter trays on rougher banks to
maintain stable performance of cleaner banks
• Controlling reagents by making incremental changes and searching for optimum cir-
cuit performance
These early systems were designed for specific cases, because no two ores are identical,
and they usually improved circuit performance by reducing variations in concentrate grades
and increasing recoveries of valuable minerals. They also improved the skills of operators
who were given much more information about the circuit by computer-based data logging
systems than was available through observation.

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HISTORY OF FLOTATION TECHNOLOGY 87

The problem with control systems in those early days was that if the ore changed signif-
icantly, it was difficult to determine on-line the new grade-recovery curve and the best oper-
ating point, so the control target was difficult to define. There has been some progress on
this problem, mainly through the use of various mathematical techniques. Software to con-
trol flotation circuits is commercially available.

O T H E R U S E S O F F L O TAT I O N
Over the decades, flotation has found uses in areas far removed from mine sites. It is used for
the removal of solids in wineries, breweries, butter and cheese factories, dairies, and sewerage
plants, among others. It is commonly used as a means for removing oil and contaminants
from water in smelters and refineries, as well as for removing algae and other organic con-
taminants from water. Other areas in which flotation can be found are the de-inking of recycled
paper, treatment of abattoir and sawmill effluent, sugar milling and refining, wool scouring, the
production of vegetable oil and margarine, paint manufacturing, and paper processing.

POSTSCRIPT
The Centenary of Flotation Symposium celebrated the life of a remarkable process and the
achievements of scientists and engineers in many countries who overcame early problems
and made flotation an advanced technology. Theodore Hoover wrote of the difficulties of
developing “concentration upside down,” as flotation was described (Ingalls 1907), into an
acceptable and standard process: “The only previous authentic case where substances
heavier than water have been made to float was the occasion of Elisha’s miracle with the axe
(2 Kings 6) and mining and metallurgical engineers are not great believers in miracles”
(Hoover 1914). But the engineers were never daunted. Flotation was very difficult to oper-
ate in its early years because of the variable nature of the ores, yet from its inception, engi-
neers have continued to extend its limits of application. The variety and extent of its uses
today could not have been imagined 100 years ago when thin scums of zinc concentrates
were being floated on top of hot, acid pulps. Progress since then has been due to the cumula-
tive achievements of a legion of engineers working on flotation processes in many countries.
There will be many advances yet in flotation technology as its capabilities for separating
valuable and waste materials are used more extensively. It is hoped that this brief history
gives incoming flotation engineers and scientists some of the fascinating background of the
process with which they will be working.

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Froment, A. 1902. British Patent 12,778. June 4.
Fuerstenau, D.W., editor. 1962. Froth Flotation 50th Anniversary Volume. New York: American
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Fuerstenau, M.C. 1999. Froth flotation: The first ninety years. Pages xi–xxxiii in Advances in Flotation
Technology. Edited by B.K. Parekh and J.D. Miller. Littleton, CO: SME.
Fuerstenau, M.C., and K.N. Han, editors. 2003. Principles of Mineral Processing. Littleton, CO: SME.
Gomez, C.O., and J.A. Finch. 2002. Gas dispersion measurements in flotation machines. CIM Bull.
95(1066):73–78.
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Fuerstenau and S. or different physical states of the same substance. Electronic edition published 2009.W. When applied to physical and chemical systems. Metallurgy. 2007 7:36 PM Some Aspects of Flotation Thermodynamics D.flotation0. type of mineral. thermodynamics includes several topics: 1. Raghavan A B S T R AC T This chapter presents a brief summary of some of the thermodynamic aspects of flotation processes. All rights reserved. One criticism that has been leveled against the practical need for studying the thermodynamics of flotation is that thermodynamics is concerned mainly with equilibrium processes and the fact that. it can help the engineer make some predictions as to how the flotation response may change with temperature. Particular attention is given to the thermodynamics of collector adsorption. exist in equilibrium 2. and so on. Though thermodynamics cannot actually report to a flotation engineer about what the mineral recovery will be at a given temperature or under given solution conditions. the system may not be in equilibrium. a chemical reaction or a phase change will take place spontaneously. . Whether. In this chapter. The conditions under which chemical substances. such as flotation. This review is not considered to be exhaustive.book Page 95 Tuesday. an attempt is made to briefly review various thermodynamic investigations and approaches undertaken to gain an insight into those interfacial processes that play a dominant role in the flotation process. Thermodynamic considerations that control interfacial and wetting behavior in mineral– water–air systems are discussed. type of collector. The effect of temperature on chemical reactions and phase equilibria 5. January 2. under certain specified conditions. Interestingly. The principles underlying the methods of measurement of those properties whose values are required for quantifying the foregoing Thermodynamics is used to predict whether or not a change will tend to occur and yet reveals nothing about the rate at which the change will take place. in the time span during which flotation takes place. 95 © 2007 by the Society for Mining. INTRODUCTION The application of the principles of thermodynamics to flotation systems has contributed significantly toward understanding some of the underlying foundations of flotation pro- cesses. 3. and Exploration. The relation between the interchange of heat and other forms of energy when a chemical reaction or phase displacement occurs 4. Wada (1960) actually defined flotation as a thermodynamic process in which gas–liquid–solid interfaces participate in separating finely divided solids from one another. but only summarizes some of the highlights.

Because the PV term is negligible for a surface. and SS is the surface entropy per square centimeter of surface.600 5. is defined by HS = ES + (PV)0 = GS + T · SS (EQ 1) where ES is the total surface energy. the surface tension decreases linearly with temperature (Adamson 1967).1 ergs/cm2. γ = 72. HS. γ. In the case of water at 20°C. both experimentally and theoretically. T is the temperature.600 Source: Adamson 1967.800 Alumina (Al2O3) 1. (EQ 4) dT For most liquids.book Page 96 Tuesday. no distinction will be made between them. from which ES is calcu- lated to be 51. The surface tension. ergs/cm2 Paraffin 25 Graphite 110 Halite (NaCl) 230 280 Fluorite (CaF2) 450 Magnesia (MgO) 1. Metallurgy. only in a one-component system are GS and γ identical. (EQ 3) ⎝ ∂t ⎠ p dT the relation between total surface energy and surface tension is dγ E S = γ – T ------.000 1. and Exploration. © 2007 by the Society for Mining. These quantities are usually given as ergs per square centimeter or dynes per centimeter. Electronic edition published 2009.75 ergs/cm2 and dγ/dT = –0. . January 2. PV is the pressure volume. the evaluation of surface energies is less straightforward. n where A is the interfacial area.16. a typical liquid hydrocarbon. These can only be considered approxi- mate. are defined by ∂G G S = γ = ⎛ -------⎞ (EQ 2) ⎝ ∂A⎠ T. γ = 21.10. Clearly. but they enable one to see how widely solids do differ. GS is the Gibbs surface free energy. and surface free energy. which are identical in magnitude. the type of chemical TABLE 1 Approximate surface energies of some materials at room temperature Material γ.80 ergs/cm2 at 20°C and dγ/dT = –0. In the case of octane.flotation0.090 Gold 1. Actually. 2007 7:36 PM 96 FLOTATION FUNDAMENTALS T H E R M O DY N A M I C S O F S U R FA C E S The enthalpy of the surface on a unit area basis. ergs/cm2 ES. but for the purpose of this review. All rights reserved. from which one evaluates the total surface energy of water to be 120 ergs/cm2. the surface energy and surface enthalpy are equivalent. P. In the case of solids. GS.900 Diamond 5. and n is the number of moles present in the system. Some typical values of the surface tension (and surface energies) of selected materials are given in Table 1. Because the surface entropy at constant pressure is given by ∂G dγ S S = – ⎛ --------S-⎞ = – ------.

and has the following form (Defay and Prigogine 1966): dγ = – S S dT – ∑ Γ i dμ i (EQ 5) i There are several ways to define Γi. that is. Overall. particularly for oxides. Γ1. Because flotation processes are often carried out at constant temperature. it should be added that mineral–water interfacial tensions are gen- erally much lower than the surface energies.i ≠ j (EQ 8) RT ∂ ln a i⎠ T. μ2…μi. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 97 bonds that hold a crystal together have a marked effect on the magnitude of the surface energy of solids. but the simplest way mathematically is to use the convention proposed by Gibbs. R is the gas constant. and j vice versa. All rights reserved. such that Γ1 = 0. then the Gibbs convention is most applicable. The Gibbs adsorption equation relates the interfacial tension between two phases to the temper- ature. and Exploration. where ai is the activity of species i in the bulk aqueous solution. Metallurgy. the chemical potentials of various species. Equation 5 can be modified as i dγ = – S S dT – ∑ Γi( 1 ) dμi (EQ 6) i=2 where Γi(1) refers to the relative adsorption of component i at the dividing surface. at an interface? The basis for the thermodynamics of the adsorption of dissolved substances was unambiguously laid down by Gibbs. T H E R M O DY N A M I C S O F A D S O R P T I O N What happens in the case of a system with several components when one or more of the components accumulates.book Page 97 Tuesday. T. adsorbs. will be positive if ( ∂γ ⁄ ∂ ln a i ) T. at the interface. wettability.i ≠ j is negative. because it quantitatively expresses the change in sur- face tension due to the adsorption of surface-active materials. Γ2…Γi. in the bulk. Equation 7 can be rearranged to give 1 ∂γ Γ i( 1 ) = – -------. the Gibbs adsorption equation is highly relevant to flotation through its applica- tion to phenomena involving frother systems. μj ⎝ The adsorption density. © 2007 by the Society for Mining. By defining the adsorption of the solvent (component 1) as zero. and T is the temperature. that the adsorption of the solvent is zero and that Γi is the excess surface concentration. January 2.⎛ ------------⎞ . namely.flotation0. of the system. Finally. Electronic edition published 2009. Excess surface concentration means the excess at the interface over that which would be expected if the solution phase were uniform up to a hypothetical plane surface that divides the two bulk phases in a heterogeneous system. Γ(1). μ1. If one measures adsorption densities from differences in bulk concentrations in dilute systems (as are usually encountered in flotation systems). and so on. the development of surface charge at mineral–water interfaces. and the surface excess or adsorption density of the various species. . μ . Equation 6 can be simplified to i dγ = – ∑ Γ i( 1 ) dμ i (EQ 7) i=2 Recalling that dμi = RT d ln ai.

the area per molecule is 27. Electronic edition published 2009. At this concentration. and Exploration. dynes/cm 60 40 Butanol/Water 20°C A 20 140 6 120 Area per Adsorbed Molecule.712 (0. sq. at an activ- ity of 0. when applied to a dilute aqueous solution of a frother such as an alcohol (ROH) in water. Å 100 Γ. To illustrate the use of the Gibbs equation in flotation. All rights reserved. The Gibbs equation. the adsorption density of butyl alcohol is 6. . there must 80 72. which are surface-active agents that have a tendency to concentrate at the air–water interface. The lowering of the surface tension of water due to the addition of alcohol shows that the alcohol is positively adsorbed at the water–air interface.8 Surface Tension. 2007 7:36 PM 98 FLOTATION FUNDAMENTALS The adsorption density can be calculated from the slope of the surface tension-versus- log activity (or concentration) curve if the surface tension of the particular interface under consideration can be determined experimentally. first consider aqueous solutions of frothers. FIGURE 1 Adsorption of butanol at the aqueous solution/gas interface: (a) Surface tension and (b) adsorption density and area per adsorbed molecule versus log butanol activity © 2007 by the Society for Mining. For proper frothing. suggesting that the adsorbed butyl alcohol on water is monomolecular.6 sq Å. Metallurgy. For example. mol/cm 2 × 10 10 4 80 60 2 40 20 B 0 0 –3 –2 –1 0 log a2 Source: de Bruyn and Agar 1962.book Page 98 Tuesday. January 2.4 sq Å. has the following form (de Bruyn and Agar 1962): dγ = ( – RT )Γ ROH d ln a ROH (EQ 9) ≈ ( – RT )Γ ROH d ln C ROH The dependence of surface tension on the frother concentration and the adsorption density of the frother at the air–water interface are shown in Figure 1 for the water–butyl alcohol system.flotation0.854 molality). Close-packed films of long- chained carboxylic acids and alcohols exhibit areas per molecule of 21.03 × 10–10 mol/cm2.

In other words. such as the salt of a fatty acid.e.flotation0. Probably the most marked lowering of surface tensions due to adsorption is that exhib- ited in solid–vapor systems.book Page 99 Tuesday. namely: ΔG = γ SG – ( γ SL + γ LG ) (EQ 13) © 2007 by the Society for Mining. This is called Traube’s rule. water vapor adsorption can lower the surface ten- sion of oxides by several hundred ergs per square centimeter. In the absence of any other electrolytes where Na+ and R– would be the only species that are adsorbing. solid–liquid. the change in the surface tension of the solution–air interface is given by dγ = – Γ R – dμ R – – Γ Na + dμ Na + (EQ 10) where R– refers to the dodecyl sulfonate anion (C12H25SO3–). and θ is the contact angle. . Metallurgy. the thermodynamic aspects of the bubble–particle contact will be reviewed and critically analyzed (Adamson 1967. then depending on the pH of the solution. and Exploration. and liquid–gas inter- faces. and γLG are the tensions of the solid–gas. γSL . January 2. showing that the same number of molecules are adsorbed per unit area of the surface. Gaudin 1957). The surface tension lowerings produced by the positive adsorption of a homologous series of n-aliphatic alcohols at the water–air interface are most conveniently compared by plotting the surface tension of the solution as a function of the logarithm of the activity (or concentration) of the alcohol (Defay and Prigogine 1966). the slope is independent of the alcohol considered. They differ from the frothers in the sense that they are generally electrolytes.. In this section. it can easily be shown that dγ = – 2RT Γ R – d ln C NaR (EQ 11) If the organic electrolyte is a weak electrolyte. the concentration ratio of two neighboring homologs is constant and approximately equal to 3. so that momentarily deformed films can withstand the shock. Collectors are heteropolar organic compounds whose main function is to adsorb at the mineral–water interface. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 99 be a surface tension–concentration gradient such as that shown in Figure 1 (i. In the concentration range corre- sponding to the lower parts of a series of such curves. the surface activity is approximately tripled for each additional –CH2– group in the molecule. For example. The general thermodynamic condition for three-phase contact is defined by Young’s equation for the system depicted schematically in Figure 2. Further. γ SG = γ SL + γ LG cos θ (EQ 12) where γSG. Taking into consideration the aqueous dodecyl sulfonate system. Electronic edition published 2009. The change in the free energy accompanying the replacement of a unit area of the solid–liquid interface by solid–gas interface is given by Dupre’s equation. respectively.2 for the same Δγ. the adsorption of neutral collector molecules must also be considered. but they also tend to adsorb at the mineral–air and water–air inter- faces. All rights reserved. T H E R M O DY N A M I C S O F W E T T I N G Bubble–particle contact is one of the key factors controlling the process of froth flotation. dγ/dC ≠ 0). Adsorption phenomena at the bubble–mineral interface appear to have a significant role in flotation.

Young’s equation (Equation 12) is valid in an ideal system where all gravita- tional effects are absent and the system is at equilibrium ( Johnson 1959). for a perfectly flat surface. namely: ΔG = γ LG ( cos θ – 1 ) (EQ 14) Thus. So when part of the deformation work is performed by gravi- tational or kinetic energy. . there will be a free energy decrease upon attachment of a mineral particle to an air bubble. Combination of Dupre’s equation with Young’s equation yields the following expres- sion for the free energy change. is capable of performing. The deformation is then gov- erned by the shape of the solid surface and. contamination. Leja and Poling (1960) conducted an interesting theoretical study on the attachment of air bubbles to flat solids.book Page 100 Tuesday. WP. Often. if a liquid-advancing contact has a different value than a liquid- receding angle. considerable hysteresis exists in measured contact angles because of surface roughness. equilibrium is not attained in the system. nonequilibrium adsorption effects. the magnitude of the contact angle. The contact angle θ is the angle between the liquid–gas and the liquid–solid interfaces. a pronounced hysteresis effect exists in this system under the conditions of this investigation. that is. Typically. even when © 2007 by the Society for Mining. Further. determines the extent of deformation that the interfacial energy pool. As can be seen in this figure. measured through the liquid. All rights reserved. Metallurgy. work must be expended by the system in deforming the air–liquid interface during attachment. WA . Figure 3 presents equilibrium. January 2. the use of Young’s equation is not valid. Under these conditions. Leja and Poling (1960) suggest that gravitational and kinetic energies (due to the motion of particles and air bubbles) affect the energy expended in deformation of the air– liquid interface. the work of defor- mation must be performed solely by the interfacial energy. 2007 7:36 PM 100 FLOTATION FUNDAMENTALS Liquid γLG Gas θ γSG γSL Solid FIGURE 2 Schematic representation of the equilibrium contact between an air bubble and a solid immersed in a liquid. If there is hysteresis. and their results will be summarized at this stage. and the actual free energy of adhesion per unit area. both in the presence and absence of gravitational effects. which can be realized only when there are no other energy-consuming effects. the geometry of the system is not taken into account in Dupre’s equa- tion. either decreasing or increasing the amount of deformation to be performed by the interfacial energy pool.2 as measured by Waka- matsu and Fuerstenau (1973). such as deformation of the bubble. Electronic edition published 2009. advancing and receding contact angles on alumina in sodium dodecyl sulfonate solutions at pH 7. for any finite value of the contact angle. In the absence of other forms of energy (gravitational and kinetic). etc. The theoretical relationship of Dupre’s equation expresses the maximum possible decrease in the free energy of the system resulting from the bubble–particle contact.flotation0. Thus. hysteresis of the practical contact angle is observed. (Adamson 1967). is smaller than the theoretically available value. θ. because the solid surface is not of the same contour as that of the air bubble. WA (equal to ΔG given by Equation 13). and Exploration.

It can be shown (Adamson 1967) that d cos θ – ΔH imm = E LG cos θ – Tγ LG -------------. with small contact angles). a correction that becomes particularly sig- nificant at the threshold of hydrophobic character (i. FIGURE 3 Equilibrium. which were determined experimentally with fairly large bubbles or drops. The temperature coefficient of the contact angle can provide thermodynamic information about wetting processes. According to Leja and Poling. A limited amount of work has been carried out on the temperature dependence of con- tact angles. refer to an article by Neumann (1974). a finite receding contact angle indicates a lower WP. mol/L Source: Wakamatsu and Fuerstenau 1973. All rights reserved. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 101 100 S S S A A A Liquid Equilibrium Liquid 80 Receding Advancing Contact Angle. January 2.2 other effects. knowledge of the temperature coefficient of contact angle provides a means of calculating the heat of immersion.book Page 101 Tuesday. For an excellent account of the temperature dependence of contact angles on low-energy surfaces. and receding and advancing contact angles on alumina in aqueous dodecyl sulfonate solutions at pH 7. surface contamination.2 Receding 24±1°C 0 10–6 10–5 10–4 10–3 Concentration of Dodecyl Sulfonate.. are excluded. than under the condition of equilibrium. should not be used in Young’s equation unless a suitable correction in their magni- tude is made to account for gravitational effects. and Exploration. Their conclusion was that the contact angles. On the other hand. degrees 60 Advancing 40 Equilibrium Alumina 20 Ionic Strength 2 × 10–3N pH 7. WP. an advancing contact angle indicates that a greater portion of WA is being converted to the actual adhesion. which is the enthalpy change upon immersing a clean. dry solid into a liquid. such as surface roughness. and so forth. (EQ 15) dT where ELG is the total surface energy of the liquid–gas interface. For example. T H I N F I L M P H E N O M E N A A N D F L O TAT I O N The well-known classical condition for the possibility of a bubble–particle contact in a given liquid medium has been specified by Equation 13 where ΔG = γ SG – γ LG – γ SL < 0 © 2007 by the Society for Mining.flotation0. .e. Electronic edition published 2009. Metallurgy.

book Page 102 Tuesday. Electronic edition published 2009. the free energy of the liquid film increases continuously during the thinning of the liquid film. GS(h) = γSL + γLG(h). For liquid–solid systems with a finite contact angle. Π. the © 2007 by the Society for Mining. Π must be negative for certain film thick- nesses (Clifford 1975). h is the thickness of the film. January 2. . When the hydration of the surface is low. GS(h) for γSG where GS is the free energy of a column of liquid layer (of height h) and solid of unit cross section. T where Vm is the molar volume of the liquid and the term ∂G/∂h is the disjoining pressure. Laskowski has made an attempt to modify this equation for the presence of a liquid layer by making the following substitutions: 1. which must be overcome for attachment to occur (Laskowski 1974). If Π is positive. according to Rehbinder. 2007 7:36 PM 102 FLOTATION FUNDAMENTALS This relation assumes that there is no liquid layer between the bubble and the particle after contact. thus preventing spontaneous attachment of the air bubble to the surface. (For curved liquid–air interfaces. and 2.= V m ⎛ -------⎞ (EQ 18) po ⎝ ∂h ⎠ A. then Derjaguin and Shcherbakov (1961) showed p ∂G RT ln ----. Metallurgy. the excess free energy of the layer. The thinning of this layer is believed to control flotation (Laskowski 1974). These substitutions lead to ΔG ( h ) = γ LG ( h ) – γ LG (EQ 16) where ΔG(h) expresses the energy barrier in the transition from no contact to bubble con- tact. the above expression has been suitably modified by Padday [1970]). Π can be positive or negative and can change sign with film thickness (Clifford 1975). the thin film is stable. and po is the vapor pressure in equilibrium with the bulk liquid. γo is the specific-surface free energy of an infinitely thick liquid film. In effect. All rights reserved. When the surface is highly hydrated (threshold hydrophilicity). Depending on the liquid and the surface.flotation0. A complete understanding of the mechanism of attachment of particles to air bubbles in flotation should be based on the analysis of changes in the surface free energies of thin films of water between the solid and the air bubbles. If p is the vapor pressure in equilibrium with a flat thin film. γLG(h) is the surface tension of the liquid–gas interface expressed as a function of the thickness of a liquid layer h.” Π. it is the change of free energy with thickness and is given by the expression ∞ γ = γ o + ∫ Π dh (EQ 17) h where γ is the specific-surface free energy of the thin liquid film. In the thinning of the water layer on the approach of a solid surface to an air bubble. Derjaguin (1932) suggested that the thermodynamic properties of thin films are differ- ent from those of the bulk phase and introduced the parameter “disjoining pressure. and Exploration. changes in relation to the initial hydration of the surface. This equation ignores the possibility of the existence of a thin liquid layer between the bubble and the solid even after attachment. as a measure of the corresponding change in the thermodynamic properties. and Π is the dis- joining pressure. Rehbinder (1949) made some theoreti- cal calculations to determine the excess free energy of thin films.

γ 1 2 3 Δγ Distance from the Surface Source: Rehbinder 1949. Chander and Fuerstenau (1972) have made an attempt to explain the natural floatability of molybdenite using this approach. From their experimental observations. In 1960. in which they observed a regular decrease in induction time with increasing tempera- ture. Eigeles and Volova commented that “the experimental data on collector action suggest that there may exist forces which are not taken into account by the present-day the- ory of coagulation of hydrophobic colloidal sols but exert a major influence on the kinetics of flotation adhesion. All rights reserved. The additional force suggested for bubble–particle Free Energy of a Thin Hydrated Layer. they evaluated an apparent activation energy for film thinning and attachment processes. Πel is an electrostatic term to account for double-layer effects. ΠSL is the disjoining pressure due to the effect of the solid on the liquid film. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 103 free energy of the thin film does not increase on initial thinning of the film. Electronic edition published 2009. and Exploration. January 2. The previous two cases are represented schematically in Figure 4.book Page 103 Tuesday. . the film would certainly be unstable and would rupture spontaneously. and (3) very weak surface hydration © 2007 by the Society for Mining. and Πi is the change in free energy due to any other specific inter- actions between the liquid layer and the surface. (2) moderate surface hydration. It is usual to consider that these effects are additive (Sheludko 1967) and that the disjoining pressure can be broken down into a number of components (Padday 1970): Π = Π LL + Π SL + Π el + Π h + Π p + Π i (EQ 19) where ΠLL is the disjoining pressure of the liquid film in the absence of a solid. FIGURE 4 Change in the free energy of a water film between a gas bubble and solid surfaces with differing hydrations: (1) maximum surface hydration. Πh is the contribution from hydrogen bonding. In the case of strongly hydrophobic solids where water vapor adsorption is far lower than a monolayer. Metallurgy.” This led to their conducting a detailed investigation of the effect of temperature on induction time. thus favoring spontaneous attachment of a bubble to a mineral. ΠP is from polar interactions. The disjoining pressure can be due to many effects. Curve 2 in this figure is most typical of practical flotation systems.” They added that “this unaccounted factor is what causes sharp accel- eration of the thinning of the boundary layer and a pronounced increase of its fluidity.flotation0.

in principle. leaving behind an adsorbed layer in equilibrium with saturated water vapor (Mellgren et al. Hence. and Exploration. Laskowski and Kitchener (1968) analyzed hydrophobic- ity (floatability) in terms of these relations and concluded that all solids would be hydrophobic if they did not carry polar or ionic groups on their surface. All rights reserved. They also empha- sized that hydrophobicity arises from the exceptionally large cohesive energy of water that is due to hydrogen bonding between water molecules. Because the function of the flotation collector is to render the surface more hydrophobic by eliminating or shielding the polar sites of the solid.flotation0. assuming that the contact angle is given by Young’s equation (cos θ = [γSG – γSL]/γLG). 1974). After detailed experi- mentation with methylated silica. a finite contact angle of an air bubble on the solid to be floated. Yoon (2000) has made extensive measurements of hydrophobic forces and applied the concept to bubble–particle interaction in flotation. and stibnite (Gaudin 1957).g. The free energy of sat- uration of the solid with water (ΔGsat) is given by the expression © 2007 by the Society for Mining. Only a few solids are naturally hydrophobic and therefore respond to flotation without adding a collector. talc. and hydrophilic solids such as oxides exhibit strong polar interactions with water and are covered with hydroxyl groups (e. investigation of the energetics of the solid–water interface. The magnitude of Wad depends on γSL which reflects the extent of interaction between the solid and water. 2007 7:36 PM 104 FLOTATION FUNDAMENTALS attachment processes in flotation by Eigeles and Volova was first observed and measured by Israelachvili and Pashley in 1982 between mica surfaces coated with cetyltrimethylammo- nium bromide.book Page 104 Tuesday. evaluation of Wad is not easy. it can be shown that Wad – Wco = γLG (cos θ – 1). using the surface force apparatus (Israelachvili and Pashley 1988). Because Wco = 2γLG (the surface tension of the liquid. 1974) for measuring solid–water interactions have been widely used: (1) adsorption of water vapor on solids and (2) calorimetric heats of immersion in liquid water. Metallurgy. sulfur. In the first method. It should be remembered that Wad is correctly defined as the work required to separate liquid water from a solid–water interface. silica). should help one to comprehend the concomitant phenomena of flotation. . flotation is possible if Wad < Wco (≤144 dynes/cm). do not exhibit significant polar interactions with water. and the energetics of the solid–liquid interface are mainly controlled by dispersion forces. Less hydrophobic surfaces have some polar interactions with water.. But for hydrophilic solids. These solids include such materials as graphite. molybdenite. two methods (Mellgren et al. the adsorption density of water vapor is determined as a function of water vapor pressure from the dry state up to (or close to) saturation. in terms of work of adhesion of water to the solid (Wad ) and the work of cohesion of the liquid (Wco). θ = 0 (Young’s equation is no longer valid under these conditions). However. which is caused by the disruption of normal hydrogen bonding in water near a hydro- phobic surface. is now called the hydrophobic force and would be an additional component in Equation 19. both in the presence and absence of a collector. January 2. This force. which is usually only slightly smaller than that of pure water) and Wad = γSG + γLG – γSL . Hydrophobic materials such as graphite. and consequently. Wad = (γLG(cos θ + 1)) can readily be obtained for hydrophobic solids given that θ > 0. Electronic edition published 2009. namely. T H E E N E R G E T I C S O F F L OATA B I L I T Y Consider the conditions for floatability.

. 1974). Heats of immersion can provide some information on the energetics for systems in cases of zero contact angles. With hydrophilic solids. which is the surface enthalpy of normal liquid water (Mellgren et al.book Page 105 Tuesday. and po is the saturation pressure. Griffiths studied the temperature coefficient of the heat of immersion of Al2O3 in water and found it to have a near-zero value. The water-vapor adsorption method has also been used to study changes in the wetta- bility of surfaces induced by the adsorption of collectors. the major contribution to ΔGsat comes from the most strongly bound water (i. Therefore. Hence. Metallurgy. –264 ergs/cm2 for calcite. Lovell. the heat of immersion of a clean solid. Griffiths (1973) analyzed the results of Wade and Hackerman (1964) on the effect of the outgasing temperature on the heat of immersion of alumina (Al2O3) in water and con- cluded that about one-half of the heat of immersion of alumina is due to the physically adsorbed water with the remainder being due to the reformation of surface hydroxyl groups lost during heat treatment. Numerous heats of immersion measurements of minerals have been reported in the lit- erature (Healy and Fuerstenau 1965. January 2..e.flotation0. © 2007 by the Society for Mining. To gain more insight into the nature of physically adsorbed water layers. He concluded that the water structure outward from the surface does not gradually grade into that of bulk water. ΔHimm. and –240 ergs/cm2 for barite (Mellgren et al. at low p/po) and the net value is much greater than 144 ergs/cm2. and Finkelstein (1970) determined the effect of adsorbed oleate on calcite and fluorite on the ΔGsat value. and Table 2 presents a brief sum- mary of some typical values. p is the water vapor pressure. Hall. Electronic edition published 2009. On a unit area basis. In his words. is given by ΔH simm = H SL – H S ≈ E SL – E S (EQ 21) The hydrophilic character of a surface is clearly revealed by a large exothermic heat of immersion. Zettlemoyer 1968). water molecules beyond the first few layers behave similar to bulk water. and Exploration. Their results gave a ΔGsat value of –300 ergs/cm2 for clean fluorite and –50 ergs/cm2 for oleate-covered fluorite. what exists “is an inner film of strongly bound water that discontinuously ends with near normal water structure (at least energetically) continuing on outward from the surface” (Griffiths 1973). the two approaches discussed in this section are still of limited value in flotation research. which indicates a strong interaction with water molecules. One study that relates the heat of immersion of oxides to the point of zero charge (which plays an important role in selective flotation and collector choice) is worth mention- ing as a final point. Some reported values are –316 ergs/cm2 for quartz. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 105 Po ΔG sat = RT ∫ Γ d ln p ⁄ p o (EQ 20) o where Γ is the adsorption density (expressed in moles per area). Healy and Fuerstenau (1965) found a quantitative linear relation between the heat of immersion and the pH of the point of zero charge for a number of inorganic oxides. the heat value falls to about 120 ergs/cm2. All rights reserved. Although values of ΔHimm are high for hydrophilic and low for hydrophobic surfaces. Specifically. 1974). there is no well-defined “critical heat of immersion” for development of contact angles. When approximately three monolayers of water vapor are preadsorbed on the solid before immersion. calori- metric heat measurements suggest that the first layer of water on polar solids is very strongly bound.

Assuming ax = Cx. 2. there has been a growing interest in whether collector adsorption at the S–L.book Page 106 Tuesday. 3. Metallurgy. by differentiating Equation 12 with respect to ln Cx at constant P and T and applying relations 22a–c. January 2. or L–G-interface is the main factor controlling flotation behavior. ΓxSG must be less than ΓxSL + ΓxLG cos θ. . ΓxSG must be greater than ΓxSL + ΓxLG cos θ. On the assumptions that the collector adsorption at each interface follows the Gibbs equation and the contact angle of an air bubble on the solid is given by Young’s equa- tion. dθ γ LG sin θ --------------. © 2007 by the Society for Mining. and θ is the contact angle of the air bubble on the solid.flotation0. the following result is obtained (Smolders 1961). ΓxSG must be equal to ΓxSL + ΓxLG cos θ. If the angle of contact increases with the increase of solute concentration (dθ/dln ax is positive). C R I T E R I O N F O R F L O TAT I O N I N T E R M S O F C O L L E C T O R ADSORPTION Starting with the work of de Bruyn. S–G. γij is the tension of the interface ij. If the contact angle decreases with increasing concentration (which may happen because of the reverse orientation of the second layer of ionic surfactants at the solid–liquid interface). ax is the activity of the collec- tor in the bulk solution. All rights reserved. Consider a collector x that is present at all three interfaces. the following results can be deduced: 1. In cases where the contact angle does not vary with concentration (dθ/dln ax = 0). which is the concentration x. and Schuhmann (1954). ergs/cm2 –Δ Contact Angle. Electronic edition published 2009. 2007 7:36 PM 106 FLOTATION FUNDAMENTALS TABLE 2 Heats of immersion and contact angles of some materials in water* Solid ΔHimm. degrees Teflon 6 108 Graphon 26 82 Quartz 260–370 0 SnO2 (cassiterite) 400–570 0 TiO2 (rutile) 550 0 Fe2O3 (hematite) 530 0 Al2O3 (alumina) 650–900 0 *The oxides were activated at 200°C. the following relations can be written: dγ LG = – RT Γ xLG d ln a x (EQ 22a) dγ SG = – RT Γ xSG d ln a x (EQ 22b) dγ SL = – RT Γ xSL d ln a x (EQ 22c) γ SG – γ SL = γ LG cos θ (EQ 22d) where Γxij represents the adsorption density of x at interface ij. and Exploration. Overbeek.= RT ( Γ xSG – Γ xSL – Γ xLG cos θ ) (EQ 23) d ln C x From Equation 23.

without directly measuring ΓSG and ΓSL . Somasundaran. and Schuhmann stressed the first result obtained from Equation 23.book Page 107 Tuesday. Sandvik and Digre (1968). In an attempt to apply the analysis of de Bruyn. They proposed a bubble-transfer hypothesis. T H E E L E C T R I C A L D O U B L E L AY E R AT M I N E R A L – WAT E R I N T E R FA C E S Because adsorption phenomena at mineral–water interfaces are controlled in most cases by the electrical double layer. Finch and Smith (1975) found a decrease in the tenacity of the bubble–solid attachment with decreasing surface tension of the liquid–air interface. neglecting the potential because of dipole effects. In a later investigation on the quartz–dodecylammonium acetate and the magnetite–dodecylammonium acetate systems. Bleier. stressed the need for looking at adsorption conditions on the bubble and at the S–G interface. Their hypothesis in fact stresses the impor- tance of adsorption at the L–G interface. Electronic edition published 2009. It should be stressed that the interface of primary importance to flotation is the solid– liquid interface. showed that the adsorption of a collector on a solid surface (silica) increased in the presence of gas bubbles. substantially below an equilib- rium concentration where an abrupt change in the adsorption density from solution takes place. and Exploration. of the L–G interface with pH. Overbeek. Aplan and de Bruyn (1963) undertook an investigation of the adsorption of hexyl mercaptan onto gold and the flotation of gold particles from an aqueous solution of hexyl mercaptan using nitrogen satu- rated with both water and mercaptan vapor as the gaseous phase. there can © 2007 by the Society for Mining. This figure also shows the drop in potential across the double layer. Overbeek.flotation0. They con- cluded that this correlation implies that the greater the adsorption of the collector at the bubble surface (higher the surface pressure). Goddard. . namely. In addition. the better the flotation. In 1968. in addition to the S–L interface. and Kulkarni (1976) later reported good corre- lation between the flotation recovery of quartz in the presence of amines and the decrease in the surface tension of the water–air interface. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 107 As early as 1954. in an attempt to explain the effect of collector chain length on flotation at concentrations below those necessary for hemimicelle association of the hydro- carbon chains at the S–L interface. They found that excellent flotation occurs at 3% to 30% surface coverage (low ΓSL). de Bruyn. one must be concerned with factors responsible for the charge on the solid surface and with the behavior of ions that adsorb as counterions to maintain elec- troneutrality (Kruyt 1952). The collector simply must adsorb at this interface in order to reduce molec- ular attractions between the solid and the liquid. thus casting a doubt on their earlier conclusion. and Schuhmann to a simple flotation system. he found that the amount of collector adsorption at the S–G interface was approximately equal to the adsorption at the S–L interface. Metallurgy. Pope and Sutton’s (1972) work did not confirm this hypothesis given that they observed a decrease in collector adsorption density at the solid after flotation. Finch and Smith (1972) found that the flotation recovery of quartz and magnetite (in the presence of dodecylamine) as a function of pH can be correlated with the variation in the surface pressure [γsolvent – γsolution]. Depending on whether ions remain hydrated or are dehydrated upon adsorption. The closest distance of approach of counterions to the surface (δ) is the Stern plane. they observed ΓSG to be greater than ΓSL in the flotation range. From the results of his investigation of the quartz-dodecylamine solution–gas system. All rights reserved. January 2. that ΓxSG > ΓxSL (for θ < 90°). which envisages the collector as being transferred from the bubble surface to the solid. Figure 5 presents a schematic representation of the electrical double layer of counterions extending out into the liquid phase.

