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Edited by

Maurice C. Fuerstenau
Graeme Jameson
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.

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

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Electronic edition published 2009.

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ISBN-13: 978-0-87335-280-2

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A Century of Developments in the Chemistry of Flotation
Processing 3
History of Flotation Technology 65


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


Flotation ReagentsA 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


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


Plant Practice: Sulfide Minerals and Precious Metals 781
Plant Practice: Nonsulfide Minerals 845


2007 by the Society for Mining, Metallurgy, and Exploration.
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2007 by the Society for Mining, Metallurgy, and Exploration.

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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

2007 by the Society for Mining, Metallurgy, and Exploration.
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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
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

2007 by the Society for Mining, Metallurgy, and Exploration.
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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 ChemistryYKI
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

2007 by the Society for Mining, Metallurgy, and Exploration.
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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

2007 by the Society for Mining, Metallurgy, and Exploration.
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The year 2005 marked the 100th anniversary of Sulman and Picards 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
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
Two international initiatives were launcheda symposium and this commemorative
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.

2007 by the Society for Mining, Metallurgy, and Exploration.
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2007 by the Society for Mining, Metallurgy, and Exploration.

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Historical Aspects of Flotation

2007 by the Society for Mining, Metallurgy, and Exploration.
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2007 by the Society for Mining, Metallurgy, and Exploration.

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A Century of Developments in the

Chemistry of Flotation Processing
Douglas W. Fuerstenau

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.

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
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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.

2007 by the Society for Mining, Metallurgy, and Exploration.

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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

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 geologists problem is correspondingly modified. The metallurgist has
been the geologists best friend, and the geologist in turn has been able to help con-
vert the metallurgists ideas into the concrete form of an increased ore supply.
Many authors of papers in Rickards 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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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.

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
Beans (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 Coppers 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: 19251926 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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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
Oils 8,818 2,665 115,218
Chemicals 1,875 1,896 108,883
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 19251926, 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 Companys 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 0.010.02 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.

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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, 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, Fe oxide
1985 Alkoxycarbonyl adducts Collectors/modifiers for sulfides and nonsulfides

Many early efforts at understanding flotation were directed toward explaining differential
flotation in terms of the relative occlusion of gases, which would be driven out to nucleate
bubbles, thereby giving rise to selective flotation. In 1916, bubbles were considered to be at
the heart of flotation science, 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,
the acid, or the apparatus, but in the bubbles. The man who understands the physics of a
soap bubble has mastered the chief mystery of flotation. As important a component as they
are in the process, bubbles usually play an inert role in flotation and merely provide a means
for levitating the desired mineral particles into a froth layer. Although industrial operators
and reagent manufacturers devoted effort toward finding cheaper chemicals that might act
as frothing agents and might alter froth characteristics, through the years bubbles have never
received the attention from flotation researchers speculated on by Rickard. However, in
1934 Gaudin commented:
Developments in flotation have been so rapid that one of the essential factors at
playnamely, the chemical effects of dissolved gaseshas received scant atten-
tion. Recent theories have shown that gases are of extreme importance in many
instances. It is not unlikely that control of flotation can be exercised through con-
trol of the gases.

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In a 1915 paper, Ralston suggested that flotation might result from the electrical attrac-
tion between negatively charged air bubbles and positively charged mineral particles, and
this postulate was actively debated for some years before eventually being discarded (Ralston
1916). However, today it is known that potential differences between bubbles and particles
enter into the kinetics of bubble-particle attachment.
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. About these
phenomena, Ralston wrote in 1915 of adsorption changing contact angles and the proper-
ties of interfacial films:
A glance at Clerk Maxwells famous paper on capillarity upon which Reinders
work is based, will suggest immediately the explanation of a contact angle, and that
it is the result of a certain equilibrium of interfacial tensions of air, water, and
solid. There can be no doubt that there is a close parallelism between the angle of
hysteresis of the contact angle and the ability of a mineral to float. To go into this
a little farther, we ought to consider the properties of the surface layers of the sub-
stances involved. 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, and there always is a definite equilibrium between
the two. The properties of these interfacial films have been found to be greatly
modified by small amounts of dissolved substances. The importance of the study of
interfacial films becomes obvious.
The first direct application of thermodynamics to systems similar to flotation was that
of von Reinders (1913). Based on Maxwells capillarity equations, von Reinders deduced
how fine solid particles would be distributed between oil and water phases. For example,
using to represent the interfacial tensions at the oilwater (ow), solidwater (sw), and
solidoil (so) interfaces, von Reinders showed that the solid will disperse in the aqueous
phase if so > ow + sw. Analogous relations give conditions under which the solid will dis-
perse in the oil phase or concentrate at the oilwater interface. 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. In 1917, Tag-
gart and Beach fairly lucidly applied these concepts directly to flotation. Several decades
would elapse before thermodynamics would become a fairly widely used tool for the analysis
of flotation phenomena.
In 1917, Anderson suggested that adsorption might play a dominant role in flotation.
Anderson discussed the Gibbs adsorption equation in relation to frother adsorption at the
air-water interface and, interestingly, stated: An electric charge on an adsorbed substance
probably would considerably influence the amount adsorbed. In 1920, Langmuir showed
that oleic acid created large contact angles on cleaved calcite and galena but only small
angles on clean glass and cleaved mica. Oleic acid was irreversibly adsorbed on calcite and
galena but not on glass and mica. He suggested further research with other kinds of reagents
on clean mineral surfaces. In 1928, 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. He wrote that powdered sulfide minerals abstracted 90% of the thiocarbanilid in a
solution and captive-bubble experiments showed the sulfide to be hydrophobic. The

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adsorbed thiocarbanilid could be leached off with ethyl alcohol. 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. With carbanilid, there was no removal from
solution. These experiments led to Taggarts formulation of the definition of the molecular
structure needed for a soluble flotation collector, namely, 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 mineralwater interface.

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, Taylor, and Knoll in 1930 for the
abstraction of potassium ethyl xanthate (KEX) by ground galena as a function of reagent
concentration in solution. 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, for radioactively marking adsorbates, for spectrophotometrically
measuring reagent concentrations in solution, and for quantitatively analyzing infrared
absorption spectra. Because nearly all of the early flotation operations involved sulfide ores,
the behavior of sulfide minerals received nearly all of the initial research attention.
Although such early researchers as Fahrenwald, Sulman, and Taggart carried out a num-
ber of experiments to elucidate flotation phenomena, the founder of the scientific basis of
flotation was A.M. Gaudin. The first systematic research that opened the way toward under-
standing the chemistry of the flotation process was the extensive, dedicated investigation
initiated in 1926 at the University of Utah under Gaudin, 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). In
1928, 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. Therefore, to obtain consistent results in flotation
research, pure minerals having a definite size should be used either by themselves or
as artificial mixtures. These minerals should have an especially clean surface,
cleaned in standard fashion, and the test should be run in a standard machine
cleaned in standard fashion, for a standard length of time after a standard preagita-
tion period at a definite temperature. All reagents should preferably be added in
solution to eliminate the necessity for conditioning. Distilled water should be used
With these guiding principles, this early work by Gaudin and his colleagues was the
beginning of the modern approach to research in flotation chemistry. In the authors opin-
ion, Gaudin was indeed the father of fundamental flotation research as it is known today.
Figure 1 illustrates the quality of flotation experiments conducted with carefully cleaned
mineral samples and high-purity reagents (Gaudin et al. 1928). In Gaudin and colleagues
original paper, the flotation recovery of 100 600 mesh galena was presented as a linear
function of the fatty acid addition in pounds per ton. By recalculating the published results

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Galena C12 C11 C10 C9 C8 C7

100 0.2 kg/t Terpineol


Flotation Recovery, %

C6 Caproic Acid
C7 Enanthic Acid
C8 Caprylic Acid
20 C9 Pelargonic Acid
C10 Capric Acid
C11 Undecanoic Acid
C12 Lauric Acid
0.01 0.1 1.0 10.0
Fatty Acid Addition, mol/t
Adapted from Gaudin et al. 1928.

FIGURE 1 Flotation of 100 600 mesh galena with fatty acids of different alkyl chain lengths
ranging from 7 to 12 carbon atoms, 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, their results show the very systematic effect of the number of carbon
atoms in the alkyl chain expected by the Traube rule. Because the carbon atom in the car-
boxyl head group is not part of the alkyl chain, lauric acid (mol wt 200) is given as an 11-carbon
reagent in Figure 1. This systematic chain-length effect indeed substantiates the validity and
care taken in their work. Interestingly, Gaudin never continued using mini-scale flotation
cells in his research after he moved from the University of Utah to the Montana School of
Flotation processing technology did not come into being as a result of an intensive fun-
damental research effort, but, in a manner similar to the development of so much of the
other technology used in the processing of raw materials, it was developed over the years
through much empirical and intuitive work on complex ores. Fundamental understanding
of flotation resulted from careful experimentation with well-controlled systems, later fol-
lowed by a firm grounding in physicochemical principles, including thermodynamics, sur-
face and colloid chemistry, and electrochemistry. Major headway in understanding the
flotation chemistry of sulfide mineral flotation started shortly before 1930, and that of non-
metallic mineral flotation shortly before 1950. Prior to about 1950, most of the fundamen-
tal investigations were directed toward the flotation chemistry of sulfide mineral
separations. To achieve the desired separations from complex ores, the early research (1925
1935) was mainly centered on interactions between mineral surfaces and sulfhydryl flota-
tion reagents. The leading researchers, chronologically, in that era were Taggart and Gaudin
in the United States, and Wark in Australia. The key issues were the mechanism of interac-
tion between the reagent and the mineral surface (by Taggart and by Gaudin), identification
of species responsible for flotation (by Gaudin), and the assessment of chemical conditions
for floatability (by Wark ). About mid-century most of the research shifted to oxides, particularly
quartz, corundum, hematite, rutile, and silicates. In the last quarter of the flotation century,
much attention was directed toward the flotation chemistry of the sparingly-soluble salt

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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.F. Gates and L.K. Jacobsen
A.M. Gaudin
5-gram scale M.C. Fuerstenau
Modified Hallimond tube flotation A.F. Hallimond
E.W. Ewers
D.W. Fuerstenau
H.S. Choi and I. Iwasaki
Captive-bubble contact angle determination A.F. Taggart, T.C. Taylor, and C.R. Ince
I.W. Wark and A.B. Cox
R.H. Ottewill
J.S. Laskowski
S. Chander and D.W. Fuerstenau
Adsorption density/isotherm A.M. Gaudin
P.L. deBruyn, I. Iwasaki, and G.A. Parks
P. Somasundaran and D.W. Fuerstenau
J.M. Cases
Electrokinetics (zeta potentials) S.C. Sun and A.M. Gaudin
A.S. Buchanan and D.J. OConnor
D.W. Fuerstenau
Infrared spectroscopy M.E. Wadsworth and A.S. Peck
Ex situ J. Leja and G.W. Poling
J.D. Miller
In situ J.A. Mielczarski
J.D. Miller
Electrochemistry I.W. Wark and A.B. Cox
Rest potential J.C. Nixon and S.G. Salamy
Polarization: voltammetry J.T. Woodcock and M.H. Jones
Impedance spectroscopy R. Woods
W.J. Trahar
S. Chander and D.W. Fuerstenau
P.A. Richardson

minerals, particularly apatite, calcite, dolomite, and bastnaesite. Problems of energy supply
gave rise to research on coal flotation and coal desulfurization. With the advent of newer
electrochemical techniques, major effort resumed in the last quarter of the flotation century
to extensive investigation of sulfide mineral flotation phenomena.
Although numerous experimental methods have been applied to investigating flotation
phenomena, several techniques have been widely used and have been responsible for the
greatest progress. These are summarized in Table 5, together with the names of several of
those who developed or applied these techniques to the study of chemical phenomena
involved in flotation. Numerous other techniques have been devised and utilized through
the years to study flotation phenomena, 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. Examples of some of these techniques (and some of researchers
who used them) include vacuum flotation (R. Schuhmann and B. Prakash), bubble-pickup
(S.R.B. Cooke), induction time measurement (I. Sven-Nilsen; V.A. Glembotsky; R.H.
Yoon), film flotation (M.C. Williams and D.W. Fuerstenau), microcalorimetry (O. Mellgren),
and radiography (I.N. Plaksin). There has been worldwide interest in surfactant adsorption
behavior at solidwater interfaces in recent years, resulting in many new tools having been

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used to probe the detailed nature of adsorbed surfactant and polymer films. For example, P.
Somasundaran and his graduate students at Columbia University have extensively used such
newer molecular-level-information-yielding techniques as absorption, emission, magnetic
resonance, and scattering spectroscopic techniques (fluorescence, electron spin resonance,
excited state resonance, Raman, etc.) along with adsorption, flotation, flocculation, and
electrokinetic studies to gather information about the microscopic properties of the
adsorbed surfactant and polymer films. X-ray photoelectron spectroscopy, or XPS (A.N.
Buckley and R. Woods), has been used to identify chemical species at mineral surfaces. Sec-
ondary ion mass spectrometry, or SIMS (D.R. Nagaraj), has recently been utilized to clearly
show the nature of complexes adsorbed at mineral surfaces. Atomic force microscopy has
been applied to the study of the nature of adsorbed surfactant films (R.H. Yoon; T.W.
Healy; J.D. Miller).
Starting in the 1950s, two of the relatively simple techniques listed in Table 5 were
widely adapted to the study of flotation chemistry effects. When it became understood that
any ion that strongly adsorbs at a mineralwater interface is reflected in its effect on the zeta
potential, the use of zeta potential measurements in flotation surface chemistry spread rap-
idly, and particularly so because of the simplicity of electrophoresis techniques. 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); this permitted direct correlation with the solution chemistry of the sys-
tem. Almost all of the experimental investigations on flotation chemistry carried out during
the first half-century involved the use of a single experimental technique, such as flotation
testing, contact angle measurement, identification of surface species, determination of
adsorption isotherms, and so forth. However, 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, and this led to a more
complete understanding of the surface chemical processes involved. An example of such a
correlation is given in Figure 2, which presents the zeta potential, adsorption density, contact
angle, and flotation response of quartz with dodecylammonium acetate (DAA) as collector
(D.W. Fuerstenau, Healy, and Somasundaran 1964). Here, two-phase mineralwater inter-
facial phenomena (adsorption density and zeta potential) correlate well with three-phase
behavior (contact angle and flotation response). The first such correlation was published in
1957 for the DAAquartz system at constant collector concentration with pH as the vari-
able; 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.)
Major advances, particularly starting in the 1950s, were achieved through better under-
standing and application of the fundamental principles of surface and colloid chemistry,
particularly electrical double-layer phenomena, to flotation systems. In part, this was
strongly influenced by Professor J.Th.G. Overbeeks year at the Massachusetts Institute of
Technology (MIT) with the mineral engineering group of Gaudin, and disseminated world-
wide by the generations of students that followed. Detailed analysis of the thermodynamic
stability of minerals and reagents, speciation of complexes in aqueous solution, and solubil-
ity phenomena have also helped expand the understanding of different types of flotation
systems. All of this, combined with application of the many new techniques for probing
mineralwater interfaces at the molecular level, led to much of the research in the second

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Quartz Hemimicelle Concentration
pH 67 +80

4 0.80 Contact Angle 80

Adsorption Density
Zeta Potential
Flotation +40
Adsorption Density, mol/m 2

Flotation Recovery, %

Zeta Potential, mV
3 0.85 60

2 0.90 40


1 0.95 20


106 105 104 103
DAA Concentration, mol/t
Adapted from D.W. Fuerstenau, Healy, and Somasundaran 1964.