For oxide minerals. fluorite (CaF2).book Page 108 Tuesday. which will be discussed in more detail in the next section. because of the substitu- tion of Al3+ for Si4+ in the silica tetrahedra or Mg2+ for Al3+ in the octahedral layer of the crystal lattice. In the case of the ionic solids such as barite (BaSO4). and Exploration. In the layer silicate minerals such as clays and micas. Those particular ions that are free to pass between both phases and therefore establish the electrical double layer are called potential-determining ions. and HCO3– because of the equilibria between these latter ions and CO32–. σs. Equilibrium is attained when the electrochemical potential ( μ = μ + vF φ where φ is the Galvani poten- tial in the phase) of these ions is constant throughout the system. on a solid in water is determined by the adsorption density of potential-determining ions on the solid surface. . and from the Stern plane into the bulk of the solu- tion. and ΓA– is that of the potential-determining anion. though. By means of a simple titration procedure (Kruyt 1952. the magnitude of the surface charge can be determined if the surface area of the solid–liquid interface is known. the potential-determining ions are Ca2+. the potential-determining ions are Ca2+ and CO32–. and OH–. All rights reserved. Similarly for apatite. Metallurgy. Parks and de Bruyn 1962). In the case of AgI. Electronic edition published 2009. The activity of potential- determining ions at which this occurs is called the point of zero charge. PO43–. For an oxide. is zero. The single most important parameter describing the surface is the condition under which the surface charge. The surface charge. © 2007 by the Society for Mining. respectively. M+ and A– can be considered as H and OH–. or PZC. ΓM+ is the adsorption density in moles per square centime- ter of the potential-determining cation. and for AgI.flotation0. silver iodide (AgI). January 2. σo δ ψo ψδ Potential Solid δ Distance FIGURE 5 Schematic representation of the electrical double layer and the potential drop across the double layer at a solid–water interface exist an inner and an outer Stern plane (Grahame 1947). hydrogen and hydroxyl ions have long been considered to be potential-determining (Fuerstenau and Healy 1972). The surface potential is ψo. σs. no distinction shall be made between the inner and outer Stern plane. σs is given by σS = F ( ΓM+ – ΓA– ) (EQ 24) where F is the Faraday constant. M+ and A– are simply Ag+ and I–. for purposes of this review. the potential determining ions are Ag+ and I–. For a solid such as calcite. CaCO3. at the Stern plane it is ψδ . 2007 7:36 PM 108 FLOTATION FUNDAMENTALS Surface Counterions. and silver sulfide (Ag2S). OH–. the surfaces of these crystal faces carry a negative charge that is independent of solution conditions. the potential drops to zero. the surface charge arises from a preference of one of the lat- tice ions for sites at the solid surface as compared with the aqueous phase. In the case of a 1–1 valent salt. with the other hydrolysis products also functioning in this role because of the complex equi- libria involved in this system. σd Charge. and also H+.

Ca5(PO4)3(F. the total double-layer potential or the surface potential. the counterions occur in a diffuse layer that extends from the surface into the bulk solution.OH) pH 6* Fluorite.5* Fluorapatite. . 1/κ is 1.7 Calcite. ψo.8 Silver chloride. where κ is given by κ = ( 8πF 2 v 2 C ⁄ εRT ) 1 ⁄ 2 (EQ 26) where v is the valence of the ions (for a symmetrical electrolyte). and so forth. and ( a M + ) PZC is the activity of the potential-determining cation at the PZC.000 Å in 10–5 M.book Page 109 Tuesday. and ε is the dielectric con- stant of the liquid. Table 3 presents PZC values for a number of ionic (salt-type) solids that have been investigated. As has been well established (Kruyt 1952). 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 109 TABLE 3 PZC for some ionic solids Material PZC Barite. 10 Å in 10–1 M solutions. If the counterions are adsorbed only by electrostatic attraction. Ca5(PO4)3(OH) pH 7* Scheelite. Electronic edition published 2009. Metallurgy. AgCl pAg 4 Silver iodide. and barite are positively charged in their saturated solution at neutral pH. The charge in the diffuse double layer σd given by the Gouy–Chapman relation (Kruyt 1952) as modified by Stern (for a symmetrical electrolyte) is σ d = – σ S = – [ ( 2εRT ⁄ π )C ] 1 ⁄ 2 sinh ( vFψ δ ⁄ RT ) (EQ 27) Further. In contrast to the situation in which the potential-determining ions are special for each system. remain constant.flotation0. any ions present in the solution can function as the counterions. AgI pAg 5. CaWO4 pCa 4. they are called indifferent electrolytes.6 Silver sulfide Ag2S pAg 10.2 Source: Fuerstenau 1971. for example. this equation shows that the adsorption density of counterions should vary as the square root of the concentration of © 2007 by the Society for Mining. January 2. if the potential does not change appreciably. CaCO3 pH 9. For a 1–1 valent electrolyte. Calcite. whereas the other materials listed are negative. fluorite. The “thickness” of the diffuse double layer is 1/κ. except for hydroxyapatite. and Exploration. The value of the surface potential at any activity of 1–1 valent potential-determining electrolyte is given by RT aM+ ψ o = -------. is considered to be zero at the PZC. BaSO4 pBa 6. CaF2 pCa 3 Hydroxyapatite.ln ---------------------. T is the temperature in degrees Kelvin. All rights reserved. Assuming that potential differences due to dipoles. (EQ 25) F ( a M + ) PZC where R is the gas constant. *The activities of the other potential-determining ions can be calculated from the hydrolysis equilibria and solubility data. 100 Å in 10–3 M. The importance of the PZC is that the sign of the surface charge has a major effect on the adsorption of all other ions and particularly those ions charged oppositely to the surface because these ions function as the counterions to maintain electroneutrality. which is uncharged at the pH shown.

book Page 110 Tuesday. δ. January 2. Because of their surface activity. Adsorption-dissociation of H+ from the surface hydroxyls can account for the surface charge on the oxide (Yopps and Fuerstenau 1964. because ζ must be zero. followed by adsorption of these complexes: M 2 O 3 ( solid ) + 3H 2 O ↔ 2M ( OH ) 3 ( aq ) (EQ 31) 3 – m + ( 3 – m )OH – M ( OH ) 3 ( aq ) ↔ M ( OH ) m (EQ 32) ( aq ) ( aq ) © 2007 by the Society for Mining. only those ions in the diffuse layer outside of the slipping plane are involved in the electrokinetic process. Thus. they will be given considerable detail in this section. and so forth. a hydroxylated surface should be expected when the solid is in equilibrium with an aqueous solution. involving partial dissolution of the oxide and formation of hydroxyl complexes in solution. Electrokinetic results are generally expressed in terms of the ζ-potential. as de Bruyn (1955) has found for the adsorption of dodecylammonium acetate on quartz at low concentrations. have found widespread use in colloid and surface chemistry. determination of the change in ζ-potentials as solu- tion conditions are varied is extremely useful. . while knowledge of the ζ-potential at some single condition may be of certain value. modes of adsorption of various kinds of ions can be ascertained if one makes the useful assumption that the slipping plane and the Stern plane coincide (Kruyt 1952).flotation0. From these changes. It should be pointed out that the case in which there is no ambiguity is when ψδ = 0. some ions exhibit surface activity in addition to electrostatic attrac- tion and adsorb strongly in the Stern plane because of such phenomena as covalent bond formation. On the other hand. This approximation seems permissible because the potential differences between the plane δ and the slipping plane are small com- pared with the total potential differences across the double layer. Given that oxide minerals form hydroxylated sur- faces when in contact with water vapor. Electrokinetic phenomena. 2007 7:36 PM 110 FLOTATION FUNDAMENTALS added electrolyte. hydrogen bonding. T H E E L E C T R I C A L D O U B L E L AY E R O N OX I D E M I N E R A L S Because oxides constitute the most important class of nonmetallic minerals. solvation effects. In this case σS = –( σδ + σd ) (EQ 28) where σδ is the charge due to adsorption in the Stern plane. Metallurgy. Parks 1967) have postulated a different mechanism for the charging of oxide surfaces. Electronic edition published 2009. which involve the interrelation between mechanical and electrical effects at a moving interface. hydrophobic bonding. Flotation collectors generally function as surface-active counterions. Zettlemoyer 1968): MOH ( surf ) ↔ MO (–surf ) + H (+aq ) (EQ 29) MOH ( surf ) + H (+aq ) ↔ MOH 2+( surf ) (EQ 30) Parks and de Bruyn (Parks and de Bruyn 1962. The two electrokinetic effects that have been most widely used are electrophore- sis and streaming potential measurements. and Exploration. which is the potential at the slipping plane when liquid is forced to move relative to the solid. All rights reserved. the charge of such surface-active counterions adsorbed in the Stern plane can exceed the surface charge.

All rights reserved. given that the counterions are the indifferent ions. or even by direct adsorp- tion of H+ and OH–. the double layer is reduced in thickness. This table shows that the surfaces of oxides range from being acidic in nature to quite basic. consider the Gibbs equation for oxide minerals in aqueous media in the presence of an electrolyte. but this will not be discussed further here. January 2.ln ---------------------. the surface potential would ideally be given by RT ( aH+ ) ψ o = -------.6 and that it increases in absolute magnitude with increasing ionic strength and increasing concentration of potential-determining ion.3RT ( Γ H + – Γ OH – ) ⋅ d ( pH ) (EQ 38) Thus. σ S ≡ F ( Γ H + – Γ ( OH ) – ) (EQ 34) Figure 6 presents the results of such titration of synthetic ferric oxide (hematite) with hydrogen and hydroxyl ions in the presence of nitrate (KNO3) as supporting electrolyte (Parks and de Bruyn 1962). The change in tension of the mineral–water inter- face due to the adsorption of H+. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 111 3 – m ↔ M ( OH ) 3 – m M ( OH ) m (EQ 33) ( aq ) m ( surf ) The formation of a surface charge by either of these mechanisms. Examples of how pH strongly affects adsorption at the surface of oxides will be shown later. As the ionic strength is increased. This figure clearly shows that the surface charge on ferric oxide reverses its sign at pH 8. Table 4 presents a tabulation of typical PZC values of several oxides.) For an oxide. Under these conditions. the adsorption isotherms given in Figure 6 are linear with pH at high ionic strengths and can be represented by an equation of the following form: ( Γ H + – Γ ( OH ) – ) = – F ( pH – pH PZC ) (EQ 35) where pHPZC is the pH of the solution at the PZC of ferric oxide. Titration of a suspension of an oxide in water at high ionic strength (with an indifferent electrolyte such as sodium chloride. and Cl– is given by dγ = – Γ H + dμ H + – Γ OH – dμ OH – – Γ Na + dμ Na + – Γ Cl – dμ Cl – (EQ 37) At constant ionic strength.059 ( pH PZC – pH ) volts (EQ 36) F ( a H – ) PZC The potential drop across the double layer at the alumina–water interface is shown schematically in Figure 7. OH–. and Exploration. and the potential at the Stern plane (δ) is reduced.= 0. Electronic edition published 2009.book Page 111 Tuesday. it can be seen that the surface tension of the mineral–water interface can be con- trolled by changing the pH at constant ionic strength. this equation simplifies to dγ = – ( Γ H + – Γ ( OH ) – )dμ H + = 2. Metallurgy. or NaCl) can yield the surface charge by assuming that all added H+ or OH– change the solution pH or are adsorbed at the surface. would result in an equivalent change in the pH of the solution. (This results as a conse- quence of the capacitance of the Stern layer being constant. Na+. . such as NaC1. The intersection of the curves yields the PZC because the adsorption density is zero at this point.flotation0. Interestingly. Figure 7 also shows schematically the © 2007 by the Society for Mining. At this point.

© 2007 by the Society for Mining. 2007 7:36 PM 112 FLOTATION FUNDAMENTALS –40 Ferric Oxide 1M KNO3 10–1 21°C 10–2 –20 10–3 10–4 Adsorption Density (ΓH+ – ΓOH–). mV Potential. μmol/g 0 +20 +40 PZC +60 5 6 7 8 9 10 11 pH Source: Parks and de Bruyn 1962. Metallurgy. and Exploration. . January 2.flotation0. FIGURE 6 Adsorption density of potential-determining ions on ferric oxide as a function of pH and ionic strength using KNO3 as the indifferent electrolyte δ +118 10–1 +118 10–3 M +59 Potential. mV +59 Distance 0 0 Distance 10–1 10–2 M –59 –59 –118 –118 pH 7 pH 11 0 Δγ 10–3 M 10–2 10–1 7 9 11 pH FIGURE 7 Electrical double layer at the alumina–water interface.book Page 112 Tuesday. showing the potential distance curves for 10–3 and 10–1 molar indifferent electrolyte at pH 7 and pH 11 (the PZC occurs at pH 9). All rights reserved. Electronic edition published 2009. The change in the solid–liquid interfacial tension with pH and ionic strength is also shown schematically.

hematite (natural) 4.8–6. Electronic edition published 2009. (EQ 42) ( a MO – ) ( a H + ) 2 From thermodynamics. the effects that temperature has on the double layer at interfaces must be considered. K. January 2. pH SiO2. The sources of oxide—its trace impurities. which presents electrophoretic mobility data for alumina and magnesia at three temperatures.8 Al2O3. change in interfacial tension of alumina with pH for several salt concentrations. Experimentally. *These are typical results.7 Fe2O3. goethite 6. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 113 TABLE 4 PZC of some oxides* Material PZC.e. Lai 1970. The maxi- mum in the interfacial tension occurs at the PZC (i.8–6. the PZC of oxides has been found to decrease with increasing tempera- ture (Parks 1960. magnesia 12 Source: Fuerstenau 1970. it is known that ΔG o = ΔH o – T ΔS o = – RT ln K (EQ 43) © 2007 by the Society for Mining. An example of this is shown in Fig- ure 8. cassiterite 4. for the charging of an oxide surface given by Equations 29 and 30 can be written as MO (–surf ) + 2H (+aq ) ↔ MOH 2+( surf ) (EQ 41) ( a MOH + ) K = -------------------------------- 2 . Metallurgy. .8–8. All rights reserved.5 ZrO2. Tewari and McLean 1972). silica gel 1–2 SiO2.. at pH 9). zirconia 4 TiO2.8 MgO. Effect of Temperature on the Electrical Double Layer In order to understand temperature effects in the adsorption of ionic collectors. rutile 5. The overall reaction and its equilibrium constant.book Page 113 Tuesday.7 Fe2O3. and Exploration. etc.—cause variations in observed values. hematite (synthetic) 8. corundum 9.flotation0.1 AlOOH. boehmite 7. α-quartz 2–3 SnO2.6 FeOOH. In view of this discussion on surface charge. method of pretreatment. the Gibbs adsorption equation for an oxide can be rewritten as dγ = – σ S dψ o – Γ Na + dμ Na + – Γ Cl – dμ Cl – (EQ 39) or at constant ionic strength as dγ = – σ S dψ o (EQ 40) The greater effect of increased ionic strength on the interfacial tension lowering (Figure 7) simply results from the greater magnitude of σs.

the PZC of oxides decreases with increasing temperature. and Exploration. Table 5 gives the results of this calculation for several oxides (Lai 1970).– -------. H o ΔS o 2 ----------. μm/sec per V/cm +2 0 –2 Al2O3 45°C –4 25°C 10°C Calculated –6 4 6 8 10 12 14 pH Source: Lai 1970.+ ----------. but the entropy is approximately constant. (EQ 45) 2RT 2R – ΔH o ΔS o ( pH ) PZC = -------------- . These calculations show that the enthalpy for protonization of surface sites varies with the nature of the metal oxide. +6 MgO 25°C 15°C +4 5°C Electrophoretic Mobility. © 2007 by the Society for Mining.book Page 114 Tuesday. (EQ 46) 4. Electronic edition published 2009. (EQ 44) ( a MO – ) ( a H + ) RT R Given that the number of positive and negative sites must be equal at the PZC. Because the process is exothermic. January 2.– -------.flotation0. the enthalpy and entropy for the protonization of the surface sites on oxides can then be evalu- ated from the shift in the PZC with temperature. The pH at which the mobility reverses sign under these conditions is the PZC.= Δ – ln -------------------------------. it can be seen that Δ H o ΔS o ln ( a H + ) = ----------. . All rights reserved.6RT 4. FIGURE 8 Electrophoretic mobilities of alumina and magnesia at different temperatures as a function of pH. 2007 7:36 PM 114 FLOTATION FUNDAMENTALS or ( a MOH + ) 2 .6R Assuming that the enthalpy does not vary over the temperature range considered. Metallurgy.

7 Source: Lai 1970. –6 5° 25° –4 45° 65° Surface Charge. and Exploration. the decrease in ε with increasing tempera- ture would account for some of the decrease. All rights reserved.2 –0. expressed for the adsorption/desorption of a single H+ Oxide (pH)PZC at 25°C ΔH° kJ/mol H+ ΔS° entropy units/mol H+ SiO2.3 –6. alumina 9. FIGURE 9 Temperature dependence of the surface charge on AgI particles. . δs.1 –10.16 7. Metallurgy. Electronic edition published 2009. and such cal- culations show that the charge decreases with increasing temperature. raising the temperature results in a decrease of σs. Figure 9 presents Lyklema’s (1966) results for the charge on silver iodide at temperatures ranging from 5°C to 85°C.1 M Ionic Strength +4 +200 +100 0 –100 –200 –300 -400 Surface Potential. January 2.59 8.65 7.flotation0.book Page 115 Tuesday. rutile 6. In addition to shifting the PZC. cassiterite 2. based on Equation 47 one can calculate the charge at various temperatures and pH’s. Ψ0.8 MgO.7 Al2O3. magnesia 11. The curves are all normalized to the PZC at the temperature of reference. mV Source: Lyklema 1966. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 115 TABLE 5 Enthalpy and entropy of hydrogen ion adsorption on oxides.05 8. temperature also affects the charge on mineral sur- faces. Lyklema suggests that the decrease in surface charge with increasing temperature might be due to a gradual desorption of counterions from the double layer. In the case of the double layer on oxides. In general. with the double layer having a more diffuse character. © 2007 by the Society for Mining. Because the surface charge also is given by the expression: ε dψ σ S = – -----. μC/cm 2 85° –2 0 +2 85° 5° Silver Iodide 0. showing the decrease in surface charge with increasing temperature.9 TiO2.8 –13.⎛ -------⎞ (EQ 47) 4π ⎝ dx ⎠ x = 0 where ε is the dielectric constant of the medium. All curves are normalized to the PZC at reference temperature.

is defined as o ΔG ads = ( μ io ) S – μ io (EQ 52) Substituting these three relations (from Equations 51 and 52) into Equation 50 yields the Stern–Grahame equation (Grahame 1947. and Exploration. . This leads to x 1S x 2 ⁄ x 2S x 1 = K (EQ 54) © 2007 by the Society for Mining. The standard free energy of adsorption. These collector ions are considered to be adsorbed as counterions in the double layer.flotation0. (EQ 50) RT This relation can be transformed into the well-known Stern–Grahame equation by making the following assumptions: a i = C(the bulk concentration) and a iS = Γ δ ⁄ 2r (EQ 51) where Γδ is the adsorption density in the Stern plane. Fuerstenau. First. given that μi = μiS. Analysis of adsorption isotherms to obtain thermodynamic data for collector adsorption has been completed using two different approaches. January 2. μiS. equilibrium in heterogeneous systems is attained when the chemical potential of species i is equal in all phases. For collector species i. has interpreted the results of his adsorption studies on biotite in terms of the theoretical isotherms established by Frumkin. Metallurgy. Electronic edition published 2009. Fuerstenau 1970) o ⁄ RT ) Γ δ = 2rC exp ( – ΔG ads (EQ 53) Another approach to developing the Stern–Grahame equation can be made by apply- ing the Law of Mass Action to a binary mixture of similarly sized molecules showing ideal behavior in both the liquid phase and in the adsorbed layer. is μ iS = ( μ io ) S + RT ln a iS (EQ 49) where (μio)S is the standard chemical potential of this species at the surface and aiS is its activity in the surface. on the other hand. Hill. Cases (1970). its chemical potential in bulk solution is given by μ i = μ io + RT ln a i (EQ 48) where μio is its standard chemical potential and ai is its activity in solution. ΔGadso. Fowler. The chemical potential of the same species at the surface. Harper. μ io – ( μ io ) S a iS ⁄ a i = exp ------------------------.book Page 116 Tuesday. and Miller (1970) have successfully used the Stern–Grahame model of the electrical double layer to explain the adsorption of alkylammonium ions at the quartz–water interface and alkyl sulfonates at the alumina–water interface. and r is the effective radius of the adsorbed ion. Both approaches will be briefly discussed in the next few paragraphs. and Halsey. At equilibrium. All rights reserved. 2007 7:36 PM 116 FLOTATION FUNDAMENTALS F R E E E N E R G Y O F C O L L E C TO R A D S O R P T I O N Information on the thermodynamic aspects of collector adsorption can be obtained from experimentally measured adsorption isotherms.

. various attempts have been made to split ΔG ads o as follows: o ΔG ads o = ΔG elec o + ΔG chem o + ΔG CH o + ΔG solv +… (EQ 58) 2 where ΔG eleco o is the electrostatic contribution to the total free energy. If the collector forms a covalent bond with metal ions in the sur- face of the mineral. On oxide minerals. then the process should be termed chemisorption. ΔG chem represents the free energy due to the formation of covalent bonds with the surface. ΔG spec o = ΔG chem o + ΔG CH + Δ G o ). When an ion exhibits surface affinity. only electrostatic interactions appear to be operative. Ca2+ and SO4= on rutile. Nitrate anions are surface-inactive on cassiterite (SnO2). respectively. An estimation of ΔG spec o can be made for conditions when ψδ is zero (e. For the adsorption of organic collectors of interest to flotation scientists. Equation 55 becomes essentially identical to the usual form of the Stern–Grahame equation (and to the Langmuir equation). and Exploration. Metallurgy. Ba2+ and SO4= on alumina. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 117 where x1 and x2 refer to the mole fraction of solute and solvent. Given that x2S = 1 – x1S. The Stern–Grahame approach is useful in that it allows one to take electrical effects into account when dealing with ionic collectors. and x1S and x2S are mole fractions in the adsorbed state. when the electrophoretic mobility of the particles is zero). All rights reserved. they appear to be specifi- cally adsorbed on Fe2O3 (Fuerstenau 1970). ⎞ (EQ 55) 1 – x1 S x 2 x 2 ⎝ RT ⎠ At small values of x1. If ions adsorb only through electrostatic interactions. Although chloride ions are not surface-active on Al2O3. It is often customary to lump the ΔG o terms other than ΔG elec o together and call it o ΔG spec o (i.= K ----1 = ----1 exp ⎛ ----------------- ------------. and ΔG solv o is the contribution of solvation effects on the polar head of the adsorbate (collector) and adsorbent (mineral) to adsorption.flotation0. and the free energy of adsorption has additional terms: o ΔG ads o = vFψ δ + ΔG spec (EQ 57) o where ΔG spec represents specific interaction terms. that is. Equation 54 can be rewritten as x kS x x – ΔG ads o .e. If the ions are adsorbed only through such forces as electrostatic attraction and through hydrophobic bonding (van der Waals interaction between hydrocarbon chains). the process should be termed physical adsorption or physisorption.. rutile (TiO2). Much of the work that © 2007 by the Society for Mining. Electronic edition published 2009. then the standard free energy of adsorption is given by o ΔG ads o = ΔG elec = vFψ δ (EQ 56) where v is the valence of the adsorbed ion including sign. ΔG CH o represents 2 the interaction due to association of hydrocarbon chain of adsorbed collector ions at the interface (sometimes called hydrophobic bonding). it is considered to be specifically adsorbed. and hydro- lyzed metal cations on a wide variety of solids (Fuerstenau 1970). alkali cations appear to be surface-inactive. Equation 57 shows that if o ΔG spec is finite. and hematite (Fe2O3). Certain inorganic ions exhibit surface activity: Ba2+ on quartz. January 2. then the ion will be positively adsorbed even if ψδ is zero or has the same sign as the adsorbing ion. Al2O3.g.book Page 117 Tuesday. in the liquid phase. . 2 solv Specific adsorption can be either physical or chemical in nature.

In the second region. The onset of hemimicelle formation is accompanied by the standard free energy of adsorp- tion becoming sharply more negative. Lin and Somasundaran (1971) have considered the transfer of aqueous surfactants to various types of interfacial states and found that transfer energies can range from –0. Dick (1972) evaluated ΔG ads o for the adsorption of sodium dodecyl sulfonate on alumina at pH 6. Γδ. of collector ions in the Stern plane in the absence of chemisorp- tion will be given by o ⁄ RT ) = 2rC exp [ ( – vFψ – n φ ) ⁄ RT ] Γ δ = 2rC exp ( – ΔG ads (EQ 60) δ From the results of Wakamatsu and Fuerstenau (1968).0 RT (for evaporation). then the total contribution is nφ if n is the number of CH2 groups in the chain. .2 and at an ionic strength of 2 × 10–3 M controlled by NaCl.0 RT (about 0. φ has been evaluated to be about –1. Somasundaran. If the standard free energy for removing 1 mol of CH2 groups from water is through association φ. with adsorption increasing markedly because of the enhanced adsorption potential as ΔG CHo becomes effective. At 2 concentrations higher than this. In this region. the electrostatic interaction opposes the specific adsorption effects. Thus. All rights reserved. and contact angle on alumina at pH 7. collector chain length will significantly affect flotation behavior (Wakamatsu and Fuerstenau 1973). resulting in a decrease in the slope of the adsorption isotherm. adsorption density. Because of the role that CH2 groups have in control- ling the adsorption free energy in these systems. By means of the Stern–Grahame model of the double layer. during the exchange. these collector ions are adsorbed as individual ions in the Stern plane but that at higher con- centrations. the contribution of the cohesive energy per mole of CH2 groups to the adsorption potential can be quantitatively evaluated. ΔG ads o again has much less dependence on the bulk concentration of sulfonate. Metallurgy. Gaudin and Fuer- stenau 1955.6 RT (for micellization) to –2. adsorption of sulfonate ions occurs by exchange with chloride ions in the double layer.6 kcal/mol of CH2 groups) in agreement with values obtained from solubility data and micelle formation. January 2. they associate at the interface into two-dimensional aggregates. which have been termed hemimicelles (Gaudin and Fuerstenau 1955).flotation0. Electronic edition published 2009. and Exploration. Adsorption in the alumina–alkyl sulfonate system has been studied in considerable detail. such as in the quartz–alkylammonium (de Bruyn 1955. The third region is reached when the zeta potential reverses. only elec- trostatic adsorption potential is active. Healy. © 2007 by the Society for Mining. 2007 7:36 PM 118 FLOTATION FUNDAMENTALS has been carried out with collector adsorption at interfaces has been concerned with physi- cal adsorption. Using data published by Somasundaran and Fuerstenau (1972). Wakamatsu and Fuerstenau 1968). Figure 10 presents the effect of the concentration of dodecyl sulfonate on the electro- phoretic mobility (zeta potential). At low concentra- tions. the adsorbed ions begin to asso- ciate. Adsorp- tion isotherms and electrokinetic measurements strongly suggest that at low concentrations. and Fuerstenau 1964) and the alumina–alkyl sulfonate systems (Somasundaran and Fuerstenau 1966.9 and his results are plotted in Figure 11. When the zeta potential reverses. it can be seen that the adsorption isotherm can be divided into three distinct regions. the zeta potential (and ψδ) remains constant.book Page 118 Tuesday. From this figure. the contribution from hydrocarbon chain association to the adsorption process is o ΔG CH = nφ (EQ 59) 2 The adsorption density.

kJ/mol –18 –16 Alumina –14 2 × 10–3 N Ionic Strength pH 6. FIGURE 11 Variation of the standard free energy of adsorption of sodium dodecyl sulfonate on alumina at 25°C and 45°C for the isotherms given in Figure 13 © 2007 by the Society for Mining. the electrophoretic mobility. and the contact angle of alumina as a function of the equilibrium concentration of sodium dodecyl sulfonate at pH 7.8 Point of Zeta Reversal +20 10–12 +30 1. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 119 10–9 Cosine θ Adsorption Density Electrophoresis III 0.0 Alumina +40 2 × 10–3 N Ionic Strength pH 7. mol/cm 2 Zeta Potential.6 0 10–11 I +10 0. . mol/L Source: Dick 1972.flotation0.book Page 119 Tuesday.4 –20 Adsorption Density.2 –40 II –30 10–10 0.2 24±1°C +50 10–13 10–5 10–4 10–3 10–2 Equilibrium Concentration of Sodium Dodecyl Sulfonate. mol/L Source: Wakamatsu and Fuerstenau 1973.2 and ionic strength 2 × 10–3 M controlled with NaCl –24 45°C –22 25°C ζ=0 –20 ΔG°ads.9 –12 10–5 10–4 10–3 Equilibrium Concentration of Sodium Dodecyl Sulfontate. mV –10 Cosine θ 0. Electronic edition published 2009. January 2. All rights reserved. FIGURE 10 Adsorption density of sodium dodecyl sulfonate. and Exploration. Metallurgy.

If φa is assumed to be a function of surface coverage.book Page 120 Tuesday.exp ⎛ ------a-⎞ A2 ⎝ kT⎠ where A2 = exp (–A/kT). and xo is the mole fraction of the adsorbate (collector) in solution at saturation (i.. and Exploration. (EQ 61) 1–f where x is the mole fraction of adsorbate in the bulk. and on hematite and numerous other minerals. 2007 7:36 PM 120 FLOTATION FUNDAMENTALS In many mineral–collector systems. φa is the differential energy of desorption per molecule. the number of coordinations and the lateral interactions are the same as in the plane of the lattice of the micelle. (3) the entropic functions are the same in the adsorbed layer and in the micelle. several examples of chemisorption may be cited. Predali and Cases (1974) assumed (1) φa = φao + fω. and fω represents the lateral interactions between the adsorbed species in the adsorbed layer. The general relation for adsorption iso- therms when the adsorption is localized without the dissociation of adsorbed molecules onto a homogeneous surface is (Cases 1970. chemisorption occurs. who consider the adsorption process as a condensation process on either a homogeneous or a nonhomoge- neous surface similar to that of gas adsorption. one can obtain the well-known Frumkin–Fowler isotherm. forming a strong zinc–mercaptan bond. and A is a constant. Equation 61 can be rearranged to give the familiar Langmuir isotherm: x f = ------------------------------------. k ln Wa is the sum of all entropic terms except the configurational entropy for a molecule in the adsorbed state (f is the fractional surface coverage). Langmuir isotherms have been widely used for estimating the free energy of adsorption from adsorption isotherms. On assuming φa to be independent of surface coverage. A different approach has been taken by Cases and his associates. Electronic edition published 2009. Metallurgy. January 2. Oleate chemisorbs on fluorite (CaF2). In terms of the concepts of Equations 57 and 58. (EQ 62) 1 G x + -----.e. Predali and Cases 1974) f -+A kT ln x = – k ln W a – φ a + kT ln --------. chemisorption occurs when ΔG chem o has some finite value. . chemisorption is of primary interest because selectivity may be obtained if there is a specific collector–mineral adsorption reaction rendering a single min- eral or group of minerals to be air avid. Hydroxamates strongly chemisorb on chrysocolla and hematite. f. Hexanethiol chemisorbs on the surface of zincite (ZnO) and willemite (Zn2SiO4). In nonmetallic flotation systems.flotation0. Predali and Cases obtained the following relation for thermodynamic equilibrium between an adsorbed layer and a dilute solution of the same substance: © 2007 by the Society for Mining. To derive an equation for thermody- namic equilibrium. which leads to the expression φo = φoo + ω/2. in equilibrium with micelles of collector). where φo is the energy to dissolve a molecule from half-crystal position in the micelle and φoo is the half of normal binding energies in micelle per molecule from half-crystal position. T is the temperature. k is the Boltzmann constant. and Ga is the free energy of adsorption per molecule = (–φa – kTlnWa). In flotation systems. forming strongly adsorbed films that are difficult to remove. and (4) k T ln xo = –k T ln Wo – φo + A where k ln Wo is the sum of all entropic terms for a molecule in the half-crystal position. All rights reserved. k ln f/ (1 – f ) is the configurational entropy of an adsorbed molecule. where φao is the normal binding energy between one adsorbed molecule and the surface. (2) in the adsorbed layer. Chemisorption is often arbitrarily referred to as an adsorption process in which the adsorbate attaches to the surface of the adsorbent with a molar free energy of approximately 42 kJ or greater.

0 Fractional Surface Coverage.0 1. this is due to the condensation on a nonhomogeneous surface. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 121 f ω kT ln ---------. as claimed by Cases (1970). and this modified equation predicts a constant slope for adsorption isotherms (f versus C plot) up to a value of f close to 1.g. FIGURE 12 (a) Schematic Frumkin–Fowler isotherm on a homogeneous surface. Hill.5 ω < 4 kT f I 0. Cases suitably modified Equation 63 for nonhomogeneous surfaces.985.5. The first has a finite slope. .5 M 0. This corresponds to a case where ω > 4 kT. that is.. A plot of f versus Δμ for two cases. C8 alkylammonium chlo- rides) and ω > 4 kT (e. Electronic edition published 2009. The second branch has an infinite slope.g. This assumption is highly questionable because water structure at a solid–liquid interface plays a key role in adsorp- tion. f C18 C16 C14 C12 N II 1. It is possible to calculate the lateral binding energy between hydrocarbon chains from the value of the slope at f = 0. ω < 4 kT (e. it can be noted that when ω < 4 kT. namely. On the other hand. Metallurgy.flotation0. and. All rights reserved. Fowler. and any water molecules released on adsorption of the collector would significantly increase the entropy of the system. Cases (1970) studied the adsorption of dodecylammonium chloride on homogeneous surfaces and found the isotherm to exhibit a constant slope up to f = 0.5 ω > 4 kT 1.( 1 – 2f ) + Δμ (EQ 63) 1–f 2 where Δμ = k T ln x/xo and is a measure of undersaturation of collector in the aqueous solu- tion. Furthermore.5 and 25°C © 2007 by the Society for Mining. the utility of the Cases approach is somewhat A B Biotite–Alkylammonium Δμ* Chlorides 2. mol/L Source: Predali and Cases 1974.5.= ( φ ao – φ oo ) – ---. and (b) adsorption isotherms of alkylammonium chlorides of different chain lengths on biotite at pH 5. January 2. C12 surfactants) is given in Figure 12a. the slope of the isotherms on homogeneous surfaces at f = 0.015. when ω > 4 kT. Though the theoretical isotherm of Frumkin. onto the first adsorbed layer (see Figure 12b). Predali and Cases (1974) consider the portion of the curve between M and N in Figure 12a to be related to a change of state because of the condensa- tion of the layer. and Halsey fits the experi- mental data. and Exploration..5 is finite.book Page 121 Tuesday. followed by an infinite slope up to f = 0. according to their developed theory. Predali and Cases (1974) studied the adsorption of long chain (> C10) alkylam- monium chlorides on biotite and found the adsorption isotherms to exhibit two well- defined branches.0 Δμ 0. which is considered to be due to condensation on a homogeneous surface—that is.0 C10 0. the entropic effects involved in the adsorption from solution are similar and equal to that involved in the adsorption from gaseous state. there is one serious assumption underlying this approach.0 10–6 10–5 10–4 10–3 Equilibrium Concentration. From the figure. the slope of the iso- therms is infinite at f = 0.

Metallurgy. = 63kJ ⁄ mol Gochin’s measured values agreed quite well with the theoretical value stated previously. Mellgren and Rao (1968) performed similar experiments with potassium diethyldithio- carbamate instead of xanthate and obtained similar results.flotation0. Gochin (1972) carried out an elaborate thermochemical study of the flotation of sphalerite and pyrite along similar lines. 2007 7:36 PM 122 FLOTATION FUNDAMENTALS limited in that the introduction of electrical double-layer concepts to adsorption is a more convenient method of dealing with the interaction of charged collectors with the mineral.g. plotting results in the form of fractional surface coverage versus concentration masks the very important effects encountered at low surface coverages. sulfate. and thiosulfate gave values equivalent to those obtained when ethyl xanthate was reacted with lead carbonate. © 2007 by the Society for Mining. or lead thiosul- fate. The heat of ethyl xan- thate adsorption on untreated galena (–83 kJ/mol of Pb2+) was equivalent to that obtained when xanthate was reacted with lead thiosulfate at neutral pH values. London. Nature of the interaction with the substrate (For example. and Exploration. Identification of the mode of attachment of flotation collectors Pioneering work on calorimetric determination of the heat of adsorption of collectors on sulfides has been conducted at the Royal School of Mines. it may be expected that type 1 reac- tions will be more exothermic than type 2. by analogy with the heats of chemisorption and physisorption of gases. The second class of col- lectors is characterized by strong hydrocarbon chain–hydrocarbon chain interaction in the Stern layer (e. Electronic edition published 2009. The interaction of long-chain carboxylates with oxides might be considered as an intermediate category. January 2.book Page 122 Tuesday. Finally. dodecylammonium chloride on quartz). This was as expected because thiosulfate was found to be the oxidation product on the galena used. he studied the heat of Cu2+ adsorption on sphalerite (ZnS) and iron sulfide (FeS) with a view toward understanding the activation of sphalerite by Cu2+. theor. and (2) long-chain ionic surfactants that adsorb physically as counterions in the electrical double layer. Heat of adsorption measurements on samples treated with carbonate. Heat of Adsorption of Collectors Collectors of interest in flotation can be classified into two types: (1) surfactants that chemisorb or chemically react at the surface (e. dodecyl sulfonate on alumina or hematite.and sulfate-treated galena surfaces were equivalent to the quantities of thiosulfate released into the solution after the treatment. . All rights reserved. ΔH 298 K.) 2. Mellgren (1966) investigated the heat of xanthate adsorption on galena samples “as ground” or previously treated with potassium carbonate. These findings suggested that metathetical reactions between the xanthate and the oxi- dation products on the surface of galena were involved.. Mellgren measured rather erratic and large ΔH values at high pH values and concluded that second- ary reactions were involved at these high pH values. oleate on fluorite or calcite.g. The quantities of xanthate adsorbed on the carbonate.. This led to the conclusion that an ion exchange mechanism might be involved in the adsorption process. which takes place according to the following reaction: o ZnS + Cu 2+ = CuS + Zn 2+ . hydroxamic acids on hematite or chryso- colla. sulfate. or thiosulfate solutions. xanthates on sulfide). Measurements of the heat of adsorption of collectors may be able to shed some light on the following aspects of the collection process: 1. In addition. lead sulfate.

From mea- surement of isotherms for the adsorption of sodium dodecyl sulfonate at two temperatures (Figure 13). At higher coverages.= ----------------- . Taking the logarithm of the adsorption density given by the Stern–Grahame equation. The heat of adsorption is calculated from adsorption isotherms obtained at two different temperatures. the heat of immersion remained at about –1. Q st is not the real heat of adsorption but represents a heat intermediate between heat of reaction and heat of adsorption. They measured a heat close to the heat of micellization of sodium dodecyl sulfate. By this model. and so forth. Electronic edition published 2009. Ball and Fuerstenau (1971) used a different approach for evaluating the heat of adsorp- tion. For collectors such as amines. Q st is the heat of “adsorption” in the real sense of the word. In those cases.) Mellgren and colleagues found evidence for sites of different adsorption energy on powdered natural hematite.100 ergs/cm2 at monolayer coverage. An indirect method for determining the heat of adsorption is to measure the amount of collector adsorbed (Γ) as a function of concentration (C) at a given solution pH at two or more different temperatures. reaching a value of –1. They did not detect any measurable heat effect when the sulfonate ions occurred only in the diffuse part of the double layer. Both types of interactions involve the removal of water in the vicinity of the surface. From a Clausius–Clapeyron type of equation: – ΔH ads o ln C⎞ ⎛ ∂-----------.100 ergs/cm2. Marabini. Somasundaran and Fuerstenau (1972) evaluated the enthalpy and entropy of the adsorption process. sulfonates. They found that as the sulfonate ions begin to adsorb (associate) in the Stern layer. They have presented a model in which adsorption occurs by a process where a layer of water molecules exists between the solid surface and the adsorbed layer of sulfonate ions. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 123 Two systematic studies on the heat of adsorption of type 2 collectors on oxides have been reported—one by Roy and Fuerstenau (1968) and the other by Mellgren et al. Their results show that the adsorption decreases with increasing temperature. working with the hematite–dodecyl sulfate system. which do not chemically react with the surface. the heat of immersion begins to become more negative than the heat of immer- sion of Al2O3 in water. All rights reserved. Roy and Fuerstenau (1968) studied the heat of immersion of alumina in aqueous solutions containing sodium dodecyl sulfonate at various pH values. (1974). they estimated an integral heat of adsorption of –5. (1974). (EQ 64) ⎝ ∂T ⎠ RT 2 This heat of adsorption is the same as the isosteric heat of adsorption. collectors such as salicylaldehyde (Rinelli. 1974) chemically react with the surface and form metal–collector complexes both on the surface and in the bulk. the propor- tions of which depend on the method of grinding (or heat treatment) of hematite.0 kJ/mol.flotation0. and Exploration. January 2. they obtained o ⁄ RT ) ln Γ δ = ln 2r + ln C – ( ΔG ads (EQ 65) © 2007 by the Society for Mining. indicating the exothermic nature of the process.book Page 123 Tuesday. found that the heat of adsorption (–5. The heat of adsorption of type 2 collectors should consist of two parts: (1) heat due to inter- actions between the charged polar head groups and the charged surface sites and (2) heat due to the interaction between the hydrocarbon chains. Q st. Mellgren et al. and Alesse 1976) and xanthates (Mellgren et al.7 kJ/mol) remained constant from an adsorption density that is about one-sixth of the monolayer coverage right up to that of the monolayer coverage. Metallurgy. . (Roy and Fuer- stenau [1968] are of the opinion that only at multilayer coverages should the heat of adsorp- tion be close to that of the heat of micelle formation. On the other hand.

(EQ 67) ⎝ ∂T ⎠ ⎝ ∂T ⎠ C RT 2 o Under conditions of constant adsorption density. (EQ 66) dT ⎝ ∂T ⎠ Γ δ dT ⎝ ∂T ⎠ C RT 2 If the radius of the adsorbing ion is assumed to be independent of temperature. o ln C⎞ ⎛ ∂ ln Γ δ⎞ ⎛ ∂-----------. .9 and ionic strength 2 × l0–3 M Differentiating this equation with respect to temperature yields o ⁄ RT ) o d ( ΔG ads ∂ ln C d ln r ∂ ln Γ – ΔH ads . Their calculations indicate large entropic effects that have been attributed to the phenomenon of hydrophobic bonding. (EQ 68) ⎝ ∂T ⎠ Γ δ RT 2 The values of isoteric heat of adsorption can be calculated from the slope of the plot of (log C)Γ against temperature. January 2. 2007 7:36 PM 124 FLOTATION FUNDAMENTALS 10–10 Adsorption Density. – ΔH ads – -------------. . and Exploration. All rights reserved.= ⎛ ------------⎞ + ----------. Electronic edition published 2009. mol/cm 2 10–11 Alumina pH 6. Because ΔG ads o can be obtained as a function of temperature from the adsorption data using Equation 65. ΔS ads o can be computed easily as o o ΔS ads = – d ( ΔG ads ) ⁄ dT. Ball and Fuerstenau (1971) used this approach to calculate vari- ous thermodynamic quantities for the process of adsorption of dodecylammonium acetate on quartz. FIGURE 13 Adsorption density at 25°C and 45°C of dodecyl sulfonate on alumina as a function of its equilibrium bulk concentration at pH 6.9 10–12 –3 2 × 10 M Ionic Strength (NaCl) 25°C 45°C 10–13 10–6 10–5 10–4 10–3 10–2 Equilibrium Concentration of Sodium Dodecyl Sulfonate. Metallurgy.book Page 124 Tuesday. © 2007 by the Society for Mining. ΔH ads becomes the isoteric heat of adsorption and is given by ln C⎞ ⎛ ∂-----------.flotation0.– ⎛ -------------δ-⎞ = ----------------- ---------------------------------. Q st = --------- .= ----------------- . mol/L Source: Somasundaran and Fuerstenau 1972.

flotation0. Below 40°C. Their explanation is that the oleic acid is physisorbed at room temperature and that chemisorption does not take place appreciably until the temperature is raised to 45°C–60°C. adsorp- tion decreases with increase in temperature. to 90%–95% at temperatures of 70°C or greater. Not much is known about entropy changes in collector adsorption processes. Metallurgy. January 2. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 125 Effect of Temperature on Collector Adsorption Investigations of the effect of temperature on the adsorption of collectors on mineral sur- faces can be classified into the following broad categories: 1. Cook and Last conducted an interesting investigation of the effect of conditioning temperature on the flotation of fluorite with oleic acid. wrote in 1949 about the value of using high temperature for the conditioning of nonsulfide ores for flotation with soaps. Systems in which the collector exhibits physisorption characteristics 2. these particular kinds of isotherms are also complicated by a shift in the PZC and a reduction in surface charge as the temperature is increased. Systems wherein the collector chemisorbs onto the mineral 3. this could result in ΔS ads having a large positive value.book Page 125 Tuesday. as a consequence. Electronic edition published 2009. Systems in which the collector seems to chemically react at the mineral surface with ions derived from the mineral surface. Figure 13. This is actually a borderline category and. Because of an activation energy. A good example of this type is the alumina– dodecyl sulfonate system investigated by Somasundaran and Fuerstenau (1972). then ΔG ads is negative. referring to a 1938 French patent. This can be achieved by the adsorption process being exothermic or by its being accompanied by a large entropy increase. but on the other hand. © 2007 by the Society for Mining. which demonstrates their results. and preferably above 60°C. for all practical purposes. the recovery of fluorite is very low. All rights reserved. They determined the effect of temperature on the electrokinetic potential of quartz in the presence of dodecylammonium acetate (see Fig- ure 14) and found it to decrease in absolute magnitude with increasing temperature. raising the temperature causes the chemisorption reaction rate to proceed reasonably rapidly during the conditioning period. there may be a significant increase in entropy because of the release of structured water molecules from the solid– water interface and/or from the collector molecule/ion. but raising the conditioning temperature causes the recovery to rise sharply. there will be an entropy decrease because of the more ordered structure of col- lector ions or molecules at the interface. and Exploration. Particularly for longer-chained col- lectors. could be classified under category 2. he mentioned conditioning above 35°C. Specifically. the free energy change is given by ΔG ads = ΔH ads – T ΔS ads (EQ 69) If the process occurs spontaneously. which points indirectly to a decrease in adsorption with increasing temperature. Type 1 systems are characterized by an exothermic heat and. Another example is the work of Ball and Fuerstenau (1971) on the aqueous dodecylammonium acetate–quartz system. the temperature dependence of the adsorp- tion of soaps on mineral surfaces has been investigated in some detail. Of the chemisorbing systems investigated. Figure 15 presents their results on the flotation of a fluorite/calcite/barite ore. Although no one has yet analyzed the results in such a manner. shows such a decrease in the adsorption density. In 1950. On the one hand. For any adsorption process. . Falconer (1949).

FIGURE 14 Zeta potential of quartz as a function of dodecylammonium acetate concentration at different temperatures 100 80 Flotation Recovery or Grade.% 60 40 20 Fluorite Grade Recovery 0 0 20 40 60 80 100 Conditioning Temperature. 2007 7:36 PM 126 FLOTATION FUNDAMENTALS –40 pH 7 25°C 15°C 5°C –30 Zeta Potential. which had been conditioned for 5 minutes with oleic acid. and Exploration.book Page 126 Tuesday. All rights reserved.°C Source: Cook and Last 1950. . quebracho. January 2. and sodium carbonate © 2007 by the Society for Mining. FIGURE 15 Effect of conditioning temperature on flotation recovery and concentrate grade for the flotation of a fluorite ore. Electronic edition published 2009. M × 104 Source: Ball and Fuerstenau 1971.flotation0. Metallurgy. mV –20 –10 0 +10 1 2 3 4 5 6 7 8 9 10 Dodecylammonium Acetate Concentration.

book Page 127 Tuesday. However. All rights reserved. show a marked increase in adsorption with increasing tempera- ture. . In conditioning at elevated temperatures. shows that the flotation recovery at low ionic strength increases as the temperature is increased.= ------------ --------. activating the adsorption process for chang- ing it from physisorption to chemisorption is illustrated schematically in Figure 16.8). which are presented in Figure 18. Optimum adsorption always occurred at about pH 8. Kulkarni and Somasundaran (1975) found that the adsorption of oleate on hematite increases as the temperature is raised from 25°C to 75°C at low ionic strengths. Fuerstenau. Using Equation 55 in the following form: – ΔG ads ⎞ o C- f . and Exploration.4. This indicates possible formation of ferric hydroxamate by surface reaction. they found ΔG adso to be approximately –32 kJ/mol and nearly indepen- dent of pH and surface coverage (for f < 0. showing the transition from physisorption to chemisorption. and Miller (1970) found enhanced flotation with increasing temperature. Raghavan and Fuerstenau (1975) have investigated the effect of concentration. and C is the collector concen- tration in solution. and temperature on the adsorption of octylhydroxamate on hematite. thereby giving rise to a larger num- ber of Fe ions for reaction at the surface. Thus. after Somasundaran and Kulkarni (1977). one effect of the temperature might simply be to increase the solubility of the mineral.flotation0. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 127 Amount Adsorbed Chemisorption Physisorption Temperature FIGURE 16 Schematic representation of an adsorption isobar. but the con- verse was observed at very high ionic strengths (due to salting-out effects at lower tempera- tures). In © 2007 by the Society for Mining. Electronic edition published 2009. Metallurgy. Their results on the effect of temperature. In an investigation of the flotation of iron oxide with octylhydroxamate and oleate as collector. Figure 17. The change from one type of process to the other could begin at about 40°C in these systems. they considered the adsorbing species to be the hydrox- amic acid molecule. (EQ 70) 1–f 55.55 ⎝ RT ⎠ where f is the fraction of the surface covered by the collector. January 2. pH. Their conclusions were that the chemisorp- tion process definitely involves increased mineral solubility as the temperature is raised. with maximum recovery always occurring at about pH 8. the observed value of ΔG adso is rather small. For a chemically adsorbing species. exp ⎛ ----------------. Harper. This implies marked increase in collector adsorp- tion with increasing temperature. Only in the transition region should the adsorption increase with increasing temperature. the isotherms for 41°C and 60°C given in Figure 18 exhibit adsorption den- sities that exceed monolayer (7 × 10–10 mol/cm2) coverage.

Electronic edition published 2009.5 2 × 10–3 M KNO3 0 0 2 4 6 8 10 12 Hydroxamate Equilibrium Concentration × 104. January 2. FIGURE 18 Effect of temperature on the adsorption density of potassium octylhydroxamate on hematite © 2007 by the Society for Mining. mol/cm 2 × 10 10 12 60°C 41°C 8 4 20°C Hematite–Hydroxamate pH 5. All rights reserved. 2007 7:36 PM 128 FLOTATION FUNDAMENTALS 100 Hematite 3 × 10–3 M KOI 80 100°C Flotation Recovery. mol/L Source: Raghavan and Fuerstenau 1975.book Page 128 Tuesday. and Exploration. % 60 94°C 75°C 40 60°C 20 25°C 0 3 4 5 6 7 8 9 10 Flotation pH Source: Somasundaran and Kulkarni 1977.flotation0. . Metallurgy. FIGURE 17 Effect of temperature on the flotation of hematite with 3 × l0–5 M potassium oleate as collector 20 16 Amount Adsorbed.

Trans. Edited by M. the pH for optimum flotation was reduced from 10 at 23°C to about 8 at 60°C. They also found that con- tact angles of calcium-activated quartz at pH 11 decreased with increasing temperature. January 2. Chander. Edited by F. New York: Plenum Press. However. © 2007 by the Society for Mining. and D.R. New York: American Institute of Mining. Fuerstenau. Trans. pH has a marked effect in flotation because of its effect on collector ionization. is quite complicated to analyze thoroughly by simple thermodynamic approaches. J.B. Iawasaki.. Pages 91–138 in Froth Flotation. Electronic edition published 2009. F. . and D. Aplan. Franks. as a consequence of its being a multiphase hetero- geneous system.A. What this chapter attempted to do is bring out a few salient features of the application of thermodynamic concepts to the understanding of flotation. and Exploration. oleic. Choi. Surface Chemistry of Flotation. except for stearic acid. AIME 251(1):62..S. Agar. Cooke. REFERENCES Adamson. Bulletin No. 1967.W. Ball. In an interesting study of the flotation characteristics of pyrolusite. Fuerstenau. 2nd edition. Cook.... J. 1971. flotation under the same conditions increased with increasing temperature. and mineral solubility. elaidic. (1965) clearly showed that raising the temperature can markedly increase flotation response. 1960. the flotation process. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 129 an earlier study. and H. Fuerstenau. surface charge. New York: Interscience Publishers. Page 117 in Flotation. but this was probably due to rather unusual frothing characteristics at pH 11. 1970. goethite.C. and R. and linolenic acids—they observed only a very slight increase in flotation and in contact angles by increasing the temperature from 25°C to 70°C. while working with octylhydroxamate and various other chelating agents as collectors for chrysocolla. and Malati (1971) found the adsorption of oleate on beta-manga- nese dioxide to be an exothermic process both in the absence and the presence of Ba2+ ions. Last.flotation0.. On the other hand. which exhibited a strong increase due to its increased solubility. S. Metallurgical. AIME 247(2):123. The optimum pH for chrysocolla flotation always occurred at about pH 6. P. and P. Utah Engineering Experiment Station. Trans. flotation increased markedly upon raising the temperature from 23°C to 60°C. Faraday Soc.L. and Petroleum Engineers. 1950. A. any tempera- ture study of flotation systems should also take into account the temperature dependence of the dissociation constant of water and pH (Harned and Owen 1958). 1962.E. Kulkarni. Iawasaki.W. and Petroleum Engineers. and activated quartz with 18-carbon aliphatic acids and related compounds. AIME 226:235. 47. Flotation characteristics of hematite. de Bruyn.M. As has already been discussed at length. Edited by D. Physical Chemistry of Surfaces. 1972. A. and A. I.D. In conclusion. Cases. and G.W. with oleate as collector for the same mineral. New York: American Institute of Mining. Disc. Normal interaction between adsorbed species and adsorbing surface. Page 79 in Water. On the other hand. de Bruyn. indicating diminished calcium adsorption. Natural floatability of molybdenite. Arafa.W. On the other hand. linoleic. Goddard. University of Utah. Peterson et al. Clifford.W. M.D. Volume 5. E. B. Fuerstenau. 52:361. Adsorption of hexyl mercaptan on gold. 1976. Bleier. Metallurgy. Properties of water in capillaries and thin films. Metallurgical. Trans. All rights reserved. Cooke. With a series of collectors—stearic.F. Fluorite Flotation II. Thus. and Choi (1960) conducted a detailed investigation of the effect of temperature on the flotation of hematite. Structural effects of amine collectors on the flotation of quartz. 1963. Fuerstenau and Rice (1968) found that flotation decreased slightly with a sulfonate when the temperature was raised from 23°C to 60°C.. S. Yousef.book Page 129 Tuesday. AIME 217:76. 1975.

Smith. 1960. 1971. Conflicts between Gibbsian thermodynamics and recent treatments of interfacial energies in solid-liquid-vapor systems. Trans. 6(4):223. Lovell. Edited by R. Dick. D. adsorption of ionic surfactants and wettability of oxide minerals. Fuerstenau. 1961. Flotation of quartz by cationic collectors. Page 271 in Proceedings of the 6th International Mineral Processing Congress. de Bruyn. College of Engineering.W.L. Griffiths.G. and D. Surface charge. 66(pt 6):1520. thesis. J. London: Institution of Mining and Metallurgy. Paper presented at the 104th AIME Annual Meeting. Eng. New York: McGraw-Hill. Trans.G. R.W. The hydrophilic-hydrophobic transition on silica..A. and Petroleum Engineers. M. H. Quartz flotation with cationic collectors. ———. University of California.S.D. Volova. AIME 202:291. Gochin. and G..G. Fuerstenau.S.R. University of California..book Page 130 Tuesday. Shcherbakov. University of London. and M.V. 1966. Can. A thermochemical study of the flotation of sphalerite and pyrite. P. Metall. and Exploration. and R. Edited by M. 1949. Healy. The adsorption of surfactants at solid–water interfaces. S. AIME 184:247. 6:519 Defay. 1955. P. thesis. Jr. 1975. 1954.A.C. Israelachvili. decaying exponentially with distance.L. thesis. H. and D.B. The Physical Chemistry of Electrolyte Solutions.M. Ph. USSR 23(1):33. Colloid J. Metallurgy. New York: Marcel Dekker. Lai. Berkeley. The effect of pH and temperature on the heat of immersion of alumina. J. Metallurgical. Pages 143–176 in The Chemistry of Biosurfaces. 1970.. Chem.. M. thesis..M. Fuerstenau. Poling. and I. D.. J. J. Derjaguin. Johnson. Sci. S. Phys. Trans.W. Harned.C. R. Effect of surface forces on phase equilibrium of multimolecular layers and on the contact angle. and L. Particle–bubble attachment in flotation. Q. and J. Lemlich. Kitchener. 3:29. Can. P. T. 1960. 1970. Hall. Fuerstenau. Healy. D.N. 1955. 1932. R. Miner. Pure Appl.A. and P. B.. M.L.M. Flotation and the Gibbs adsorption equation. Owen. Nature 300:341. Kruyt. Finch.T. 1958. Fuerstenau.. New York: American Institute of Mining.A. 1. 2007 7:36 PM 130 FLOTATION FUNDAMENTALS de Bruyn. 11(4):569. Chem. University of Melbourne. 63:1655. All rights reserved. Faraday Soc.W. College of Engineering. Trans. The hydrophobic interaction is long range. A. The electrical double layer and the theory of electro-capillarity. Gaudin. 1947. J. On the interpretation of contact angle. V.D.. Pages 92–131 in Adsorptive Bubble Separation Technique. Trans. Surfactant adsorption at the oxide–water interface. New York: John Wiley & Sons. R. Hydroxamate vs. Liquid–vapor interface in the study of particle–bubble attachment. AIME 202:66. Harper. AIME 247(1):69. Interfacial processes in mineral/water systems. J. Pashley. 1957. 2nd edition. London: Institution of Mining and Metallurgy.A. . Laskowski. Volume 1.W. Amsterdam: Elsevier. Falconer. Adsorption of water vapor on ionic solids containing preadsorbed sodium oleate. AIME 241(4):453.. Page 325 in Proceedings of the 5th International Mineral Processing Congress. © 2007 by the Society for Mining.W.L. Kulkarni. Berkeley. M. Principles of mineral flotation. and D. and J.W. Calcium fluoride. Eng.W.W. 41:441. January 2. 1972. Flotation. 20(4):376. temperature and surface condition on the adhesion of bubbles to mineral surfaces. Phys. 1968. and T. 1968. Eigeles. B.M. Leja.A. 24(1):135. fatty acid flotation of iron oxide. Prigogine. 14(1):47.V. 1974. 1973.E. M. and R. Overbeek.W. Ph. 1988. 1972. Colloid Sci. Pretreatment of mineral surfaces for froth flotation. Oleate adsorption at hematite/solution interface and its role in flotation. 1970.. R. 1972. 1972. Kinetic investigation of the effect of contact time. and N.C. Chem. Flotation characteristics of pyrolusite. 1970. Chem. Q. J. Rev. Derjaguin. 1965.flotation0.. Surface Tension and Adsorption. 1952. 29:670.M.D. Laskowski. Oxide–water interface: Interrelation of the zero point of charge and the heat of immersion. J.P. ———. A. Finkelstein. New York: Academic Press. 1959. Miller. Trans. J. Grahame. Bubble–solid attachment as a function of bubble surface tension.D. Somasundaran. and B. Electronic edition published 2009.. Gaudin.S.. J. 1975. and G. Colloid Interface Sci. D. Fuerstenau.S. Colloid Science. The rigidity of thin layers of water. Rice. Schuhmann. Hair. Metall.. New York: Reinhold.. R. Min.

Colloid Interface Sci.D. McLean. 1966. . Colloid Interface Sci. IMM 77( June):C65.. 1960. Sheludko.C.L. Phys. 2007 7:36 PM SOME ASPECTS OF FLOTATION THERMODYNAMICS 131 Lin.J. IMM 77( June):C61. Adv. Kitchener.D. Electronic edition published 2009. Collector adsorption during froth flotation. Page 549 in Flotation. P.L. and Exploration. 1972. C. T.A.W. de Bruyn. AIME 232(4):389. Parks. and D. and P. Fuerstenau. Padday.L. Contact angles.A.M. Mellgren. P. Ph. measurement. Trans. 1972.W. J. 80:650. 1968. Pages 451 in Proceedings of the 10th International Mineral Processing Congress. Faraday Soc. and J. Marabini.. Fuerstenau. 1967. Neumann. and Petroleum Engineers. Miller.. Somasundaran.I. G. Heat and entropy of adsorption and association of long-chain surfactants at the alumina–aqueous solution interface. Rehbinder.J. Relation between adsorption at different interfaces and flotation behavior. J.. Trans.. Thermochemical measurements in flotation research. Phys.. Trav. Somasundaran. A. Faraday Soc. Fuerstenau. and J. Gochin.F. Effect of reagentizing temperature and ionic strength and their interactions in hematite flotation. Free-energy changes on transfer of surface-active agents between various colloidal and interfacial states.A.flotation0. and P. ———. All rights reserved. Mechanisms of alkyl sulfonate adsorption at the alumina–water interface.. P. 42:81.R. Rickard. Massachusetts Institute of Technology. Trans. Alesse. thesis. Adv. Jones. Fuerstenau. 40(2):267.. Fuerstenau. Predali. 1961. 4(2–3):105.D. Chem. J.. Fuerstenau.W. H.W. Somasundaran. 1968. 1974.W. Lyklema. Adsorption of aqueous octylhydroxamate on ferric oxide. O.C. Pope. Digre. 1974. 1974. Peterson. Chem. 68(12):3567.. Healy. Mellgren. AIME 252(3):275. 1971. G. 26(1):102. and J. 1966. A. J.A. G. and D. Cohesive properties of thin films of liquids adhering to a solid surface. P.M. Thin liquid films. J. AIME 262(2):120. 1972.W. P. Heat of adsorption and surface reactions of potassium ethyl xanthate on galena.book Page 131 Tuesday. Somasundaran. Shergold. and R. Aqueous surface chemistry of oxides and complex oxide minerals: Isoelectric point and zero point of charge. Metallurgical. Chem. Rinelli. 1966. Colloid Interface Sci. 1965.J. 50(2):319.. and M. Edited by M. interpretation. R. Trans. ———. Cases. 37(4):731.D. II. 5(2):101. Kulkarni. Rao. 1977. Page 473 in Proceedings of the 10th International Mineral Processing Congress. O. wetting and dewetting of mercury. and D. and D. I. 1962. J. Moscow University. O. 67:121. © 2007 by the Society for Mining. Trans. Colloid Interface Sci. 1949. 1:64. General course in colloidal chemistry.J. Chrysocolla flotation by the formation of insoluble surface chelates. and D. London: Institution of Mining and Metallurgy. J. Edited by M. Zero point of charge of oxides. Theory of wetting. Chim. Flotation of cassiterite with salicylaldehyde as collector. Jones. January 2. and A. J.W. H. J. 1967. 1975. Mellgren.H. Sandvik. Adv. Trans. and application. 1968. Special Disc. Tewari. 1976. Disc. Raghavan. Sutton. K. Roy. Phys. Colloid Interface Sci. Adsorption of amine on quartz through bubble interaction. and V. Metallurgy.. Contact angles and their temperature dependence: Thermodynamic status. 1(4):391. Parks. P. Edited by M. AIME 241(1):105. Smolders.J. Somasundaran. AIME 235:46. 1970. Ser.. Colloid Interface Sci. 1968. Rec. 1964. Electrical double layer on silver iodide: Influence of temperature and application to sol stability. Thermodynamics of the adsorption of collectors.A. 66:967. Trans. 70(1):90. Temperature dependence of point of zero charge of alumina and magnetite. A. London: Institution of Mining and Metallurgy. Surfactant adsorption at the solid–liquid interface: Dependence of mechanism on chain length..I.. and S. M. Heat of immersion of alumina into aqueous sodium dodecyl sulfonate solutions. New York: American Institute of Mining.S. R. Heat of adsorption and surface reactions of potassium diethyldithiocarbamate on galena. Chem. M. Powder Tech. J. S. P. A study of the surface of ferric oxide in aqueous systems.

Adsorption of sulfite. 1968.book Page 132 Tuesday. Adv. Metallurgy. The zero point of charge of α-alumina. J. 2000. Colloid Interface Sci. Chem.-H.A.W. T. . Electronic edition published 2009. Yopps. 1968. J. Fuerstenau. © 2007 by the Society for Mining. J. The wetting of solid in solutions of surface-active substances as a function of solute concentration.. London: Institution of Mining and Metallurgy. and Exploration. Hydrophobic surfaces. Thermodynamics of wetting of solid oxides. Effect of hydrocarbon chain length on the adsorption of sulfonates at the solid/water interface. and manganese(II) ions by β-manganese dioxide and its activation in flotation. 1973. Hackerman. Wakamatsu. 79:161. R. and M. J. Trans. Chem. 1964. 21(7):200. 43:222. Zettlemoyer. Int. oleate.. Effect of alkyl sulfonates on the wettability of alumina. Chem.H. Page 287 in Proceedings of the 6th International Mineral Processing Congress. W. 1960. M. Appl. January 2.A. AIME 254(2):123.. Process.A. 1971. Fuerstenau. 28(3–4):343. 1964.W. The role of hydrodynamic and surfac3 forces in bubble–particle interactions. 19(1):61. Arafa. Wade.C. Ser.flotation0. J. and D. All rights reserved. 2007 7:36 PM 132 FLOTATION FUNDAMENTALS Wada. Ser. A.A. A. 58:129.. and N. M. Colloid Sci. ———. Biotechnol. Yousef. Miner. Malati. Adv. Yoon. and D.

aqueous films between hydropho- bic surfaces. They established that in addi- tion to the normal DLVO (Derjaguin–Landau–Verwey–Overbeek) forces due to disper- sion and electrostatic interactions. on the other hand. for instance. 2007 7:36 PM The Nature of Hydrophobic Attraction Forces Jan Christer Eriksson and Roe-Hoan Yoon INTRODUCTION To gain an improved understanding of the molecular basis of hydrophobicity and hydro- phobic attraction forces is of crucial importance for several scientific and technological fields. Early experiments indicating the existence of long-range hydrophobic attraction forces were carried out by Blake and Kitchener (1979) on thin water films sandwiched between hydrophobic surfaces. many enzymatic reactions take place while the substrate is locked in a hydrophobic pocket. and Stewart (1996). This particular research area. Metallurgy. alternatively.” a term originally coined by Blake and Kitchener (1979). The instability observed was due to the attractive forces operating across the film that arise because of the contact of the water with the hydrophobic surfaces. such as surface and colloid science. Electronic edition published 2009. can be traced to the tendency of hydrocarbon chains to associate when present in a water medium at a high enough (though still very low) concentration. the atomic force micro- scope (AFM) (Figure 2). was inaugurated in 1982 by Israelachvili and Pashley by using mica surfaces and successively adding the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) to the water medium (Israelachvili and Pashley 1982. which focuses on thin. and Muller (1987).book Page 133 Tuesday. Several years later. they identified this surface force as the “hydrophobic force. Ninham. Claesson and Christenson (1988) and Christenson and Claesson (1988) experimented with mica surfaces that had been modified by Langmuir–Blodgett (LB) deposition of dioctadecyldimethylammonium (DODA) bromide or. the hydrophobic attraction was considerably stronger and of longer range than observed by Israelachvili and Pashley 133 © 2007 by the Society for Mining. and Exploration. long-range hydrophobic attraction forces contribute to establishing the mineral–particle/ air–bubble attachment necessary to achieve selective ore enrichment. or some similar direct-surface force measurement device such as the measurement and analysis of surface interaction forces (MASIF) of Parker (1994) and the interfacial gauge of Yaminsky. referring to a large body of experimental results. biochemistry. All rights reserved. Derjaguin and Churaev (1974) and Derjaguin. and mineral processing. In addition. January 2. In the field of flotation. Churaev.flotation0. a double-chain cationic fluorocarbon surfactant. For these cases. 1984). a long-range attractive interaction force operates as a consequence of the hydrocarbon–water contact. The forma- tion of surfactant micelles and biomembranes. developed by Tabor and Winterton (1969) and Israelachvili and Tabor (1972) (Figure 1). Hence. discussed the same effect in terms of “the structural com- ponent of the disjoining pressure.” Most of the hydrophobic force measurements conducted during the last several decades have been based on employing the surface force apparatus (SFA). .