FIGURE 2 Correlation of adsorption density, contact angles, and zeta potentials with the
flotation of quartz at pH 67 as a function of DAA concentration

half of the flotation century being devoted to elucidating the detailed principles of mineral
reagent interactions in flotation. In the sections that follow, some of the major advances in
understanding the flotation chemistry of various mineral systems will be briefly reviewed.

Because flotation was first applied to the recovery of sulfide minerals from ores, all of the
early research was conducted on sulfide minerals, particularly galena, sphalerite, chalcocite,
chalcopyrite, and pyrite. 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. 1928). Their initial research was concerned with the behavior of galena.
Gaudin (1932) stated that
pure, unoxidized galena floats readily without the addition of a collecting agent,
a frother alone being required. This can be ascertained by grinding pure galena par-
ticles in water under anaerobic conditions, and floating immediately. In practice
galena particles are more or less oxidized during grinding and classification, requiring
varying amounts of collecting agents.
For fatty acids as collector, Figure 1 illustrates the quality of their results. Most of their
work was conducted with xanthates and other sulfhydryl reagents as the collector, and Fig-
ure 3 presents the results of Gaudin et al. (1928) for the flotation of galena with xanthates of
different chain length, but again with the xanthate additions being recalculated in terms of
moles per metric ton, rather than pounds per ton, and plotted semilogarithmically. The
amount of xanthate required for complete flotation with xanthates of two or three methyl-
ene groups is extremely low, merely about 0.1 mol/t of mineral, 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. Although no specific numbers are available, nearly all of the

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Flotation Recovery, %

40 Methyl

0.05 kg/t Terpineol

0.5 kg/t Sodium Carbonate
0.01 0.1 1.0 10.0
Potassium Alkyl Xanthate Addition, mol/t
Adapted from Gaudin et al. 1928.

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. In the case of fatty acid flotation,
there probably was considerable residual carboxylate left in solution.
Given that the surface of galena readily oxidizes, the oxidation products must enter into
the adsorption process. In 1934, Taylor and Knoll conducted a careful set of experiments to
quantitatively determine the exchange process involved in the uptake of ethyl xanthate by
galena, using an iodometric titration technique to determine the xanthate concentration in
solution. Taking one set of measurements as an illustration of their findings, with all concen-
trations being expressed as equivalent to 25 mg KEX per liter of solution, the original con-
centration of xanthate in solution was 200.0 mg/L, the amount of xanthate ion abstracted
was 58.3 mg, and the stoichiometric equivalent of reduced sulfur-oxygen ions emitted was
13.8 mg, 16.1 mg sulfate ions emitted, and 27.2 mg carbonate ionsor a total stoichiomet-
ric equivalent of 57.1 mg. Clearly, xanthate uptake by galena was exactly balanced by an
exchange with oxidation product ions at the surface.
In 1934, 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. 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. The results tend toward the maximum contact angle of 60, after increasing
sharply to about 50 at concentrations below 20 or so micromoles per liter. The 1928 results
from Gaudin et al. were recalculated in terms of micromoles per kilogram of 100 600 mesh
galena and are also plotted in Figure 4. This plot shows that about 400 mol/kg of galena is
required to achieve 90% recovery. Assuming that most of the added xanthate was adsorbed,
in 1957 Gaudin estimated that roughly monolayer adsorption was achieved at this ethyl
xanthate addition. However, in that same year, Bogdanov et al. (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,
together with their effect on flotation response. 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. These experiments show the strong affinity of a sulfhydryl collector for the surface

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Contact Angle: mol/L Solution

100 60


Contact Angle, degrees

Flotation Recovery, %



Contact Angle

0 0
0 20 40 60 80 100
Collector Addition, [ mol/kg galena][0.1]
Adsorption Density, % 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), 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.
1957), and the flotation of galena as a function ethyl xanthate addition expressed in terms of
mol/kg (data from Gaudin et al. 1928)


Flotation Recovery, %



0.015 kg/t KAX
0.10 kg/t Terpineol

0 2 4 6 8 10 12 14
Adapted from Gaudin 1929.

FIGURE 5 Effect of pH on the flotation of 100 600 mesh chalcocite and pyrite with KAX as

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
Regulation of pH has been the most important method for regulating flotation chemis-
try. In 1929, Gaudin first published the results of his measurements of the flotation of a

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variety of minerals as a function of pH. Figure 5 presents the flotation recovery of chalcocite
and pyrite as a function of pH with 0.015 kg/t of potassium amyl xanthate (KAX) and
0.10 kg/t terpineol as frother. 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. This was definitive work showing the
depressant role of pH in the flotation of sulfide minerals. Gaudin on several occasions com-
mented that not patenting the use of pH control for selective flotation was one of his oversights.
In the early 1930s at the University of Melbourne, I.W. Wark (personal communica-
tion) initiated an important program to understand the flotation chemistry of sulfide min-
erals. Warks research group spent a prolonged effort, essentially a year or more, in first
refining the contact angle measurement technique of Taggart, Taylor, and Ince (1930) and
sample preparation so that reliable and reproducible results could be obtained. In 1934,
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, and for the behavior of a wide variety of modifiers and depres-
sants with various collectors. Figure 6 presents one of their critical pH diagrams for three
sulfide mineralsnamely, pyrite, galena, and chalcopyritewith sodium diethyldithio-
phosphate as collector. In each case, flotation should occur under conditions to the left of
the curve. Diagrams such as these provide a means for predicting conditions under which
flotation separations can be made. If one considers that hydroxyl ions adsorb competitively
with collector ions, that the amount of collector adsorbed under conditions of incipient flo-
tation is constant, and also that the standard free energy of adsorption is constant, then each
line in Figure 6 must be characterized by [X]/[OH] being constant. These critical pH
curves were a major contribution to early flotation theory and they show, for example, the
pH and collector concentration at which flotation does or does not take place. In discussion
of the 1934 Wark and Cox paper where KEX was used as the collector, 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. Gaudin (1957) interpreted the results in terms of ion exchange between adsorbed
X and OH for surface sites.
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. For example,
they found the contact angle of collectors having an ethyl group on the nonpolar chain
to be 60 on all sulfides. This included xanthate, mercaptan, dithiophosphate, disubstituted
dithiocarbamate, and others. Methyl xanthate and disubstituted dithiocarbamate produced
contact angles of 50.
For nearly 25 years, there was spirited and ongoing debate about the mechanism of col-
lection in sulfide mineral systems. Gaudin was a strong proponent of adsorption as the
means of collector uptake by minerals. In 1927 he wrote, The mechanism by which xan-
thates float other sulfides than galena may involve an adsorption of xanthate ions without
further reaction. On the other hand, Taggart was convinced that collectors coated mineral
surfaces by chemical reaction. In 1930, Taggart, Taylor, and Knoll wrote, All dissolved
reagents which, in flotation pulps, either by action on the to-be-floated or on the not-to-be-
floated particles affect their floatability, by function of the reason of chemical reactions of
well recognized types between the reagent and the particle affected. Taggarts shortcoming
was his belief that the chemical theory of flotation was all-inclusive, even with regard to oils
on naturally hydrophobic minerals, and for collectors that do not form insoluble products

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Pyrite Galena Chalcopyrite

Collector Concentration, mg/L






2 3 4 5 6 7 8 9 10 11

Adapted from Wark and Cox 1934.

FIGURE 6 Critical pH curves for the flotation of pyrite, galena, and chalcopyrite with sodium
diethyl dithiophosphate as collector

such as amines on minerals. In reality, Taggarts chemical theory of collection is merely

exchange adsorption (as was shown by Taylor and Knoll [1934]). Overall, Wark was another
advocate of the adsorption theory of collector uptake. In 1934, Wark and Cox wrote, We
find there is a strong connection between adsorption of xanthates and the solubility of the
heavy-metal xanthates, but we are unable to decide if this is an identity. In 1950, 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. They wrote, Assuming a complete or nearly complete monolayer of ions on the
mineral particles, one would obtain a bulk concentrate with so much charge that it would
explode with greater violence than an equal weight of nitroglycerine! M.A. Cook, an
expert in explosives and an outstanding solution physical chemist, did not think in terms of
the electrical double layer because in all cases of ion adsorption, counterion adsorption or
exchange adsorption keeps the system electrically neutral. Note that Cooks 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. There are many examples where the collector indeed
appears to adsorb in its neutral molecule form. In 1967, 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. Such results indicate that the chemisorption of the neutral molecule may
indeed have a role in flotation in this mineralcollector system. Raghavan and Fuerstenau
(1975) demonstrated that the neutral hydroxamic acid molecule appears to be the active
adsorbing species in the hematitehydroxamate system. However, as will be subsequently
discussed, when a cationic amine collector hydrolyzes to the neutral molecule species with
oxide minerals, flotation ceases. In 1957, Nixon wrote, Prominent theories could be recon-
ciled by the electrochemical approach. In 1984, 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 processeschemisorption, reaction

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Absorption, %







1,300 cm1 1,200 1,100 1,000 900 800 700

Adapted from Leja, Little, and Poling 19621963.

FIGURE 7 Infrared spectra showing adsorption of ethyl xanthate onto an evaporated PbS film:
(a) bulk lead ethyl xanthate, solid on Nujol mull; (b) freshly evaporated PbS film after
atmospheric oxidation; (c) PbS film treated in aqueous solution of ethyl xanthate; (d) after
prolonged washing in ether; and (e) after washing in pyridine

to form a metal collector compound, and the formation of a dithiolateplays a role in cre-
ating hydrophobic surfaces.
New instrumentation permitted identification of species at the surface and quantifica-
tion of energies involved in surface reactions. In a seminal study, Leja, Little, and Poling
(19621963) applied infrared spectroscopy to demonstrate the nature of collector species at
mineral surfaces. Figure 7 presents their classic infrared spectra showing the adsorption of
ethyl xanthate onto an evaporated lead sulfide (PbS) film. The top curve (a) in Figure 7,
taken from their work, shows the infrared spectrum of bulk lead ethyl xanthate, and the sec-
ond spectrum (b) is for a lead sulfide film that has been oxidized in the atmosphere. After
exposing that film to xanthate in solution, they obtained the spectrum (c) that is virtually
identical to that of lead ethyl xanthate, showing that indeed a chemical compound is formed
at the surface. Washing with ether (d) removed some of the surface lead xanthate, but it took
a strong solvent, pyridine, to completely remove the xanthate, returning the spectrum (e)
back to that of a lead sulfide (oxidized) surface. Infrared spectroscopy has become a widely
used tool to study the nature of adsorbed films in flotation systems.
The energetics of the interaction of xanthate with galena was carefully determined by
Mellgren (1966) using microcalorimetry techniques. First, Mellgren reacted lead sulfate
with xanthate. Then he reacted xanthate with galena that had lead sulfate on its surface and
again measured the heat that evolved. Mellgrens measurements of the heat of reaction for
these two cases gave identical results; namely, that the enthalpy is 22 kcal/mol Pb2+ in each
case. 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. He conducted similar studies with lead carbonate. Mellgren also observed that

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at high pH, galena ceases to float because basic lead compounds form on the surface in pref-
erence to lead xanthate. Thus, depression in this system may also occur by a chemical reac-
tion mechanism, that is, by the formation of a surface compound that is more insoluble than
the surface collector salt.
As early as 1931, Kamienski measured the rest potential of a galena in xanthate solu-
tion. In 1934, Wark and Cox presented a direct correlation of the potential of a copper elec-
trode and the prevention of xanthate adsorption on chalcopyrite. However, about two
decades elapsed before electrochemical methods were again used in flotation research for
investigating mechanisms of thiol collectorsulfide mineral interaction. Salamy and Nixon
(1953) found that the concentration of xanthate determines the rest potential of the mer-
cury electrode, which corresponds to the xanthatedixanthogen reversible potential. They
concluded that the adsorbing species at the metalsolution interface is dixanthogen, the oxi-
dation product of the xanthate ion. Definitive papers on xanthate flotation of pyrite, pub-
lished independently by M.C. Fuerstenau, Kuhn, and Elgillani (1968) and by Majima and
Takida (1968), showed dixanthogen to be the surface species responsible for flotation in this
system. The former researchers used infrared spectroscopy and oxidation potential (Eh)
measurements, and the latter conducted polarization experiments in basic medium with a
pyrite electrode. It is interesting to note that Gaudin and Wilkinson wrote in 1933 that
Pyrite, or ferric iron derived from it by oxidation, changes xanthate to dixanthogen; the
dixanthogen can be extracted from the mineral surface provided oxidation of the dixantho-
gen is prevented. Their observation lay dormant for the next 35 years.
Numerous electrochemical investigations have been made in sulfide mineral flotation
systems, particularly conducting linear potential sweep voltammetry for various systems.
Chander and Fuerstenau (1975) first combined this technique with the measurement of
contact angles. Woods (1984), Woods and Richardson (1986), and Chander (1985) pre-
sented thorough reviews of the electrochemistry of sulfide mineral flotation. 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.
The products of the anodic reaction depend on the mineral and the collector used, and the
pretreatment of the mineral surface. They have been identified as chemisorbed collector,
dithiolates, and metalcollector compounds. As suggested by Woods and Richardson
(1986), the reactions for the anodic oxidation of the collector can be written as follows:

A. Charge transfer chemisorption of a thiol ion (X):

X = X ( ads ) + e

B. Oxidation of a thiol ion to the disulfide:

2X = X 2 + 2e

C. Formation of a thiol compound with a metal component of the mineral:

MS + 2X = MX 2 + S + 2e

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This mixed potential model does not actually contradict earlier theories of sulfide min-
eral flotation. Gaudins and Warks adsorption models would be equivalent to Reaction A,
whereas Taggarts chemical reaction theory would be represented by the anodic process
given by Reaction C, which can be a two-step reaction involving oxidation of the mineral
and metathesis.
In a classic paper, Allison et al. (1972) presented the results of a detailed study of the
products resulting from the interaction of sulfide minerals with thiol collectors. Table 6 pre-
sents a summary of their identification of surface products in ethyl xanthatesulfide mineral
systems and a correlation of those results with the rest potential of the minerals. These
results clearly indicate that, with the exception of covellite, sulfide minerals that display a
rest potential below the corresponding reversible potential for the oxidation of the collector
to its disulfide (dixanthogen, in this case) will react with thiols, forming metal tholates.
Those sulfide minerals whose rest potentials are above this value oxidize the thiol to its
disulfide, and this product is now accepted as the collecting species in these systems. Similar
results were reported for the diethyl dithiocarbamatesulfide systems. A necessary condi-
tion for sulfide mineral floatability is the thermodynamic stability of the hydrophobic entity
formed at the surface. If this compound forms at a rate that is too slow compared to the rate
at which the sulfide mineral oxidizes, however, 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 the
species is decomposed by oxidation, strong oxidizing conditions would be detrimental to
flotation. Knowledge of the Eh of the system is therefore vital in sulfide mineral flotation. It
is possible to predict the oxidizing and reducing conditions necessary for a substance to be
thermodynamically stable by constructing the appropriate EhpH diagram.
Chander (1985) grouped sulfide minerals into two typesreversible and passivated
based on their electrochemical behavior in aqueous solutions. The reversible group of sul-
fide minerals includes galena and chalcocite. The potentials for oxidationreduction reac-
tions can be predicted if metastability of elemental sulfur is considered. In the passivated
group of sulfide minerals in which Chander included pyrite, chalcopyrite, and bornite, the
reactions are irreversible. The surfaces of passivated sulfides are normally covered with a
layer of oxidation products. The potential of such surfaces cannot be predicted thermody-
namically but are so-called mixed potentials. Chander also pointed out that the collecting
species for sulfides with sulfhydryl collectors such as xanthate can also be divided into two
categories. He observed that metal-xanthate salts form at the surface of reversible sulfides,

TABLE 6 Rest potential and reaction product of sulfide minerals with KEX solutions
Mineral Rest Potential, V Reaction Product*
Sphalerite 0.15 NPI
Stibnite 0.13 NPI
Galena +0.06 MX
Bornite +0.06 MX
Chalcocite +0.14 X2
Chalcopyrite +0.16 X2
Molybdenite +0.21 X2
Pyrite +0.22 X2
Arsenopyrite +0.22
Adapted from Allison et al. 1972.
*MX = metal xanthate; NPI = not positively identified; X2 = dixanthogen.
Potential for X 2 + 2e 2X at 0.625 mM KEX = 0.13 V.