FIGURE 2 Schematic representation of AFM (1982. . All rights reserved. The distance between the sphere and flat plate (sample) is measured by monitoring the deflection of the cantilever spring using a laser beam. January 2. decay length about 15 nm—and measurable up to about 80 nm. and Exploration. Independently. making it difficult © 2007 by the Society for Mining. Metallurgy.book Page 134 Tuesday. The lower surface is attached to a cantilever spring. 1984)—about 100 times stronger than the van der Waals attraction. An abundance of biased and bewildering results have been presented by many investigators. The deflec- tion of the cantilever of a known spring constant gives the force at a given separation distance (Flinn 1997). 2007 7:36 PM 134 FLOTATION FUNDAMENTALS Fringes Piezoelectric Coarse Tube Separation Distance Control Curved Double-Beam Mica Cantilever Surfaces Clamp to Adjust Spring Stiffness White Light NOTE: The interacting (mica) surfaces have cylindrical shape. Subsequent control experiments employing a variety of prepared hydrophobic surfaces have only partially confirmed the previous findings and perceptions. FIGURE 1 SFA based on the original design by Tabor and Winterton (1969) and Israelachvili and Tabor (1972) Laser Beam Cantilever Deflection Flat Plate Sample Microsphere Piezoelectric Tube NOTE: The top portion shows a drawing of a triangular cantilever with an attached glass sphere. Electronic edition published 2009. which yielded mostly equivalent results (Figure 3). measurements were also conducted in Moscow by Rabinovich and Derjaguin (1988) using silanated silica filaments. the deflection of which serves to determine the interaction force (Flinn 1997). and their separation is determined optically by means of an interferometric technique.flotation0.

The corresponding experimental points are scattered around the dotted line within a factor of about 3.book Page 135 Tuesday. h. January 2.6 mJ/m2 and b–1 = 15.flotation0. Electronic edition published 2009. F/R. A very long-range attractive force with exponential decay operating between a variety of hydrophobic surfaces. Nevertheless. between stable hydrophobic surfaces 2. A fairly short-range but strongly attractive force.1 mM KCl (potas- sium chloride) solution. FIGURE 3 Plot of the attractive surface force. or adsorption from solution of an ionic amphiphile © 2007 by the Society for Mining. All rights reserved. in particular those hydrophobized by means of Langmuir– Blodgett deposition on mica or silica. the surface separation. vs. the dotted line shows the surface force function determined by Rabinovich and Derjaguin (1988) for silica filaments immersed in 0. Christenson and Claesson (2001) presented a detailed account of the scientific state of the art from an experimental perspec- tive. An attraction of variable strength and range caused by the presence of small bubbles sporadically adhering to hydrophobic surfaces 3. for DODA- covered mica surfaces in contact with pure water to summarize the current status of research.8 nm from Equation 31. μN m–1 –103 –104 NOTE: The points demark experimental values measured by Claesson and Christenson (1988). obtained by inserting B = 0. They classified the non-DLVO attractive forces observed between hydrophobic sur- faces into the following classes: 1. For comparison. nm 0 10 20 30 40 50 60 70 80 –10 Rabinovich and Derjaguin (1988) –102 F / R . 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 135 h. much stronger than the van der Waals force. Metallurgy. . and Exploration. The solid line represents Equation 56.

On this point. January 2. as to what extent the novel findings and ideas about the structural aspects of liquid water will necessitate revising the conventional molecular picture based on four-coordinated water molecules in small clusters having exter- nal surfaces with less-well-bonded molecules (Ludwig 2001). At this point. and extensive reference lists are included in their papers (Meyer. The ultimate purpose is to scrutinize whether there is enough evidence today in support of the existence of a “true” hydrophobic force (i. X-ray absorption spectroscopy (XAS). Wernet et al. and X-ray Raman scattering (XRS) (Miranda and Shen 1999. it has been established that about one-fourth to one-fifth of the water molecules in the top monolayer of the water–air interface have a non-hydrogen-bonded OH group as a unique feature. These novel methods include sum-frequency generation (SFG) spectroscopy. After dwelling on the thermodynamics of the surface force experiment. . Metallurgy. It remains to be assessed.book Page 136 Tuesday. and Exploration. the concept of an ideal hydrophobic surface is introduced. rod-shaped surfactant micelles. 2005). Cavalleri (2004) has recently found that for bulk water there is also a tendency to form linear aggregates of water molecules (based on two strong hydrogen bonds rather than four of medium strength). Evidently. More recently. First. In the absence of any long-range forces. papers by Tsao. and Pashley (1998) incorporate illuminating discussions about the possible origins of the hydrophobic force. and Israelachvili 2005. compared to the situation in bulk water. however. All rights reserved.. 2007 7:36 PM 136 FLOTATION FUNDAMENTALS Spalla (2000) presented a complementary paper. Electronic edition published 2009. one may note that according to Hill’s small-system thermodynam- ics. considerable progress has been made in the probing and modeling of the molecular state of bulk as well as of surface water. Evans. Israelachvili and co-workers have begun to critically re-examine the entire issue. Ninham. a large part of the comparatively high surface energy of water is connected with the excess of broken hydrogen bonds in the surface. Lin. Hence. a surface force of long range that is related to the structural response of a thin water film between hydrophobic sur- faces). a mechanism of this thermodynamic nature is decisive for the formation of elongated. 2004). resulting in rings and chains of water molecules.flotation0. the chapter focus is on some typical results obtained for the main hydro- phobic surfaces investigated so far. for hydrophobic surfaces that are of superior quality. thus providing a frame of reference for judging experiments with real hydrophobic surfaces that usually exhibit many deficiencies. a distribution of linear aggregates may arise insofar as the free energy cost of introducing one additional molecule in the central part of such an aggregate is small enough to become compensated by the fluctuation entropy contribution that is inherent in the length distribu- tion. One section is devoted to the possible formation of bridg- ing air bubbles (and cavities) for hydrophobic surfaces with (equilibrium) contact angles against water in excess of 90°. Rather surprisingly. Furthermore. and in particular.e. however. A similar scheme can be applicable even for chains of water molecules and might be at the root of water effects of long range. and can be rationalized on the notion of oriented oxygen double layers similar to those present in the ice Ih lattice (Figure 4). Lin et al. © 2007 by the Society for Mining. M O L E C U L A R O R G A N I Z AT I O N O F WAT E R AT I N T E R FA C E S Because of the advent of novel spectroscopic and computational methods in recent years. The dangling –OH group spectral peak for a hydrocarbon–water interface remains essentially the same as for the free water surface toward air. and Wenner- ström (1993) and Craig. primarily dealing with the theoretical understanding of the hydrophobic force. some recent findings as to the molecular organization of water interfaces and hydrophobic interactions in general are discussed.

and Woodward 1996) indicate that a significant surface effect is noticeable only for short distances in liquid water. A crucial and much-debated question arises: How deep toward the bulk may such a network prevail? Interestingly. whereas a more disordered water structure prevails for the water–air and water–hexane interfaces. although thermodynamically significant. Moreover. This has already been indicated by the fact that the predictions of the melting point of ice using water models of this kind are. imposes bonding constraints on the successive layers of water molecules beneath it so as to generate a surface-induced net- work. this would result in a roughly tangential alignment of the water dipoles. Speaking in broad terms. structural rearrangements can occur without sensible volume changes. bear in mind the ongoing endeavors to probe and to simulate interfacial and bulk water by means of molecular dynamics. McCammon. McCammon. an atomically smooth. Electronic edition published 2009. on the order of © 2007 by the Society for Mining. to only explore density changes in a thin water film might not be sufficient because minor. In a cooperative fashion. grossly in error. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 137 712 275 275 450 FIGURE 4 The ideal ice Ih structure. for the most part. and Rossky (1984). The classical simulations of Lee. On average.flotation0. thus forming a clathrate-resembling contact mono- layer of water molecules. when considering hydrophobicity and hydrophobic surface forces. All rights reserved. and Exploration. may have been based on a simplistic water potential (of ST2 type). as would actually be the case for any liquid. chemically inert solid surface that is subject to thermal motions of small amplitudes may be expected to • Force the water molecules to pile up against the surface. such a contact monolayer. in turn. . Jönsson. January 2. which are often referred to in this context. The previously mentioned simulations by Lee. and Rossky (1984) and similar ones by other researchers (Forsman.book Page 137 Tuesday. The numbers represent dimensions in picometers. characterized by stacked oxygen double layers. the SFG spectra recorded by Miranda and Shen (1999) indi- cate that a well-ordered. ice-like water structure predominates at a solid hydrophobic surface. Metallurgy. and • Force the hydrogen bond network to rearrange in its vicinity so as to limit the num- ber of broken hydrogen bonds. which may result in a substantially revised basis for a comprehensive theoretical treatment of these phenomena (Cavalleri 2004). Thus.

there is always a slight solubility.book Page 138 Tuesday. With sign reversed. Generally. d ln x hc Δh hc 0 ----------------- . Δs 0 . for entropic reasons. January 2. As xhc is approximately inde- pendent of temperature within the room-temperature range. the solubility of a hydrocarbon in water is nearly temperature-independent at about room temperature. which in turn means that the difference between the standard state chemical poten- tials is given by 0 = Δh 0 – T Δ s 0 ≈ – T Δ s 0 Δμ hc (EQ 4) hc hc hc 0 is largely determined by the (negative) entropy change. Eventually. Referring to the thermodynamic Gibbs–Helmholtz equation for the case under discussion. do not mix with water. Tanford (1980) was able to quantify the Gibbs (free) energy change associated with transferring a –CH2– or a –CH3 group from bulk hydrocarbon to the dilute water state. Electronic edition published 2009. All rights reserved. . 2007 7:36 PM 138 FLOTATION FUNDAMENTALS 1 nm.548k B T 3 (EQ 1) 0 Δμ CH = 1. provided that the concentration of the chains exceeds the normal water solubility of the bulk hydrocarbon. Δμ hc hc accompanying the hydrocarbon dissolution in water. occasionally. the reasons for these widely contrasting results will have to be determined before a convincing theoretical description can be achieved for why and how the hydropho- bic attraction arises. Metallurgy. even longer.flotation0. such as oil and hydrocarbons. In contrast. (EQ 2) d( 1 ⁄ T ) kB where xhc denotes the mole fraction of dissolved hydrocarbon. Δμ CH 0 0 and Δμ CH determine the driving force for aggregation of 3 2 hydrocarbon chains present in water. Yet. a condition that can easily be realized by attaching a polar group to the hydrocarbon chain. even for hydrocarbons. many surface force measurements (detection limit ≈ 10 μNm–1) are indicative of non-DLVO attractions extending as far as 50 nm and. In other words.492k B T 2 where kB = R/NAvogadro and is the Boltzmann constant and T is the absolute temperature. thus forming an amphiphilic molecule. and Exploration. These thermo- dynamic quantities are necessarily positive and of the following magnitude at room temper- ature (per methyl or methylene group): 0 Δμ CH = 3. that reflects the local energetic conditions of a single hydrophobic solute molecule surrounded by water molecules. © 2007 by the Society for Mining. H Y D R O P H O B I C E F F E C T S I N S O L U T I O N S A N D AT T H E WAT E R – A I R I N T E R FA C E The concept of hydrophobicity stems from the common observation that many substances.= ---------- . this relation implies that the enthalpy change for the process hc (bulk hydrocarbon) → hc (water) (EQ 3) is small. By analyzing the (mole–fraction-based) solubility in water of a number of straight-chain hydrocarbons.

A few decades ago. the overall excess free energy due to the water structuring can be reduced by hydrocarbon association. this energy expense is almost exactly counterbal- anced by the energy released upon structuring the surrounding water to create a more 0 is ordered hydration shell. compare Figure 5. thus. be traced back to the formation of hydrogen-bonded clusters and networks in water. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 139 According to Frank and Evans (1945). . hence. however. non-hydrogen-bonded liquids. Metallurgy.1379t – 0. these thermodynamic results can be understood in the following way. a neg- ative quantity. a value of about 25 J/K·mole (approximately one-fourth of the entropy of vaporization) is typical (Eriksson 1966). ordinary surfactant micelles start to form in solution (and hemimicelles on surfaces) at some fairly low “critical” surfactant con- centration (i. Moreover. This conclusion is supported by the temperature dependence observed for the SFG spectrum of the pure water–vapor interface that indicates a relative loss of ordered water as the temperature is raised (Miranda and Shen 1999). then. T Δs structure may be identified as being the main driving force for hydrocar- bon association in a water environment at ordinary temperatures. much the same explanation accounts for the relatively low surface entropy of liquid water.2717 × 10 –3 t 2 ( mNm –1 ) (EQ 6) where t denotes temperature in centigrade. it takes a certain amount of energy to form a nano-cavity where the hydrocarbon molecule can reside.book Page 139 Tuesday. the surface entropy of water increases with temper- ature. On a molar basis. as appears from the following experimentally determined surface tension function for pure water (Cini. Because the surface entropy is an excess property relative to the entropy of water in the bulk state. At room temperature. the prevailing belief being that release of structurally con- strained water molecules furnishes the free energy required to accomplish the association. for an ordinary liquid the surface entropy is expected to be practically T-independent.e. To insert a hydrocarbon molecule into water. recalling that the surface entropy is determined by (the negative of ) the temperature derivative of the following function: γ w. for example. The similarities with clathrate formation for inert gases in water were also frequently men- tioned as supporting evidence. January 2. What is left. structurally related properties at lower temperatures. which shows that water exhibits “normal” liquid properties at high temperatures where the solubility of a hydrocarbon increases with temperature but spe- cial. one can readily rationalize why. to obtain an estimate of Δμ hc largely the concomitant entropy change: 0 ≈ Δs Δs hc structure ≈ Δh structure ⁄ T (EQ 5) that pertains to a process similar in nature to a freezing phase transition and is.653 – 0. air = 75. the critical micelle concentration). All rights reserved.flotation0. The full experimental picture is. © 2007 by the Society for Mining. Basically. and Shinoda (1978). This behavior can. this entropy amounts to about 10 J/K·mole.. The fact that the surface entropy of water increases with temperature is thus indicative of a gradual breakdown of an interfacial hydrogen-bond-dependent structure. Electronic edition published 2009. In this way. The last approximate relation in Equation 5 follows because for such a phase transition. Conversely. the negative thermodynamic quantity Δs structure discussed above was often attributed to “iceberg” formation that was considered to be the general cause of hydrocarbon association in water. whereas for normal. and Ficalbi 1972). at ordinary temperatures. Δh structure . In other words. however. there is almost no net change in Gibbs energy. and Exploration. somewhat more complex. Loglio.

2 2. . being less for a strongly curved droplet of a hydrocarbon fluid than for a planar hydrocarbon– water interface.5 1/T × 103 NOTE: Typically. 2007 7:36 PM 140 FLOTATION FUNDAMENTALS ºC 200 180 160 140 120 100 80 60 40 20 2 3 Benzene log X 2 Toluene 4 Ethylbenzene Extrapolated Experimental Solubility Solubility Curve Curve 5 2. Source: Data from Shinoda 1978. however. All rights reserved.4 2. January 2.8 3. There- fore.0 3.0 2. Calculations and molecular dynamics simulations using various water interaction potentials made thus far show that the range having a molecular organization different from that of bulk water may extend merely about 1 nm. whereas some surface force © 2007 by the Society for Mining. and Exploration.2 3. it can be assumed that the hydrophobic free energy is a curvature-dependent quantity. the solubility passes through a flat minimum at about room temperature.book Page 140 Tuesday. Although there is presently consensus among theoretical physicists and chemists about the ability of liquid water to respond structurally to the formation of “internal” microscopic as well as “external” macroscopic interfaces. obviously there is an unresolved issue about the range that is affected.flotation0. Electronic edition published 2009. FIGURE 5 Diagram displaying how the solubilities of alkylbenzenes in water vary with temperature For the case of a planar geometry.4 3.6 2. Metallurgy. the enthalpy change associated with the structure formation is insufficient to counterbalance the energy expenses because of ruptur- ing hydrogen bonds toward air and the concomitant loss of dispersion interactions. The effect of water structuring is related with the vertical distances to the corresponding extrapolated lines.

Based on discussions in the previous paragraph. in an attempt to bridge the gap between theory and experiment.book Page 141 Tuesday. would exhibit a contact angle of 0°. LW + γ AB γ 13 = γ 13 (EQ 8) 13 © 2007 by the Society for Mining. To what extent do the experimental hydrophobic surfaces employed actually mimic an ideal hydrophobic surface? The questions presented in no. one realizes that even surfaces exhibiting a contact angle substantially less than 90° are presumably capable of exerting a structural hydrophobic effect on water.6° (EQ 7) where the term γ 12 – γ 13 (= 30 mJ m–2) is referred to as the “superficial tension” of water in contact with the hydrophobic surface. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 141 measurements indicate attractive hydrophobic forces for water films as thick as 100 nm. accounts for the tendency of water to contract on a solid surface. whereas a completely water-indifferent. Thus. Electronic edition published 2009. as shown in Figure 6. C O N TA C T A N G L E M E A S U R E M E N T S T O A S S E S S HYDROPHOBICITY It is common practice to quantify the hydrophobicity of a solid surface 1 by means of mak- ing contact-angle measurements. A prerequisite for the above identification is that no.0 mJm–2 at θ = 60°. usually employing pure water 3 as the contacting liquid. How realistic are the molecular model calculations/simulations for thin water films carried out thus far? Do they comply with the notion of restructuring at a minor free-energy expense? Would they be capable of predicting film tensions with the necessary precision? 2. γ1 and γ13 have been plotted as func- tions of contact angle (cosθ). pertinent questions to consider are as follows: 1. Certainly. and Exploration. the difficulties encountered along this fundamentally oriented route are rather formidable. or just minute amounts of. January 2. and invoking γ32 = 72 mJm–2. γ13. Hence. with γ13 = 0 mJm–2 and γ32 = 72 mJm–2. the reversible cleavage work in water (compare Eriksson 1969) to be γ13 = 51 mJm–2 (i. . This particular tension. fol- lowed by using the Young equation. one can readily predict the contact angle of the hydro- phobic surface to be –1 –1 θ = cos [ ( γ 12 – γ 13 ) ⁄ γ 32 ] = cos ( – 30 ⁄ 72 ) = 114.0 mJm–2 at θ = 90° and 18. The latter question is more practically oriented and leads to the almost arcane art of measuring contact angles in order to assess the hydrophobicity/polarity of solid surfaces. Metallurgy.flotation0. Assuming the solid–liquid interfacial tension (γ13). introduced by Gibbs. 1 above are currently being pursued by means of novel spectroscopic and computational methods. between solid 1 and water 3 can be considered to consist of apolar and polar components. taking the hydrophobic surface against air 2 to have a corresponding interfacial tension value of γ12 = 21 mJm–2. According to Equation 7.e. It is expected that γ13 = 36.. the same as for an entirely fluid hydrocarbon–water interface). water vapor adsorbs at the hydro- carbon–air interface. polar solid surface resembling ice. Thus. All rights reserved. The interfacial tension. or more precisely. a contact angle of 90° is reached when the superficial tension equals zero.

. one obtains γ 13 = ⎛⎝ γ 1LW – γ 3LW ⎞⎠ + 2 ⎛⎝ γ 1+ – γ 3+ ⎞⎠ ⎛⎝ γ 1– – γ 3– ⎞⎠ (EQ 11) From the following fundamental relationships: γ i = γ iLW + γ iAB (EQ 12) where the subscript i refers to phases of interest. 2007 7:36 PM 142 FLOTATION FUNDAMENTALS 60 50 γ13 40 γ. and γ 3LW is the LW component of water. respectively. Metallurgy. Good and Girifalco (1960). and Fowkes (1963) showed that 2 LW = ⎛ γ 13 LW LW ⎞ (EQ 9) ⎝ γ1 – γ3 ⎠ where γ 1LW is the LW component of the surface free energy of solid. and AB refers to acid– base (polar) interactions.. and γ iAB = 2 γ i+ γ i– (EQ 13) © 2007 by the Society for Mining. Electronic edition published 2009. January 2.3 0. the cosine of the contact angle of water (cosθ ) and the solid–water (γγ13) and solid–air (γγ1) interfacial tensions depend on the polarity/ hydrophobicity of a solid surface where LW refers to Lifshitz–van der Waals (i.5 –0.0 0. van Oss.1 0.book Page 142 Tuesday.4 0.4 –0. in theory.e.3 –0. apolar) interactions. Inserting Equations 9 and 10 into Equation 8. All rights reserved. and Good (1987) showed that AB = 2 ⎛ γ 13 + +⎞ ⎛ – –⎞ (EQ 10) ⎝ γ1 – γ3 ⎠ ⎝ γ1 – γ3 ⎠ where γ 1+ and γ 3+ are the acidic components of the surface free energy of the solid and water. and Exploration.flotation0.1 0.2 0. Chaudhury. and γ 1– and γ 3– are the basic components of the same.5 cos (θ) FIGURE 6 Diagram showing how.2 –0. For the acid–base interactions. mJm–2 30 γ1 20 10 120°C Hydrophobicity θ = 90°C Polarity 60°C 0 –0.

Metallurgy. It is also possible that the second inflection point of the plot is caused by a flat (or flip- flop) orientation of the additional OTS molecules adsorbing at high surface coverages. Teflon.e. the major role of a surfactant would be to decrease γ 1+ and γ 1– by blocking the hydrogen donor or acceptor sites of the solid surface. and Yoon 1994). If γ 1+ and γ 1– are small (i. who showed that both advancing and receding water contact angles on thiol-coated gold increase with increasing fraction of CH3 groups relative to that of OH groups (Figure 8). Note also that the surface free-energy data given in Figure 7 agree well with the approximate relationship between surface and interfacial tensions (γ1 and γ13) and cos θ shown in Figure 6.5 mJ/m2) and basic compo- nents ( γ 3– = 25. Electronic edition published 2009. γ 1– . © 2007 by the Society for Mining.. These findings are consistent with the work of Ederth (1999). All rights reserved. which means that water molecules form hydrogen bonds with the surface hydroxyl groups and render the surface hydrophobic. one obtains the following expression: 2 ΔG 131 = – 2 ⎛⎝ γ 1LW – γ 3LW ⎞⎠ – 4 ⎛⎝ γ 1+ γ 1– + γ 3+ γ 3– – γ 1+ γ 3– – γ 1– γ 3+ ⎞⎠ (EQ 16) in which the first term is small for hydrophobic solids (e.5 mJ/m2) of water are fixed under most experimental conditions. the free energy of hydrophobic interaction vanishes at γ 1– > 28. the hydrophobic interaction van- ishes)..e. K increases with increasing advancing contact angle (θa) of the silica surfaces. . Because the acidic ( γ 3+ = 25. if the value(s) of γ 1+ and/or γ 1– is large. additional non-DLVO attraction.g. It is important to note here that K increases with decreasing γ 1+ . The interfacial tension (γ13) can be used to obtain the free energy of hydrophobic inter- action (ΔG131) between two solid surfaces 1 in water 3 as follows: ΔG 131 = – 2γ 13 (EQ 15) Hence. as suggested by Equation 14. cavitation may occur and cause a strong. The results are given in Figure 7. As shown. and γ 1LW . As the contact angle increases in excess of 90°. Surfactants are used to render various solids hydrophobic.. Guzonas. the free energy of the hydrophobic interaction arises predominantly from the 4 γ 3+ γ 3– (= 102 mJm–2) term. The sharp increase in K at θa close to 90° may represent a change in orientation of the OTS molecule from flat to vertical orientation (Flinn. and Exploration.e. from Equation 11. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 143 one can rewrite Equation 11 to yield the following expression: γ 13 = γ 1 + γ 3 – 2 γ 1LW γ 3LW – 2 γ 1+ γ 3– – 2 γ 1– γ 3+ (EQ 14) The values of γ 1+ and γ 1– of many hydrophobic substances (e.. a solid is apolar). hydrocarbons or alkanes adsorb- ing on a solid surface).book Page 143 Tuesday. and γ 1LW = 40 mJm–2. Pazhianur and Yoon (2003) conducted surface force measurements between silica sur- faces treated with octadecyltrichlorosilane (OTS) using an AFM and compared the results with the changes in the surface free energies of the treated surfaces. and dodecane) are zero and therefore have high interfacial tensions. polypropylene. Laskowski and Kitchener (1969) noted that hydrophobic- ity arises when water molecules are prevented from forming hydrogen bonds with the polar sites on the surface of a solid. in which K (of Equation 35) represents the magnitude of a hydrophobic force measured. If a solid is basic (i.flotation0. January 2. γ 1+ = 0.3 mJm–2 (van Oss 1994). providing an explanation for the change in slope of the K versus θa plot. On the other hand..g. because the values of γ 1LW and γ 3LW are close to each other. ΔG131 becomes positive (i.

and the changes in hydrophobic force constant. Electronic edition published 2009. γ1. whereas γ1+ and γ1– denote acidic and basic components. % Source: Ederth 1999. FIGURE 7 Changes in surface free energy of OTS-treated silica plate in air contact as a function of the advancing water contact angle.book Page 144 Tuesday. γ1LW and γ1AB are the nonpolar and polar components of the surface ten- sion of the solid surface. 2007 7:36 PM 144 FLOTATION FUNDAMENTALS 45 40 10–16 γ1LW 35 30 Surface Free Energy. respectively. as a function of the water contact angle 100 90 θ 80 70 55 60 65 70 75 80 85 Solution Fraction C16. K. mN/m 10–17 25 K. Metallurgy. Joules 20 γ1– 10–18 15 γ1AB 10 10–19 5 γ1+ 0 10–20 50 60 70 80 90 100 110 120 θ2 (Water) NOTE: K is a parameter of a power law (Equation 35). FIGURE 8 Advancing ( ) and receding ( ) contact angles of water with surfaces prepared from mixtures of C16 and C16OH-thiols of various mixing ratios © 2007 by the Society for Mining. of γ1AB. January 2. .flotation0. and Exploration. All rights reserved.

A question remains then as to how the hydrophobic force decays with the distance separating two macroscopic particles.e. Laskowski and Kitchener (1969) suggested that the multimolecular water layer on the sur- face of a hydrophobized silica is unstable. the so-called (Derjaguin) disjoining pressure has to be applied. using Derjaguin’s terminology. . solid surfaces © 2007 by the Society for Mining. is acting. eventually caus- ing the water film tension to diminish as the thickness shrinks. The free energy gain due to the hydrogen bond interactions among water mol- ecules is large as compared to the interaction with the hydrophobic surfaces. and Exploration. about 100 mNm–1). In order to keep the film at a certain thickness h. FIGURE 9 Schematic of a thin liquid film between two planar. which in turn is manifested as a hydrophobic attraction or a negative disjoining pressure. T H E R M O DY N A M I C A S P E C T S O F S U R FA C E F O R C E MEASUREMENTS Consider an idealized thin film/surface force experiment using two plane-parallel.” πD Water Solution γf πD NOTE: The excess (interaction) pressure operating perpendicular to the film is. laterally homogeneous hydrophobic surfaces with a thin water solution film between them (Figure 9). In lateral directions. January 2. atomi- cally smooth.flotation0. γf. the disjoining pressure. a lateral tension γf develops in the film which at large thicknesses of h will be equal to twice the interfacial tension of the hydrophobic surface–water solution interface (i. an extra pressure. πD. a film tension. This pressure. These investigators were the first to recognize the existence of a long-range. has alter- natively been called surface “interaction pressure. which is ascribed to a less favorable state of molec- ular association at a certain distance from the surface than in ordinary (bulk) water. non-DLVO hydro- phobic force and to suggest that the long-range character arises from the structural proper- ties of water.. The thermodynamic variables of prime interest as determined in the adjacent bulk water solution are the temperature T and the solute chemical potential μS(or the concentration cS of solute). the hydrophobic interaction is seen to be related to the strong cohesive energy of liquid water. positive (repulsive) or negative (attractive). πD.book Page 145 Tuesday. To establish equality of the chemical potentials everywhere. The surface force is defined as 2π times the difference in film ten- sion between a thin film with interacting film faces and an infinitely thick film. Electronic edition published 2009. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 145 Thus. All rights reserved. Metallurgy.

This means that the Gibbs equimolecular dividing surfaces of the (hydrocarbon-covered) hydrophobic surfaces are being employed to delimit the water film in the direction perpendicular to the film faces. whereas πD > 0 means repulsion and a film ten- sion that increases with decreasing h. μs Hence. n sf. The film tension γf is formally an Ω-potential per unit area. = –πD (EQ 19) ⎝ ∂h ⎠ T. h stating that the amount of (surfactant) solute in the film will become less with decreasing thickness if the disjoining pressure tends to increase when raising the chemical potential of the solute. and cs and cw are the corresponding bulk phase concentrations.ex d μ s + π D dh (EQ 17) which constitutes an extension of the classical Gibbs surface tension equation to cover the case of interacting solid surfaces separated by the film thickness h (compare to the appendix at the end of this chapter).ex ⁄ A = G f ⁄ A – Γ wf μ w – Γ sf μ s (EQ 21) Thus. Electronic edition published 2009. n sf. and. All rights reserved. . will result when the film ten- sion γf decreases as the thickness diminishes. p..ex (where A denotes the area of the film) is an excess quantity in the following sense: n sf. Furthermore. and Exploration. beyond the range of the surface forces). The film thickness may most conveniently be defined as the separation between the hydrophobic surfaces devoid of any loosely adsorbed solute. γ f = Ω ⁄ A ≡ G f.ex Γs ⎞ ∂π D⎞ ⎛ ∂-----------.ex ≡ A Γ sf. Metallurgy. Equation 17 includes an interesting Maxwell relation. an attractive surface force. In addition. the thin film system obeys the following thermo- dynamic fundamental equation to a very good approximation: – d γ f = Γ sf.e.ex represents the film content of the solute component in excess of what would be a corre- sponding slab of bulk solution containing the same amount of water as is present in the film.ex = n sf – n wf c s ⁄ c w (EQ 18) where n sf and n wf denote the actual mole numbers of surfactant and water in the film. μs ⎝ ∂μ s ⎠ T. Δγf. 2007 7:36 PM 146 FLOTATION FUNDAMENTALS At constant temperature and pressure. p. when equilibrium prevails at constant T. p. p. characterized by πD < 0. respectively. From Equation 17 it can be seen that the disjoining pressure πD is generally related to the film tension by the derivative γ-f⎞ ⎛ ∂-----.= ⎛ --------. To derive the film tension change. the film tension γf is necessarily at a minimum. Equation 19 can be integrated as follows while assuming that the bulk phase state will remain the same: © 2007 by the Society for Mining. In other words. January 2. f. μs.book Page 146 Tuesday. arising because of diminishing the thickness from h = ∞ where πD = 0 (i.flotation0. (EQ 20) ⎝ ∂h ⎠ T.

At this point. constitutes a geometrical integration of Equation 19 (com- pare Figure 10). Although they are actually based on the very circumstance that (equi- librium) surface forces represent little else but film tension changes that arise when the inter- acting surfaces are brought close to contact. Next. the local tangential pressure pT will have to h1 = h + r 2/2R R r Sphere h Ring of Radius r Volume 2π drdh dr dh FIGURE 10 Diagram of the geometrical disjoining pressure integration involving the Derjaguin (1934) approximation © 2007 by the Society for Mining. it has become common practice to report surface forces “normalized” in the form F/R. These simple relations effectuate the transformation from a curved to a planar geometry. the amazingly powerful Derjaguin approximation (1934) takes place that. or crossed cylinder– cylinder configurations. sphere–plane. yielding an additional geometry-dependent factor such that the measured surface force F becomes equal to F = 2πRΔγf or sphere–plane and crossed cylinder–cylinder geometry and F = πRΔγf for sphere–sphere geometry. January 2. it is not feasible to employ a plane-parallel experimental setup as that indicated in Figure 9. They are valid for various surface inter- action forces insofar as the ranges of these forces are much less than the inverse curvature of the surfaces involved. Instead. Because of the unfavor- able water–hydrocarbon contact combined with the necessity of attaining a uniform value of the water chemical potential everywhere.book Page 147 Tuesday. corresponding to 2πΔγf and πΔγf for these two standard geometries. Electronic edition published 2009. Metallurgy. and Exploration. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 147 h Δγ f = γ f ( h ) – γ f ( ∞ ) = – ∫ π D dh (EQ 22) h=∞ In practice. in effect. .flotation0. All rights reserved. one has to resort to sphere–sphere. consider a pure water film between hydrophobic surfaces.

In the following paragraphs.w (EQ 25) The last of these relations assumes that there is no residual excess free energy associated with the touching surfaces in direct adhesive contact. pT(0) denotes the tangential pressure next to the hydrophobic solid surface.w (EQ 26) that is. as given by the Derjaguin–Muller–Toporov relation (for nondeformed interacting cylindrical sur- faces. integrate Equation 23 to yield (crossed cylinders): F ⁄ ( 2 π R ) = Δγ f = – const. Equation 23 assumes an exponential decay (decay length = D) of the thermodynamic effect caused by the presence of the surface as a function of the distance x from the surface. Equation 23 might constitute a reasonable first approximation. an exponential behavior of the (attractive) surface force with respect to the film thickness h can be predicted. Accordingly. 2007 7:36 PM 148 FLOTATION FUNDAMENTALS assume a variable negative value. for the large separation part of a surface force versus thickness isotherm on this admittedly oversimplified basis. Moreover. Pull-off forces refer to the forces mea- sured when two surfaces in contact with each other are separated. 2005). However. at least when the outer part of the surface zones begin to overlap (compare Marčelja and Radic 1976). Hence p – p T ( x ) = [ p – p T ( 0 ) ] × exp ( – x ⁄ D ) (EQ 23) Here. 2γhc. Electronic edition published 2009. which predicts a pull-off force equal to F adhesion ⁄ R ≅ 3 πγ hc. All rights reserved. × exp ( – h ⁄ 2D ) (EQ 24) Hence. water molecules with slightly higher (Helmholtz) free energy than in the bulk are being released from the thin water film and transferred to the adjacent bulk water. the JKR ( Johnson.e. a more elabo- rate and more realistic treatment of the structural effect arising for the water in a thin film between ideal hydrophobic surfaces is considered.flotation0. Rob- erts) theory instead applies. when surface deformations are significant. compare Israelachvili 1991): F adhesion ⁄ R = 2 πΔγ f ( h = 0 ) ≅ 4 πγ hc. Kendal. this means that upon diminishing the film thickness. thereby lowering the overall free energy of the film. making the reasonable assumption that the surface force arising as the two hydrophobic surfaces are brought closer is entirely due to the elimination of surface-affected water molecules. The additional 2πR-factor in Equation 25 originates from the Derjaguin approximation.w represents all the free energy per square meter that is gained in the planar case upon eliminating the hydrocarbon–water contact area. replacement of surface-located water) is responsi- ble for the adsorption of surfactant and polymers at the air–water interface in the dilute Henry’s law region (Kumpulainen et al.book Page 148 Tuesday. Evidently. corresponding to tension for each water layer located at x outside the solid surface. January 2. hydrocar- bon-covered surfaces (compare Israelachvili 1991). Metallurgy. © 2007 by the Society for Mining. Diminishing film thickness from infinity to h = 0 will yield the adhesion force. . whereas p represents the atmospheric pressure of the surroundings. Essentially the same mechanism (i. the maximal adhesion force between fully hydrophobized solid surfaces in water is estimated to be 640 mN m–1. a maximal pull-off force of about 480 mN m–1 for two crossed-cylindrical. Physically. and Exploration..

and have them fairly densely packed on the surface. Regarding smoothness. an “ideal” hydrophobic surface in the theoretical. Electronic edition published 2009. and so forth. one might prefer the hydrocarbon chains to be in a “semifrozen” solid (rather than close-packed crystalline) state. should not occur. having a packing density between 0. this requires a smooth enough substrate. the answer seems simple: a minimal roughness at the atomic level is desired. molecular constitution. and at the same time preserving surface smoothness at the atomic level.25 nm2 per single chain.book Page 149 Tuesday. one may easily end up with studying the effects of vapor/air cavi- ties and bridging bubbles rather than the hydrophobic attraction per se.1 nm in peak-to-valley distance. the latter approaching adsorption equilibrium at an amazingly slow rate (Zhang et al. hydrophobic surface would exhibit an advancing contact angle against water of about 110°. the answer may seem almost self-evident at first: maximal hydrophobicity calling for fluorocarbon rather than hydrocarbon chains. the hydrocarbon chains used as modifying agents must be attached in such a man- ner that the smoothness is maintained. For a less crowded amphiphile monolayer in a liquid-expanded state. on average approaching 0. By making such an extreme choice. All rights reserved. January 2. hydrophobicity. and if smooth enough from the © 2007 by the Society for Mining. there seems to be a big difference between C16 and C18 cationic surfactants in this regard. In summary. Clearly. Concerning hydrophobicity. and Exploration. however. however. For mica and silica substrates. Smoothness is likely to be a crucial factor for the occurrence of a long-ranged hydro- phobic attraction force. in principle at least. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 149 The Ideal Hydrophobic Surface Versus Real Hydrophobic Surfaces For experimental purposes. Yet. mica. silica. The fairly high mechan- ical tension acting in the water adjacent to the hydrocarbon film will further tend to dampen the thermal amplitudes in the interface. As to the molecular constitution. and would in some solid state maintain a certain degree of molecular mobility but nevertheless be smooth on the atomic scale. motional state. and for this reason. forc- ing them to adopt a crystalline state with tilted chains may cause complicating domain struc- tures and grain boundaries to arise. Concerning the motional state. it should be fully verified. one would preferably desire the hydrocarbon chains employed to be sufficiently long (≥ C16 ).22 and 0. 2005). fluidity. an ideal. to make up a certain minimum thickness of the resulting surface-modifying layer. First of all. stability toward water solu- tions and other media. Metallurgy. In addition. Chemical reaction and polymerization schemes for the bonding of alkyl or silyl chains can be risky in this regard as they may involve strong mechanical pressures/tensions to operate in the surface during the reactions. If properly balanced in terms of its mechanical properties to withstand mechanical loads. or at least making equilibra- tion times exceedingly long. when ionic head groups are attached to the bonding sites of opposite charge on a solid surface for which the thermal amplitudes are small. philosophical sense is often realized. one might well prefer surfaces exhibiting a contact angle against water slightly less than 90° for which capillarity phenomena of this extraneous nature. The main experimen- tal difficulty encountered in this context involves obtaining a sufficient degree of stability for the hydrophobic layer attached. . stable. The question immediately arises about the most desirable properties of such a surface as to smoothness. one runs the risk of the thermal motions making the water–hydrocar- bon phase boundary fuzzy. the chains may end up in some “frozen” gel state. or glass is usually preferred. an almost-perfect hydrophobic surface and. For this reason. hampering the equilibration of the adsorbate. hence.flotation0.

Real surfaces that exhibit pronounced hydrophobic properties to a variable degree are listed as follows: 1.1. surface morphology and the © 2007 by the Society for Mining.25 nm2 per single chain. [2005]) fulfils the quality criteria with respect to smoothness and motional state but shows lack of sta- bility toward salt solutions and even toward passage through the water–air inter- face.book Page 150 Tuesday. which. For mica sur- faces. to quote Christenson and Claes- son (2001): “Experimental results with silylated surfaces have shown great variabil- ity depending on exact preparation conditions. Lin. the hydrophobic surfaces employed by Claesson and Christenson [1988] and. A surface that is similar to point 1 but instead relies on adsorption from a cyclohex- ane solution to attach the double-chain cationic surfactant onto the mica. Evans. Conse- quently.50 nm2). which started by forming (by electron beam evaporation) a 1-nm titanium layer. Cho. silica. Claesson.5 nm. Electronic edition published 2009. and Claesson 1989). a circumstance that was utilized by Ederth. more recently.. January 2. Cleaved mica with a deposited LB layer of a double-chain cationic surfactant (i. However. and Exploration. matches almost exactly the anionic site density of the mica surface (≈0. hysteresis might be limited and the risk minimized for having bubbles attaching and bridging between approaching surfaces. . These surfaces exhibit a hydropho- bic attraction of medium range but have been plagued by sporadic bridging bubble steps in the surface force curves. This scheme was successfully applied by Tsao. In particular. Glass. who obtained hydrophobized mica surfaces that were quite similar to those made according to point 1. stability toward salt solutions was less satisfactory than for the corresponding LB monolayers prepared according to point 1. Stability is not a problem.e. 2. 4. Yet. or mica surfaces rendered hydrophobic by reaction with silanation agents (e. (tridecafluoro-1. and Israelachvili [2005] and Lin et al. and Liedberg (1998) to prepare hydrophobic surfaces on borosilicate glass substrates. All rights reserved. Parker and Claesson 1994) and capable of reacting with surface OH groups.flotation0.. fol- lowed by a 10-nm gold layer. the attraction becoming weaker and less long-ranged at higher temperature. the whole ion exchange pro- cess is prone to be facilitated kinetically by the presence of small ions. The hydrocarbon chains become tilted and are tightly packed in a crystalline state. 2007 7:36 PM 150 FLOTATION FUNDAMENTALS outset for such a surface contact angle. stability toward salt solutions is obtained for this type of hydrophobic surface. and Wennerström (1993) and Tsao et al. a water plasma pretreatment is necessary to introduce surface OH groups (Parker. upon screening (by adding salt). for example. As a rule. The gold surfaces made in this manner are slightly rough with peak-to-through values of ~1. by means of AFM they convincingly demonstrated that their surfaces were laterally homogeneous and free of defects over great distances. on the order of microns. by Meyer. by the way. and significant tempera- ture effects were noted. (1991). there is a tendency for the surfactant to pass over to some less strained (bilayer) state.2. Further.2-tetrahydrooctyl)dimethylchlorosilane. a substantially smaller attraction force was recorded for C16 than for C18 chains. One must realize that the chemical potential of the attached amphiphile is raised by compressing the monolayer spread on the Langmuir trough to the desired packing density of about 0. 3. Self-assembling alkylthiols dissolved in. Metallurgy. alcohol are known to bind strongly to gold surfaces. Interestingly.g. and further underscored the critical connection between details of surface chemistry.

could perhaps be investigated in this manner by changing the temperature. particularly in flotation. for the most desirable chain length.flotation0. changes of state arising in the residual thin water film itself are also considered. Rather. 6. it seems hardly feasible to fully control a silanation reac- tion scheme so as to generate a sufficiently smooth. the best option is to concentrate on those surface force curves that show the strongest hydrophobic attraction rather than to try to sort out the exact electrostatic mechanisms that operate at concentrations different from the CNC. often denoted as the charge neutralization concentration (CNC). for instance. . 5. adsorption equilibrium is only approached very slowly at room temperature. Wood and Sharma (1994) believed that one might succeed in making a more stable and better characterized hydrophobic surface by first polymerizing OTS at the air– water interface (pH = 2) on a Langmuir trough. fundamental studies are hampered by the variable state of the hydrophobic surfactant layer. This listing. Electronic edition published 2009. may serve as a ranking list of hydrophobic surfaces based on experiences from several laboratories during the past several decades.book Page 151 Tuesday.” Hence. However. Though easily prepared. gives rise to a likewise exponentially decay- ing surface force. A quasi-thermodynamic/structural model for hydrophobic attraction forces was pre- sented in 1989 by Eriksson. though certainly not complete. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 151 measured forces. or silica. Adsorption from water solution of a cationic surfactant such as CTAB or C18TAC (octadecyl-trimethylammonium chloride) onto mica. Although hydrophobic surfaces prepared by adsorption of surfactants from solution are at the bottom of the list. The temperature dependence of the hydrophobic force. Hydrophobic Attraction Forces Under Ideal Conditions For large separations between two interacting hydrophobic surfaces. January 2. followed by adjustment of the surfactant concentration to recover a minimal surface charge. and laterally homogenous hydrophobic surface. in spite of the circumstance that the phe- nomenon of the long-range hydrophobic attraction is readily observed provided that the right surfactant concentration is chosen. Certainly. Presumably. pT. In this type of model. range. Hence. for closer distances between the two hydrophobic surfaces. and Exploration. it has been refuted by the vague claim that long-ranged struc- tural effects are virtually excluded for (normal) liquids. the surfaces obtained proved stable toward salt solutions but laterally inhomogeneous on the micrometer-length scale. an exponentially decay- ing. No long-range hydrophobic attraction was observed. C18. Metallurgy. followed by LB deposition and chemical grafting to a mica surface. these types of surfaces have a major drawback: they are uncharged (or carry a minimal surface charge) only at one particular surfactant concentration. and nature of the hydrophobic force. Furthermore. glass. Podgornik. However. In contrast to most of the other tentative explanations of hydrophobic force. Pre- paring hydrophobic surfaces of sufficient quality is of crucial importance for making reliable conclusions about the strength. with its ability to form a © 2007 by the Society for Mining. All rights reserved. Ljunggren. presumably because of the lack of molecular smoothness required. they are probably the most important ones in terms of applications. and Zeks (1982)—to account for repulsive hydration forces. negative tangential pressure component. similar to one by Cevs. charge-free. a more elaborate model is necessary—in principle. this model has not been properly falsified in the Popper sense. and Claesson (1989).

Hence. . The cooperatively enhanced tendency to avoid rupturing hydrogen bonds causes the surface-induced structure to be propagated (with a certain decay rate) toward the center of the thin film. The film tension attained after these first two equilibration steps are denoted by γ 0f . Alternative attempts to fully understand the hydrophobic attraction will also be addressed. it is worthwhile to again scrutinize the basis of the water- structure-based model and assess its predictive power by comparing it with the wider range of experimental results that are available today. The final (inhomogeneous) water state in the film reflects a balance between the favor- able molecular reorganization occurring in the first (contact) layer of water molecules and the induced. Relatively speaking. it may be assumed that s(x) mirrors the local increase of the average number of hydrogen bonds per water molecule in the film. this model might serve as a valid point of departure for a deeper understanding of the hydrophobic force. All rights reserved. unfavorable restructuring of the remainder of the film. © 2007 by the Society for Mining. and they are laterally close to being homo- geneous in every respect. In the following discus- sion. The hydrophobic solid surfaces that interact in a liquid water medium are ideal: they are geometrically smooth to within about 0. 2007 7:36 PM 152 FLOTATION FUNDAMENTALS variety of hydrogen-bonding patterns. resulting in a somewhat larger average number of hydro- gen bonds per water molecule in the film than in the bulk.flotation0.book Page 152 Tuesday. January 2. owing to the imposed hydrogen-bond network formation. they exhibit small thermal amplitudes at room temperature. there is a free-energy decrease associated with the molecular reorganization of the first monolayer of water molecules next to the hydrophobic surfaces because of minimizing the number of hydrogen bonds broken when con- tacting water with the hydrophobic surfaces. assuming only short-range interaction forces. Now imagine that the final equilibrium state of the thin water film sandwiched between two hydrophobic surfaces is reached in a stepwise fashion. and Exploration. The third step comprises a reorganization of the hydrogen-bond network throughout the film. whereby the parameter s becomes a function of the x coordinate and the final equilib- rium value of γf is reached. Metallurgy. After all. which is a measure of the local increase of the free-energy density in the thin water film as compared with a corresponding slab of bulk water (x denotes the coordinate perpendicular to the thin film). water is still far from being a well-understood liquid at the molecular level. Starting from a thin film cut out of the bulk state. the first step involves establishing the proper molecular interac- tions at hydrocarbon–water interfaces while retaining the average spherical-symmetric ori- entation of all the water molecules in the film. these free-energy changes are accounted for by making use of a dimensionless order parameter s(x). Electronic edition published 2009. Alternatively. The premises are as follows: 1. The second step implies a change of the packing and of the average orientation of the water molecules in each of the first molecular layers next to the hydrophobic surfaces to yield a less dense and more ordered molecular state with an increased number of hydrogen bonds and a preference for tangential alignment of the H–O–H bisectors of the water molecules. Hence.1 nm at 0 K. 3. 2. or the associated decrease in local density. there is a free-energy increase arising throughout the core of the thin film.

book Page 153 Tuesday. Upon minimizing the film tension γf while taking into account the proper boundary conditions. the following is readily derived a cosh ( bx ) s ( x ) = ⎛ ----------⎞ ---------------------------. (EQ 28) ⎝ 2c 3 b⎠ sinh ( bh ⁄ 2 ) and γ f ( h ) = γ 0f – ( a 2 ⁄ 4c 3 b ) coth ( bh ⁄ 2 ) = γ 0f – as 0 ⁄ 2 (EQ 29) = γ 0f – ( B ⁄ 2 π ) coth ( bh ⁄ 2 ) The constant b stands for the quotient. that is. a lowering of the film tension caused by the imposed structuring due to the hydrophobic surfaces is obtained: γ f ( h = ∞ ) – γ 0f = – B ⁄ 2 π (EQ 30) implying that B/4π is the corresponding reduction of the interfacial tension between water and a hydrophobic surface. in this range. Inclusion of the squared gradient term is essential because it furnishes a mechanism of energetic coupling between successive layers of water molecules.flotation0. in the (weak overlap) regime. that is. whereas the integral accounts for the free energy expense associated with structur- ing the core of the thin water film. ln (–F/R) is predicted to be a linear function of h. Hence. the packing density) for the water layers in direct contact with the hydrophobic surfaces. For infinitely large film thicknesses. Electronic edition published 2009. January 2. frequently used in the past to model liquid–vapor interfaces. All rights reserved. Metallurgy. Moreover. whereas the interaction constant B introduced in Equation 29 can also be written in the form B = π a 2 ⁄ 8c 2 c 3 . the constant c3 reflects the (average) tendency to cooperative structure generation. hence. the model features invoked previously can be expressed in the following manner: h⁄2 γ f = γ 0f – as 0 + ∫ [ c 2 s 2 + c 3 ( ds ⁄ dx ) 2 ] dx (EQ 27) –h ⁄ 2 The second term on the right-hand side of this expression (where a is a constant) accounts for an assumed linear free-energy reduction because of changing the order parameter s0 (and. It can be estimated to be ≈ 50 μNm–1. On the other hand. to just about 0. in line with Equation 23. Equation 31 is more general because it also accounts for the free energy changes arising © 2007 by the Society for Mining. By taking the difference between Equation 29 and Equation 30 and making use of the Derjaguin approximation. b–1 has the nature of a decay length.1% of the total interfacial tension value of approximately 50 mNm–1. the right-hand side of this equation becomes equal to –2Bexp(–bh). The assumption invoked to derive Equation 23 was that the removal of surface-perturbed water (due to the overlap of surface zones) is predominantly free energy-wise. and Exploration. the hydrophobic attraction force as measured by means of an SFA with cylindrically shaped hydrophobic surfaces having radii equal to R is given by the following expression: F ⁄ R = 2 πΔγ f = – B [ coth ( bh ⁄ 2 ) – 1 ] (EQ 31) For sufficiently large film thicknesses. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 153 In an approach similar to the so-called square gradient approximation. .

whereas above about 15 nm. by a surface force of electrostatic origin). in many cases. As a consequence. the hydrophobic surface force increases in magnitude at an accelerating rate when the film thickness is diminished (compare Figure 17). January 2.g. and Exploration. Another convenient. the strength of the hydrophobic attraction can easily be judged by comparing the value of the constant K with the corresponding value of the Hamaker constant. All rights reserved. Hence. as derived theoretically. experimental hydrophobic interaction curves may appear to belong to two distinct regimes: below and above 10–20 nm. 2007 7:36 PM 154 FLOTATION FUNDAMENTALS in the residual thin film itself due to the elimination of the outer parts of the water surface zones that are energetically perturbed by the hydrophobic surfaces. Electronic edition published 2009.flotation0. which is usually on the order of joules. the common practice of making use of a double-exponential expression entailing four parameters instead of just two is understandable. s(x = 0) decreases very slowly in an almost linear fashion with h (Figure 12). and can thus easily be concealed (e. respec- tively (Figure 11). The first exponent yields the largest contribution for small separations. whereas the second one dominates at large separations. Below about 15 nm. which can be derived from Equation 31 by differen- tiation with respect to h (compare Equation 19). © 2007 by the Society for Mining. and λ2 = 20 nm. has been shown to represent experimental surface force data satisfacto- rily in a wide separation range. The major contribution to this part of the lowering of the film tension is an additional reduction of the number of broken hydrogen bonds for the contact layers of water molecules. However. at most about 1 mNm–1. C2 = 1 mNm–1. Metallurgy. Typical values derived are C1 = 0. Δγ f = ( – K ⁄ 12 π )h –2 (EQ 34) resulting in the one-parameter surface force expression: – F ⁄ R = ( K ⁄ 6 )h –2 (EQ 35) Obviously. that is.2 Nm–1. λ1 = 2 nm. manner to represent experimental surface force data is to invoke an expression of the same mathematical form as for the van der Waals attraction. unlike Equation 31. Equation 31 can be placed in an approximate double-exponential form. . The same holds true for the order parameter s in the middle of the thin film (where x = 0). though somewhat less accurate.book Page 154 Tuesday. namely – F ⁄ R = C 1 e –h ⁄ λ1 + C 2 e –h ⁄ λ2 (EQ 33) which. The disjoining pressure expression. namely F ⁄ R = – 2B ( e –bh + e –2bh ) (EQ 32) where the second exponent accounts for the amplification of the surface force usually seen at medium separations. is as follows: 2 π D = – ( bB ⁄ 2 π ) [ coth ( bh ⁄ 2 ) – 1 ] (EQ 36) Especially when displayed in this derivative mode. as compared with ≈500–600 mNm–1 for the maximum adhesion force at h = 0. Equation 32 does not extrapolate properly down to small h-values.. s(x = 0) rapidly diminishes with the film thickness h. The hydrophobic surface forces arising within the large separation range are generally rather weak. Typical K values range between 10–18 and 10–19 J.

which in turn is strongly © 2007 by the Society for Mining.02 0. Å FIGURE 11 Surface interaction pressures between mica surfaces modified with dihexadecyldimethylammonium (DHDA). All rights reserved. Note that the surface force curves are indistinguishable for DODA (C18 chains) and DEDA (C20 chains). Nm –2 4 10 103 0 100 200 300 400 500 600 h. According to the theory summarized.10 0. it is estimated the excess free energy per water molecule in the middle of the water film where the pressure tensor is likely to be approxi- mately isotropic.book Page 155 Tuesday. and dieicosyldimethylammonium (DEDA) monolayers in water at 25°C as measured by Tsao et al. January 2. DODA.06 s(x=0) 0. (1991). the strength of the hydrophobic attraction force is determined by the interaction constant B = πa 2 ⁄ 8c 2 c 3 . this excess free energy amounts to about 4 × 10–4 kBT per molecule. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 155 106 DHDA DODA DEDA 105 –(2π)XπD.08 0. nm FIGURE 12 Order parameter s (x ) in the mid-plane of a thin water film sandwiched between hydrophobic surfaces (Eriksson. .04 0.00 0 5 10 15 20 25 30 35 h.flotation0. and Claesson 1989) Further. Ljunggren. and Exploration. Metallurgy. h ≈ 10 nm. ≈ 7 kBT. 0. on the basis of Equation 36. Electronic edition published 2009. in the medium separation range. Typically. again recognizing the very minute thermody- namic effects by means of a sensitive SFA or AFM setup. as compared with the energy of a hydrogen bond at room temperature.

that is. there is definitely a need for more sophisticated models based on the con- cept of structure generation in water due to contact with a hydrophobic surface. a shorter decay length. Parker Claesson. B U B B L E AT TA C H M E N T A N D C AV I T Y F O R M AT I O N AT H Y D R O P H O B H I C S U R FA C E S Upon observing more or less distinct steps in the surface force curves for hydrophobic surfaces (plasma-treated mica silylated with (tridecafluoro-1. This may set the stage for extended water clusters of var- ious shapes to occur. becoming large if structuring occurs readily (as for bulk water at the freezing point) or when there is a strong tendency to avoid rapid changes of the order parameter s(x). Such a coupling might result in a larger constant c2 and. One must bear in mind. Salt effects for uncharged or nearly uncharged surfaces are expected to be rather minor. Yet a fundamental problem related to this approach is that it does not provide an understanding as to why the effect. 2007 7:36 PM 156 FLOTATION FUNDAMENTALS dependent on the constant a that is related to the free-energy change associated with the reorganization of the contact layers of water molecules. it is seen that the quasi-thermodynamic theory due to Eriksson. In conclusion. and that Angarska et al. and Attard (1994) suggested that these steps might actually demark the onset of the hydrophobic © 2007 by the Society for Mining. these features have been experimentally documented. and Exploration. larger clusters are inher- ently more stable than smaller ones. if the hydrophobic surfaces are also charged and (overlapping) electrostatic double layers are present. Furthermore. All rights reserved. as well as for novel experimental methods by which one can investigate the detailed state of thin water films. a thermodynamic scenario that is familiar from the field of surfactant aggregation. Ljung- gren. provided that the hydrophobic surfaces themselves are stable in contact with salt solutions.1. is capable of systematizing several experimental findings concerning the attractive hydrophobic surface force. hence. However. (2004) have shown that Equation 31 applies even for thin foam films at high salt concentrations. when cooperativeness plays a significant role. Generally.flotation0. Metallurgy. the decay length b –1 = c 3 2c 2 should depend primarily on the properties of the water in the thin film. On the other hand. that is. gen- eralization of the water-structure-based theory to the case of an unsymmetric aqueous thin film between two different hydrophobic surfaces has been accomplished recently.2-tetraoctyl)dimethyldichlorosilane) submerged in water at surface separations in the range of 100 nm. and Rabinovich (1997). can be of such an amazingly long range that it can be detected even for separations beyond 100 nm. January 2. in some instances. B is anticipated to vary strongly with the degree of hydrophobicity as well as the smoothness on the molecular scale of the solid (or liquid) surface. Thus. Electronic edition published 2009. provided that the associated free-energy expenses are small enough to be counterbalanced by corresponding size-fluctuation entropies. one must anticipate competition between the (tangential) polarization of the water molecules due to the hydrophobic surfaces and the (perpendicular) dipole alignment in the electrostatic (mean) field. note that the strength of the hydrophobic attraction scales semi-quantitatively with the contact angle for water on hydrophobic surfaces (Figure 6).book Page 156 Tuesday. and Claesson (1989).2. that the long-ranged hydrophobic surface forces are extremely weak and represent very minute thermodynamic effects and that hydrogen-bonded networks and chains of water molecules are known to be cooperatively stabilized. which focuses on the rather minor free-energy effects that are associated with restructuring of water in contact with hydrocarbon surfaces. Nevertheless. an inter- esting case that has been studied experimentally by Yoon. . Flinn. however. In particular.

is the option that a limited number of small bubbles. there are many difficulties associated with the claim that a capillary mechanism of this kind is the chief reason for the long-range effects observed. adhesion of small air bubbles is nonetheless a rare event because of the limited life span of these bubbles. it is significant as well as under- standable. All rights reserved. Gas super- saturation in the surrounding water phase may likewise prolong the lifetime of an adhering bubble. contain defects that presumably play a crucial role in pro- moting bubble adhesion to occur to some minor extent. Metallurgy. which have survived (because they started out as relatively large bubbles). Moreover.3 × 104 nm2. the excess (Laplace) pressure will be efficiently cancelled. as a rule. It is about 10 ms for a radius of 1 μm. Nevertheless.flotation0. eventually giving rise to a huge surface force. What remains. suddenly form bridging (quasi-cylindrical) bubbles. are generated upon contacting two hydrophobic surfaces in an SFA device filled with water and then followed by pulling them apart before starting the measurements. that it has met with experimental difficulties to positively verify the presence of adhering air bubbles on hydrophobic surfaces (Lin et al. very small open air bub- bles are not expected to adhere to an ideal hydrophobic surface in a stable manner (Kral- chevsky 1996. A primary difficulty is that very small air bubbles nucleated in a water phase are surpris- ingly short-lived. air-filled cavity. Ljunggren and Eriksson 1997). appealing. unlike the situation for larger air bubbles. and a bridging bubble can consequently sub- sist for a long time. the curvature is likely to decrease as some air dissolves. Because of the rather sizeable Laplace excess pressure. In this way. Hence. following the “bubble-mechanism” line of reasoning. the occurrence of adhering air bubbles depends strongly on the nature of the hydrophobic surface. January 2. which (because of the small excess pressure) can be treated as if they were thermodynamically closed. however. the formation of one large. and that a few of these adhering bubbles rather quickly form approximately cylindrical air bridges to the approaching hydrophobic surface. would have to be inferred. Although the concept of bridging bubbles is. The surface area covered by such a bub- ble would be ≈ 1. one must invoke an adhering (spherical cap) bubble that fulfils the contact angle con- dition. 2004). 2005. of course. whereas a bubble that is millimeter-sized may subsist for days or even months (Epstein and Plesset 1950. albeit an attraction that is totally different from the water-structure-based one discussed thus far. As is easily confirmed. and about 1 μsec for a 10-nm bubble. Eriksson and Ljunggren 1999. Electronic edition published 2009. in view of the short lifetime and submicroscopic size of such a bubble. Supposing the three-phase contact line to be pinned in a fixed position on some surface defects. the formation of a bridging bubble out of an adhering bubble is likely to be advantageous free-energy-wise. having a radius of curvature of about 70 nm. Mao et al. upon the approach of the hydrophobic surfaces.book Page 157 Tuesday. Most real hydrophobic surfaces. To judge from the evidence available today. happen to adhere in an irreversible. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 157 attraction. . Simple calculations show that in order to account for the surface force steps observed by Ederth (1999). Ryan and Hemmingsen 1993). and Exploration. To assume irreversibility for the wetting behavior is essential here. This might be anticipated. the air dissolves and the bubbles diminish in size at an accelerating rate. Straightforward calculations show that the lifetime of a small air bubble in water scales with the bubble radius squared. in many ways. because non-ideal features in the hydrophobic surfaces themselves are likely to play a decisive role. they attributed the attraction to tiny adhering air bubbles that. © 2007 by the Society for Mining. which amount to about 2 × 10–8 N in terms of force (rather than surface force). Other- wise. defect-dependent manner to the hydro- phobic surfaces. thus lowering the Laplace pressure and extending the expected lifetime of the bubble. Although air bubbles.

h.flotation0. Lin. All rights reserved. is greater than zero. January 2. 2005). It may occur when the surface tension of a solid surface in contact with air (or vapor) is less than the surface tension of the solid surface in contact with a liquid so as to make the cavity state the thermodynamically favored state.book Page 158 Tuesday. Conversely. large-scale cavity formation is a capillary phenomenon that is fairly well understood. Expressed otherwise. 2007 7:36 PM 158 FLOTATION FUNDAMENTALS R rc h FIGURE 13 Two approaching spheres with a bridging (quasi-cylindrical) air bubble For a few years. it is a pre- requisite that the (equilibrium) contact angle exceeds 90°.= r c ( h + r c2 ⁄ R ) γ air. several investigators have emphasized that the long-range hydrophobic attraction is actually present for several hydrophobic sur- faces for which there are no signs of bubbles whatsoever. and Shchukin (1983) is discussed in the following paragraphs. Hence.w [ r c ( h + r c2 ⁄ R ) + r c2 cos θ eq ] 2π (EQ 37) where rc denotes the cylinder radius. Yaminsky. Strong additional support for this conclu- sion has recently been obtained from careful degassing experiments (Meyer. For the free energy of cavity formation.air ) = γ air. A somewhat simplified. Electronic edition published 2009. fulfilled) and a maximum for some smaller rc value. Consider the case of two approaching hydrophobic spheres (radii = R) submerged in water (Figure 13). only when the distance of approach. it was a widely held belief that the long-ranged part of the hydrophobic attraction is an artifact that can be attributed to a capillary bridging mechanism of the previ- ously mentioned character. and Israelachvili 2005. More recently. and Exploration. the following approximate expression is obtained: ΔG ------. the supposition that small adhering bubbles which collapse into bridging bubbles is the major cause of the “true” long- range hydrophobic attraction. Zhang et al. (compare Figure 14).w – γ hc. however. Metallurgy. the free-energy value at the minimum (representing the formation of a fully equilibrated air-filled cavity) will have a negative value. must be rejected. Suppose a quasi-cylindrical (minimal-surface) cavity is formed that has almost no excess air pressure associated with it. the intervening barrier will usually prevent the cavity from forming © 2007 by the Society for Mining. The expression in Equation 37 is apparently a third-order function of the cylinder radius rc with a minimum for a rather large value (where the contact angle condition is. . whereas the gain in free energy is due to replac- ing the hydrocarbon–water interface by hydrocarbon–air interface. in principle. however. However.w – r c2 ( γ hc. implying that the cavity state constitutes the thermodynamically stable state of the system. though still sufficiently accurate version of the classical treatment presented by Yushenko. Provided that the equilibrium contact angle is large enough. The free-energy cost of forming such a cavity stems from forming the air–water interface. The barrier associated with the maximum is present. and the r c2 ⁄ R term develops because the curvature of the spherical hydrophobic surfaces is taken into account to the first order.

the second (negative) term can no longer outweigh the first term.0002 0. The cavity state can easily be realized. These assumptions seem more and more questionable when the surface charge density is smaller. J 0.5 rc .0E – 09 θ = 105° 0 θ = 115° –1E – 15 0. Yaminsky. Electronic edition published 2009. when the thin film state is approached by gradually diminishing the surface separation.0006 ∆G/2π. which accounts for the thermodynamically stable cavity formation between spherical. and Shchukin (1983).3 0.0E – 09 0. the nonlinearized.2 0.book Page 159 Tuesday. thus providing the impetus for cavity annihilation.0000 0. by first bringing the hydrophobic sur- faces into contact.4 0. By increasing the surface separation h. mean-field Poisson– Boltzmann (PB) scheme is usually applied in some numerical version.0004 0. the thin film state of water between hydrophobic surfaces is actually a metasta- ble state. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 159 1E – 15 1. hydrophobic surfaces submerged in water.0E + 00 θ = 105° θ = 115° –1. resulting in a minimum with a positive ΔG value. lack of complete equilibration for the air dis- solved as well as complications arising because of contact angle hysteresis must be considered. January 2. The disappearance of the cavity for some rather large h value is likewise readily under- stood on the basis of the previously mentioned simple equation. © 2007 by the Society for Mining. The attractive surface forces arising because of a large equilibrium cavity with an air pressure somewhat less than atmospheric pressure (undersaturation) may approach as much as about 1 N when the cavity is formed in an SFA between crossed cylinders (R = 1 cm). from a great distance. All rights reserved. The inset shows the barrier at short separations that prevents cavity formation when the surfaces are brought close. and Exploration. however. the experimental experience is in line with the thermodynamic description of cavity formation as outlined here. however. then slowly pulling them apart. thus reducing the barrier to zero. .0 0. Metallurgy. as was noted earlier by Blake and Kitchener (1979). though not touching. Electrostatic Interaction Forces To estimate repulsive electrostatic double-layer forces.flotation0.1 0. mm FIGURE 14 Interfacial free-energy function according to Yushenko. At the same time. In general. The theory behind it assumes an evenly-smeared-out surface charge and a laterally homogeneous counterion dis- tribution outside the charged (geometrical) surface. the entire ΔG function is rotated counterclockwise. the magnitude of the repulsion becomes less. Eventually. however. In other words. making the problems that may arise redundant in any case.

according to the Debye–Hückel scheme.book Page 160 Tuesday. Taking this circumstance into account and making use of the Gibbs surface tension equation. the surface tension drops linearly with the surfactant concentration. e the proton charge. which deviates substantially from unity. and Exploration. Metallurgy. which is the case for dilute ionic surfactant © 2007 by the Society for Mining. in fact. especially when S becomes less than about 10. and acharge is the area per surface charge. εr is the relative dielectric number for water. where γel constitutes the chief contribution to the reduction of the overall surface tension. From this background. whereas ≈ 1 kBT stems from the polarization of the water in the electrostatic mean field (Ljunggren and Eriksson 1988). In this range. This discrepancy immediately conveys that the current the- oretical description of electrostatic interactions has its weak points. which characterizes the extension of the diffuse part of the double layer. For the Gouy–Chapman case. depends on the electrolyte concentra- tion but not on the surface charge density. about 1 kBT stems from the osmotic effect of the counterions.flotation0. briefly consider the case of an (1:1) ionic surfactant adsorbed at an air–water interface in the dilute Henry’s-law regime. January 2. Fur- ther. the Debye length. In this context. Electronic edition published 2009. and ct is the total (1:1) electrolyte concentration. the surface potential is given by the following expression: φ 0 = ( 2k B T ⁄ e ) [ S + ( S 2 + 1 ) 1 ⁄ 2 ] (EQ 39) and the electrostatic contribution to the surface tension is given by γ el = ( – 2k B T ⁄ a charge ) [ ( S 2 + 1 ) 1 ⁄ 2 – 1 ] ⁄ S (EQ 40) where the negative sign indicates that this contribution is actually a surface pressure. from Equation 40 it appears that the Gouy–Chapman theory incorpo- rates an additional factor [(S2 + 1)1/2 – 1]/S. gel. All rights reserved. 2007 7:36 PM 160 FLOTATION FUNDAMENTALS The special case of one single (noninteracting) double layer is known as the Gouy– Chapman approach. Evidently. On the other hand. from the following set of equations: g el = e φ 0 + γ el a charge (EQ 38) where γel is the electrostatic contribution to the surface tension. Evans and Ninham 1983). the Debye length is introduced by means of the following expression (F denotes the Faraday constant): κ –1 = F –1 ε 0 ε r RT ⁄ 2c t (EQ 42) Hence. in Equation 40. considering S to be >>1. one can readily show that the gas law–like relation – γ el a charge = 2k B T (EQ 43) must hold exactly for thermodynamic reasons. . This particular equation is. according to which can be obtained the electrostatic free energy per charge. Furthermore. twice the –kBT/acharge can be attributed to the pressure effects of both anions and cations in the surface. generally valid within the realm of the PB theory ( Jönsson 1981. reduced-charge parameter S introduced previously is defined by S = ( σ 2 ⁄ 8RT ε 0 ε r c t ) 1 ⁄ 2 (EQ 41) where σ is the surface charge density. the dimensionless.

and Exploration. On average. in the PB scheme. All rights reserved. no added salt): π Del = c ion RT ( e e φm ⁄ kB T + e –e φm ⁄ kB T – 2 ) (EQ 44) where φm represents the mid-plane potential and cion for the bulk concentration (moles per cubic meter) of positive and negative ions. Still. a major difference from the theoretical standpoint is that the electrostatic double- layer repulsion can be rationalized by referring to the well-established osmotic effect of dissolved (point) ions in a structureless solvent medium. π Del ≈ ( ε r ε 0 κ 2 ⁄ 2 ) φ m2 ≈ 64k B Tc s Γ 02 e –κ h (EQ 45) where Γ 0 = tanh ( eφ 0 ⁄ 4k B T ) (EQ 46) By integrating Equation 45. This is in sharp contrast with. to the particular model feature of a geometrical (i. Moreover. This latter shortcoming also shows up in the fairly low surface potentials and charge densi- ties that are commonly derived from surface force data. resulting in an overall attraction. In other words. volume- less).flotation0. whereas up to this point. the large deviations from PB theory for charged systems with diva- lent ions have been accounted for while at the same time verifying that the same PB theory as a rule is reasonably accurate for systems containing monovalent ions. © 2007 by the Society for Mining. in addition. the electrostatic disjoining pressure is primarily given by the following expression (for simplicity. provided that there is a significant surface charge. The main reason behind these deficiencies is probably related to both the mean-field concept as such and. in spite of its many virtues. 1984.e. In particular.. Metallurgy.book Page 161 Tuesday. On this basis. evenly charged surface devoid of entropy of mixing for the charged groups with water. the Poisson–Boltzmann description has a serious flaw. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 161 layers. . the Flory–Huggins theory of poly- mer solutions. the electrostatic surface force contribution can readily match the hydrophobic contribution in strength. a firm fundamental basis is lacking for an explanation of the hydrophobic attraction in terms of the molecular properties of water. it was realized that correlation effects may become significant. for example. In the 1970s. January 2. the fluctuations cause more weight to be given to attractive rather than repulsive configurations. there is a formal similarity (though the sign is opposite) between the electrostatic repulsion and the water-structure-dependent hydrophobic attrac- tion treated previously. the corresponding contribution to the surface force is easily found: ( F ⁄ 2 π R ) = 64k B Tc s Γ 02 e –κ h ⁄ κ (EQ 47) implying an exponential asymptotic behavior determined by the (salt-dependent) Debye length. for large separations. as it does not show a correct limiting behavior for charged equilibrium (Gibbs) monolayers. Nevertheless. Electronic edition published 2009. especially for interacting double layers encompassing divalent counterions (Guldbrand et al. in the much-employed weak-overlap approximation that is applicable insofar as the surface potential is small (< 25 mV). Thus. laterally inhomogeneous counter- ion distributions outside the charged surfaces. An attraction of this origin is conceptually similar to the dispersion interaction because it relies on instantaneous. Kjellander and Marčelja 1984).