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0.02 mM KEX
(0.014 mM for Cu2S)

pH 9.2
Flotation Recovery, %

Cu2S Cu5FeS4 CuFeS2 FeS2




0.6 0.4 0.2 0.0 0.2
Potential, V (vs. SCE)
Adapted from Richardson and Walker 1985.

FIGURE 8 Relationship between flotation recovery and conditioning potential for chalcocite,
bornite, chalcopyrite, and pyrite with KEX as collector at a concentration of 0.02 mM with the
exception of 0.0144 mM for chalcocite (potentials given versus the standard calomel electrode,
or SCE)

whereas dixanthogen is the oxidation product on passivated sulfides, although this remains
an area for further study.
Using in-situ electrodes in microflotation cells, 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. 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, Richardson and Walker (1985) investigated the xanthate flotation of
bornite, chalcocite, chalcopyrite, and pyrite as a function of the electrochemical potential.
The flotation response of these sulfides, shown in Figure 8, is strongly dependent on the
conditioning potential and occurs only under moderately oxidizing conditions. At a certain
reducing potential, depending on the mineral, flotation ceases. Identification of the products
of the sulfide mineralethyl xanthate interaction was conducted by linear sweep voltammetry
and ultraviolet (UV) spectroscopy. They found that surface hydrophobicity appears to be metal
xanthates or surface analogs of metal xanthates formed by chemisorption on chalcocite and
bornite, dixanthogen on pyrite because the potential at which flotation begins is that at
which xanthate is oxidized to dixanthogen, and both metal xanthate and dixanthogen (at
higher potentials) on chalcopyrite. Trahar (1984) used chemical means to control the pulp
potential and observed similar behavior in the flotation of sulfide minerals.
In much of the early flotation literature, there are discussions of how low the adsorption
density of collector is for flotation. A subsequent detailed study of the flotation of chalco-
cite and pyrite using the electrochemical flotation cell, together with determination of the
amount of xanthate collector adsorbed, was carried out by Gebhardt and Richardson
(1987). Their results for the flotation of these two sulfides individually are plotted in Figure 9.
Collection of chalcocite occurs by chemisorption. The plots given in Figure 9 indicate that

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Flotation Adsorption 14
5 10 M KET, pH 9.2

Adsorption Density, mol/m 2

Flotation Recovery, %


40 6


0 0
0.8 0.6 0.4 0.2 0.0 0.2
Potential, V (vs. SCE)
Adapted from Gebhardt and Richardson 1987.

FIGURE 9 Flotation recovery and ethyl xanthate adsorption as a function of potential for
single-component chalcocite and pyrite beds at pH 9.2 in an electrochemical flotation cell at a
collector concentration of 0.05 mM

when complete flotation of chalcocite occurs, the adsorption density of xanthate is in the
range of their calculated monolayer, which would be the situation for any chemisorption
process. Flotation of pyrite does not begin until the potential for dixanthogen formation
occurs, and the dixanthogen coating that hydrophobizes pyrite could exceed monolayer cov-
erage. 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.
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, but dissolution products from pyrite had no effect on the flotation of chalcocite.

With the exception of sphalerite and pyrrhotite (Sutherland and Wark 1955), sulfide miner-
als respond well to flotation with short-chain xanthate collectors. Even methyl xanthate will
float galena, as can be seen from the plots given in Figure 3. Although there is no flotation
with ethyl xanthate at low concentrations, Gaudin (1930) showed that sphalerite exhibits
some response with amyl xanthate and significant flotation with heptyl xanthate, reaching
100% recovery at a collector addition of 0.2 kg/t. M.C. Fuerstenau, Clifford, 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. Flotation increased sharply once the necessary collector concentration was
reached, indicating zinc xanthate precipitation enters into the process. Fifty percent recovery
was achieved at an ethyl xanthate concentration in solution of 10 mM, whereas only 0.1 mM
hexyl xanthate was necessary to achieve the same degree of flotation. Flotation response cor-
relates exactly with the solubility products of the various zinc xanthate. Most importantly,

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upon the addition of copper salts, sphalerite readily responds to flotation with low additions
of short-chain xanthates. As discovered by Leslie Bradford in 1913 in Australia, this means
of enhancing the floatability of sphalerite has become the classic example of activation in
flotation technology, and since then, the inorganic salt, copper sulfate, has proved to be
indispensable for effectively concentrating zinc sulfide ores by flotation. 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, 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, Gaudin commented that from a geological standpoint, the action of
copper sulfate and similar salts on sphalerite had long been known, with some experiments
having been conducted on the reaction as far back as 1911 by Rogers. The coating on
sphalerite was shown to be covellite. In 1930, 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, followed by a slow process. He correctly attributed this to slow
diffusion as the copper sulfide coating thickens. About 20 years later, Gaudin again became
interested in this problem and with radioactive 64Cu showed that there indeed is a 1:1 CuZn
exchange, that the first two or three layers rapidly exchange, and that the reaction rate then
continues by solid-state diffusion (Gaudin, Fuerstenau, and Mao 1959). 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. If copper sulfate is added under alkaline conditions, hydrolyzed
cupric species form and are rapidly adsorbed. Because CuS is far more stable than copper
hydroxide, the adsorbed copper hydroxy compounds subsequently transform to CuS and
thereby activate the sphalerite. In 1930, Gaudin also conducted some preliminary experi-
ments on the deactivation of sphalerite with sodium cyanide, and this early interest in deac-
tivation reactions were taken up again by Mao (Gaudin, Fuerstenau, and Mao 1959), who
quantitatively investigated this phenomenon with 64Cu and several copper-complexing
Through contact-angle measurements and flotation experiments, Wark and Wark
(Sutherland and Wark 1955) examined the activation behavior of sphalerite with a wide
range of metal salts. Their results indicate that successful activators are salts of metals which,
alone or with their sulfides, readily respond to flotation with thiol collectors. Salts of lead,
cadmium, silver, and mercury fall within this category. D.W. 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. In flotation plants, the oxidation of
galena provides sufficient lead ions to activate sphalerite. It is for this reason that the addi-
tion of zinc sulfate became standard practice in lead-zinc flotation mills.
In the flotation separation of complex sulfide ores, selective depression of different sul-
fide minerals is desired. Depressants include such inorganic reagents as hydroxyl ions,
sodium sulfide, sodium cyanide, and alkali sulfites, and their mechanism of action has been
the basis for much discussion through the years (Sutherland and Wark 1955; Gaudin 1957).
In his 1985 paper, Chander interpreted depressant mechanisms in terms of whether the
mineral is a reversible or passivated sulfide (MS). This is schematically shown in Figure 10.
As pointed out by Chander, if the hydrophobic entity at the surface is X2, depression of the

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Reversible Sulfides Passive Sulfides

1.0 1.0




Eh, V

Eh, V
0.0 0.0 MS


1.0 1.0
0 7 14 0 7 14
pH pH

Flotation Metal/collector compounds Oxidation product of collector

Species MX, MX2 X2

Depressant (a) Mineral oxidation product (a) Mineral oxidation product

Species layer MO, M(OH)n, etc. layer MO, M(OH)n, etc.

(b) Hydrophilic layer of mineral (b) Hydrophilic MD layer

depressant compound, MD

(c) Removal of surface MX, MX2 (c) Removal of surface X2

by oxidation, reduction, or by reduction
Adapted from Chander 1985.

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, if the depressant decomposes X2 by reduction, or if the depressant reacts
chemically or electrochemically to form a hydrophilic metal-depressant (MD) coating. If
MX is the hydrophobic entity, depression of a reversible sulfide mineral would occur if the
mineral oxidizes to a hydrophilic coating, if MX decomposes by oxidation or by reduction,
if MX decomposes by hydrolysis, or if the depressant reacts chemically or electrochemically
to form a hydrophilic coating. Each of the sulfide mineralcollectordepressant systems can
be interpreted in terms of the foregoing mechanisms.
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.
Comparison of xanthate collector required for the flotation of chalcocite with that for mal-
achite is quite striking. To achieve 50% recovery of 100 600 mesh chalcocite with potas-
sium heptyl xanthate (mol wt = 230), a collector addition of 0.0022 mol/t is required,
whereas for similar flotation of 100 600 mesh malachite, 4.4 mol/t is required (Gaudin
1957). The results of that same investigation permit comparison for KEX (mol wt = 160) at
20% recovery, namely 0.062 mol/t for chalcocite and 11.2 mol/t for malachite. These huge
differences show the disparity between collector adsorption on chalcocite and chemical
exchange reaction on malachite. Fleming (1952a) quantitatively studied the metathetical
exchange of xanthate for carbonate with cerussite. Gaudin (1957) discussed the results of a
study of the uptake of amyl xanthate by cerussite conducted years earlier, where a coating
several hundreds of ions thick was formed. He commented that because the new phase does
not have much crystal-chemical resemblance to the old solid phase (cerussite), the connection
between the substratum and coating is fragile. To overcome the high collector consumption,

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these oxidized minerals have long been sulfidized before adding the collector, a process that
converts the mineral surface to a sulfide. The most common activator for this purpose is
sodium sulfide (Gaudin 1957). The interaction of sodium sulfide with cerussite was investi-
gated in detail by Fleming (1952b), who observed this to be a metathetical reaction with an
equilibrium constant of about 3 1016. Sulfidization is similar to copper activation of
sphalerite in that, initially, the uptake is rapid and the process then continues more slowly by
diffusion as the sulfide layer increases in thickness. In contrast to the CuZnS (copperzinc
sulfide) system, sulfidized coatings often do not adhere strongly (as noted previously by
Gaudin for the collector coating). Herrera-Urbina, Sotillo, and Fuerstenau (1999) con-
ducted detailed flotation and pulp potential measurements on the sulfidization reaction and
flotation behavior of cerussite with KAX as collector. A summary of their complex findings
can be seen in Figure 11. The effect of adding sodium sulfide to the system manifests itself in
consecutive steps. The first addition of sulfide ions precipitates the lead ions in solution as
PbS particles that coagulate onto the cerussite. After all the dissolved lead has been precipi-
tated, 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. Upon further addition of sodium sulfide, the sulfidization reaction
begins to take place and flotation sharply increases. The surface reaction is rapid until the
PbS coating reaches about 7 monolayers, at which point the residual sulfide ions in solution
again reach the concentration for depression of PbS flotation, causing a pronounced cessa-
tion in flotation of the sulfidized cerussite. At this point, 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, but at a reduced rate due to diffusion control. Thus, in
industrial flotation practice, the addition of sodium sulfide must be closely controlled,
which can be accomplished by measurement of pulp potential.

100 25

0.05 mM KAX
80 5 mM KNO3, pH 9.5 20
Residual Sulfide, M 10 5

Residual Sulfide
Number of Monolayers,
Flotation Recovery, %

60 15

40 10

20 5

0 0
106 105 104 103 102
Sodium Sulfide Addition, mol/L
Adapted from Herrera-Urbina, Sotillo, and Fuerstenau 1999.

FIGURE 11 Flotation recovery of cerussite at pH 9.5 with 0.05 mM KAX as collector, the
residual aqueous sulfide in solution, and the number of sulfide monolayers as a function of
added sodium sulfide in 5 mM potassium nitrate open to the atmosphere

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Many people involved in flotation considered gas bubbles to be the crux of flotation (Rick-
ard 1916). In 1928, 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. He carried out extensive investigations with the common sulfide minerals plus graph-
ite and sulfur using a range of gases that included air, hydrogen, oxygen, nitrogen, and
carbon dioxide. He concluded from his experiments that the floatability of minerals
depends on the nature of the gas being used. However, in their extensive contact-angle inves-
tigation, 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, including air, oxygen,
hydrogen, nitrogen, carbon dioxide, and sulfur dioxide. In the 1950s, Plaksin extensively
studied the effect of nitrogen gases and dissolved gases on the flotation of various minerals,
particularly the effect of the oxygen in water (Plaksin 1959; Klassen and Mokrousov 1963).
Flotation in closed cells with nitrogen as the flotation gas is used industrially in the final sep-
aration stage of copper-molybdenum concentrates, the main savings being reduction in
sodium sulfide consumption. For the flotation of an auriferous pyrite that oxidizes so readily
that it rapidly loses its floatability, a nitrogen flotation system was installed at the Lone Tree
mine in Nevada (Simmons et al. 1999).
It was not until 1958, in a study of the effect of chemical reagents on the motion of air
bubbles in water, that D.W. Fuerstenau and Wayman published the first results which clearly
showed that the adsorption of organic surface-active agents (frothers) retarded the velocity
of bubbles. Previous investigations had shown that bubbles in distilled water, before they
begin to distort from spherical shape, rise faster than solids of the same specific gravity due
to circulation within the bubble. By adding a frother (terpineol) to distilled water, 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. This
retardation was similar to that observed earlier for air bubbles in tap water. In distilled water
in the absence of terpineol, solutions containing about 20 mg/L of potassium hydroxide
(KOH), KCl, or KEX did not have any appreciable effect on the rise velocity of bubbles.
However, 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 primary role of gas bubbles in flotation, of course, is to attach to hydrophobic min-
eral particles, levitate them to the surface, and maintain a froth layer that lasts long enough
for effective recovery of the desired mineral particles. This requires organic compounds
(frothers) that create a surface tension gradient at the airwater interface. Long-chained sur-
factants such as amines, sulfonates, and fatty acids function not only as collectors but also as
frothers. Typical frothers are alcohols (ROH), either straight-chain with 6 to 9 carbon
atoms or branched-chain compounds with 6 to 16 carbons. Pine and eucalyptus oils repre-
sent typical cyclic alcohols, with the active molecule being terpineol. In more recent
decades, alkoxy-substituted paraffin-type frothers (such as triethoxy butane) contain no
hydroxyl groups but gain their polarity from ether linkages. Another class of frothers
includes the hydroxylated polyglycol ethers (King 1982). Interest in frothers has increased
because of overall economic factors. For example, 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, the maximum particle size that can be recov-
ered decreases while at the same time selectivity increases. More research is needed in this area.

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The immersion of a mineral into an aqueous solution produces a region of electrical inho-
mogeneity at the solidsolution interface; namely, 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). This is the electrical double layer. Useful monographs that dis-
cuss the electrical double layer are those of Hunter (1981), King (1982), and Stumm (1992).
Electrical double-layer phenomena have a limited role in the collection of sulfide minerals
but are very important in nonmetallic mineral flotation, particularly with oxides and sili-
cates. Figure 12 is a simple model of the electrical double layer at a mineralwater interface,
showing the charge on the solid surface and the counterions extending as a diffuse layer out
into the aqueous phase. This figure also shows the drop in potential across the double layer.
The closest distance of approach of hydrated counterions to the surface, , is called the Stern
plane. The total double-layer potential, or surface potential, is o, and the potential at the
Stern plane is . From the Stern plane out into the bulk of the solution, the potential drops
exponentially to zero. The electrokinetic or zeta potential, , is the potential just outside the
Stern plane where the diffuse layer is able to slip relative to the solid surface. In the case of
ions that directly interact with surface sites, either chemically or by some other strong spe-
cific adsorption force, the adsorbed ions may lie closer to the surface at a plane called the
inner Stern plane. However, these discussions simply refer to adsorption in the Stern plane.
Several different parameters that quantify the electrical double layer are useful in interpret-
ing flotation behavior, particularly the selective adsorption of collectors. This includes such
factors as the magnitude of the surface charge, the point of zero charge (PZC) of the min-
eral, interfacial potentials, thickness of the electrical double layer, specific adsorption of col-
lectors, and ion exchange phenomena (D.W. Fuerstenau and Healy 1972).
The surface charge in systems of importance to flotation may arise in a number of ways.
For example, the surface charge on an oil droplet or an air bubble may result from the
adsorption of long-chained surfactant ions at the oilwater or airwater interface. In the
case of layer-silicate minerals (such as clays and micas), because of substitution of Al3+ for
Si4+ in the silica tetrahedra and Mg2+ for Al3+ in the octahedral layer of the crystal lattice,
the surfaces of these crystal faces carry a constant negative charge that is independent of


Surface Counterions, d
Charge, o

o Shear



NOTE: Shown are the surface potential, the Stern layer potential, the zeta potential at the
slipping or shear plane, and the potential decrease to zero-out into the bulk solution. The
distance 1/ is the center of gravity of the diffuse layer of counterions.

FIGURE 12 Simple schematic of the electrical double layer showing the surface charge on the
solid and the counterions adsorbed in the diffuse layer, with their closest distance of approach
being the Stern plane

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solution conditions. For two of the layer-silicate minerals, talc and pyrophyllite, the charge
is exactly balanced within sheets that constitute the layer structure, the faces of these crystals
are uncharged, and the minerals are naturally hydrophobic. In the case of salt-type minerals
such as barite (barium sulfate), fluorite (calcium fluoride), argentite (silver sulfide), iodyrite
(silver iodide), and so forth, the surface charge arises from the preference of one of the lattice
ions for the solid relative to the aqueous phase. Equilibrium is attained when the electro-
chemical potential of these ions is constant throughout the system. Those particular ions
that are free to pass between both phases and therefore establish the electrical double layer
are called potential-determining (PD) ions. For oxide and silicate minerals, 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), 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 PDZ are the PD
ions of valence z in more general terms) for an oxide mineral, then the surface charge (o) is
simply given by

o = zF ( H + 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. 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. If the adsorption of the positive PD
ion exceeds that of the negative PD ion, the surface of the mineral is positively charged, and
vice versa if the adsorption of the negative PD ion exceeds that of the positive PD ion. If
adsorption of counterions occurs only because of electrostatic interaction, then the diffuse
layer charge, d, is oppositely equal to the surface charge, o. Such counterions are called
indifferent ions. The relationships among surface charge, diffuse layer charge, and are
given for a symmetrical electrolyte with ions of valence z (where z = z+ = z) by the Gouy
Chapman equation, as modified by Stern (Hunter 1981):

d = o = ( 8 o RTC ) 1 2 sin h ( zF 2RT ) (EQ 5)

where is the dielectric constant of the liquid, o is the permittivity constant, R is the gas
constant, T is the temperature, and C is the concentration of indifferent electrolyte in solu-
tion. If the net adsorption density of PD ions is zero, the surface of the mineral is uncharged
and the solid is at its PZC.
With regard to flotation behavior, 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, a, of the PD cation of valence z. The surface potential is considered
to be zero at the PZC, and in the case of oxides (if the Nernst equation is assumed to be
valid), its value at any other pH is given by

o = -------- ln [ a ( H + ) a ( H + ) PZC ] = 0.059 [ pH PZC pH ] volt (EQ 6)

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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, and particularly those charged oppositely to
the surface.
Typical values of the PZC for some of the oxide minerals are as follows (D.W. Fuer-
stenau and Healy 1972; King 1982): quartz (SiO2), pH 2; cassiterite (SnO2), pH 4.5; zirco-
nia (ZrO2), pH 4; rutile (TiO2), pH 5.6; natural hematite (Fe2O3), pH 4.86.7; synthetic
hematite, pH 8.6; corundum (Al2O3), pH 9.1; and magnesia (MgO), pH 12. The PZCs of
silicate minerals are affected by crystal chemistry and selective leaching of metal cations or
silica from the surface. Typical values of the PZC of some silicate minerals are as follows
(D.W. Fuerstenau and Raghavan 1980; King 1982): kyanite (Al2SiO5), pH 7.8; zircon
(ZrSiO4), pH 5.8; olivine [(Mg,Fe)2SiO4], pH 4.1; almandine [Fe3Al2(SiO4)3], pH 5.8;
beryl [Be3Al2(Si6O18)], pH 3.4; spodumene [LiAl(SiO3)2], pH 2.6; rhodonite (MnSiO3),
pH 2.8; talc [Mg6(Si8O20)(OH)4], pH 3.6; muscovite [K2Al4(Al2Si6O20)(OH,F)4], pH 1;
and orthoclase [K(AlSi3O8)], pH 1.8.
A useful method for the study of adsorption phenomena in solidliquid systems is the
measurement of electrokinetic potentials that result from the interrelation of mechanical
fluid dynamic forces with interfacial potentials. In making electrokinetic measurements, 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). More recently, electro-
acoustophoresis has also been used to evaluate zeta potentials, particularly with concen-
trated suspensions. From the appropriate theory, one evaluates the potential at the slipping
plane, which generally is considered to be just outside the Stern plane. The potential at the
slipping or shear plane is the zeta potential, , and is often assumed to approximate the Stern
plane potential, , although < , as can be seen in Figure 12. The determination of zeta
potentials has been a powerful tool in delineating flotation adsorption phenomena. Early
on, not everyone believed in discussing electrokinetic phenomena in terms of zeta potentials.
Because of his concern with regard to the equations connecting electrophoretic mobilities to
zeta potentials, the distinguished surface and colloid chemist, Victor LaMer (1967), 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. Of course if you have something to sell, zeta potential is a
much better advertising catch word than is electrophoretic mobility. The natives
are mystified and admire with great awe the black box which gives the results on
the dials. This above shows that much of the recent hullabaloo about zeta
potentials is meaningless.
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.
When counterions adsorb in the Stern plane through forces in addition to simple elec-
trostatics, such counterions are considered to be specifically adsorbed. Flotation collectors for
oxide minerals, for example, are such ions. Such phenomena as covalent bond formation,
hydrophobic bonding, hydrogen bonding, solvation effects, and so forth, lead to specific
adsorption. Because of their surface activity, the charge in the Stern plane can exceed the sur-
face charge, and the sign of is reversed. Actually, indifferent and specifically adsorbed
ions may lie in different planes because of ionic size and hydration. Chemisorbed ions may
lie closer to the surface because they are dehydrated, in what is termed the inner Stern plane.
These discussions will not differentiate between an inner and outer Stern plane. Stern first

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suggested specific adsorption of counterions in terms of a Langmuir-type adsorption equa-

tion. For adsorption densities less than about 30% coverage, Grahame (1947) derived a
Boltzmann-type relation, now generally called the SternGrahame equation, expressed here
in terms of adsorption-free energies and adsorption densities, rather than in terms of charge
and potentials as performed by Grahame:
o RT )
= 2rC exp ( G ads (EQ 7)

where is the adsorption density in moles per square centimeters, Gadso is the standard
free energy of adsorption, r is the effective radius of the adsorbed ion, and C has to be the
bulk concentration in moles per cubic centimeter. Another form of the relation expressing
adsorption in the Stern plane is given as fractional coverage:

- C o RT )
------------ = ---------- exp ( G ads (EQ 8)
1 55.5
In this equation, C is the concentration of adsorbate in moles per liter, and 55.5 is the
number of moles of water in a liter. If ions are adsorbed at the Stern plane only because of
electrostatic interactions, then the standard free energy of adsorption is given by
G ads o
= G elec = zF (EQ 9)

When an ion exhibits surface activity, such as the case for a flotation collector, then the
standard free energy of adsorption has additional terms:
G ads o
= zF + G spec (EQ 10)

where Gspeco represents the specific interaction terms. These can be comprised of various
G spec o
= G chem + G ho + G hpb
o o
+ G solv o
+ G hpb* + .... (EQ 11)

where the individual terms represent changes in the standard free energy due to chemical
bonding, hydrogen bonding, hydrophobic bonding, and solvation effects, respectively. The
term G hpb* represents the specific adsorption phenomena through surfactant chain inter-
action with a hydrophobic solid, such as talc or graphite, and would be absent for a hydro-
philic mineral, such as quartz. Depending on the mechanisms involved in the interaction of
the collector with the mineral surface, the contributions to the change in adsorption free
energy can be essentially zero or have a finite value. This approach will be used in explaining
the behavior of various types of collectors on nonmetallic minerals. There are two parts to
the usual ionic collectorthe charged head group and the hydrocarbon chainand both
can give rise to specific adsorption effects in the Stern layer.

As first clearly defined by Taggart, the molecular structure of chemical flotation collectors
requires that it has a polar group and a nonpolar hydrocarbon chain. 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. The former type of interaction is chemisorption, as exemplified

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by xanthates on sulfide minerals and gold, whereas the latter type of interaction is one of
physical adsorption. In this case, such factors as the size of the head group, its electrical
charge, and whether the head group hydrolyzes are important. Of particular importance is
the alkyl chain of the collector given that it enters into the process because of hydrophobic
bonding phenomena.
When surfactant ions or molecules in solution become sufficiently concentrated, they
aggregate through association of their hydrocarbon chains into clusters containing about 50
to 80 surfactant ions called micelles. The charged heads orient outward to the solution so
that the chains are effectively removed from water. The driving force is as a consequence of
the desire for water molecules to hydrogen-bond with themselves, which results in a free
energy decrease of about 1 kT per CH2 group (or 1 RT or 0.6 kcal/mol) removed from
water (where k is the Boltzmann constant, R is the gas constant, and T is the absolute tem-
perature). Thus, the number of ions in the micelle and the concentration at which micelles
form, the critical micelle concentration or CMC, depends on the number of carbon atoms
in the hydrocarbon chain of the surfactant. Based on his findings of how the adsorption of
dodecylammonium ions affected the zeta potential of quartz, in 1953 D.W. Fuerstenau first
proposed that similar phenomena can take place at the mineralwater interface. In their
1955 paper, 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). As the adsorption density increases in the Stern plane, the adsorbed
surfactant ions come sufficiently close together that they begin to associate into two-
dimensional aggregates similar to micelle formation in bulk solution. When hemimicelles
begin to form, the free energy of adsorption is given by
G ads o
= zF + G hpb = zF + N (EQ 12)

where N is the number of CH2 groups in the hydrocarbon chain, and is the free energy
change on removal of one mole of CH2 groups from water. Through these same chain asso-
ciation effects, organic molecules (such as alcohols) can co-adsorb with adsorbed organic
ions. 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 67, conditions under
which the quartz surface itself is negatively charged. At about 104 M DAA, there are abrupt
changes in the amount of aminium ions adsorbed and the zeta potential becomes sharply
positive. This is because the hydrophobic bonding contribution to the adsorption free
energy dominates, that is, N > zF . It is also seen that the onset of rapid flotation occurs
under conditions where hemimicelles begin to form, clearly indicating that good flotation
depends on strong collector adsorption in the Stern plane. If the driving force for the
adsorption of physisorbing surfactants were only electrostatic, flotation with such collectors
would be limited.
Careful delineation of surfactant adsorption phenomena under controlled ionic
strength was first conducted by Somasundaran and Fuerstenau (1966), and continued by
Wakamatsu and Fuerstenau (1968). Combining zeta potential measurements with adsorp-
tion phenomena in the aluminasodium dodecylsulfonate system clearly showed the exist-
ence of a three-step isotherm, which later was shown to be a four-step isotherm when
surfactant concentrations were taken above that used in flotation, namely, all the way up to
the CMC. This so-called SF isotherm can be illustrated in terms of the results obtained for
the adsorption of sodium dodecylsulfonate on alumina at pH 7.2 (Figure 13). The plots

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8 10

Carbon Atoms

Number of

pH 5 14
4 pH for C12
No. C for pH 7.2 16

2 18
Contact Angle 80
Adsorption Density
Zeta Potential 70 40

Contact Angle, degrees

1.0 60
Adsorption Density, mol/m 2

50 20

Zeta Potential, mV

0.1 30 0


10 20

0.01 0

2 mM Ionic Strength
pH 7.2
105 104 103 102
Sodium Dodecylsulfonate Concentration, M

NOTE: Because the maximum contact angle is reached at the PZR, the dependence of the
PZR on alkylsulfonate chain length at pH 7.2 and on pH for dodecylsulfonate are given in the
upper portion of this figure.

Adapted from D.W. Fuerstenau and Wakamatsu 1973.

FIGURE 13 For alumina at pH 7.2 and 2 mM ionic strength, the effect of sodium
dodecylsulfonate on the collector adsorption density, zeta potential, 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, which can be interpreted in terms
of the SternGrahame equations. In Region I, the sulfonate ions adsorb individually by elec-
trostatic interaction and ion exchange with chloride ions, and the zeta potential is therefore
constant given that excess adsorption in the Stern plane is absent. 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 boundary between regions II and III occurs precisely at the
concentration where the zeta potential reverses (the PZR), 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. In Figure 13, 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.W. Fuerstenau and Wakamatsu 1973). At the PZR, in all cases the contact
angle reached its maximum and remained such as the concentration of sulfonate was

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C18 C16 C14 C12 C10 C8 C6 C4

100 Quartz
pH 67
RNH3 Acetate

Flotation Recovery, % 80




107 106 105 104 103 102 101 100
Alkylammonium Acetate Concentration, M
Adapted from D.W. Fuerstenau, Healy, and Somasundaran 1964.