This was realized by Fors- man. At large separations. Although these matters. for example. it seems implausible that all observations regarding the hydrophobic attraction can be accounted for on the basis of correlation attractions alone. and Yoon and Ravishankar (1996) that correlations among colloidal-grained. (1994).. Although these concepts about ionic correlation attractions may be of some relevance for hydrophobic surfaces formed by adsorbing (e. Craig. the correlation attraction should decay with a decay length equal to κ–1/2(i. glass. Evans. starting at the critical hemimicelle concentration where the hydrophobic attraction is already high. (1991). Returning to the subject of hemimicelle formation. who argued that more sizeable contributions of this nature can be obtained for charged sur- faces that are heterogeneous. at least insofar as no salt is added when making the surface force runs.book Page 162 Tuesday. The surface characterizations carried out as well as the preparation protocols employed seem to leave little room for speculation in this direction.flotation0. are not yet resolved. the Ninham– Parsegian expression holds true for the disjoining pressure. an aggregation of this kind is antic- ipated for hydrophobic surfaces prepared by surfactant adsorption from water solution. Furthermore. it seems unacceptable to employ them to account for the archetypal long-ranged hydrophobic attraction documented for the LB-monolayer-modified mica sur- faces prepared by Claesson and Christenson (1988) or the corresponding mica surfaces pre- pared by adsorption from cyclohexane solution by Tsao et al. In a similar vein. containing (mobile) charged surfactant aggregates of some size. it is evident that charge correlation attraction arising at the molecular (ion) length scale is not sufficiently strong to rationalize the experimentally measured hydrophobic attraction. 2007 7:36 PM 162 FLOTATION FUNDAMENTALS For the correlation interaction between surfaces carrying mobile charges. (1994) were able to demonstrate that at relatively high salt concentration. and Wennerström (1993). it was suggested by Tsao.e –2 κ h h » κ –1 (EQ 48) κh The magnitude of the attractive interaction pressure predicted by means of this equa- tion is.e. Miklavic et al. or silica).. ordered dipole domains across the thin film may give rise to sizable attractions. half of the Debye length) upon increasing the surface separation. Herder (1990) demonstrated that upon adsorbing a cationic surfactant onto Langmuir–Blodgett–DODA-modified mica. their calculations presuppose that the surface density of adsorbed micellar aggregates is basically independent of the concentration of added salt. Miklavic et al. In particular.g. however. However. . Jönsson. January 2. it takes on the following limiting form: 3 π D = – kT κ ------------. and Kekicheff and Spalla (1995). Ninham. such as. Parker and Claesson (1994) arrived at the same conclusion using the MASIF setup and silanated glass spheres. perhaps. far stronger than the van der Waals interaction. and Åkesson (1998). and Pashley (1998) thoroughly investigated the interaction between silica surfaces in dilute CTAB and cetylpy- ridinium chloride (CPC) solutions in the presence of electrolytes. on the order of the van der Waals attraction. a condition that for the most part is unlikely to be fulfilled. hemimicelles. and firmly concluded that a direct electrostatic mechanism for the hydrophobic attraction is hardly an option. Hence. a water-soluble cationic surfactant onto mica. the hydrophobic attraction rapidly vanishes and is replaced by electrostatic repulsion.

resulting in a packing density close to 0. one to each anionic mica site. however. In the end. Moreover. with bromide or acetate as the counterions. More recently. In particular.25 nm2 per single chain). though quite cumbersome. capillary effects have been investigated in detail. Full stability toward salt solutions was. DODA. this is not the case for the DHDA and DODA mono- layers. In order to cope with the long-ranged hydrophobic attraction. Later. for one and the same temperature. [1991]). prepared by means of adsorption from cyclohexane solutions of cationic surfactants of different chain lengths: DHDA. This finding was later corroborated by Rabinovich. it is probably time to turn back to where the surface–force-based development phase started—the measurements by Israelachvili and Pashley (1982). not achieved using this surface preparation method. January 2. it has become abundantly clear that the molecular understanding of liquid water is incomplete to an extent that renders it virtually excluded for making reliable theoretical predictions about (transient) H-bond-generated structures. a few different approaches than the water-structure method have been rather thoroughly scrutinized. the aforementioned authors demonstrated that while the DEDA monolayer preserves a frozen chain state at 50°C. and more trivial. These authors made use of mica surfaces submerged in dilute CTAB solu- tion and interpreted the results rather straightforwardly in terms of the hydrophobic effect. Correlating changes were observed in the surface force curves.flotation0. These investiga- tors made use of hydrophobized mica surfaces (mounted in an SFA). The chain length primarily matters in the sense that it determines where on the temperature scale chain melting occurs. To further reveal the extent to which the water–structure-based theory of the hydro- phobic force compares with experimental data. Guzonas. and DEDA. and Yoon (1993) by means of Fourier transform infrared (FTIR) measurements. however. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 163 S U R FA C E F O R C E D ATA S U P P O R T I N G T H E WAT E R - STRUCTURE MECHANISM After about two decades of research efforts devoted to searching for the mechanism that gives rise to the hydrophobic attraction. whereas DODA melts in the range between 40° and 50°C. and that they remain quantitatively bonded to their sites (though in a metastable state) even after contacting the surface with water and raising the temperature to 50°C. smooth hydrocarbon monolayer of frozen hydrocarbon chains causes the strongest hydrophobic attraction. . In fact. perhaps the most illuminating and most well-documented experimental surface force study carried out so far will be examined—one that clarifies the hydrophobic attraction (presented by Tsao et al. however. Moreover. the decay length at large separations was found to be nearly the same. both of these major alternative approaches have turned out to be untenable. The latter phenomena include the formation of cavities and bridging bubbles between (hysteretic) hydrophobic surfaces submerged in water. and it was concluded that a well-organized. it was verified that the double-chain surfactant cations employed are electrostatically bonded.50 nm2 (0. DHDA appears to be present in a melted chain state already at 25°C. electrostatics beyond the standard PB mean-field description have been reexam- ined. Much inspiration came from Pauling’s (1960) investigations of the hydrogen bond and from the fascinating field of clathrate physical chemistry (Franks 1973). The resulting adsorption layers were characterized by AFM. In the 1960s. Hence. the “mysteries” of water were still fashionable topics for study.book Page 163 Tuesday. the tendency to restrict the discussion to structural aspects only—instead of employing the full statistical- mechanical machinery—and the polywater affair made this research direction fall in disrepute.

Δ S f. the decay length b–1.ex ⁄ A )dT (EQ 51) Upon deducting Equation 51 from Equation 50. it seems very likely that a stronger response (larger a) in terms of the lowering of free energy should result for the con- tact monolayer insofar as it is fairly unperturbed by the thermal motions of the hydrocarbon surface.ex = – ------------. d γ f = ( V f. which partic- ipates in the expression for the constant B in Equation 31: πa2 B = ---------------.ex ⁄ A )dT – π D dh (EQ 52) This equation is the appropriate thermodynamic relation for dealing with surface force data for thin films consisting of pure water.ex ⁄ A )dp – ( Δ S f. Also. just a modest dependence on temperature is anticipated. however. which is for the most part observed. 2007 7:36 PM 164 FLOTATION FUNDAMENTALS These observations fit well into the theoretical model description presented previously that presumes structural water effects. For an infinitely thick film. More importantly. The excess entropy Sf. make the structuring of the film core more costly in terms of free energy.book Page 164 Tuesday. Revisit the thermodynamic fundamental equation governing the present film case (see appendix to this chapter). raising the temperature should tend to make a smaller. which is given by c 3 ⁄ 2c 2 .ex ⁄ A )dp – ( S f. and. next obtain d ( Δγ f ) = ( Δ V f. implying a smaller c2 and a longer decay length. (EQ 53) ⎝ ∂T ⎠ p. This dependence may suffice to account for the distinctly different surface force behaviors recorded by Tsao et al. (EQ 49) 8c 2 c 3 In view of the cooperative nature of water structure generation. the (unintentional) presence of a polarizing electrostatic field would tend to increase c2 and hence shorten the decay length.ex is analogously defined. obtain the following: d γ f ( ∞ ) = ( V ∞f. Similarly. (1991) can be carried through. On the other hand. whereas the presence of inert gas molecules in the form of clathrate guest molecules might conceivably make it less costly to restructure the water film core. h A . yielding a higher c2. For a pure water film in contact with water. the strength of the hydrophobic force is determined primarily by the constant a of the (linear) response function –as0 .ex represents the volume in excess of the volume of a slab of bulk water that contains the same number of water molecules as the film of a certain thickness. Concerning c3. surface-thermodynamic analysis of surface force data as complete as those of Tsao et al. (1991) for hydrocarbon surfaces in a frozen (larger B) or melted (smaller B) state. that should likewise tend to diminish B. depends inversely on c2 and should thus diminish with temperature.ex ⁄ A )dp – ( S ∞f. a virtually model-independent.ex ⁄ A )dT – π D dh (EQ 50) where Vf.flotation0. Accordingly. It obviously includes the partial derivative ( Δγ f )-⎞ ⎛ ∂--------------. in addition. accordingly. January 2.

this evaluation result would imply that the thin water film is actually more ordered than an imaginary water film of the same thickness encompassing two noninteracting surface zones of water next to the hydrophobic surfaces. Regarding the numerical values.ex other than the one arising in the water film. Equation 31 with B-. who used similarly prepared hydrophobic sur- faces).flotation0. The relative excess film entropies per unit area. (1991) Thus. which is about 30 times more than the entropy reduction quantified from the surface force measurements. as soon as the surfaces interact. the film tension reduction is larger at room temperature than it would be if the room temperature were greater. resulting in the curves shown in Figure 16. Also. it necessarily results in ΔSf. By invoking the entropy of fusion of ice (≈ 22 J mol–1 K–1) for a 5-nm water film. ΔSf. which in the present case means that the attractive hydrophobic surface force becomes less negative when the temperature is raised. estimate f ΔS freezing = – 6 mJm –2 K –1 . . Consequently. especially for the frozen hydro- carbon surfaces. it is illuminating to compare with the entropy reduc- tion one would get for a corresponding slab of bulk water that undergoes freezing to ice. Å FIGURE 15 Film tension changes for thin water films between hydrophobized mica surfaces at different temperatures derived from the disjoining pressure data presented by Tsao et al. In turn. mJm –2 3 2 1 0 0 50 100 150 200 250 300 350 400 h. can be quantified using Equa- tion 53. These curves display the crucial feature discussed previously. that is.ex as a negative quantity. By integrating the disjoining pressure functions derived experimentally by Tsao et al. if the surface force increases with temperature. Provided that the hydrophobic surfaces themselves do not suffer any changes in their intrinsic thermodynamic properties as the film thickness varies (which should not be the case. yields a reasonably good fit for the film tension curve obtained by Tsao and colleagues for DODA at room temperature. especially if the surfaces are solid). (1991). In other words. ΔSf. Evidently.values generated from the measure- ments of Claesson and Christenson (1988. the corresponding relative film tensions can be obtained (compare Figure 15). 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 165 6 DEDA (s) and DODA (s) at 25°C DEDA (s) at 50°C 5 DODA (s) at 40°C DHDA (l) at 25°C DHDA (l) at 40°C 4 –F/2π R. January 2. DODA and DEDA.ex is always a negative quantity. the enhanced molecular order in the thin film is equivalent to introducing about 3% of ice ordering. b. there will be no contribution to ΔSf. the excess entropy becomes increasingly more negative when the water film gets thinner.book Page 165 Tuesday. upon diminishing the surface separation.ex/A.

observe that for every thickness h. The disjoining pressure data recorded by Tsao et al. and DEDA. This circumstance apparently restricts the num- ber of alternative mechanisms and. The most important assumptions on which these conclusions rest are the following: 1. DODA. ΔG = 0.ex ≈ ΔH f. . which means that a relation similar to Equation 55 is exactly fulfilled. 2007 7:36 PM 166 FLOTATION FUNDAMENTALS 250 DODA (s) 200 –∆S f.ex ⁄ A (EQ 54) This inequality necessarily implies that the (negative) relative excess entropy of the film is approximately counterbalanced by a corresponding enthalpy term. μJm–2K–1 150 DEDA (s) 100 50 DHDA (l) 0 0 50 100 150 200 250 300 h. it would be meaningless to propose an interaction mechanism incapable of giving rise to a sig- nificant reduction of the water film entropy. T ΔS f. For freezing of water at 0°C. Conversely. Furthermore. This was briefly discussed in relation with Equation 5. hence. Å FIGURE 16 Excess film entropies as functions of the separation between mica surfaces hydrophobized with DHDA.ex/A . comparing with the relative film tensions shown in Figure 15. It is envisaged that the structure formation is most pronounced for smooth hydrophobic surfaces that are free of charges and made up of hydrocarbon chains in a frozen state.book Page 166 Tuesday.ex (EQ 55) Such an enthalpy–entropy compensation is perhaps the most distinguishing feature accom- panying structural changes in water. that is. lends support to the idea that a water structuring effect caused by the contact with hydrophobic surfaces is being addressed. (1991) are representative of a water film state where the film itself is fully equilibrated.flotation0. The difference between the DODA and DEDA curves is presumably due to experimental uncertainty. whereas the (smooth) hydrophobic surfaces remain in the same metastable frozen state all the time. January 2. It is not necessary to invoke any mechanistic model whatsoever or to introduce any speculative assumptions about the nature of the thin film system in order to make the pre- ceding purely thermodynamic evaluation of the change in water film entropy. it holds true that Δγ f << T ΔS f.

It is not necessary to assume that different physical mechanisms are operating at small and large separations. An additional advantage of the water restructuring model should be brought up explic- itly. h⁄2 --F. B. The reversibility demonstrated with respect to temperature changes and the close quantita- tive agreement with surface force data from other laboratories using similarly prepared hydro- phobic surfaces lend support to point 1.600 coth ⎛ ----------⎞ – 1 ( mJm –2 ) (EQ 56) R ⎝ 15. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 167 2.1 F/R. b-parameter values obtained by fitting the data of Claesson and Christianson (1988). compared with the surface force function (Equation 31). It is evident that the function in Equation 56 produces an amazingly good fit. (2005) at 25°C for DODA-modified mica surfaces in water.flotation0. the surface force strength parameter.04 × 10 3 coth ⎛⎝ ----------⎞⎠ – 1 ( Nm –2 ) (EQ 57) 15. especially for short separations.book Page 167 Tuesday. Likewise. nm FIGURE 17 Surface force data points recorded by Lin et al. Point 2 is further discussed in the following paragraphs.01 0. the seemingly different mechanisms observed at small and large separations can be accounted for within one frame- work. and the decay length. January 2.8 nm . namely.6 mJm–2 and b –1 = 15.8⎠ (where h is in nanometers) together with the surface force data reported by Lin et al. can reproduce the strong temperature dependence and the characteristic enthalpy– entropy compensation documented for the thin water film sandwiched between hydrophobic surfaces. (2005). other than the water restructuring mechanism. No conceivable mechanism.. the disjoining pressure function (Equation 36) is given by: 2 h⁄2 π D = – 6.8 0.= – 0. By making use of Equation 31 and introducing two parameters (i. where the fitting parameters of B = 0. mNm–1 1 10 100 0 10 20 30 40 50 h.e. Figure 17 shows a surface force function of the form given by Equation 31 and with B-. b–1).

primarily.000 0 10 20 30 40 50 60 h. are expected to contribute about equally. nm FIGURE 18 Comparison between the disjoining pressure data reported by Tsao et al. in other words. (1991). T H E S U R FA C E C L U S T E R M O D E L Having recognized the significance of the strong temperature dependence of the hydropho- bic force demonstrated by Tsao et al. the surface force is predicted to vary inversely with h. On the contrary.ex and Δγf are expected to be proportional.000 (2π) x πD. approximately ΔSf. 2007 7:36 PM 168 FLOTATION FUNDAMENTALS 1. Nm –2 10.e. (1991) and the disjoining pressure expression given by Equation 36 and inserting the parameter values of B = 0.000 1.ex = – -----------. Furthermore.000. . the B[coth(bh/2)–1] func- tion can be approximated by 2B/bh. (EQ 58) ∂T 4 π ⎝ sinh 2bh ⁄ 2 ⎟⎠ where the (negative) terms on the right-hand side..8 nm which according to Figure 18 fairly well represents the data recorded by Tsao et al.flotation0. Still. January 2. There are no strong indications that the hydrophobic surfaces primarily referred to here (i. add an expression for ΔSf. (1991) for DODA and DEDA at 25°C. AFM studies showed that they were homogeneous over a micrometer scale.⎜------------------------. The good fit in the short separation range displayed in Figure 17 is noteworthy.6 mJ/m2 and b –1 = 15. which can be derived by combining Equations 31 and 53: ∂ ln B Bbh ⎛ ∂ ln b ⁄ dT ⎞ ΔS f. This particular feature is clearly observed in the thermodynamic surface force data (compare Figures 15 and 16).book Page 168 Tuesday. it is hardly conceivable that the model concepts introduced to derive Equation 31 would apply below ≈2 nm. questions are raised about alternative mechanisms to account for the hydrophobic forces that are distinctly different from the one based on the surface-induced water restructuring that have been favored thus far. the agreement may appear reassuring but is presumably little else than fortuitous.Δγ f – --------. [1991]) would be laterally inhomogeneous. those used by Tsao et al.ex.000 DODA DEDA 100. and the ensuing conclusion concerning the lowering of the water film entropy. For completeness. Thus. For h values that are small enough (less than about 2 nm). that is.

(EQ 59) R 32k B Th 4 where ρ is the surface density of dipoles and m is the dipole moment. this expression yields an attractive surface force amounting to 1. which could interact by an electrostatic correlation mecha- nism and give rise to a strong attraction pressure. Primarily. A distance dependence of h–4 type is likewise obtained using the more general Lifshitz approach. even if a good fit to experimental data can be obtained in the middle separation range. 1966). an average patch size 20 × 20 nm. the K/h2 function that accounts for the hydrophobic surface force. Making a Hamaker type of approach and assuming independent surface dipoles. it is not anticipated that the hydro- phobic surfaces will grow inhomogeneous under the experimental conditions. Nevertheless. though evidently more appropriate than const. the h4 factor in the denominator makes it virtually impossible to simultaneously generate accept- able fits for short and large separations.6 mJm–2. respectively.flotation0. Incidentally. the implicit assumption of cluster dipole moments on the order 103 – 104 D would need additional justification. does not yield an entirely satisfactory description of experimental data. 1966). Equation 59 was derived on the basis of the concept presented in Section 5. one can theoretically estimate the corresponding surface force by means of the following expression: ( ρ m2 ⁄ εr ε0 )2 --F. The main thermodynamic relation governing this case is the counterpart of the Gibbs surface tension equation.= – ------------------------------ .3 of Evans and Wenerström (1999).·h–4. However. it was invoked to facilitate making comparisons between the strength of the hydrophobic force with the van der Waals attraction as well as devising theo- retical descriptions of experimental film systems where both dispersion as well as electro- static interaction forces must be considered. January 2. development of a well-bonded clathrate-like water monolayer next to a hydrophobic surface might possibly involve the formation of small planar patches or islands. Although it has been claimed that huge dipole moments can arise for hydrophobic colloidal particles in water (Tolstoi et al. Hence. EFFECT OF SOLUTES Brief comments will be made on the effect of adding a solute to the water phase that is in equilibrium with a thin film. large (cluster) dipole moments may arise at each of the interfaces. This is the key idea (in a slightly modified version) of the hydrophobic force theory that was advanced by Pazhianur and Yoon (2003). However. it is an appealing feature that the strong temperature dependence observed for the hydrophobic force might be linked to the temperature-sensitive dipole moments of the correlated planar cluster domains.book Page 169 Tuesday. These areas would comprise strongly correlated water dipoles pointing approximately in the same tangential direction in the interface. Consequently. it does not appear straightforward to formulate a fully satisfactory theory of the hydrophobic force on the basis presently being discussed. which at constant T and p reads: . For a surface separation of 10 nm. thus setting the stage for various forms of attractive ionic or dipolar correlation interactions (Tolstoi et al. and an effective cluster dipole moment equal to 6 × 103 D. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 169 there is little reason to suspect that surfactant micelles or similar aggregates might be loosely adsorbed onto the surfaces insofar as they are exposed to nothing else but pure water that is continuously checked for contaminants. In this way. regardless of the lateral dipole interaction mode assumed within the surfaces. which is the correct order compared with experiments.

Hence.ex > 0. is strongly coupled with the constant B becoming larger as the chemical potential μs is raised: the H-bond network in the film is reinforced by introducing inert gas molecules. By applying Equation 61 to films of 10 to 20 nm thickness. the air gases are enriched in the thin water film between hydrophobic surfaces in comparison with an infinitely thick film that was scaled down to the same thickness.ex is ∂ ln B Bbh ∂ ln b ⁄ d μ s ⎞ ΔΓ sf. and Israelachvili (2005). an analogous equation for ΔΓ sf.ex (EQ 61) ⎝ ∂μ s ⎠ T. Very recently.ex = – -----------. = – ΔΓ sf. Within most of the separation range below 50 nm. From this expression. Concerning the addition of alcohols and surfactants that readily adsorb on hydropho- bic surfaces. ΔΓ sf. January 2. Lin. the derivative is Δγ-f⎞ ⎛ ∂---------. referring to dissolution of the main air components N2 and O2.flotation0. Lin. 2007 7:36 PM 170 FLOTATION FUNDAMENTALS d Δγ f = – ΔΓ sf. Moreover. the change in solute excess. This observation is in fair agreement with the idea of an enhanced water structure in thin water films delimited by hydrophobic sur- faces. Referring to Equation 58. This is true for alcohols as well as nonionic surfactants. Relatively speaking.ex d μ s – π D dh (EQ 60) where μs denotes the chemical potential of the solute.ex . such as found in the case under discussion. Conversely. For a contact monolayer mixed with such surface-active species. similar to when the temperature is reduced to below room temperature. an increase in ΔΓ sf. on this basis. that is. as observed by Meyer. as examples.book Page 170 Tuesday. the film excesses of N2 and O2 are about the same as the amount of dissolved gases in corresponding (imaginary) thin films made up of bulk solution. at least in a preliminary way. p . it seems most likely that the effects of deaeration documented by Pashley (2003) on the stability of colloids and emulsions can also be understood. deaera- tion should tend to diminish the magnitude of the attractive hydrophobic force. the higher content of the gas solutes for thin films will cause the film tension to become more negative in accordance with Equation 61. This obviously implies that ΔΓ sf. The solvent properties of the water change as additional water cage volume becomes available to the (clathrate-forming) gas molecules. having access to equi- librium data on the surface force for a certain film thickness as a function of the solute con- centration. in the dilute regime the situation is principally opposite: The surface force rises with μs.⎛⎜----------------------------- -⎟ (EQ 62) ∂μ s 4π ⎝ 2 sinh ( bh ⁄ 2 ) ⎠ which should be relevant insofar as the solute concentration is kept low and the extent of solute adsorption is limited on the hydrophobic surfaces. yielding a negative ΔΓ sf. Consequently. can be interpreted in terms of a smaller constant B and a diminishing decay length b–1.ex that. h has a negative sign.ex . for a film of that thickness as compared with an infinitely thick film can be obtained. such SFA data were published by Meyer. there is simply less free energy to be gained by . aiming to clarify the effect of degassing (pure) water contacted with DODA-modified mica surfaces. a reduction due to degassing of the magnitude of the hydrophobic force is clearly seen. according to the quasi-thermodynamic relation (Equation 62).Δγ f – --------. and Israelachvili (2005).

This agrees with a multitude of observations using hydro- phobic surfaces that are sufficiently stable. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 171 0. The advancing contact angles are 94° (12.flotation0. showing the pronounced effect on the hydrophobic attraction of adding alcohol. On the other hand. the kinetics of which is controlled by the surface forces involved.0 F/R. esti- mate ΔΓ sf. the chief reason being that small ions do not mix with the water in the contact monolayers adjacent to the hydrophobic surfaces. adding salts should not change the situation very much with respect to the hydrophobic force (provided that the metastable attachment of hydrocarbon chains remains unaffected).10 0. insofar as the ions do not interfere significantly with the H-bond network formation. In view of their high interfacial tensions in water.20 0 10 20 30 40 50 60 Separation. air bubbles should be considered hydrophobic. Evidently. It appears that the sur- face force is substantially reduced in magnitude by adding alcohol.10 12.05 0.book Page 171 Tuesday. Thermodynamically. respectively. mN/m –0.ex to –4 × 1016 molecules m–2 for a 10-nm-thick film in contact with ≈16% alcohol solution to be compared with the alcohol content of a corresponding bulk solution film: ≈ 2 × 1018 m–2. and hydrophobic forces. hydrophobic particles are selectively collected on bubble surfaces and separated from the hydrophilic particles suspended in aqueous slurry.5% Ethyl Alcohol 20% Ethyl Alcohol –0. The reason why the surface force diminishes as alcohol is added is that the lowering of the film tension γf is larger for an infinitely thick film than for a thinner film. van der Waals.05 Water –0. the bubble–particle interaction occurring during flotation may be seen as a hydrophobic interaction.5%) and 88° (20%). this is because adding alcohol to the thin film counteracts the favorable structure formation. In turn. January 2. nm FIGURE 19 Surface force isotherms presented by Ederth (1999) for water and ethanol–water mixtures between hexadecanethiol surfaces. for ionic surfactants. Thus. Using Equation 61.15 –0. restructuring (smaller a). Surface force curves for water and ethanol–water mixtures recorded by Ederth (1999) using C16-alkylthiolated gold surfaces are reproduced in Figure 19. The electrostatic forces are repulsive when . the electrostatic (double layer) repulsion must also be invoked. Hence. the bubble– particle adhesion occurs when contact angle of the particle is larger than zero. the B constant should be left much the same. Hydrophobic Forces in Flotation In flotation. namely elec- trostatic. and likewise b–1.

Two decades ago. Various electrostatic interaction mechanisms have been subjected to critical tests. the hydrodynamic force is much reduced because of the hydrodynamic resistance against film thinning. the original proposition that the hydrophobic surface force is related to the structural response of water contacted with a solid hydrophobic surface appeared as quite a natural hypothesis. 2007 7:36 PM 172 FLOTATION FUNDAMENTALS both particles and bubbles are negatively charged. which is driven by the hydrophobic force. In general. which extends over much larger space than the molecular correlations. Hydrophobic forces also play a role in particle–particle interactions. Yoon and Mao 1996. also plays an important role in flotation. increase the particle size may be conducive to improving fine particle flotation. Therefore. In flotation. In general. Yet. it is difficult to explain flotation without considering the existence of the attractive hydrophobic force dis- cussed in this chapter. he writes. a flotation rate equation has been developed both under quiescent and turbulent flow conditions (Schimol- ler. flotation rate decreases with decreasing particle size. In the end. that is probably at the root of the long-range solvation interactions of water. and likewise the adhering–bridging bubble track. Gaudin (1957) showed. “It is the energy (or entropy) associated with the H-bonding network and proton hopping defects.” After having scrutinized the sci- entific issues standing today regarding the origin of the amazingly strong and long-ranged hydrophobic attraction. Thus. The van der Waals forces operating in wetting films are also repulsive according to the Lifshitz theory. however. none of these approaches has been applicable for the most ideal hydrophobic surfaces one can prepare where the hydrophobic attraction is strongest. hence. S U M M A RY In Jacob Israelachvili’s book. Intermolecular and Surface Forces (1991). a paradigm shift occurred within the scientific community. By assuming that the probability of the bubble– particle adhesion is determined by the hydrodynamic and surface forces. The hydropho- bic coagulation. and Yoon 1994. and eventually the concept of water restructuring was considered to . which may be attributed to the hydrophobic coagulation. January 2. Luttrell. the authors agree with Israelachvili. they have to be abandoned as possible starting points of a more elaborate theoretical modeling. This approach made it possible to develop a model that can predict flotation rates using both hydrodynamic and surface chemistry parameters. 1990). The hydrodynamic forces become comparable to the surface forces as the separation distance between bubble and particle reaches the critical rupture thickness of the wetting film between the two surfaces. No equally convincing approach to gain a closer understanding of the hydrophobic surface force has so far been proposed. Hydrophobic par- ticles coagulate at a pH well above the isoelectric point.book Page 172 Tuesday. use of a stronger collector that can increase the hydrophobicity of mineral particles and. Mao and Yoon 1997. how- ever. which cannot be explained without assuming the existence of a hydrophobic force (Xu and Yoon 1989. After some time.flotation0. The process can be “slow” if the hydrophobic force is too small to counterbalance the repul- sive electrostatic force. Do and Yoon 2005). surface forces are weaker than the hydrodynamic forces operating in a flota- tion cell by orders of magnitude. It is well known that flotation rate increases with increasing particle hydrophobicity and decreasing double-layer potentials. however. the role of the hydrophobic force is to reduce the energy barrier so that the bubble–particle interaction becomes a “fast heterocoagulation” process. that the flotation rate of galena particles stayed constant at particle sizes <10 μm. As a particle approaches a bubble in close proximity.

the film considered that has the thick- ness h (equal to the distance between the two dividing surfaces) only encompasses liquid matter in the form of water and a solute component denoted by subscript s.flotation0. January 2. However. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 173 be nothing but a “bold conjecture. πD is the disjoining (interaction) pressure. In the Equation A. for example. using. implying that the free energy per water molecule depends on the cluster size. This equation is a straightforward extension of the Gibbs surface tension equation. Thus. Today. close to a real hydrophobic surface.book Page 173 Tuesday. as well as in thin water films sandwiched between hydrophobic surfaces. APPENDIX T H E R M O DY N A M I C S O F A P L A N A R .1) Here. water has long been known to be an associated liquid where three-dimensional networks play a significant role. by means of the following relation: . As considered by Gibbs (1961) and treated in more detail by Eriksson (1969). how- ever. by using the (solid) dividing surfaces in the Gibbs notation. Given the background presented in this chapter to attempt resolving the long-standing issue about the origin of the hydrophobic force. that is. will be difficult to make. p is the ambient pressure. it may not be surprising that the introduction of an (infinite) hydrophobic solid surface can promote an extensive structure generation in the adjacent water. the latter equation only holds true as long as the state of strain of the solid surfaces remains unchanged. The versatility exhibited by water molecules to form clathrate cages for guest molecules of various size and shape indicates that reliable predictions of the structural state of water. the SFG or XAS tech- nique. it seems most urgent to (a) make several more studies of the temperature dependence of the hydrophobic force with the purpose of fully assessing the thermodynamic water film properties. Furthermore.1. (b) probe the state of the water next to carefully prepared and characterized hydrophobic surfaces. Therefore. these results indicate that there is hardly any alternative route that might be fruitful when aiming at a molecular understanding of the hydrophobic attraction. It is emphasized that γf is energetically (rather than mechanically) defined. T H I N A Q U E O U S F I L M B E T W E E N H Y D R O P H O B I C S O L I D S U R FA C E S Treating the thermodynamics of a (symmetric) thin aqueous solution film between two plane-parallel hydrophobic solid surfaces starts with the thermodynamic fundamental equa- tion of the film in the following form: d γ f = – ( S f ⁄ A )dT + hdp – π D dh – Γ wf d μ w – Γ sf d μ s (EQ A.” maybe even too bold to be taken seriously. Together. the association process is of a cooperative nature. it is presupposed that the properties of the thin film are estimated by using the equimolecular dividing surfaces with respect to the solid component. particularly because the molec- ular description of liquid water is still much in dispute. and that confinement of water in a thin film between two hydrophobic surfaces might strongly promote additional restructuring. and (c) make extensive experimental studies of the effect on the hydrophobic surface force of various clathrate-forming inert gases and other well-chosen solutes. a vast amount of experimental results has been accumulated. and γf is the film tension.

p where the coefficients dT. ex RTd ln c s (EQ A. ex ⎛ ----------- . γf has also a rather clear-cut mechanical significance. γf is primarily the free energy per unit area compared to what would be noted for a thin film of bulk phase properties containing the same amounts of water and sol- ute. ex ⁄ A )dp – π D dh – Γ sf.3 must be brought in harmony with the phase rule by invoking the Gibbs–Duhem relation for the bulk phase (denoted by superscript b): S b dT – V b dp + n w d μ w + n s d μ s = 0 (EQ A. the integrated tangential pressure pT profile across the film thickness h to a good approximation corre- sponds to –γ f. Stated another way.2) Accordingly. ex ⁄ A )dT + ( Δ V f. ex ⁄ A = Ω f ⁄ A (EQ A.7) In these expressions. . ex ⁄ A )dT + ( V f. and cw and cs represent the bulk phase concentrations of water and solute.8) with obvious definitions of the coefficients dT. Next. ex ⁄ A )dp – π D dh – Γ sf. dp. In addition. and dμs as the differences for the proper- ties in question between a thin and an infinitely thick film. it is formally the same as the Ω potential per unit area of the thin film. Because almost all residual con- tributions from the solid surfaces to the thermodynamic film properties cancel upon forming these differences. it corresponds to the reversible cleavage work up to a certain surface separation h. compare the equivalent equation presented by Gibbs for the noninteracting case (Equation 678 in work by Gibbs [1961]). Δγf corresponds almost exactly to the change in overall lateral mechanical tension of the film when comparing a thin and a very thick film. The (reversible) surface force measured in a surface force device is proportional to the film tension difference Δγ f = γ f ( h ) – γ f ( ∞ ) for which the following equation is obtained. Equation A. dp. ex ⁄ A = S f ⁄ A – Γ wf s wb – Γ sf s sb (EQ A. ex ⁄ A = h – Γ wf ν wb – Γ sf ν sb (EQ A. furthermore. January 2. and. the constraint of a constant surface strain can be disregarded.1). sb and νb denote partial molar volumes in the bulk solution.5) V f. 2007 7:36 PM 174 FLOTATION FUNDAMENTALS γ f = G f ⁄ A – Γ wf μ w + Γ sf μ s ≡ G f. Because only minor contributions to the excess free energy as well as to the lateral tensions arise in the hydrocarbon part of the two interfaces. For the special case under discussion.flotation0.6) and Γ sf. however. d ln c s (EQ A.book Page 174 Tuesday.4) ⎝ ∂ ln c s⎠ T. the following is obtained: ∂μ s ⎞ d γ f = – ( S f. respectively. regarding a thin film between hydro- phobic surfaces and made out of a dilute water solution. ex = Γ sf – Γ wf c S ⁄ c w (EQ A. assuming an ideal solution of the solute and noting that π D ( ∞ ) = 0 : d Δγ f = – ( Δ S f.3) Upon eliminating dμw and switching to the solute concentration cs as variable from (A. and dμs are given by S f.