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. One interpretation is that after the PZR, with continued adsorption, some of the
surfactant ions adsorb in reverse orientation. This behavior was observed for sodium dode-
cylsulfonate at different pH values and also for alkylsulfonates of different chain lengths at
pH 7.2. These results are summarized in the upper portion of Figure 13, which shows the
concentration where the maximum contact angle (the PZR) is reached for sulfonates of dif-
ferent chain lengths at pH 7.2 and for dodecylsulfonate at different pH values. 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).
Because the formation of hemimicelles depends on the length of the hydrocarbon
chain, the flotation of quartz with alkylammonium salts should exhibit a regular depen-
dence on chain length, similar to the well-known Traube rule. Figure 14 presents the flota-
tion of quartz with amine collectors ranging from 4 to 18 carbon atoms. Because of the N
term, collectors having a longer hydrocarbon chain (greater N) adsorb more strongly and
function effectively as flotation reagents at more dilute concentrations. It is interesting to
note that a 4-carbon amine requires about 1 molar residual concentration for complete flo-
tation of quartz, which is in sharp contrast to such strongly chemisorbing sulfhydryl collec-
tors as ethyl xanthate on sulfide minerals. The role of the hydrocarbon chain in galena
flotation with carboxylic acids is apparent by the results of Gaudin et al. (1928), given in
Figure 1.
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.

During the period from 1953 to 1956, D.W. Fuerstenau began to develop the concept that
flotation collectors which physically adsorb must function as counterions in the electrical
double layer, and that oxide mineral flotation with physisorbed anionic collectors should be

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100 105

Zeta Potential, mV
50 102




Flotation Recovery, %


4 105M, C12

20 RNH3Cl

0 2 4 6 8 10 12 14

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. The lower curve represents the flotation
response of corundum with 0.04 mM SDS, sodium dodecylsulfonate, and DAC as a function
of pH, showing the dependence of flotation on the PZC and the collector.

Adapted from Modi 1956; Modi and Fuerstenau 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. These concepts, which have been termed the electrostatic model of flotation,
are briefly summarized here. Experiments to confirm these ideas were conducted by H.J.
Modi as part of his doctoral thesis at MIT (Modi 1956). 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. Figure 15 presents the
results of the very first experiments carried out to test these concepts, which were first pre-
sented in Modis doctoral thesis in 1956 and then published by Modi and Fuerstenau in
1960. The upper part of Figure 15 presents the zeta potential of corundum (synthetic sap-
phire), determined by streaming potential measurements as a function of pH with various
additions of sodium chloride as indifferent electrolyte. All the curves intersect and cross at
zero zeta potential at about pH 9, which is the PZC of this material. Flotation experiments
were conducted at a solution concentration of 4 105 M with three different high-purity
collectors: dodecylammonium chloride (DAC), sodium dodecylsulfate (SDS), and sodium
dodecylsulfonate. The lower part of Figure 15 clearly shows that corundum responds to

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Corundum pH 9.1
Goethite pH 6.7
104 M
Ilmenite pH 5.6
Quartz pH 2.4


Flotation Recovery, %




3 2 1 0 1 2 3 4

Adapted from D.W. Fuerstenau and Herrera-Urbina 1989.

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, and
to the cationic collector at higher pH values where corundum is negatively charged. The
pKa of dodecylamine is 10.4; at pH 10.4, the DAC in solution will be 50% aminium ions
and 50% amine molecules. Under these conditions, flotation is maximal because of coad-
sorption of aminium ions and amine molecules. As the pH is raised to about 12, flotation
drops sharply and ceases at pH 12.6. Under these conditions, there are insufficient aminium
ions to bind the collector to the surface. This upper pH limit for flotation with primary
amine collectors is virtually universal. 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.
After returning to the University of Minnesota upon completing his doctorate at MIT
in 1957, 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, Cooke, and Columbo
1960; Iwasaki, Cooke, and Choi 1960). The flotation response of oxide and silicate minerals
to these types of collectors is characteristically similar to that presented in Figure 15, as can
be seen from the plots given in Figure 16, 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. 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.
In an excellent investigation of the flotation of iron oxides with 12- and 18-carbon col-
lectors, Iwasaki, Cooke, and Choi (1960) showed that the flotation response of hematite
with 12-carbon alkyl amines and sulfates is that predicted by the PZC. Their results, given
in Figure 17, show that the 18-carbon surfactants continue to function as collectors at about

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m/sec/V/ cm



104 M
Flotation Recovery, %

C12 C12

40 C18 C18


0 2 4 6 8 10 12 14
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.

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 mineralwater 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

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chemisorption of collectors on oxide and nonmetallic minerals include the oleatehematite,

hydroxamatehematite, hydroxamateMnO2, and oleatefluorite 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

Oleic Acid
90 1kg/t

Flotation Recovery, %


2 9
1 3 4
1 2 3 4 5 6 7 8 9 10 11 12 13
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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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-
erals 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 oleatehematite 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 cm1 that was the
result of the formation of a surface cationcollector 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
(2.2 105 mol) of oleic acid as collector in 275 mL of water, giving a starting collector con-
centration of 8 105 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:


(EQ 13)
M-OHHOl 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.

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

80 Flotation
Flotation Recovery, %

Acid Soap




4 5 6 7 8 9 10 11

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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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 3 105 M
potassium oleate and 8 105 M potassium nitrate are plotted together with the calculated
concentration of the acid-soap dimer. The maximum in their plot corresponds to 4.8 108
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 FeOCr2O3, 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


Flotation Recovery, %



20 1 104 M
5 105 M

0 2 4 6 8 10 12 14

Adapted from Palmer, Fuerstenau, and Aplan 1975.

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

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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.


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

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 acidiron 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 (25C), contact angles on hematite with 3 105 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 70C, 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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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


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




Flotation Recovery, %



20 Sodium Oleate, 0.1 mM
Sodium Linoleate
Sodium Linolenate

0 2 4 6 8 10 12

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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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.

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 5 105 M, but at 1 104 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 104 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 104 M potassium oleate are also shown in Figure 22.


Flotation Recovery, %



20 Iwasaki
M.C. Fuerstenau

0 2 4 6 8 10 12 14

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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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 3 105 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.

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:

Mn OH + Mn + H2O

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80 106 M SDS
Flotation Recovery, % 104





1 105 M HXm
1 104
3 104
Flotation Recovery, %





Sodium Oleate
5 105 M
1 104
5 104
Flotation Recovery, %




0 2 4 6 8 10 12 14
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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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 oleatemineral 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 m, 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.

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

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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 5.7 105 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+

Flotation Recovery, %

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



0 2 4 6 8 10 12 14

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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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 104 M sulfonate
collector and 104 M metal salt as activator was as follows: Fe(III), pH 2.93.8; Al, pH 3.8
8.4; Pb, pH 6.512.0; Mn(II), pH 8.59.4; Mg, pH 10.911.7; 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
102 M NaF
No NaF

4 105 M DAC


Contact Angle, degrees




0 2 4 6 8 10
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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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 bubbleparticle 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
hematitequartz 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 SternGrahame equation. In the absence of specific adsorption, the

100 0.1 mM DAA
pH 6.5

80 60
Flotation Recovery, %

Zeta Potential, mV



20 Flotation -Potential

0 0
107 106 105 104 103 102 101 100
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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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.

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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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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100 0

0.002 M KNO3

Flotation Recovery, %

Induction Time, sec





Flotation Without Collector 200
Induction Time Without Collector
Flotation with Dextrin

0 240
0 2 4 6 8 10 12 14
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

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.

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 25C to 70C. An increase with rising temperature is a direct indication of activated
chemical reaction taking placethe 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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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 metalcarboxylate 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 nave 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, 3 106 M
oleate was required and 4 105 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 10137; fluorite (CaF2),
5.0 1011; and calcite (CaCO3), 4.6 019. Their measured solubilities of calcium ions in
solution after 15 minutes were 2.5 105, 1.3 104, and 1.5 104 M for fluorapatite,

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Interaction Energy Calculation Fluorite Apatite Calcite

by Molecular Modeling: 52.6 kcal/mol 46.8 kcal/mol 40.2 kcal/mol
pH 10
Flotation Recovery, %




106 105 104 103
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 mol/m2 for apatite, fluorite, and calcite, respectively. Because
monolayer coverage is 6 mol/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 1016, 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
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

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Reaction Onset
2 BaSO4 to BaCO3

Electrophoretic Mobility, m/sec per V/cm


1 BaCO3

24 Hours Equilibration


10 BaCO3
Equilibrium pH

4 +[
Solution HC
8 O
7 [SO

106 105 104 103 102 101
Initial Sodium Carbonate Concentration, mol/L
Adapted from Pradip and Fuerstenau 1991.

FIGURE 29 Surface transformation of barite to barium carbonate by the addition of sodium

carbonate, as shown by zeta potential measurements and solution equilibrium pH

though it were BaCO3, as indicated by the electrokinetic behavior of the mineral. This sur-
face transformation is controlled by bulk thermodynamics, as would be expected when any
of these processes are a surface chemical reaction. Finally, in this system, the flotation
response of the barite under these conditions must be that of a carbonate.
When working with single minerals of calcite, azurite, and malachite, 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, 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. Gaudin and Martin aptly com-
mented: It is indeed very remarkable that azurite and malachite, two minerals which are
very similar in chemical composition, and crystallographically, can be separated by flotation

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with one of the lower fatty acids, while the carbonates of copper cannot, by any means now
known, be separated from calcite, by this same reagent.
Similar to the foregoing statement, in a complex mixture of salt-type minerals such as
calcite and apatite, dissolution of the minerals can put carbonate, phosphate, and fluoride
ions into solutionions that can all chemisorb onto the different minerals and compete
with the collector. Likewise, calcium ions can precipitate the collector if the solubility of the
calcium soap is exceeded (the KSP of calcium oleate is 1015.6). Using the known equilibria of
the various species that would be involved with apatite and calcite in water, Anathapad-
manabhan and Somasundaran (1984) constructed a diagram showing the amount of Ca2+
in solution from apatite, calcite (closed and open to the atmosphere), apatite, and calcite
supernatants, and also calcium oleate. Any condition where the concentration of Ca2+
exceeds that of calcium oleate can cause collector precipitation and hence depression, partic-
ularly when the mineral is in equilibrium with the solution before the collector is added.
The researchers also conducted detailed experiments on the flotation of apatite and calcite
in water, in their supernatants, and with added nitrate, carbonate, and phosphate salts. Fig-
ure 30 presents their results for the oleate flotation of calcite in water and in supernatants of
calcite and apatite. In the case of calcite flotation in water, conditions were such that little cal-
cite would have dissolved during the experiments. 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. Turbidity measurements after the addition of oleate to the supernatants, but at
slightly lower oleate concentration without added potassium nitrate, are also given in Figure
30 and show the precipitation of calcium oleate from these solutions. Added calcium nitrate
depressed calcite flotation similar to that shown in Figure 30 for the effect of supernatants.
For this system, depression results from the bulk precipitation of the collector as calcium



Turbidity, % transmittance
Flotation Recovery, %

Turbidity 80
0.1 mM Potassium Oleate

60 Apatite Supernatant
Calcite Supernatant


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

Adapted from Ananthapadmanabhan and Somasundaran 1984.

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

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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 99.5 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.

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 67 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 89.
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 24, or with sodium oleate at pH 68. Quartz can be floated
away from hematite with an amine at pH 67, or at pH 1112 with sodium oleate as collec-
tor after activating the quartz with calcium ions and depressing the hematite with starch.

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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 22.5, 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 99.5 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 78 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.

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 collectormineral 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 oresbut conducted with an aim toward quantifying
what is going on and not just ore testing.

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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

Adams, A.S. 1928. Gas sorption in flotation. Page 216 in Flotation Practice. New York: American
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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
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Pugh, R., and P. Stenius. 1985. Solution chemistry studies and flotation behavior of apatite, calcite
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History of Flotation Technology

A.J. Lynch, J.S. Watt, J.A. Finch, and G.E. Harbort

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.


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 18501900 and moved from the era of black powder, hand carts, stamp

TABLE 1 World production of copper, lead, zinc, and coal, 18501900

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.

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TABLE 2 Production rates and profits at Broken Hill Proprietary Company, 18861902
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 problemfine 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 simplefind 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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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 19101915 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

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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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 Eversons work,
although it was not a commercial success as was Bessels 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 Eversons 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. Eversons process was successful in small plants but not on a
larger scale (Megraw 1918), perhaps because the ores were unsuitablesulfide 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 Eversons
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 19011915.
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

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PROCESS, 19011925

Zinc and Lead at Broken Hill, 19011915

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. Potters 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 8288C (180190F).
About 90,000 tons of zinc concentrate was made annually from 300,000 tons of tailings.
A film flotation process that was similar to Bradfords 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 oilinsufficient to give a buoyant effectcaused 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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To Vacuum Pump
Acid Separating
9 ft

Oil Acid
Froth Feed

15 ft Baffles


Tailing Concentrate

Potter-Delprat Cell Elmore Vacuum Cell

Corrugated Cone
Water Level
Regulating Wheel
for Discharge Valve Overflow

Agitation Froth
Box Launder

Water Level

Feed Frothing
Discharge Tailing

Minerals Separation Cell De Bavay Cone

Source: Truscott 1923.

FIGURE 1 Flotation cells at Broken Hill, 19021910



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, 19111913

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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 400500C 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, 19111920

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

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6 ft Water Level



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, 1720% 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 Thompsons 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. Ricketts 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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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

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 millclassifier 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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Zinc and Lead at Cominco in Canada, 19171922*

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 millslikely 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 MSCs 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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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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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-
thatesthe 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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TABLE 5 World mine production of copper and zinc, 19502000

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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TABLE 6 Maximum size of Outokumpu mechanical flotation cells (m3), 19502000

1970 1976 1980 1995 1997 2002 2004
16 38 60 100 160 200 300
Source: S. Ronkainen, personal communication.

Wash Water

2 1
1 Feed
2 Concentrate
3 Tailing 1
4 Air

4 4
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 useda 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 froththe 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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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 frothpulp 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 Gasp (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 BoutinTremblay 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
cellsreliable 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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Tank Air

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

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 airpulp 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 particlebubble 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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Tailing Concentrate

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


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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Wash Water

Froth Product Wash Water Inlet

Air Feed Inlet Pressure Transducer
Frother Inlet
Slurry Manifold
Inlet from Pump
Tailing Outlet

Control Valve
Outlet to Pump

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 operators 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 OSAcomputer 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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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 19591960 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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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 67 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 worlds 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.
Watts 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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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 19661968 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 034 wt % being determined to
0.6 wt % (1) (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 19681971 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 CRAAAEC trials

Density Probe

Pb Probe Pulp In

Zn Probe

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

FIGURE 11 Radioisotope probes immersed in a plant mineral slurry

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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
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.

2007 by the Society for Mining, Metallurgy, and Exploration.

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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.

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.

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 Elishas 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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Arbiter, N. 1999. Development and scale-up of large flotation cells. Pages 345352 in Advances in
Flotation Technology. Edited by B.J. Parekh and J.D. Miller. Littleton, CO: SME.
Barlin, B., and N.J. Keys. 1963. Concentration at Bancroft. Min. Eng. 15(9):4752.
Bennett, A.J.R., and C. Dell. 1963. Improvements in or relating to methods of and apparatus for
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Bessel, G. 1877. Berlin Patent 42. July 2.
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Blainey, G. 1968. Page 70 in The Rise of Broken Hill. Australia: Macmillan.

2007 by the Society for Mining, Metallurgy, and Exploration.

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Boutin, P., and R.J. Tremblay. 1963. Froth flotation method with counter-current separation. U.S.
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Boutin, P., and D.A. Wheeler. 1967. Column flotation development using an 18 inch pilot unit. Can.
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Bradford, H. 1885. U.S. Patent 345,951. June 22.
Brake, I.R. 1998. The development and commissioning of a new Microcel column flotation circuit for
BHP Coals Peak Downs coal preparation plant. Pages 767776 in XIII International Coal
Preparation Congress, Brisbane Australia. Edited by A.C. Partridge and I.R. Partridge. New
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Chapman, W.R., and R.A. Mott. 1928. The Cleaning of Coal. London: Chapman and Hall.
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Flotation Fundamentals

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Some Aspects of Flotation

D.W. Fuerstenau and S. Raghavan

This chapter presents a brief summary of some of the thermodynamic aspects of flotation processes.
Thermodynamic considerations that control interfacial and wetting behavior in mineral
waterair systems are discussed. Particular attention is given to the thermodynamics of collector

The application of the principles of thermodynamics to flotation systems has contributed
significantly toward understanding some of the underlying foundations of flotation pro-
cesses. When applied to physical and chemical systems, such as flotation, thermodynamics
includes several topics:
1. The conditions under which chemical substances, or different physical states of the
same substance, exist in equilibrium
2. Whether, under certain specified conditions, a chemical reaction or a phase change
will take place spontaneously.
3. The relation between the interchange of heat and other forms of energy when a
chemical reaction or phase displacement occurs
4. The effect of temperature on chemical reactions and phase equilibria
5. 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. 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, it can help the engineer make some
predictions as to how the flotation response may change with temperature, type of collector,
type of mineral, and so on. 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, in the time span during which flotation takes place,
the system may not be in equilibrium. Interestingly, Wada (1960) actually defined flotation
as a thermodynamic process in which gasliquidsolid interfaces participate in separating
finely divided solids from one another. In this chapter, 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. This review is
not considered to be exhaustive, but only summarizes some of the highlights.

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The enthalpy of the surface on a unit area basis, HS, is defined by

HS = ES + (PV)0 = GS + T SS (EQ 1)

where ES is the total surface energy, PV is the pressure volume, GS is the Gibbs surface free
energy, T is the temperature, and SS is the surface entropy per square centimeter of surface.
Because the PV term is negligible for a surface, the surface energy and surface enthalpy are
equivalent. The surface tension, , and surface free energy, GS, are defined by

G S = = ------- (EQ 2)
A T, P, n

where A is the interfacial area, and n is the number of moles present in the system. These
quantities are usually given as ergs per square centimeter or dynes per centimeter, which are
identical in magnitude. Actually, only in a one-component system are GS and identical,
but for the purpose of this review, no distinction will be made between them. Because the
surface entropy at constant pressure is given by

G d
S S = --------S- = ------- (EQ 3)
t p dT

the relation between total surface energy and surface tension is

E S = T ------- (EQ 4)
For most liquids, the surface tension decreases linearly with temperature (Adamson
1967). In the case of water at 20C, = 72.75 ergs/cm2 and d/dT = 0.16, from which one
evaluates the total surface energy of water to be 120 ergs/cm2. In the case of octane, a typical
liquid hydrocarbon, = 21.80 ergs/cm2 at 20C and d/dT = 0.10, from which ES is calcu-
lated to be 51.1 ergs/cm2.
In the case of solids, the evaluation of surface energies is less straightforward, both
experimentally and theoretically. Some typical values of the surface tension (and surface
energies) of selected materials are given in Table 1. These can only be considered approxi-
mate, but they enable one to see how widely solids do differ. Clearly, the type of chemical

TABLE 1 Approximate surface energies of some materials at room temperature

Material , ergs/cm2 ES, ergs/cm2
Paraffin 25
Graphite 110
Halite (NaCl) 230 280
Fluorite (CaF2) 450
Magnesia (MgO) 1,000 1,090
Gold 1,800
Alumina (Al2O3) 1,900
Diamond 5,600 5,600
Source: Adamson 1967.

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bonds that hold a crystal together have a marked effect on the magnitude of the surface
energy of solids. Finally, it should be added that mineralwater interfacial tensions are gen-
erally much lower than the surface energies, particularly for oxides.

What happens in the case of a system with several components when one or more of the
components accumulates, that is, adsorbs, at an interface? The basis for the thermodynamics
of the adsorption of dissolved substances was unambiguously laid down by Gibbs. The
Gibbs adsorption equation relates the interfacial tension between two phases to the temper-
ature, T, of the system; the chemical potentials of various species, 1, 2i, in the bulk; and
the surface excess or adsorption density of the various species, 1, 2i, at the interface;
and has the following form (Defay and Prigogine 1966):

d = S S dT i d i (EQ 5)

There are several ways to define i, but the simplest way mathematically is to use the
convention proposed by Gibbs, namely, that the adsorption of the solvent is zero and that i
is the excess surface concentration. 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. If one
measures adsorption densities from differences in bulk concentrations in dilute systems (as
are usually encountered in flotation systems), then the Gibbs convention is most applicable.
Overall, the Gibbs adsorption equation is highly relevant to flotation through its applica-
tion to phenomena involving frother systems, wettability, the development of surface charge
at mineralwater interfaces, and so on, because it quantitatively expresses the change in sur-
face tension due to the adsorption of surface-active materials. By defining the adsorption of
the solvent (component 1) as zero, Equation 5 can be modified as
d = S S dT i( 1 ) di (EQ 6)

where i(1) refers to the relative adsorption of component i at the dividing surface, such that
1 = 0. Because flotation processes are often carried out at constant temperature, Equation 6
can be simplified to
d = i( 1 ) d i (EQ 7)

Recalling that di = RT d ln ai, where ai is the activity of species i in the bulk aqueous
solution, R is the gas constant, and T is the temperature, Equation 7 can be rearranged to give

i( 1 ) = -------- ------------ ;i j (EQ 8)
RT ln a i T, j

The adsorption density, (1), will be positive if ( ln a i ) T, ;i j is negative, and

vice versa.

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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. To illustrate the use of the Gibbs equation
in flotation, first consider aqueous solutions of frothers, which are surface-active agents that
have a tendency to concentrate at the airwater interface. The Gibbs equation, when
applied to a dilute aqueous solution of a frother such as an alcohol (ROH) in water, has the
following form (de Bruyn and Agar 1962):

d = ( RT ) ROH d ln a ROH
(EQ 9)
( RT ) ROH d ln C ROH

The dependence of surface tension on the frother concentration and the adsorption
density of the frother at the airwater interface are shown in Figure 1 for the waterbutyl
alcohol system. The lowering of the surface tension of water due to the addition of alcohol
shows that the alcohol is positively adsorbed at the waterair interface. For example, at an activ-
ity of 0.712 (0.854 molality), the adsorption density of butyl alcohol is 6.03 1010 mol/cm2.
At this concentration, the area per molecule is 27.4 sq . Close-packed films of long-
chained carboxylic acids and alcohols exhibit areas per molecule of 21.6 sq , suggesting
that the adsorbed butyl alcohol on water is monomolecular. For proper frothing, there must


Surface Tension, dynes/cm


40 Butanol/Water


6 120
Area per Adsorbed Molecule, sq.

, mol/cm 2 10 10

4 80


2 40

0 0
3 2 1 0
log a2
Source: de Bruyn and Agar 1962.

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

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be a surface tensionconcentration gradient such as that shown in Figure 1 (i.e., d/dC 0),
so that momentarily deformed films can withstand the shock.
The surface tension lowerings produced by the positive adsorption of a homologous
series of n-aliphatic alcohols at the waterair 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). In the concentration range corre-
sponding to the lower parts of a series of such curves, the slope is independent of the alcohol
considered, showing that the same number of molecules are adsorbed per unit area of the
surface. Further, the concentration ratio of two neighboring homologs is constant and
approximately equal to 3.2 for the same . In other words, the surface activity is approximately
tripled for each additional CH2 group in the molecule. This is called Traubes rule.
Collectors are heteropolar organic compounds whose main function is to adsorb at the
mineralwater interface, but they also tend to adsorb at the mineralair and waterair inter-
faces. They differ from the frothers in the sense that they are generally electrolytes. Taking
into consideration the aqueous dodecyl sulfonate system, the change in the surface tension
of the solutionair interface is given by

d = R d R Na + d Na + (EQ 10)

where R refers to the dodecyl sulfonate anion (C12H25SO3). In the absence of any other
electrolytes where Na+ and R would be the only species that are adsorbing, it can easily be
shown that

d = 2RT R d ln C NaR (EQ 11)

If the organic electrolyte is a weak electrolyte, such as the salt of a fatty acid, then
depending on the pH of the solution, the adsorption of neutral collector molecules must
also be considered.
Probably the most marked lowering of surface tensions due to adsorption is that exhib-
ited in solidvapor systems. For example, water vapor adsorption can lower the surface ten-
sion of oxides by several hundred ergs per square centimeter. Adsorption phenomena at the
bubblemineral interface appear to have a significant role in flotation.

Bubbleparticle contact is one of the key factors controlling the process of froth flotation.
In this section, the thermodynamic aspects of the bubbleparticle contact will be reviewed
and critically analyzed (Adamson 1967; Gaudin 1957).
The general thermodynamic condition for three-phase contact is defined by Youngs
equation for the system depicted schematically in Figure 2.

SG = SL + LG cos (EQ 12)

where SG, SL , and LG are the tensions of the solidgas, solidliquid, and liquidgas inter-
faces, respectively, and is the contact angle. The change in the free energy accompanying
the replacement of a unit area of the solidliquid interface by solidgas interface is given by
Dupres equation, namely:

G = SG ( SL + LG ) (EQ 13)

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FIGURE 2 Schematic representation of the equilibrium contact between an air bubble and a
solid immersed in a liquid. The contact angle is the angle between the liquidgas and the
liquidsolid interfaces, measured through the liquid.

Combination of Dupres equation with Youngs equation yields the following expres-
sion for the free energy change, namely:

G = LG ( cos 1 ) (EQ 14)

Thus, for any finite value of the contact angle, there will be a free energy decrease upon
attachment of a mineral particle to an air bubble.
The theoretical relationship of Dupres equation expresses the maximum possible
decrease in the free energy of the system resulting from the bubbleparticle contact, which
can be realized only when there are no other energy-consuming effects, such as deformation
of the bubble. Thus, the geometry of the system is not taken into account in Dupres equa-
tion. Further, Youngs equation (Equation 12) is valid in an ideal system where all gravita-
tional effects are absent and the system is at equilibrium ( Johnson 1959).
Often, considerable hysteresis exists in measured contact angles because of surface
roughness, contamination, nonequilibrium adsorption effects, etc. (Adamson 1967). If
there is hysteresis, that is, if a liquid-advancing contact has a different value than a liquid-
receding angle, equilibrium is not attained in the system. Under these conditions, the use of
Youngs equation is not valid. Figure 3 presents equilibrium, advancing and receding contact
angles on alumina in sodium dodecyl sulfonate solutions at pH 7.2 as measured by Waka-
matsu and Fuerstenau (1973). As can be seen in this figure, a pronounced hysteresis effect
exists in this system under the conditions of this investigation.
Leja and Poling (1960) conducted an interesting theoretical study on the attachment of
air bubbles to flat solids, both in the presence and absence of gravitational effects, and their
results will be summarized at this stage. Typically, because the solid surface is not of the same
contour as that of the air bubble, work must be expended by the system in deforming the
airliquid interface during attachment, and the actual free energy of adhesion per unit area,
WP, is smaller than the theoretically available value, WA (equal to G given by Equation
13). In the absence of other forms of energy (gravitational and kinetic), the work of defor-
mation must be performed solely by the interfacial energy. The deformation is then gov-
erned by the shape of the solid surface and, for a perfectly flat surface, the magnitude of the
contact angle, , determines the extent of deformation that the interfacial energy pool, WA ,
is capable of performing.
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, either decreasing or increasing the amount of deformation to be performed
by the interfacial energy pool. So when part of the deformation work is performed by gravi-
tational or kinetic energy, hysteresis of the practical contact angle is observed, even when

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100 S S S

Liquid Equilibrium Liquid

80 Receding Advancing

Contact Angle, degrees



Equilibrium Alumina
20 Ionic Strength 2 103N
pH 7.2
Receding 241C

106 105 104 103
Concentration of Dodecyl Sulfonate, mol/L

Source: Wakamatsu and Fuerstenau 1973.

FIGURE 3 Equilibrium, and receding and advancing contact angles on alumina in aqueous
dodecyl sulfonate solutions at pH 7.2

other effects, such as surface roughness, surface contamination, and so forth, are excluded.
According to Leja and Poling, an advancing contact angle indicates that a greater portion of
WA is being converted to the actual adhesion, WP, than under the condition of equilibrium.
On the other hand, a finite receding contact angle indicates a lower WP. Their conclusion
was that the contact angles, which were determined experimentally with fairly large bubbles
or drops, should not be used in Youngs equation unless a suitable correction in their magni-
tude is made to account for gravitational effects, a correction that becomes particularly sig-
nificant at the threshold of hydrophobic character (i.e., with small contact angles).
A limited amount of work has been carried out on the temperature dependence of con-
tact angles. The temperature coefficient of the contact angle can provide thermodynamic
information about wetting processes. For example, knowledge of the temperature coefficient
of contact angle provides a means of calculating the heat of immersion, which is the enthalpy
change upon immersing a clean, dry solid into a liquid. It can be shown (Adamson 1967) that

d cos
H imm = E LG cos T LG -------------- (EQ 15)
where ELG is the total surface energy of the liquidgas interface. For an excellent account of
the temperature dependence of contact angles on low-energy surfaces, refer to an article by
Neumann (1974).