91:391–436. Kolloid-Z. K. Thesis. 1999. The free energy.K. and R. B. Self-assembled monolayers of alkanethiolates on thin gold films as substrates for surface force measurements: Long-range hydrophobic interactions and electrostatic double-layer interactions. and N. and B. Podgornik. Derjaguin. Hence.D.2 and the free enthalpy definition results in Δ G f. Churaev.P. Detection of the hydrophobic surface force in foam films by measurements of the critical thickness of the film rupture.V. Liedberg.M.V. Soc. Very long range attractive forces between uncharged hydrocarbon and fluorocarbon surfaces in water. gaining knowledge about ΔSf. Colloid Interface Sci. T. 1998. Ficalbi. Cavitation and the interaction between macroscopic hydrophobic surfaces. New York: Consultants Bureau. Colloid Interface Sci. 1982. Ninham.flotation0. Langmuir 14:3326–3332. ex ⁄ A – T Δ S f. producing the proper sets of data and analyzing them thermodynamically might greatly contribute to resolving the current research issues about the nature and properties of thin water films between hydrophobic surfaces. 1988. J.J. Ederth. 2007 7:36 PM THE NATURE OF HYDROPHOBIC ATTRACTION FORCES 175 For the case of 1:1 electrolyte being the solute. Direct measurements of the force between hydrophobic surfaces in water.. Danov. Chem. Temperature dependence of the surface tension of water by the equilibrium ring method. A flotation model under turbulent flow conditions. In particular.A. Using Equation A. V. Faraday Trans.V. P. 91:193. B. January 2. and A. and A. ex ⁄ A = Δ H f. Christenson.8 must be multiplied by a factor of 2.. the last term in Equation A. Phys.V..K.S. J. Colloid Interface Sci. Phys. 1998. Yoon. Novel Surfaces for Force Measurements. In all likelihood. Langmuir 20:1799–1806. Structural component of disjoining pressure. p. Do. important information can be gathered as to the ther- modynamic thin film (excess) properties ΔSf.S. Muller. Stockholm University. Zeks. Local structure of hydrogen-bonded liquids.W. T. Chem. ———.J. Craig.D. B.ex . G.M. and cs for fixed surface separations h. Dimitrova. 1988. Science 239:390. whereas the effect of solutes on the surface force is intimately related with ΔΓ sf. Claesson. Kitchener.A. G. Kralchevsky.book Page 175 Tuesday. Chapter 7 in Surface Forces. Sweden. Pashley..J. Friction and adhesion IV: The theory of adhesion of small particles.. Appreciation is also extended to Per Claesson for critically reading the manuscript and making several useful comments. 1987. 1979. Stockholm: Royal Institute of Technology. K. Cavalleri. Ederth.ex/A and ΔHf. 92:1650. Lett.M. and H. . Stability of aqueous films on hydrophobic methylated silica. R. Cini. enthalpy and entropy of hydration of phospholipid bilayer membranes and their difference on the interfacial separation.ex .. T..K. and ΔΓ sf. Study of the long-range hydrophobic attraction in concentrated salt solutions and its implications for electrostatic models.M. N. Christenson. Claesson. P.. 41:287. Claesson.ex/A. and J. Adv. 49:249. 2005.V. Ananthapadmanbhan. P. Blake. 68:1435–1442. J. and P. ΔVf. H. AC K N OW L E D G M E N T S The authors wish to thank Atte Kumpulainen and Jinhong Zhang for many illuminating discussions and for assistance with the figures. and B. and R.. Loglio. ex ⁄ A = Δγ f (EQ A.ex/A. J. Cevs.ex/A will be crucial for understanding the structural aspects of thin aqueous films. Colloid Interface Sci. and V. Lips. 2001. REFERENCES Angarska. by plotting Δγf as a function of the state variables T.. 69:155. B. B.M. 1974. Chem. M. 2004.9) implying that the corresponding enthalpy difference is readily derived. Derjaguin. 1934. 1972..-H. Derjaguin. Churaev. Langmuir 14:4782–4789. H. R. 2004.

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R. V.A. D. Yushenko. 1993. Y. Evidence of the existence of rigid electrical dipole moment in colloidal particles—estimation of the dipole values and their direction. Nilsson. Odelius. Langmuir 7:3154–3159. D. Evans. C. and L. Rabinovich. J. van Oss. 2005. J. Ogasawara. Stewart. and surface force techniques.. Ravishankar.G. Ojamä. Evans.V. 181:613–626. Surface activity and ion exchange: A study via surface tension. 2007 7:36 PM 178 FLOTATION FUNDAMENTALS Tolstoi. 1991. M.H.. Colloid Interface Sci. Electro-optical properties of lyophobic colloids IV. 1983. R.V. Spartakov. Xu. Mao... ———.F. Yoon.D. J. H.-H..A. Colloid Interface Sci. 179:391. Wernet.-H. New York: Marcel Dekker. Tsao. Wood. Wennerström.book Page 178 Tuesday. and E. A. Nordlund. The role of hydrophobic interactions in coagulation. 1987. 28:881.-H. A. Langmuir 12:3357.A.V. Application of extended DLVO theory. Monopolar surfaces. Ninham. C. U. Yoon. 1994. and W. January 2. 185:363–370. D.X. 1990.M. van Oss. 28:35. and H. B. and A. Yang. and H. Wennerström. Hydrophobic interactions between dissimilar surfaces. IV: Derivation of flotation rate equation from first principles. R. Hirsch.A. Sharma.A.. 2004. 1994. 1989. Langmuir 9:779–785. Preparation of a robust hydrophobic monolayer on mica.I. 132:532–541. Khilko.-H. Effects of degassing and ionic strength on AFM force measurements in octadecyltrimethylammonium chloride solutions. 1966. S. L. Page 208 in Interfacial Forces in Aqueous Media. Colloid Interface Sci. Langmuir 10:2307–2310. D. A study of hydrophobic coagulation.. Colloid Interface Sci. Flinn. M. Science 304:995–999. 134:427–434. 1996. Trusov.. Interaction between particles in a nonwetting liquid. Interactions between hydrophobic surfaces: Dependence on temperature and alkyl chain length. Pettersson. J. M. Long-range hydrophobic forces between mica surfaces in dodecylammonium chloride solutions in the presence of dodecanol. Z.. Y. J. Kolloid. Mao. T. V. 96:307.. Good. and G. Yoon.-H. Colloid Interface Sci. Cavalleri. Langmuir 21:5831–5841.M.J. Ph. and R.I. and Y. Bergmann. L. Long-range attraction between a hydrophobic surface and a polar surface is stronger than that between two hydrophobic surfaces. and S. Yaminsky. Yaminsky. and R. Zh. . Näslund.F.K. Colloid Interface Sci. P.Å. 1997. Glatzel. Chaudhury. L. 1996. Zhang.J. J. Yoon. Tsao. The structure of the first coordination shell in liquid water. and A. wetting tension. Shchukin. Ducker. R..S. and R. J. Colloid Interface Sci. J. Yoon. V. M.J. Adv.flotation0. N..K.. 1996.

Because of its high selectivity and relatively low cost. Thus. and Plaksin 1972). T. Considerable advances in flotation were made after the development of flotation reagents that can control or modify the surface properties of minerals selectively. hydrophobicity is imparted to the mineral particles by the adsorption of surface-active agents (surfactants and some polymers). The larger the contact angle. January 2. The former particles can. and M.flotation0. Ducker. and liquid–gas interfacial tensions. Adsorption of surfactants and polymers on minerals 179 . and the easier it is for the bubble to attach and result in flotation. food. first of all. and γlg are solid–gas. In most cases. Flotation depends. W. Herrera-Urbina. and about 95% of the base metals produced are beneficiated through this process (Matis and Zouboulis 1995). Somasundaran. or hydrophilic particles that are made hydrophobic by surface-active reagents (surfactants). the flotation process has been modified and used in many other industries. and remediation (Matis and Zouboulis 1995). In this process.C. 2007 7:36 PM Adsorption of Surfactants and Its Influence on the Hydrodynamics of Flotation P. attach to the gas bubbles in the pulp and are levitated to the froth. The ability of the gas bubbles to attach to the particles is a function of the hydro- phobicity of the particles. solid–liquid. pharmaceutical. Klassen. respec- tively. Beyond the mining industry. the difference in hydrophobicities of various particles can be used as the basis of their separation by flotation.book Page 179 Tuesday. L. R. paper. thus. Zhang. recycling. flotation became the economically competitive process to treat low-grade and complex ores that would have otherwise been treated as waste. such as chemical. the resulting contact angle is given by Young’s equation in terms of the interfacial energies (see Figure 1): γ sg – γ sl = γ lg cos θ (EQ 1) where γsg . billions of tons of ores are treated by the flotation process annually. Healy. Today. on the probability of attachment of the bubbles to the particles. Adhesion of the gas bubbles to the particles in the suspen- sion requires a contact angle that is significantly larger than zero. Flotation was first used in the mineral industry as an enrichment process for sulfide ores about 100 years ago (Glembotskii. with most other particles remaining in the bulk. Few minerals. the greater is the hydrophobicity of the particle. γsl. Fuerstenau INTRODUCTION Flotation is a process that separates various particles based on the differences in their surface properties. hydrophobic particles.W. When a solid particle is attached to a gas bubble in a liquid. such as natural sulfur and graphite. and θ is the contact angle. be separated from the matrix by separating the froth from the bulk pulp (Gaudin 1957). are naturally hydrophobic.

The effect of surfactant adsorption on major interfacial parameters can be seen in Figure 2. (e.. This marked increase in adsorption density is accompanied by concomitant sharp changes in contact angle. phosphates (e. January 2. sylvite).g. This chapter will show that. By adjusting that potential.. and Somasundaran 1964). The variable of pH is also impor- tant in sulfide flotation systems. either through the use of a polarized elec- trode or by the use of a redox couple in the solution phase. cal- cite). 2007 7:36 PM 180 FLOTATION FUNDAMENTALS γlg Gas Liquid θ γsl γsg Solid FIGURE 1 Solid–liquid–gas interface depicting contact angle and surface tension forces acting at the boundaries can lead to changes in their wetting and dispersion behavior and the resultant flotation response. fluorite). silica. Healy.g. if the redox potential is changed for any reason (i. that redox couple is supplied by a surfactant moiety. The present review focuses on adsorption of surfactants at mineral–solution interfaces. sulfates (e. soluble salt minerals (e. and complex aluminosilicates. they can self- assemble into aggregates in solutions and at solid–liquid interfaces through the hydropho- bic effect above certain concentrations.g. on quartz is given along with contact angle. increase in adsorption due to association of surfactants adsorbed at the solid–liquid interface into two dimensional aggregates called hemimicelles occurs at about 10–4 M DAA. The principal variable is pH for minerals such as the inorganic oxides (e. barite). but not always. In contrast to sulfide flotation systems. and flotation recovery (D. In the nonsulfide mineral adsorption–flotation area. the most famous being the xanthate–dixanthogen redox couple.g.g.g. In sulfide systems. fluorides.flotation0. zeta potential. For DAA and quartz at neutral pH. That pH change can. zeta potential. Also. Often.. in a both a simple and also in a deriv- ative way. alu- mina. feldspars. where the adsorption density of the cationic surfactant. alkaline earth carbonates (e. halite. pH is able to define the parameter of proton activity that is always necessary to begin to understand surfactant adsorption in such systems. Fuerstenau. dodecyl ammonium acetate (DAA). the Eh is changed).. The action of surfactants to control the hydrophobicity of the sulfide–water interface differs in a fundamental way from the effect of surfactants on other mineral–water inter- faces. there can be a concomitant change in pH.. the principal control variable is the redox potential imposed on the mineral–water system. sulfides can acquire hydrophobic- ity.book Page 180 Tuesday. apatite). . in turn. it is rarely necessary to consider redox effects to understand surfactant adsorption in nonsulfide flotation systems. The conformation of surfactants at solid–liquid interfaces also has a governing role in determining the interfacial properties. Surfactant molecules contain both hydrophilic and hydrophobic moieties. affect the interfacial processes in nonsulfide systems. They can modify the interfacial properties significantly at very low concentrations...e. goethite).W.

An understanding of the mechanism of adsorption is neces- sary to choose appropriate flotation reagents. and gas phases. flotation is controlled not only by the physical chemistry of the system but also by the hydrodynamics of the pulp. mol/cm 2. is also examined. mol/L Source: D. flotation response. the solid surface. mV Relative Flotation 30 60 50 0 20 40 30 –40 10 20 10 –80 0 10–6 10–5 10–4 10–3 10–2 Concentration of DAA. desolvation of the polar group of the . is governed by various processes at all of the solid–liquid–gas interfaces in systems. degrees and Zeta Potential. 2007 7:36 PM ADSORPTION OF SURFACTANTS 181 Contact Angle +80 Adsorption Density 40 Zeta Potential 80 Flotation Response Adsorption Density.flotation0. being the result of fruitful contacts among solution. Adsorption is the selective partitioning of the surfactant into the interfacial region as the result of energetically favorable interactions among the surfactant. suggesting that these phenomena depend primarily on the adsorp- tion of surfactants at the solid–liquid interface. solid. In this chapter. Separation of minerals from each other depends on the selective adsorption of surfactants on only the mineral particles to be floated. Adsorption of surface-active agents (includ- ing surfactants and certain polymers) and their effects on flotation processes are discussed.book Page 181 Tuesday. particularly collectors. and zeta potential for quartz as a function of the cationic surfactant DAA concentration at pH 6 to 7 and flotation recovery. FIGURE 2 Correlation of adsorption density. and solution. ion exchange covalent bonding. Important effects of water chemistry of surfactants and minerals on the flotation process are also reviewed. contact angle. surfactant adsorption at the liquid–gas interface also plays an important role in affecting the flotation (Somasundaran 1968). Fur- thermore. × 1011 70 +40 Contact Angle. and Somasundaran 1964. January 2. and particularly conformation and orientation. the physicochemical as well as hydrodynam- ics aspect of the flotation process are addressed. Flotation. in addition to adsorption at the solid–liquid interface. A D S O R P T I O N O F S U R FA C TA N T S O N M I N E R A L S Adsorption of surfactants at solid–liquid interfaces can drastically alter interfacial proper- ties such as wetting and hydrophobicity that are critical to the flotation process. In fact. Application of various spectroscopic and imaging techniques to explore the characteristics of the adsorbed layers. for optimum separa- tion conditions. The driving force for adsorption involves one or more of the following factors: coulombic interaction.W. Fuerstenau. Healy.

Charge on the particle surface. For salt-type . For each surfactant–solid system. electrostatic inter- actions play a governing role in the adsorption process. 2007 7:36 PM 182 FLOTATION FUNDAMENTALS collector. hydrocarbon chain-water. as one transfers the chain of –CH2– groups from bulk water to the new bulk or interfacial aggregate state. Electrostatic Adsorption of Surfactants In systems where the surfactants and the particles are oppositely charged. micellar or other bulk self-assembly structures) or interfacial domains or regions. and ΔG 0 H 2 O is the term owing to dehydration of the adsorbate species or any species displaced from the interface because of adsorption. R is the gas constant. an increase in the magnitude of ΔS0 for the system. surfactant concentration. desolvation of the surface and hydrogen bonding.W. the major forces involved in surfactant adsorption are discussed. Fuerstenau 1971). in the case of oxides. The adsorption density of the surfactant is commonly interpreted using the Stern–Grahame equation: – ΔG ads 0 Γ δ = 2rC exp ⎛ -----------------⎞ (EQ 2) ⎝ RT ⎠ where Γδ is the adsorption density in the Stern plane δ. there is a gain in entropy—that is.flotation0. depending on the solid and the surfactant type. The energy gained through such transfers is often a linear function of the energy gained per –CH2– group.book Page 182 Tuesday. several of the previously mentioned terms can be contributing. is a result of the hydrolysis of surface species followed by pH-dependent dis- sociation of the surface hydroxyl groups: MOH = MO – + H + (EQ 4) + H + + MOH = MOH 2 (EQ 5) where M represents the interfacial metal atom. The pH at which the surface charge is zero is called the point of zero charge (PZC). T is the absolute 0 is the standard free energy of adsorption (D. The magnitude of the energy gained per –CH2– decreases from that of the process of transfer from water to bulk saturated hydrocarbon oil.W. F is the Faraday constant. In each case. and so forth. temperature. and hydrophobic and van der Waals interactions. to that of trans- fer to a spherical micelle. ΔG chem 0 is the chemical term due to covalent bonding. C is the bulk concentration of the surfactant. Fuerstenau 1971): 0 – ΔG ads 0 = ΔG elec 0 + ΔG chem 0 + ΔG 0 + ΔG 0 + ΔG hyd (EQ 3) H H2 O 0 is the electrostatic interaction term and is equal to zFψ where z is the valence of the ΔG elec δ adsorbate species.g. to that of transfer to a two-dimensional aggregate at a hydrophobic solid–water interface.. Oxides carry a positive charge in solutions that are more acidic than the PZC and a negative charge in those that are more alkaline. and – ΔG ads The driving force for adsorption is the sum of several contributing forces mentioned previ- ously and can be written as follows (D. 0 and ΔG hyd is the free energy gained when hydrocarbon moieties are transferred from bulk water into bulk (e. In the following section. temperature. and ψδ is the potential in the δ plane where the surfactant head group is located. r is the effective radius of the adsorb- ing ion. ΔG H 0 is the hydrogen bonding term. January 2. to that of a two-dimensional aggregate at a hydrophilic solid–water interface (Lin and Somasundaran 1971).

but it does so to different extents.2). In these regions. mol/L Source: D. Wakamatsu and Fuerstenau 1968. FIGURE 3 Adsorption isotherms for the aqueous SDS–alumina system at several pH values. and Healy 1971. 10–9 pH 3. Healy. Fuerstenau and Wakamatsu 1975.2 6. the charge generation could be due to preferential disso- lution of lattice ions. at low concentrations. 25°C. Experimentally obtained adsorp- tion isotherms of sodium dodecyl sulfonate (SDS) on alumina at fixed pH and ionic strength are S-shaped and exhibit three distinct regions in the pH range 3. Fuerstenau. Much detailed research work on surfactant adsorption via electrostatic attraction has been conducted on alumina using alkyl sulfonates (Somasunda- ran and Fuerstenau 1966. These isotherms have strongly suggested that in Region I.W.2 –13 10 10–6 10–5 10–4 10–3 Equilibrium Concentration of SDS.flotation0.6 10–12 pH 9.2 to 8.W. and constant ionic strength of 2 × 10–3 M NaCl (sodium chloride) . Fuerstenau and Waka- matsu 1975) and the alkyl benzene sulfonate–alumina systems (Dick. Measurements of the electrophoretic mobility of colloidal alumina in aqueous SDS support the proposed physical adsorption mechanism involving mainly an electrostatic attraction between dodecyl sulfonate anions and positively- charged alumina through an ion-exchange process (Somasundaran and Fuerstenau 1966). January 2. Somasundaran. Alkyl Sulfonate–Alumina.2 5. mol/cm 8. the surfactant anions adsorb as individual counterions on the positively- charged surface of alumina (PZC at pH 9.2 when the isotherm is plotted on a log–log scale (see Figure 3).2 10–10 2 Amount Sulfonate Adsorbed. 2007 7:36 PM ADSORPTION OF SURFACTANTS 183 minerals such as calcite and apatite. followed by hydrolysis of dissolved species in the bulk and subsequent adsorption of the resulting complexes. and again is small in Region III.book Page 183 Tuesday. but it abruptly becomes large with small surfactant concentration increments in Region II. and Fuerstenau 2003).2 7. the adsorption density increases linearly with the equilibrium surfactant concentration.2 10–11 8.2 4. D. The increase in adsorption density with surfactant concentration is small in Region I.

the ionic strength and the hydrocarbon chain length also affect the adsorption of alkyl surfactant ions at the interface. Under these con- ditions. a possibility that was first proposed by D.4 × 10–5 M for C14 (D. Recently. Region III of the adsorption isotherm is also characterized by a low dependence of the adsorption density on the surfactant concentration. In Region III. As shown in Figure 4. This association enhances the adsorption of sulfonate anions consid- erably and leads to the formation of two-dimensional aggregates of adsorbed surfactant anions at the surface. and hemimicelle formation through association of the hydrocarbon chains of the adsorbed sulfonate ions. Healy. Fuerstenau. The onset of Region II corresponds to the following bulk concentration of sodium alkyl sulfonates: 7 × 10–4 M for C10. a further increase in adsorption density with sulfonate concentration has been explained in terms of bi-layer adsorption of sulfonate ions (Somasundaran and Fuerstenau 1966). and Fuerstenau (2003) have reported the isotherms for the adsorption of a variety of branched and straight-chain alkyl benzene sulfonates (ABSs) on a low-surface-area alumina at different pH values. In the case of octyl sulfonate. Similar to the adsorption isotherms previously obtained with a high-surface-area alumina (Dick. The equilibrium SDS concentration at which Region II begins has been identified as the critical hemimicelle concentration (Somasundaran and Fuerstenau 1966). This adsorption behavior seems to indi- cate saturation of sulfonate ions adsorbed electrostatically at the interface.flotation0. The alkyl sulfonates containing a hydrocarbon chain length of 16 carbon atoms give an adsorption isotherm with only two distinct linear portions (Regions II and III) with different slope. dodecyl-. in all cases the adsorption density shows an abrupt increase at a particular equilibrium . 2007 7:36 PM 184 FLOTATION FUNDAMENTALS In Region II. a behavior that is more marked at lower pH values where the slope decreases significantly. Fuerstenau 2002). These isotherms clearly show that Region I is independent of chain length and that the onset of hemimicelle formation (beginning of Region II) shifts to lower sodium alkyl sulfonates as the chain length increases. Fuerstenau (1953) and by Gaudin and Fuerstenau (1955). and indicates that there is no hemimicelle formation for this relatively short-chain sulfonate. Effect of Hydrocarbon Chain. the adsorption mechanism involves electrostatic attraction between the sulfonate anions and the positively-charged alumina surface. In addition to the pH.W.2. suggesting that at higher con- centrations specific adsorption phenomena may occur through association of the hydrocar- bon chains of surfactant anions adsorbed electrostatically at the Stern plane (Somasundaran and Fuerstenau 1966). The shape of the adsorption isotherm of alkyl sulfonate on alumina is dependent on the hydrocarbon chain length (Wakamatsu and Fuerstenau 1968).book Page 184 Tuesday. and tetradecyl sulfonates at pH 7. and Healy 1971). its adsorption isotherm exhibits single linear behavior (corresponding to Region I) all along the range of equilibrium concentrations of sodium octyl sulfonate investigated. 6 × 10–5 M for C12. who termed these bi-dimensional surfactant aggregates hemimicelles. Somasundaran. In this region. January 2.W. the electrostatic and hydrophobic bonding contributions to the free energy of adsorption are opposite in sign. The standard free energy of adsorption for Regions II and III is given by the following expression: 0 ΔG ads 0 = ΔG elec 0 + ΔG CH = zFψ δ + nφ (EQ 6) 2 where n is the number of carbon atoms in the chain. three-region adsorption isotherms are obtained with decyl-. the slope of the isotherm becomes steeper. and φ is the free energy decrease upon removal of 1 mol of CH2 group from water. and 1.

Alkyl Ammonium Adsorption on Quartz.flotation0. suggesting that the benzene ring adds the equivalent of 3. and shows that at concentrations lower than 2 × 10–4 M DAA. a very remarkable finding of these results is the close similarities between the form of the adsorption isotherms of alkyl and alkyl aryl sulfonates.2 CH2 groups of the hydrophobic energy to the overall adsorption process. the hemimicelle hypothesis is equally applicable to ABS adsorption on alumina. as was postulated by Dick Fuerstenau. As opposed to the adsorption of alkyl sulfonates on alumina. 25°C. and Healy (1971). and the total concentration of added surfactant is virtually in the cationic form. II. undergoes protolysis. constant ionic strength of 2 × 10–3 M NaCl. the adsorption density follows a linear behav- ior that can be expressed mathematically by the following empirical relation: . FIGURE 4 Adsorption isotherms for the aqueous sodium alkyl sulfonate–alumina systems at pH 7. and several hydrocarbon chain lengths concentration of the sodium alkyl benzene sulfonate. mol/cm 2 10–10 10–11 10–12 C16 C14 C12 C10 C8 10–13 10–6 10–5 10–4 10–3 10–2 Equilibrium Concentration of Sodium Alkyl Sulfonate. At con- centrations below the critical micelle concentration (CMC). this alkyl ammonium salt dis- sociates completely at this pH.2. January 2. the adsorption of alkyl benzene sulfonates is independent of pH over a wide range.book Page 185 Tuesday. In addition. and III of alkyl sulfonate isotherms. mol/L Source: Wakamatsu and Fuerstenau 1968. which shows significant pH dependence. The experimental adsorption isotherm pre- sented in Figure 6 shows the adsorption density of dodecyl ammonium ions on quartz as a function of the equilibrium concentration of DAA at neutral pH (deBruyn 1955). Because the C9 and C10 alkyl benzene sulfonate isotherms exhibit the characteris- tic Regions I. identified as the hemimicelle concen- tration (Figure 5). 2007 7:36 PM ADSORPTION OF SURFACTANTS 185 10–8 10–9 Monolayer Adsorption Density. This isotherm is typical of the cationic surfactant adsorption from solution at the oxide mineral–aqueous solution interface.

the rapid rise in flotation recovery . as predicted from the Gouy–Chapman equation. Fuerstenau.2 × 10 –6 C 1. January 2. and Somasundaran (1964). In this region. This break in the curve pro- vides the concentration at which the alkyl chains of the adsorbed cationic surfactants begin to associate at the interface through hydrophobic bonding to form hemimicelles (Gaudin and Fuerstenau 1955).2 (EQ 8) Excellent evidence supporting the hemimicelle premise is the flotation data provided by D.1 × 10 –9 C 0. Healy. mol/cm 2 II 10–11 C12 SO3–Na+ I 10–12 C10 SO3–Na+ C12 SO3–Na+ C9 SO3–Na+ 10–13 10–6 10–5 10–4 10–3 Equilibrium Concentration of ABS. and C12 alkyl benzene sulfonates on alumina at pH 7. and their adsorption density is proportional to the square root of the equilibrium concentration of DAA.book Page 186 Tuesday. Under these conditions. Flotation recovery increases dramati- cally above specific concentrations for each of the amines of varying hydrocarbon chain length (Figure 7). this linear behavior of the adsorption density can be represented by the following empirical equation: Γ DAA = 2. The slope of the adsorption isotherm presented in Figure 6 changes abruptly at an equi- librium concentration close to 2 × 10–4 M DAA in solution. 2007 7:36 PM 186 FLOTATION FUNDAMENTALS 10–9 III 10–10 Adsorption Density of ABS Surfactant.5 (EQ 7) where ΓDAA is given in moles per square centimeter and C is the bulk concentration of DAA in moles per liter.2 and 10–3 M NaCl Γ DAA = 8. the dodecyl ammonium cations adsorb electrostatically. and Fuerstenau 2003.W. the adsorption density increases signifi- cantly and even exceeds monolayer coverage. Above this concentration.flotation0. Similar to deBruyn’s (1955) results. FIGURE 5 Isotherms for the adsorption of C9. C10. mol/L Source: Healy. Somasundaran.

flotation0. mol/cm 2 10–9 Monolayer 10–10 10–11 10–12 10–13 10–8 10–7 10–6 10–5 10–4 10–3 10–2 DAA Concentrate. Healy. and Somasundaran 1964.book Page 187 Tuesday. FIGURE 7 The effect of alkyl chain length on the relative flotation response of quartz in the presence of alkyl ammonium acetate solution with dodecyl amine also occurs about 1 × 10–4 M. . These authors showed that a plot of col- lector concentration at which a rapid rise in flotation recovery occurs as a function of the number of carbon atoms in the hydrocarbon chain is a straight line with a slope that corre- sponds to a specific adsorption potential of –0. This is the free- energy decrease associated with hydrocarbon chain removal from solution. mol/L Source: deBruyn 1955. Fuerstenau.62 kcal/mol CH2 group. % 60 40 C18 C16 C14 C12 C10 C8 C6 C4 20 0 10–8 10–7 10–6 10–5 10–4 10–3 10–2 10–1 1 Concentration.W. January 2. 2007 7:36 PM ADSORPTION OF SURFACTANTS 187 10–8 Adsorption of Dodecyl ammonium Salt. FIGURE 6 Isotherm for the adsorption of dodecyl ammonium ions on quartz at pH 6–7 100 80 Flotation Recovery. mol/L Source: D.

These results were explained on the basis of hemimicelle formation involving co-adsorption of RNH3+ and RNH2(aq) on the quartz surface.3 × 10 –4 (EQ 10) Laskowski.book Page 188 Tuesday.flotation0. degrees +20 90 Surface Coverage. and flotation recovery of quartz in presence of 4 × 10–5 M DAA The important role that surfactant adsorption exhibits in determining interfacial prop- erties is shown as a function of pH for the dodecyl amine–quartz system in Figure 8. FIGURE 8 Correlation of adsorption density. % 0 80 Contact Angle. Smith 1973) RNH 2 ( s ) ↔ RNH 2 ( aq ) K = 2 × 10 –5 (EQ 9) RNH 2 ( aq ) + H 2 O ↔ RNH 3 + + OH – K = 4. The amine colloids are charged in solution. and Liu (1988) have suggested that the colloids of precipitated amine formed in alkaline solution may be responsible for quartz flotation under these con- ditions (see Figure 9). The pH region in which the amine colloids form is the same as that in which optimal flotation of quartz is obtained. Vurdela. mV Flotation Recovery. January 2. Equilibria are (Ralston 1984. and they have a PZC at relatively high pH. % of monolayer Zeta Potential. contact angle.W. and flotation recovery. zeta potential. for example. dodecyl amine has a PZC at pH 11. Surface Coverage. Flotation Recovery –20 70 –40 60 Zeta Potential. Fuerstenau 1957. zeta potential. 2007 7:36 PM 188 FLOTATION FUNDAMENTALS 100 Contact Angle. Interactions in the interfacial region depend essentially on the relative concentrations of surfactant required to form . The marked increase in adsorption density is accompanied by concomitant sharp changes in contact angle. mV –60 50 –80 40 –100 30 –120 20 10 0 0 2 4 6 8 10 12 14 pH Source: D. The association of hydrocarbon chains either as hemimicelles or as a precipitate of col- lector salt on the mineral surface is desirable for flotation.

8 (Takeda and Usui 1987).” or “chemisorption. The points shown are experimental solubility ( ) and redispersion ( ) determined from the transmittance curves. mol/L 10 Precipitation (Colloidal Solution) 10–3 No Precipitation 10–4 Solubility Limit 10–5 6. through . hemimicelles and to precipitate the surfactant salt.0 8. Surfac- tant ions that adsorb on mineral surfaces through chemical forces show more selectivity toward a particular mineral and. FIGURE 9 Thermodynamic equilibrium diagram showing the CMC (30°) and the lines of critical pH of precipitation and solubility limit at 25°C. The adsorption density of dodecyl ammonium species on quartz has also been deter- mined at pH 5 and pH 9.0 10. respectively. and. thus. January 2.” is adsorption in which the forces involved are valence forces of the same kind as those operating in the formation of chemical compounds (Everett 1972). If the HMC (concentration of hemi- micelle formation) is the lower of the two. hence. Chemisorption takes place between the polar head group of the sur- factant (cationic or anionic) and the anionic or cationic surface sites. Chemisorption is involved in systems in which the metal ions do not leave their lattice sites.book Page 189 Tuesday.0 pH Source: Laskowski. Complete quartz flota- tion at pH 5 was achieved at a DAA adsorption density of about 1% of a monolayer.0 12. Chemical Adsorption of Surfactants “Chemical adsorption. Vurdela. and the extent of adsorption has been correlated with the flotation behavior of –10 μm quartz particles. whereas at pH 9.flotation0. provide the means for more effective mineral separa- tions by froth flotation. and Liu 1988. the formation of hemimicelles would be preferred over salt precipitation. 2007 7:36 PM ADSORPTION OF SURFACTANTS 189 10–1 DAA-HCI Break of Transmittance Micellization Leveling Off of Transmittance CMC –2 Critical pH of Precipitation Concentration. adsorption is limited to a monolayer of surfactant ions.8 greater than a monolayer was required.