The well-known classical condition for the possibility of a bubbleparticle contact in a
given liquid medium has been specified by Equation 13 where

G = SG LG SL < 0

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This relation assumes that there is no liquid layer between the bubble and the particle
after contact. This equation ignores the possibility of the existence of a thin liquid layer
between the bubble and the solid even after attachment. The thinning of this layer is
believed to control flotation (Laskowski 1974). Laskowski has made an attempt to modify
this equation for the presence of a liquid layer by making the following substitutions:
1. GS(h) for SG where GS is the free energy of a column of liquid layer (of height h)
and solid of unit cross section, and
2. GS(h) = SL + LG(h). LG(h) is the surface tension of the liquidgas interface
expressed as a function of the thickness of a liquid layer h.
These substitutions lead to

G ( h ) = LG ( h ) LG (EQ 16)

where G(h) expresses the energy barrier in the transition from no contact to bubble con-
tact, which must be overcome for attachment to occur (Laskowski 1974).
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, , as a
measure of the corresponding change in the thermodynamic properties. In effect, it is the
change of free energy with thickness and is given by the expression

= o + dh (EQ 17)

where is the specific-surface free energy of the thin liquid film, o is the specific-surface
free energy of an infinitely thick liquid film, h is the thickness of the film, and is the dis-
joining pressure. If p is the vapor pressure in equilibrium with a flat thin film, and po is the vapor
pressure in equilibrium with the bulk liquid, then Derjaguin and Shcherbakov (1961) showed

p G
RT ln ----- = V m ------- (EQ 18)
po h A, T

where Vm is the molar volume of the liquid and the term G/h is the disjoining pressure, .
If is positive, the thin film is stable. (For curved liquidair interfaces, the above expression
has been suitably modified by Padday [1970]). Depending on the liquid and the surface,
can be positive or negative and can change sign with film thickness (Clifford 1975). For
liquidsolid systems with a finite contact angle, must be negative for certain film thick-
nesses (Clifford 1975).
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. Rehbinder (1949) made some theoreti-
cal calculations to determine the excess free energy of thin films. In the thinning of the water
layer on the approach of a solid surface to an air bubble, the excess free energy of the layer,
according to Rehbinder, changes in relation to the initial hydration of the surface. When the
surface is highly hydrated (threshold hydrophilicity), the free energy of the liquid film
increases continuously during the thinning of the liquid film, thus preventing spontaneous
attachment of the air bubble to the surface. When the hydration of the surface is low, the

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free energy of the thin film does not increase on initial thinning of the film, thus favoring
spontaneous attachment of a bubble to a mineral. The previous two cases are represented
schematically in Figure 4. Curve 2 in this figure is most typical of practical flotation systems.
In the case of strongly hydrophobic solids where water vapor adsorption is far lower than a
monolayer, the film would certainly be unstable and would rupture spontaneously.
The disjoining pressure can be due to many effects. 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):

= LL + SL + el + h + p + i (EQ 19)

where LL is the disjoining pressure of the liquid film in the absence of a solid, SL is the
disjoining pressure due to the effect of the solid on the liquid film, el is an electrostatic
term to account for double-layer effects, h is the contribution from hydrogen bonding, P
is from polar interactions, and i is the change in free energy due to any other specific inter-
actions between the liquid layer and the surface. Chander and Fuerstenau (1972) have made
an attempt to explain the natural floatability of molybdenite using this approach.
In 1960, 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. 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. This
led to their conducting a detailed investigation of the effect of temperature on induction
time, in which they observed a regular decrease in induction time with increasing tempera-
ture. From their experimental observations, they evaluated an apparent activation energy for
film thinning and attachment processes. The additional force suggested for bubbleparticle
Free Energy of a Thin Hydrated Layer,

Distance from the Surface

Source: Rehbinder 1949.

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, (2) moderate surface hydration, and
(3) very weak surface hydration

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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, using the surface force apparatus (Israelachvili and Pashley 1988). This
force, 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. Yoon (2000) has made extensive measurements of hydrophobic forces and
applied the concept to bubbleparticle interaction in flotation.

Consider the conditions for floatability, namely, a finite contact angle of an air bubble on
the solid to be floated, in terms of work of adhesion of water to the solid (Wad ) and the work
of cohesion of the liquid (Wco). Because Wco = 2LG (the surface tension of the liquid,
which is usually only slightly smaller than that of pure water) and Wad = SG + LG SL ,
assuming that the contact angle is given by Youngs equation (cos = [SG SL]/LG), it can
be shown that Wad Wco = LG (cos 1). Hence, flotation is possible if Wad < Wco
(144 dynes/cm). It should be remembered that Wad is correctly defined as the work
required to separate liquid water from a solidwater interface, leaving behind an adsorbed
layer in equilibrium with saturated water vapor (Mellgren et al. 1974). After detailed experi-
mentation with methylated silica, 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. They also empha-
sized that hydrophobicity arises from the exceptionally large cohesive energy of water that is
due to hydrogen bonding between water molecules.
The magnitude of Wad depends on SL which reflects the extent of interaction between
the solid and water. Only a few solids are naturally hydrophobic and therefore respond to
flotation without adding a collector. These solids include such materials as graphite, sulfur,
talc, molybdenite, and stibnite (Gaudin 1957). Hydrophobic materials such as graphite, in
principle, do not exhibit significant polar interactions with water, and the energetics of the
solidliquid interface are mainly controlled by dispersion forces. Less hydrophobic surfaces
have some polar interactions with water, and hydrophilic solids such as oxides exhibit strong
polar interactions with water and are covered with hydroxyl groups (e.g., silica). Because the
function of the flotation collector is to render the surface more hydrophobic by eliminating
or shielding the polar sites of the solid, investigation of the energetics of the solidwater
interface, both in the presence and absence of a collector, should help one to comprehend
the concomitant phenomena of flotation. Wad = (LG(cos + 1)) can readily be obtained
for hydrophobic solids given that > 0. But for hydrophilic solids, = 0 (Youngs equation
is no longer valid under these conditions), and consequently, evaluation of Wad is not easy.
However, two methods (Mellgren et al. 1974) for measuring solidwater interactions have
been widely used: (1) adsorption of water vapor on solids and (2) calorimetric heats of
immersion in liquid water.
In the first method, 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. The free energy of sat-
uration of the solid with water (Gsat) is given by the expression

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G sat = RT d ln p p o (EQ 20)

where is the adsorption density (expressed in moles per area), p is the water vapor pressure,
and po is the saturation pressure. With hydrophilic solids, the major contribution to Gsat
comes from the most strongly bound water (i.e., at low p/po) and the net value is much
greater than 144 ergs/cm2. Some reported values are 316 ergs/cm2 for quartz, 264 ergs/cm2
for calcite, and 240 ergs/cm2 for barite (Mellgren et al. 1974).
The water-vapor adsorption method has also been used to study changes in the wetta-
bility of surfaces induced by the adsorption of collectors. Hall, Lovell, and Finkelstein
(1970) determined the effect of adsorbed oleate on calcite and fluorite on the Gsat value.
Their results gave a Gsat value of 300 ergs/cm2 for clean fluorite and 50 ergs/cm2 for
oleate-covered fluorite.
Heats of immersion can provide some information on the energetics for systems in cases
of zero contact angles. On a unit area basis, the heat of immersion of a clean solid, Himm, is
given by

H 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, which indicates a strong interaction with water molecules. Specifically, calori-
metric heat measurements suggest that the first layer of water on polar solids is very strongly
bound. When approximately three monolayers of water vapor are preadsorbed on the solid
before immersion, the heat value falls to about 120 ergs/cm2, which is the surface enthalpy
of normal liquid water (Mellgren et al. 1974). Therefore, water molecules beyond the first
few layers behave similar to bulk water.
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. To gain more insight into the nature of physically adsorbed water
layers, Griffiths studied the temperature coefficient of the heat of immersion of Al2O3 in
water and found it to have a near-zero value. He concluded that the water structure outward
from the surface does not gradually grade into that of bulk water. In his words, 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).
Numerous heats of immersion measurements of minerals have been reported in the lit-
erature (Healy and Fuerstenau 1965; Zettlemoyer 1968), and Table 2 presents a brief sum-
mary of some typical values.
Although values of Himm are high for hydrophilic and low for hydrophobic surfaces,
there is no well-defined critical heat of immersion for development of contact angles.
Hence, the two approaches discussed in this section are still of limited value in flotation
research. 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. 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.

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TABLE 2 Heats of immersion and contact angles of some materials in water*

Solid Himm, ergs/cm2
Contact Angle, degrees
Teflon 6 108
Graphon 26 82
Quartz 260370 0
SnO2 (cassiterite) 400570 0
TiO2 (rutile) 550 0
Fe2O3 (hematite) 530 0
Al2O3 (alumina) 650900 0
*The oxides were activated at 200C.

Starting with the work of de Bruyn, Overbeek, and Schuhmann (1954), there has been a
growing interest in whether collector adsorption at the SL, SG, or LG-interface is the
main factor controlling flotation behavior. Consider a collector x that is present at all three
interfaces. 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 Youngs equa-
tion, the following relations can be written:

d LG = RT xLG d ln a x (EQ 22a)

d SG = RT xSG d ln a x (EQ 22b)

d SL = RT xSL d ln a x (EQ 22c)

SG SL = LG cos (EQ 22d)

where xij represents the adsorption density of x at interface ij, ax is the activity of the collec-
tor in the bulk solution, ij is the tension of the interface ij, and is the contact angle of the
air bubble on the solid.
Assuming ax = Cx, which is the concentration x, by differentiating Equation 12 with
respect to ln Cx at constant P and T and applying relations 22ac, the following result is
obtained (Smolders 1961).

LG sin --------------- = RT ( xSG xSL xLG cos ) (EQ 23)
d ln C x

From Equation 23, the following results can be deduced:

1. If the angle of contact increases with the increase of solute concentration (d/dln ax
is positive), xSG must be greater than xSL + xLG cos .
2. In cases where the contact angle does not vary with concentration (d/dln ax = 0),
xSG must be equal to xSL + xLG cos .
3. 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
solidliquid interface), xSG must be less than xSL + xLG cos .

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As early as 1954, de Bruyn, Overbeek, and Schuhmann stressed the first result obtained
from Equation 23, namely, that xSG > xSL (for < 90). In an attempt to apply the analysis
of de Bruyn, Overbeek, and Schuhmann to a simple flotation system, 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. They found that excellent
flotation occurs at 3% to 30% surface coverage (low SL), substantially below an equilib-
rium concentration where an abrupt change in the adsorption density from solution takes
place. In addition, they observed SG to be greater than SL in the flotation range.
In 1968, Somasundaran, 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 SL interface, stressed the need for looking at adsorption conditions on
the bubble and at the SG interface, in addition to the SL interface. From the results of his
investigation of the quartz-dodecylamine solutiongas system, he found that the amount of
collector adsorption at the SG interface was approximately equal to the adsorption at the
SL interface. Sandvik and Digre (1968), without directly measuring SG and SL , showed
that the adsorption of a collector on a solid surface (silica) increased in the presence of gas
bubbles. They proposed a bubble-transfer hypothesis, which envisages the collector as being
transferred from the bubble surface to the solid. Their hypothesis in fact stresses the impor-
tance of adsorption at the LG interface. Pope and Suttons (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 [solvent solution], of the LG interface with pH. They con-
cluded that this correlation implies that the greater the adsorption of the collector at the
bubble surface (higher the surface pressure), the better the flotation. In a later investigation
on the quartzdodecylammonium acetate and the magnetitedodecylammonium acetate
systems, Finch and Smith (1975) found a decrease in the tenacity of the bubblesolid
attachment with decreasing surface tension of the liquidair interface, thus casting a doubt
on their earlier conclusion. Bleier, Goddard, 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 waterair interface.
It should be stressed that the interface of primary importance to flotation is the solid
liquid interface. The collector simply must adsorb at this interface in order to reduce molec-
ular attractions between the solid and the liquid.

Because adsorption phenomena at mineralwater interfaces are controlled in most cases by
the electrical double layer, 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). Figure 5 presents a schematic representation of the electrical
double layer of counterions extending out into the liquid phase. This figure also shows the
drop in potential across the double layer, neglecting the potential because of dipole effects.
The closest distance of approach of counterions to the surface () is the Stern plane.
Depending on whether ions remain hydrated or are dehydrated upon adsorption, there can

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Surface Counterions, d
Charge, o




FIGURE 5 Schematic representation of the electrical double layer and the potential drop
across the double layer at a solidwater interface

exist an inner and an outer Stern plane (Grahame 1947); for purposes of this review,
though, no distinction shall be made between the inner and outer Stern plane. The surface
potential is o, at the Stern plane it is ; and from the Stern plane into the bulk of the solu-
tion, the potential drops to zero.
In the case of the ionic solids such as barite (BaSO4), fluorite (CaF2), silver iodide
(AgI), and silver sulfide (Ag2S), 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. Equilibrium is
attained when the electrochemical potential ( = + vF where is the Galvani poten-
tial in the phase) of these ions is constant throughout the system. Those particular ions that
are free to pass between both phases and therefore establish the electrical double layer are
called potential-determining ions. In the case of AgI, the potential determining ions are Ag+
and I. For a solid such as calcite, CaCO3, the potential-determining ions are Ca2+ and
CO32, and also H+, OH, and HCO3 because of the equilibria between these latter ions
and CO32. Similarly for apatite, the potential-determining ions are Ca2+, PO43, and OH,
with the other hydrolysis products also functioning in this role because of the complex equi-
libria involved in this system.
For oxide minerals, which will be discussed in more detail in the next section, hydrogen
and hydroxyl ions have long been considered to be potential-determining (Fuerstenau and
Healy 1972). In the layer silicate minerals such as clays and micas, 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, the surfaces of these crystal faces carry a negative charge that is independent of
solution conditions.
The surface charge, s, on a solid in water is determined by the adsorption density of
potential-determining ions on the solid surface. In the case of a 11 valent salt, s is given by

S = F ( M+ A ) (EQ 24)

where F is the Faraday constant, M+ is the adsorption density in moles per square centime-
ter of the potential-determining cation, and A is that of the potential-determining anion.
For an oxide, M+ and A can be considered as H and OH, respectively, and for AgI, M+
and A are simply Ag+ and I. By means of a simple titration procedure (Kruyt 1952; Parks
and de Bruyn 1962), the magnitude of the surface charge can be determined if the surface
area of the solidliquid interface is known. The single most important parameter describing
the surface is the condition under which the surface charge, s, is zero. The activity of potential-
determining ions at which this occurs is called the point of zero charge, or PZC.

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TABLE 3 PZC for some ionic solids

Material PZC
Barite, BaSO4 pBa 6.7
Calcite, CaCO3 pH 9.5*
Fluorapatite, Ca5(PO4)3(F,OH) pH 6*
Fluorite, CaF2 pCa 3
Hydroxyapatite, Ca5(PO4)3(OH) pH 7*
Scheelite, CaWO4 pCa 4.8
Silver chloride, AgCl pAg 4
Silver iodide, AgI pAg 5.6
Silver sulfide Ag2S pAg 10.2
Source: Fuerstenau 1971.
*The activities of the other potential-determining ions can be calculated from the hydrolysis equilibria and solubility data.