This is clearly apparent in Figure 10.book Page 190 Tuesday.” Surface reaction is probably the most dominant chemical adsorption mechanism .W. and Choi (1960). they can adsorb even on charged surfaces with an electric charge similar to that of the surfactant polar head group.001 4 5 6 7 8 9 10 11 pH Source: D. however. 2007 7:36 PM 190 FLOTATION FUNDAMENTALS 10 10–4 M PZC –5 3 × 10 Collector Adsorption Density. Cooke. This was also clearly shown by Iwasaki. the PZC of the mineral is not determinant of surfactant adsorption as it is in those systems in which the collector ion adsorbs electro- statically. μmol/m 2 1 –3 10 10–5 10–4 10–5 M 0.01 Alumina (SDS) Hematite (Sodium Oleate) I = 2 × 10–3 M. and pH 11 with oleic acid. who investigated the flotation response of hematite (PZC at pH 6. FIGURE 10 Isotherms for the adsorption of dodecyl sulfonate on alumina (physical adsorption) and of oleate on hematite (chemical adsorption) as a function of pH at 23°C covalent or coordinate bonds. In systems where chemisorption takes place.7) as a function of pH using three unsaturated fatty acids that are known to react chemically with iron. In the case of hematite. adsorption of oleate occurs greater than two pH units above the PZC under which condi- tions both the surface and oleate have the same charge. and results in the formation of a new surface compound. January 2. These researchers found that this hematite sample floats well up to about pH 9 with linolenic. Therefore.1 PZC 0. Fuerstenau 1984. 23°C 0. It is noted that adsorption of dodecyl sul- fonate is possible only below the PZC of alumina. when ionic surfactants chemisorb on mineral surfaces. this has been termed “surface reaction. Surface Reaction/Precipitation Another type of chemical adsorption is involved when metal ions comprising the mineral move out of their lattice sites and interact with the collector. pH 10 with linoleic.flotation0.

Prolonged rinsing with ether removed much of the xanthate from the surface (d).115 0 50 E 987 0 Source: Leja. The anodic curve in the presence of ethyl xanthate exhibits a peak at about 0 V. and Poling (1962–1963). What has been termed chemisorption in the past was probably surface reaction.195 50 D 990 1. In those sulfide systems in which surface reactions are involved (e.200 1. Little. The curve in (b) shows the spectrum of the PbS film that has been oxidized in air. January 2. and (e) after washing in pyridine. the top curve (a) shows the infrared spectrum of bulk lead ethyl xanthate.110 1. The discharge reaction given in Equation 11 is believed to account for this peak. the spectrum located in (c) was obtained.210 50 1.g.. and the total charge passed was found to correspond to monolayer coverage. fatty acid–semisoluble salts. pyridine.014 50 1.112 1. metal collector salts form at the surface as lead ions move from the lattice into solution. to return the surface to that of oxidized PbS (e). . and sphalerite). After exposing this film to ethyl xanthate.212 1. 1. FIGURE 11 Infrared spectra showing adsorption of ethyl xanthate onto an evaporated PbS film: (a) bulk lead ethyl xanthate. % 0 1. but it took a strong solvent. and Poling 1962–1963. In the case of galena. (d) after prolonged washing in ether.000 900 800 700 100 1. and fatty acid– hydroxamate-insoluble oxides and silicates. Examples include xanthate–sulfide minerals.140 50 C 1. the first stage comprises chemisorption of xanthate ion on surface lead sites.flotation0. chalcocite. galena.300 cm–1 1. In both cases.140 0 1. (c) above treated in aqueous solution of ethyl xanthate. (b) freshly evaporated PbS film after atmospheric oxidation. Sulfide Minerals. An infrared adsorption study of ethyl xanthate on a precipitated lead sulfide (PbS) film was presented by Leja. which is nearly identical to that of bulk precipitated lead ethyl xanthate. adsorption occurs in two stages. Woods (1976) has presented a voltammogram established with a galena electrode in the absence and presence of ethyl xanthate.110 A 1. In Figure 11. 2007 7:36 PM ADSORPTION OF SURFACTANTS 191 in flotation.book Page 191 Tuesday.100 1. the electrode behaves reversibly. Little. X – ↔ X ads + e – (EQ 11) With surface oxidation.020 1. solid on Nujol mull.110 0 986 B 1.020 Absorption.

and Kuhn (1974) who also showed that flotation of unactivated sphalerite is controlled by the formation and adsorption of zinc xanthate for various xanthates. In the case of xan- thate.C. oxidation of the collector to a dithiolate occurs. but it is thought to involve interaction between the sulfur of the collector molecule and sulfur atoms contained in the pyrite surface. FIGURE 12 Distribution of amyl xanthate species after adsorption of amyl xanthate on chalcocite In their work with chalcocite. arsenopyrite. This potential is termed the “rest potential.flotation0. develop a potential when placed in water. meq Source: Gaudin and Schuhmann 1936.” When the rest potential is greater than the equilibrium oxidation–reduction potential of a sulfhydryl collector. the following reaction occurs at the pyrite surface. though. These observations are in agreement with those of Plaksin and Anfimova (1954) who concluded that two forms of adsorption occur in this system. Fuerstenau.book Page 192 Tuesday. Sulfide minerals are electronic conductors and. This . is that chemisorption is not involved. Clifford. 2007 7:36 PM 192 FLOTATION FUNDAMENTALS 14 12 Milliequivalents 10 8 ce urfa 6 lS a er in M on e Cuprous 4 a bl ch Xanthate ea nl U 2 Excess Xanthate in Filtrate 0 0 2 4 6 8 10 12 14 Xanthate. Oxygen or ferric iron can serve as xanthate oxi- dant. the oxidized species is dixanthogen. The presence of bulk precipitated zinc dodecyl xanthate on sphalerite after contact of sphalerite with dodecyl xanthate was shown by Yamasaki and Usui (1965). In the case of oxygen. These results are shown in Figure 12. January 2. Gaudin and Schuhmann (1936) observed an unleachable layer of xanthate and a leachable layer of cuprous xanthate on chalcocite after contact with xanthate. as such. Examples of this phenomenon when xanthate is used as collector are pyrite. and pyrrhotite. 2X – + 1 ⁄ 2O 2 ( aq ) + H 2 O ↔ X 2 ( ads ) + 2OH – (EQ 12) The mechanism of adsorption of dixanthogen on pyrite is not clear. Similar phenom- ena were also observed for hexyl xanthate by M. such as xanthate. What is known.

Fuerstenau. With several insoluble oxides and silicates. at about pH 11. FIGURE 13 Zeta potential of pyrite as a function of pH in the absence and presence of ethyl xanthate in the presence of air many may be seen from Figure 13. Yap et al. 1965). thus producing an iron oleate compound at the interface. 1981). However. 2007 7:36 PM ADSORPTION OF SURFACTANTS 193 40 Xanthate Addition None 1 × 10–4 M C2 20 Zeta Potential.book Page 193 Tuesday. and Aplan 1975). Because it has been shown that oleate reacts with iron species and forms iron oleate compounds (Peck. specific adsorption of oleate on hematite can be explained by chemisorption of oleate ion on iron surface sites. even when the surface is highly negatively charged (Kulkarni and Somasundaran 1980. Kuhn. flotation takes place in the pH region in which hydrolysis of metal ions comprising the mineral occurs (Peterson et al. Research on chrysocolla with hydroxamate as collector revealed the presence of multi- layers of cupric hydroxamate by visual observation (Peterson et al.flotation0. which shows that the zeta potential of pyrite is the same in the absence and presence of xanthate. M. Ruby. This is the pH region of hydrolysis of Mn2+ so that dissolution of Mn4+ and subsequent reduction of Mn2+ must occur. such as hematite.C. Chemisorption would have resulted in the forma- tion of a new phase on the pyrite surface and a corresponding difference in zeta potential. Modest adsorption of Ca2+ occurs below pH 10. and Wadsworth 1966). mV 0 –20 –40 –60 0 2 4 6 8 10 12 14 pH Source: M. Palmer. January 2. Insoluble Oxides/Silicates. dissolution of the surface metal atoms is facilitated by hydroxyl ion at these pH values. Chrysocolla . Fuerstenau and Rice 1968. Because of the stability of the hydroxy complexes. the pH at which Ca2+ starts to hydrolyze to CaOH+ and Ca(OH)2(s). Under these conditions. whereas the response at about pH 9 is due to surface reaction between MnOH+ and oleate ion (M. The adsorption potential of hydroxy complexes is high. extensive adsorption takes place. adsorption phenomena in this system can only be explained by specific adsorption of the oleate anion on hematite. A flotation system illustrating these phenomena well is the pyrolusite–oleate system (Figure 16). 1965. The flotation response at about pH 4 is due to physical adsorption of oleate. Fuerstenau.C.C. A speciation diagram for cal- cium species is presented for comparison in Figure 15. Oleate species have been found to adsorb on relatively insoluble oxide minerals. Fuerstenau and Rice 1968). which is apparent in the adsorption of calcium species on quartz presented in Figure 14 (Clark and Cooke 1968). and Elgillani 1968.

January 2. FIGURE 14 Adsorption of calcium species on quartz as a function of pH from solutions 100 ppm in calcium 10–3 Ca2+ 10–4 Concentration. mol/cm × 10 2 20 10 Surface Precipitation 0 4 6 8 10 12 14 pH Source: Clark and Cooke 1968. M CaOH+ 10–5 Ca(OH)2(s) 10–6 10 11 12 13 14 pH FIGURE 15 Speciation diagram for 1 × 10–3 M Ca2+ .book Page 194 Tuesday.flotation0. 2007 7:36 PM 194 FLOTATION FUNDAMENTALS 40 Initial Ca2+ = 100 mg/kg 30 10 Adsorption.

January 2. 2007 7:36 PM ADSORPTION OF SURFACTANTS 195 100 80 Flotation Recovery.0 × 10–5 M. the region of hydrolysis of Cu2+ to CuOH+ and Cu(OH)2(s) (Figure 17). 49°C 80 5. Fuerstenau and Rice 1968. FIGURE 17 Flotation recovery of chrysocolla as a function of pH with various concentrations of octyl hydroxamate changed color from its characteristic blue to apple green. Adsorption isotherms of octyl hydroxamate on chrysocolla were established by Herrera- Urbina (1985) at various values of pH (Figure 18). % 60 40 20 0 4 5 6 7 8 9 10 11 pH Source: Peterson et al.0 × 10–5 M. FIGURE 16 Flotation recovery of pyrolusite as a function of pH with 1 × 10–4 M oleate 100 3.C. enhancing the dissolution of the chrysocolla. 1965. maximal . the color of cupric hydroxamate. 22°C Flotation Recovery.flotation0. Maximal flotation response occurs at about pH 6. Confirmation was made with infrared absorption analysis. The beneficial role of elevating temperature can also be noted. Of the pH values involved. 23°C 1. but to a lesser extent. 22°C 5.3 × 10–4 M. % 60 40 20 0 0 2 4 6 8 10 12 14 pH Source: M.book Page 195 Tuesday.0 × 10–4 M. Nagaraj and Somasundaran (1979) also observed favorable flotation of chrysocolla with a hydroxyoxime (benzophenone) at pH 5–6 and also at pH 10.

Young and Miller 2000). Rao and Forssberg 1991a. The change in slope indicates a change in mechanism of hydroxamate adsorption (i. Lu. Harper. The adsorption of oleate on such semisoluble minerals as calcite (Somasundaran 1969. but if the precipitated metal oleate is consid- ered. Vasudevan. then the isotherm exhibits a maximum in adsorption density. and Miller 1970).e. A good representation of chemisorption and surface reaction between relatively insolu- ble oxides and silicates. in many cases. If the isotherm is determined from the total uptake of oleate. Semisoluble Salts. surface reaction and even precipitation of oleate compounds in the bulk can occur. and Blackmeer 1987. apatite (Moudgil. Fuerstenau.0 11. 2000).C. the adsorption density increases monotoni- cally with the residual oleate concentration. 2000). and Miller 1998).9. and scheelite (Rao and Forssberg 1991b) has been investigated by various researchers using spectroscopic techniques and the traditional depletion from solution method. Oleate reaction with sparingly soluble salt minerals is more complex because in addition to true chemisorption. and chemically bonding reagents is given in Figure 19. dissolution) with hematitic ores increased flotation recovery significantly. one can predict a sharp . 2007 7:36 PM 196 FLOTATION FUNDAMENTALS 12 Chrysocolla –200 Mesh 2 × 10–3 M KNO3. Mielczarski et al. hence. corresponding to the flotation data in Figure 17. Depending on the experi- mental conditions and method used. mol/L × 10 Source: Herrera-Urbina 1985.flotation0.2 9. Drelich. In addition. These authors also noted that increasing the conditioning time (and. FIGURE 18 Isotherms for the adsorption of octyl hydroxamate on chrysocolla at ionic strength of 2 × 10–3 M KNO3 at several pH values adsorption is noted at pH 5. 2 g/L 10 Hydroxamate Adsorption Density. the concentration at which cupric hydroxamate is formed and adsorbed). Both the pH and the solid– liquid ratio have been found to determine the extent of oleate adsorption on these minerals.. fluorite (Rao and Forssberg 1991a.2 0 4 5 6 7 8 9 10 11 4 Equilibrium Hydroxamate Concentration. Rao and Forssberg 1991a. If the metal cation from the mineral lattice forms insoluble metal oleates. mol/g × 10 4 8 6 4 pH 5.9 2 7. A change in color was observed before and after contact with octyl hydroxamate. January 2. the shape of the adsorption isotherm even depends on the method of sampling when depletion of oleate from solution is analyzed (Mielczarski et al.book Page 196 Tuesday. the adsorption isotherms reported in the literature for the same mineral are significantly different. Multilayers of ferric hydroxamate were also observed on hematite (M.

These researchers determined an in situ near-infrared-based adsorption isotherm at pH 9. and found that it compared well with isotherms reported previously.W. calcium oleate deposits onto the calcite surface. 2007 7:36 PM ADSORPTION OF SURFACTANTS 197 Chemisorption Me2+ + Xm– Me2+ Xm– 2+ 2+ – + Me + HXm Me Xm + H 2+ – 2+ – Me + OH Me OH Adsorption with Surface Reaction 2+ Me + HXm (MeXm)+ + H+ 2+ – + Me + Xm (MeXm) Me2+ + OH– (MeOH)+ 2+ – + Me + HCO3 (MeHCO3) Surface Reaction (MeOH)+ – + Xm (MeXm)+ + OH– + + (MeOH) + HXm (MeXm) + H2 O + – (MeOH) + OH Me(OH)2 (MeOH)+ + 2HXm Me(Xm)2 + H+ + H2O Source: D. surface precipitation is assumed to be dominant with some bulk precipitation of calcium oleate. which are ion exchange (D. Young and Miller (2000) have reported their results on the adsorption of oleate on cal- cite. Flotation occurs only after precipitation of collector salt in some cases.flotation0.2 and 20°C. precipitation of calcium dioleate and its adsorption with oleate ions is postulated.book Page 197 Tuesday. FIGURE 19 Representation of chemisorption and surface reaction between relatively insoluble minerals and chemical bonding reagents increase of the adsorption density of the oleate under conditions where the metal oleate is more stable (insoluble) than the mineral. The nature of soluble salt flotation is considerably more complex than that of other groups of minerals because of the high ionic strengths of the solutions. Fuerstenau and Fuerstenau . In Region II. the adsorption density increases steadily as this concentration increases. Their isotherm for the adsorption of oleate on calcite shows two regions. At low residual sodium oleate concen- tration in the bulk. the isotherm rises steeply. At concentrations lower than 1 × 10–5 M. in which the oleate concentrations are below that necessary for calcium oleate pre- cipitation. Oleate adsorption on apatite was studied by Moudgil. adsorption is attributed to chemisorption. oleate adsorption is explained in terms of chemisorption. At about 3 × 10–5 M residual sodium oleate. however. adsorption is attributed to multilayer formation and precipitation of cal- cium dioleate. and Blackmeer (1987). January 2. Soluble Salts. In Region III. An adsorption isotherm with four distinct regions is presented in Figure 21. Various mechanisms have been advanced to explain soluble salt flotation. In Region I. which presents the isotherm for the adsorption of oleate ions at the calcite–aqueous solution interface at pH 9. which is on the order of 5 M. At higher oleate concentrations.6 (Somasundaran 1969). Vasudevan. Adsorption in Region IV is assumed to approach the limit of surface saturation. Fuerstenau and Pradip 1984. though it is not necessary in other systems. which sug- gests that at concentration higher than this value.W. This adsorption behavior is clearly shown in Fig- ure 20.

0 wt % 10. 2007 7:36 PM 198 FLOTATION FUNDAMENTALS 10–4 –5 Oleate Adsorbed. and Blackmeer 1987.0 wt % 101 Adsorption Density. January 2. Vasudevan. mol/L Source: Somasundaran 1969. FIGURE 20 Isotherm for the adsorption of oleate on calcite at pH 9. mol/g of calcite 10 10–6 –7 10 10–7 10–6 10–5 10–4 Residual Oleate Concentration.book Page 198 Tuesday. FIGURE 21 Isotherm for adsorption of oleate on apatite . μmol/g 100 10–1 10–2 I II III IV 10–3 10–7 10–6 10–5 10–4 10–3 3 Residual Oleate Concentration.6 102 5. kmol/m Source: Moudgil.flotation0.

however. mol/L Source: Matthe and Schneider 1977.book Page 199 Tuesday. January 2. FIGURE 22 Flotation recovery of sylvite with various amines 101 C12 C10 C18 100 C8 Fractional Surface Coverage 10–1 –2 10 Sylvite (KCl) RNH3Cl 10–3 10–4 –8 –7 –6 –5 –4 –3 –2 –1 10 10 10 10 10 10 10 10 Alkylammonium Chloride Concentration. Adsorption isotherms of various amines on sylvite were established by Schubert (1971) and by Matthe and Schneider (1977. surface charge–ion pair model (Roman. flotation occurs prior to precipita- tion of octyl amine chloride. Fuerstenau. but relatively high concentrations are necessary.flotation0. As shown in Figure 22. FIGURE 23 Adsorption isotherms of alkly ammonium chlorides on potassium chloride in saturated brine . This is also true for tetradecyl amine. mol/L Source: Roman. and Seidel 1968. and a water breaker/former model (Hancer and Miller 2000). a crystallographic properties model (Bachmann 1951). % 60 Solubility Limit Solubility Limit 40 20 0 –6 –5 –4 –3 –2 10 10 10 10 10 Amine Addition. collector and surface hydration model (Rogers and Schulman 1957). insoluble reaction product between surface ions and collector (Halbich 1933). Figure 23). Fuerstenau. and Seidel 1968). In the case of octyl amine. 2007 7:36 PM ADSORPTION OF SURFACTANTS 199 1956). Comparison of the isotherm for dodecyl ammonium 100 80 Dodecyl Tetradecyl Flotation Recovery. flota- tion occurs only after precipitation of dodecyl ammonium chloride occurs. A method involving surface reaction is the dodecyl amine–sylvite system.

For example. micellization . The interactions in mineral–surfactant–solution systems include dissociation. The complexity of these systems is further demonstrated by sylvite flotation occurring with alkyl sulfonates prior to precipitation of collector salts.flotation0. and the desolvation free-energy change is nec- essarily positive. water chemistry also plays an overwhelming role in the adsorption process by affecting the various interactions among mineral. the mineral- solution equilibria and. flotation occurs only after precipitation of the sodium carboxylate in solu- tion).e. thus. The fatty acid–halite system is another that exhibits sur- face reaction (i. as weakly acidic fatty acids will undergo associative interactions that can influence their adsorption and flotation properties. These interactions include the surfactant-solution equilibria. E F F E C T S O F WAT E R C H E M I S T R Y O N S U R FA C TA N T – M I N E R A L I N T E R AC T I O N S In addition to mineral-surfactant interactions. including those introduced due to dissolution from all the minerals present in the ore and those from the water source. micellization and precipitation of the surfactant. and the interactions between dissolved mineral species with surfactant in the bulk in various forms. are the major ele- ments that affect the water chemistry. oleic acid undergoes dissociation to form ions (Ol–) at high pH values and neutral molecules (HOl) at low pH values. Water Chemistry of Flotation Reagents Long-chain fatty acids. phenolic. complexation and precipitation of the dis- solved species.book Page 200 Tuesday. resulting in greater adsorption of amine on the sylvite. the interactions between the surfactants and the mineral particles.. In the intermediate region. Desolvation Energies When a hydrated surfactant head group leaves the bulk water environment and inserts itself into the interfacial region of the mineral–water system. As the surfactant concentration is increased. carboxylic and amine groups. Hydrogen Bonding Hydrogen bonding between surfactant species and the particle surface species is responsible for adsorption of a number of reagents. The dissolved species. January 2. the ionic and the neutral molecular species can associate to form dimer complexes [(Ol)2H]–. there must be a partial desolvation of the secondary salvation shell around the surfactant head group ( James and Healy 1972). the hydrogen bond formed between the collector functional group and a mineral surface moiety is stronger than the hydrogen bond formed by that moiety and interfacial or bulk water molecules. particularly those containing hydroxyl. Zhang et al. Flotation processes using fatty acids are greatly affected by solution conditions such as pH. are among the commonly-used flotation reagents in nonsulfide flotation. surfactant and solution. dissolution of solids in response to solubil- ity product equilibria followed by hydrolysis. an unfavorable process. In relation to claims of hydrogen bonding. adsorption of nonionic surfactant ethoxylated alcohols and sugar-based alkyl glucosides has been proposed to involve hydrogen bonding (Doren. and Goldfarb 1975. 2007 7:36 PM 200 FLOTATION FUNDAMENTALS chloride with the flotation data reveals a change in slope of the isotherm at about the con- centration at which precipitation of dodecylammonium chloride occurs. 2002). For example. such as oleic acid. Desolvation is. consequently. Vargas.

In addition.95 (EQ 14) 2Ol – = ( Ol ) 22– pK d = – 2. which is a sensitive function of pH (Ananthapadmanabhan and Somasundaran 1988). surfactant spe- cies can associate to form other aggregates such as the dimer ion (Ol22–) in pre-micellar solu- tions. Also.6 (EQ 13) RH ( aq ) = R – + H + pK a = 4.0 Ksol = 2. The pH of precipitation of oleic acid calculated as a function of total oleate is shown in Figure 24. R represents oleate ion. 2007 7:36 PM ADSORPTION OF SURFACTANTS 201 –4.flotation0. . The solution equilibria of oleic acid (HOl) are expressed as below.95 (EQ 16) The species distribution of oleic acid as a function of pH based on the above equilibria at a given concentration is shown in Figure 25.6.book Page 201 Tuesday. 2. as shown in Figure 24. Ananthapadmanabhan 1980). FIGURE 24 pH of oleic acid precipitation or precipitation of the surfactant can also occur in the solution.0 –9.51 × 10–8 –8.0 –7.3 (EQ 15) R – + RH = R 2 H – pK = – 4.0 –5. HOl l = H + + Ol – pK sp = 7.0 Log (Total Oleate Activity) –6. The activities of oleic monomer and dimer remain almost constant above the pre- cipitation pH and decrease sharply below it. January 2. The pH of the precipitation of oleic acid at the given concentration is 7. oleic acid has very limited solubility.0 0 2 4 6 8 10 12 pH Source: Ananthapadmanabhan 1980. 1.

the effects of concentration. the surface of apatite can be converted to calcite and vice versa through surface reactions or bulk precipitation of the more stable phase. complexation. The activity of the acid-soap (Ol)2H– exhibits a maximum in the neutral pH range. the . In the case of carbonaceous phosphate ores containing such sparingly soluble minerals as apatite and calcite. they undergo dissolution. In fact. depending on the solution conditions. In a system containing soluble or sparingly soluble minerals in which the extent of dissolu- tion is markedly higher than that in most oxide–silicate systems. Somasundaran. depending on the pH of the solution. 2007 7:36 PM 202 FLOTATION FUNDAMENTALS –4 – –5 R K-Oleate 3 × 10 kmol/m3 R22– –6 Log (Activity of the Species) R2H– –8 –10 RH 3 4 6 8 10 12 13 pH Source: Ananthapadmanabhan 1980. to understand the role of adsorption of collectors on minerals. 4. and Ananthapadmanabhan 1985a. apatite can be converted to calcite if the total carbonate in solution exceeds a certain value. b): Ca 10 ( PO 4 ) 6 ( OH ) 2 ( s ) + 10CO 32– = 10CaCO 3 ( s ) + 6PO 42– + 2OH – (EQ 17) It can be seen from this equation that. FIGURE 25 Oleate species distribution as a function of pH (total oleate concentration = 3 × 10–5 M) 3. the effect of dissolved min- eral species can be drastic. The dissolved mineral species can undergo further reactions. adsorption. Water Chemistry of Minerals When mineral particles come in contact with water. The stoichiometry of the equilibrium governing the conversion of apatite to calcite can be written as follows (Amankonah. Above pH 8 and 10–4 mol dm–3 total oleate. ionic strength.flotation0.book Page 202 Tuesday. Clearly. and precipitation. the extent of which is dependent on solubility product of the mineral and the solution composition. such as hydrolysis. The dominant equilibria at pH 8 and 10–4 mol dm–3 is HOl in equilibrium with Ol–. and activities of the various possible collector species on the adsorption process must be considered. January 2. pH. a small region of dimeric (solid) exists before micellization or precipitation occurs. The complex equilibria involving all such reactions can be expected to determine the interfacial properties of the minerals and their flotation behavior.

Amankonah. Surface conversion due to the reaction of the dissolved species with the mineral surface has been proven experimentally. FIGURE 26 Illustration of the effect of supernatants on the zeta potential and isoelectric point of calcite and apatite amount of dissolved carbonate from atmospheric CO2 does exceed that required to convert apatite to calcite under high-pH conditions. respectively (Somasundaran.book Page 203 Tuesday. electrokinetic data obtained for the calcite–apatite system in water and in the supernatant of each other are shown in Figure 26. mV 0 –20 –40 5 6 7 8 9 10 11 12 13 pH Source: Somasundaran. leading to loss of selectivity in the adsorption of reagents. 2007 7:36 PM ADSORPTION OF SURFACTANTS 203 60 2 × 10–3 kmol/m3 KNO3 Calcite in Water Apatite in Water Apatite in Calcite Supernatant 40 Calcite in Apatite Supernatant 20 Zeta Potential. Amankonah. sug- gesting surface conversion of apatite to calcite and calcite to apatite. and Ananthapadmanabhan 1985. In addition to surfactant adsorption at the solid–liquid interface. and Ananthapadmanabhan 1985). It is clear that dissolution equilibria of dissolved mineral species can alter the mineral surface properties to such an extent that surface properties of various minerals become indis- tinguishable. All these interactions can affect the surfactant adsorption and the subsequent flotation of the mineral phase.flotation0. its zeta potential shifts to that of calcite and vice versa. Role of Water Chemistry in Adsorption of Surfactant on Minerals Chemical equilibria in aqueous solutions containing both the minerals and the surfactants can be expected to be much more complex than those in either of the individual systems dis- cussed previously. When apatite is con- tacted with calcite supernatant. interac- tions between dissolved mineral species with various surfactant species can be expected. . January 2.

00E-03 1. hence. Plant Water 1. Both supernatants of calcite and apatite are found to depress calcite flotation by oleic acid in the tested pH range. In fact. it is the kinetics of these processes that may dominate.E-06 1. Interestingly. equilibrium adsorption/desorption may not be reached and. Similar results have also been obtained for apatite flotation.flotation0.E-04 1. under plant conditions.00E-01 Conditioning Time. The effect of dissolved species of calcite and apatite on fatty acid flota- tion of both minerals has. whereas under plant conditions the solids loading was 72 wt %. Adsorp- tion is markedly higher under laboratory conditions than under plant conditions.00E-05 1.book Page 204 Tuesday. with apatite supernatant exhib- iting a greater depressing effect. Adsorption Under Plant Conditions Flotation is a dynamic process.E-09 1. Kinetics of surfactant adsorption on solids and flotation can be expected to be affected by the total solution chemistry. On the other hand. It is evi- dent. then. min FIGURE 27 Adsorption isotherms of oleic acid adsorption on francolite in distilled water and plant water under laboratory and plant conditions . that the adsorption of surfactant on a mineral is a complicated process involving 1. in actual plant operations. Distilled Water Plant Condition. mol/m 2 1. The effect of water chemistry on oleic acid adsorption on francolite during anionic conditioning has been studied under plant conditions along with laboratory conditions for reference. been studied using mineral supernatant solutions containing various dissolved species. Distilled Water Plant Condition. in fact. (Figure 27).E-08 Laboratory Condition.00E-04 1. The supernatants of calcite and apatite depress the apatite flotation under all tested pH con- ditions (Ananthapadmanabhan and Somasundaran 1984).E-05 Oleic Acid Adsorption Density.00E-06 1. 2007 7:36 PM 204 FLOTATION FUNDAMENTALS From this discussion on apatite–calcite conversion. the adsorption is similar in distilled water and plant water. it is clear that a flotation separation scheme designed on the basis of the surface properties of a single mineral is not likely to per- form satisfactorily.E-07 1. These observations clearly show the crucial role of water chemistry in the flotation of mineral–surfactant systems. The laboratory process used low-solids loading (10 wt %).00E-02 1. January 2. the effect of dissolved species is reduced under plant conditions.

book Page 205 Tuesday. I3/I1. The data are shown in Figure 28. This abrupt change occurs in a region that is well below the CMC and corresponds with the transition in the adsorption isotherm from Region I to II (i. The fluorescence measurements are gener- ally carried out by a steady-state fluorescence spectrofluorometer. the I3/I1 value coincides with the maximum I3/I1 value for SDS solutions (Figure 28a). Fourier transform infrared. adsorption. the ratio of relative intensities of the third peak to the first peak. The structure of these states plays a critical role in determining the interfacial processes. mineral dissolution. such as surfactant self-association. bulk precipitation. Various spectroscopic and imaging techniques such as fluorescence. small-angle neutron scattering. hence. and information on such structures. Through the fluorescence spectroscopic technique. The lifetime of fluores- cence is determined by a time-resolved fluorescence lifetime instrument. In steady-state fluorescence spectroscopy. particularly at microscopic and molecular levels. electron spin resonance (ESR). I3/I1 values for pyrene were determined for alumina–SDS–water systems for various regions of the adsorption isotherm. January 2. indicating the . the hemimicelle concentrations). These techniques are reviewed here. on a pyrene emission spectrum shows the greatest solvent dependency. The nature of this phenomenon depends significantly on the environment of the light-absorbing species and has been exploited for a long time in support of exploring the solution behavior of surfactants. considerable work has been done to elucidate the physicochemica1 and hydrodynamic mechanisms that govern the formation of interfacial states. 2007 7:36 PM ADSORPTION OF SURFACTANTS 205 interactions. and excited-state resonance Raman have been applied in mineral–surfactant systems to obtain information on microstructure of adsorbed layers on a molecular level. neutron reflection. The surfactant aggregation process on the surface of a solid as described and shown in Figure 3 has been a generally accepted model for surfactant adsorption on oppositely charged solids. the exact nature of these aggregates in the adsorbed layers has been revealed. Other advanced techniques that are being explored to probe the nanostructures in solution and on solids include analytical ultracentrifugation. and atomic force microscopy (AFM). The technique has been adapted to investigate the structure of adsorbed layers at the mineral surfaces to obtain information on the micropo- larity.e. S P E C T R O G R A P H I C A N D I M A G I N G S T U D I E S O F S U R FA C TA N T ADSORPTION Because of the important role of adsorbed surfactant layers in adsorption and subsequent flotation processes. These interactions are further complicated by the kinetic effects of the various reactions. and the aggregation number of the sur- factant species adsorbed at the interface. FLUORESCENCE SPECTROSCOPY Fluorescence emission is the radiative emission of light by an excited molecule returning to its ground state energy level. In the plateau region.. which is marked by an abrupt change in the local polarity of the probe from an aqueous environment to a relatively nonpolar micelle-type environment. This ratio increases as the polarity decreases and. the microviscosity of the probe environment. can be helpful for control- ling flotation. The dependence of fluorescence intensity and lifetime on the physicochemical environment of the fluorescing molecules has been studied extensively.flotation0. and surface precipitation. can be used to estimate the solvent polarity of an unknown microenvironment in which the pyrene probe is situ- ated.

I1 = 374 nm) completion of aggregation on the surface. A kinetic analysis based on this relation was carried out from the decay profiles of pyrene in the adsorbed layer of the alumina–SDS adsorption system. FIGURE 28 I3/I1 fluorescence parameter of pyrene in (a) SDS solutions in 0.5. Somasundaran. The lifetime of the probe under quenching conditions would be determined by the concentrations of the quencher and the probe as well as the rate at which they diffuse and encounter each other. Thus.1 M NaCl) 0.5 1. mol/L Source: Chandar.book Page 206 Tuesday.5 0. The SDS aggregation numbers obtained are marked on the adsorption isotherm in Figure 29.0 SDS Micelle (1.0 0 10–5 10–4 10–3 10–2 Dodecyl Sulfate Concentration.1 M NaCl) I3/I1 Water (0. mol/L B 1.0 CMC I3/I1 0.300). fluorescence studies provide a means to measure the micropolarity of the adsorbed layers. 2007 7:36 PM 206 FLOTATION FUNDAMENTALS A 1. its decay is enhanced in the presence of molecules that act as quenchers.0 0 10–5 10–4 10–3 10–2 Residual Dodecyl Sulfate. when a fluorescence probe is excited by a short nanosecond pulse of light. and Turro 1987. The aggregates in Region II appear to be of relatively uniform size (120 to 1. Kinetic analysis of the fluorescence decay profiles can therefore provide information on the local concentration of the reactants and hence the size of the local aggregates.5 0. January 2. These results are of special significance with respect to the evolution of the structure of the adsorbed layer and their interfacial .5 1. pH 6. (b) SDS– alumina slurries in 0. But in Region III there is a marked growth in the aggregate size (160 to 360).flotation0. In the fluorescence lifetime method.1 M NaCl.1 M NaCl. (I3 = 383 nm.

Somasundaran. mV 20 I 0 III –20 CMC –40 IV –60 –80 1. The transition between Regions II and III has a surface excess of about 0. mol/L Source: Chandar.flotatio