Assuming that potential differences due to dipoles, and so forth, remain constant, the
total double-layer potential or the surface potential, o, is considered to be zero at the PZC.
The value of the surface potential at any activity of 11 valent potential-determining
electrolyte is given by

RT aM+
o = -------- ln ---------------------- (EQ 25)
F ( a M + ) PZC

where R is the gas constant, T is the temperature in degrees Kelvin, and ( a M + ) PZC is the
activity of the potential-determining cation at the PZC. Table 3 presents PZC values for a
number of ionic (salt-type) solids that have been investigated. Calcite, fluorite, and barite
are positively charged in their saturated solution at neutral pH, whereas the other materials
listed are negative, except for hydroxyapatite, which is uncharged at the pH shown.
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. In contrast to
the situation in which the potential-determining ions are special for each system, any ions
present in the solution can function as the counterions. If the counterions are adsorbed only
by electrostatic attraction, they are called indifferent electrolytes. As has been well established
(Kruyt 1952), the counterions occur in a diffuse layer that extends from the surface into the
bulk solution. The thickness of the diffuse double layer is 1/, where is given by

= ( 8F 2 v 2 C RT ) 1 2 (EQ 26)
where v is the valence of the ions (for a symmetrical electrolyte), and is the dielectric con-
stant of the liquid. For a 11 valent electrolyte, for example, 1/ is 1,000 in 105 M, 100
in 103 M, 10 in 101 M solutions.
The charge in the diffuse double layer d given by the GouyChapman relation (Kruyt
1952) as modified by Stern (for a symmetrical electrolyte) is

d = S = [ ( 2RT )C ] 1 2 sinh ( vF RT ) (EQ 27)

Further, if the potential does not change appreciably, this equation shows that the
adsorption density of counterions should vary as the square root of the concentration of

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added electrolyte, as de Bruyn (1955) has found for the adsorption of dodecylammonium
acetate on quartz at low concentrations.
On the other hand, 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, hydrophobic bonding, hydrogen bonding, solvation effects, and so forth.
Because of their surface activity, the charge of such surface-active counterions adsorbed in
the Stern plane can exceed the surface charge. In this case

S = ( + d ) (EQ 28)

where is the charge due to adsorption in the Stern plane, . Flotation collectors generally
function as surface-active counterions.
Electrokinetic phenomena, which involve the interrelation between mechanical and
electrical effects at a moving interface, have found widespread use in colloid and surface
chemistry. The two electrokinetic effects that have been most widely used are electrophore-
sis and streaming potential measurements. Electrokinetic results are generally expressed in
terms of the -potential, which is the potential at the slipping plane when liquid is forced to
move relative to the solid; only those ions in the diffuse layer outside of the slipping plane
are involved in the electrokinetic process. Thus, while knowledge of the -potential at some
single condition may be of certain value, determination of the change in -potentials as solu-
tion conditions are varied is extremely useful. From these changes, 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). This approximation seems permissible
because the potential differences between the plane and the slipping plane are small com-
pared with the total potential differences across the double layer. It should be pointed out
that the case in which there is no ambiguity is when = 0, because must be zero.

Because oxides constitute the most important class of nonmetallic minerals, they will be
given considerable detail in this section. Given that oxide minerals form hydroxylated sur-
faces when in contact with water vapor, a hydroxylated surface should be expected when the
solid is in equilibrium with an aqueous solution. Adsorption-dissociation of H+ from the
surface hydroxyls can account for the surface charge on the oxide (Yopps and Fuerstenau
1964; 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; Parks 1967) have postulated a different
mechanism for the charging of oxide surfaces, involving partial dissolution of the oxide and
formation of hydroxyl complexes in solution, 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 )

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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, or even by direct adsorp-
tion of H+ and OH, would result in an equivalent change in the pH of the solution.
Titration of a suspension of an oxide in water at high ionic strength (with an indifferent
electrolyte such as sodium chloride, 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. Under these
conditions, given that the counterions are the indifferent ions,

S F ( H + ( 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). This figure clearly shows that the surface charge on ferric oxide
reverses its sign at pH 8.6 and that it increases in absolute magnitude with increasing ionic
strength and increasing concentration of potential-determining ion. The intersection of the
curves yields the PZC because the adsorption density is zero at this point. Interestingly, 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:

( H + ( OH ) ) = F ( pH pH PZC ) (EQ 35)

where pHPZC is the pH of the solution at the PZC of ferric oxide. (This results as a conse-
quence of the capacitance of the Stern layer being constant, but this will not be discussed
further here.)
For an oxide, the surface potential would ideally be given by

RT ( aH+ )
o = -------- ln ---------------------- = 0.059 ( pH PZC pH ) volts (EQ 36)
F ( a H ) PZC

The potential drop across the double layer at the aluminawater interface is shown
schematically in Figure 7. As the ionic strength is increased, the double layer is reduced in
thickness, and the potential at the Stern plane () is reduced.
Table 4 presents a tabulation of typical PZC values of several oxides. This table shows
that the surfaces of oxides range from being acidic in nature to quite basic. Examples of how
pH strongly affects adsorption at the surface of oxides will be shown later.
At this point, consider the Gibbs equation for oxide minerals in aqueous media in the
presence of an electrolyte, such as NaC1. The change in tension of the mineralwater inter-
face due to the adsorption of H+, OH, Na+, and Cl is given by

d = H + d H + OH d OH Na + d Na + Cl d Cl (EQ 37)

At constant ionic strength, this equation simplifies to

d = ( H + ( OH ) )d H + = 2.3RT ( H + OH ) d ( pH ) (EQ 38)

Thus, it can be seen that the surface tension of the mineralwater interface can be con-
trolled by changing the pH at constant ionic strength. Figure 7 also shows schematically the

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40 Ferric Oxide 1M
KNO3 101

Adsorption Density (H+ OH), mol/g





5 6 7 8 9 10 11
Source: Parks and de Bruyn 1962.

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

+118 101 +118

103 M
Potential, mV

Potential, mV

0 0
Distance 101
102 M
59 59

118 118

pH 7 pH 11

103 M

7 9 11

FIGURE 7 Electrical double layer at the aluminawater interface, showing the potential
distance curves for 103 and 101 molar indifferent electrolyte at pH 7 and pH 11 (the PZC
occurs at pH 9). The change in the solidliquid interfacial tension with pH and ionic strength is
also shown schematically.

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TABLE 4 PZC of some oxides*

Material PZC, pH
SiO2, silica gel 12
SiO2, -quartz 23
SnO2, cassiterite 4.5
ZrO2, zirconia 4
TiO2, rutile 5.86.7
Fe2O3, hematite (natural) 4.86.7
Fe2O3, hematite (synthetic) 8.6
FeOOH, goethite 6.8
Al2O3, corundum 9.1
AlOOH, boehmite 7.88.8
MgO, magnesia 12
Source: Fuerstenau 1970.
*These are typical results. The sources of oxideits trace impurities, method of pretreatment, etc.cause variations in
observed values.

change in interfacial tension of alumina with pH for several salt concentrations. The maxi-
mum in the interfacial tension occurs at the PZC (i.e., at pH 9).
In view of this discussion on surface charge, the Gibbs adsorption equation for an oxide
can be rewritten as

d = S d o Na + d Na + Cl d Cl (EQ 39)

or at constant ionic strength as

d = S d o (EQ 40)

The greater effect of increased ionic strength on the interfacial tension lowering (Figure 7)
simply results from the greater magnitude of s.

Effect of Temperature on the Electrical Double Layer

In order to understand temperature effects in the adsorption of ionic collectors, the effects
that temperature has on the double layer at interfaces must be considered.
Experimentally, the PZC of oxides has been found to decrease with increasing tempera-
ture (Parks 1960; Lai 1970; Tewari and McLean 1972). An example of this is shown in Fig-
ure 8, which presents electrophoretic mobility data for alumina and magnesia at three
temperatures. The overall reaction and its equilibrium constant, K, 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 = --------------------------------
- (EQ 42)
( a MO ) ( a H + ) 2

From thermodynamics, it is known that

G o = H o T S o = RT ln K (EQ 43)

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( a MOH + )
- =
ln -------------------------------- H o S o
----------- -------- (EQ 44)
( a MO ) ( a H + ) RT R

Given that the number of positive and negative sites must be equal at the PZC, it can be seen

H o S o
ln ( a H + ) = ----------- -------- (EQ 45)
2RT 2R

H o S o
( pH ) PZC = --------------
- + ----------- (EQ 46)
4.6RT 4.6R
Assuming that the enthalpy does not vary over the temperature range considered, 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. Table 5 gives the results of this calculation
for several oxides (Lai 1970). These calculations show that the enthalpy for protonization of
surface sites varies with the nature of the metal oxide, but the entropy is approximately constant.
Because the process is exothermic, the PZC of oxides decreases with increasing temperature.


+4 5C
Electrophoretic Mobility, m/sec per V/cm



4 6 8 10 12 14

Source: Lai 1970.

FIGURE 8 Electrophoretic mobilities of alumina and magnesia at different temperatures as a

function of pH. The pH at which the mobility reverses sign under these conditions is the PZC.

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TABLE 5 Enthalpy and entropy of hydrogen ion adsorption on oxides, expressed for the
adsorption/desorption of a single H+
Oxide (pH)PZC at 25C H kJ/mol H+ S entropy units/mol H+
SiO2, cassiterite 2.2 0.65 7.9
TiO2, rutile 6.3 6.05 8.7
Al2O3, alumina 9.1 10.16 7.8
MgO, magnesia 11.8 13.59 8.7
Source: Lai 1970.

4 45
Surface Charge, s, C/cm 2


5 Silver Iodide
0.1 M Ionic Strength

+200 +100 0 100 200 300 -400

Surface Potential, 0, mV
Source: Lyklema 1966.

FIGURE 9 Temperature dependence of the surface charge on AgI particles, showing the
decrease in surface charge with increasing temperature. All curves are normalized to the PZC
at reference temperature.

In addition to shifting the PZC, temperature also affects the charge on mineral sur-
faces. In general, raising the temperature results in a decrease of s. Figure 9 presents
Lyklemas (1966) results for the charge on silver iodide at temperatures ranging from 5C to
85C. The curves are all normalized to the PZC at the temperature of reference. Lyklema
suggests that the decrease in surface charge with increasing temperature might be due to a
gradual desorption of counterions from the double layer, with the double layer having a
more diffuse character. Because the surface charge also is given by the expression:

S = ------ ------- (EQ 47)
4 dx x = 0

where is the dielectric constant of the medium, the decrease in with increasing tempera-
ture would account for some of the decrease. In the case of the double layer on oxides, based
on Equation 47 one can calculate the charge at various temperatures and pHs, and such cal-
culations show that the charge decreases with increasing temperature.

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Information on the thermodynamic aspects of collector adsorption can be obtained from
experimentally measured adsorption isotherms. Analysis of adsorption isotherms to obtain
thermodynamic data for collector adsorption has been completed using two different
approaches. Fuerstenau, Harper, and Miller (1970) have successfully used the SternGrahame
model of the electrical double layer to explain the adsorption of alkylammonium ions at the
quartzwater interface and alkyl sulfonates at the aluminawater interface. These collector
ions are considered to be adsorbed as counterions in the double layer. Cases (1970), on the
other hand, has interpreted the results of his adsorption studies on biotite in terms of the
theoretical isotherms established by Frumkin, Fowler, Hill, and Halsey. Both approaches
will be briefly discussed in the next few paragraphs.
First, equilibrium in heterogeneous systems is attained when the chemical potential of
species i is equal in all phases. For collector species i, its chemical potential in bulk solution is
given by

i = io + RT ln a i (EQ 48)

where io is its standard chemical potential and ai is its activity in solution. The chemical
potential of the same species at the surface, iS, is

iS = ( io ) S + RT ln a iS (EQ 49)

where (io)S is the standard chemical potential of this species at the surface and aiS is its
activity in the surface. At equilibrium, given that i = iS,

io ( io ) S
a iS a i = exp ------------------------- (EQ 50)
This relation can be transformed into the well-known SternGrahame equation by making
the following assumptions:

a i = C(the bulk concentration) and a iS = 2r (EQ 51)

where is the adsorption density in the Stern plane, and r is the effective radius of the
adsorbed ion. The standard free energy of adsorption, Gadso, is defined as
G ads = ( io ) S io (EQ 52)

Substituting these three relations (from Equations 51 and 52) into Equation 50 yields the
SternGrahame equation (Grahame 1947; Fuerstenau 1970)
o RT )
= 2rC exp ( G ads (EQ 53)

Another approach to developing the SternGrahame 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. This leads to

x 1S x 2 x 2S x 1 = K (EQ 54)

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where x1 and x2 refer to the mole fraction of solute and solvent, respectively, in the liquid
phase, and x1S and x2S are mole fractions in the adsorbed state. Given that x2S = 1 x1S,
Equation 54 can be rewritten as

x kS x x G ads o
- = K ----1 = ----1 exp -----------------
------------- (EQ 55)
1 x1 S x 2 x 2

At small values of x1, Equation 55 becomes essentially identical to the usual form of the
SternGrahame equation (and to the Langmuir equation).
The SternGrahame approach is useful in that it allows one to take electrical effects
into account when dealing with ionic collectors. If ions adsorb only through electrostatic
interactions, then the standard free energy of adsorption is given by
G ads o
= G elec = vF (EQ 56)

where v is the valence of the adsorbed ion including sign. On oxide minerals, alkali cations
appear to be surface-inactive, that is, only electrostatic interactions appear to be operative.
Nitrate anions are surface-inactive on cassiterite (SnO2), rutile (TiO2), Al2O3, and hematite
(Fe2O3). Although chloride ions are not surface-active on Al2O3, they appear to be specifi-
cally adsorbed on Fe2O3 (Fuerstenau 1970).
When an ion exhibits surface affinity, it is considered to be specifically adsorbed, and
the free energy of adsorption has additional terms:
G ads o
= vF + G spec (EQ 57)
where G spec represents specific interaction terms. Certain inorganic ions exhibit surface
activity: Ba2+ on quartz, Ba2+ and SO4= on alumina, Ca2+ and SO4= on rutile, and hydro-
lyzed metal cations on a wide variety of solids (Fuerstenau 1970). Equation 57 shows that if
G spec is finite, then the ion will be positively adsorbed even if is zero or has the same
sign as the adsorbing ion. An estimation of G spec o can be made for conditions when is
zero (e.g., when the electrophoretic mobility of the particles is zero).
For the adsorption of organic collectors of interest to flotation scientists, various
attempts have been made to split G ads o as follows:

G ads o
= G elec o
+ G chem o
+ G CH o
+ G solv + (EQ 58)

where G eleco o
is the electrostatic contribution to the total free energy, G chem represents
the free energy due to the formation of covalent bonds with the surface, G CH o represents
the interaction due to association of hydrocarbon chain of adsorbed collector ions at the
interface (sometimes called hydrophobic bonding), and G solv o is the contribution of solvation
effects on the polar head of the adsorbate (collector) and adsorbent (mineral) to adsorption.
It is often customary to lump the G o terms other than G elec o together and call it
G spec o
(i.e., G spec o
= G chem o
+ G CH + G o ).
2 solv
Specific adsorption can be either physical or chemical in nature. 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. If the collector forms a covalent bond with metal ions in the sur-
face of the mineral, then the process should be termed chemisorption. Much of the work that

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has been carried out with collector adsorption at interfaces has been concerned with physi-
cal adsorption, such as in the quartzalkylammonium (de Bruyn 1955; Gaudin and Fuer-
stenau 1955; Somasundaran, Healy, and Fuerstenau 1964) and the aluminaalkyl sulfonate
systems (Somasundaran and Fuerstenau 1966; Wakamatsu and Fuerstenau 1968). Adsorp-
tion isotherms and electrokinetic measurements strongly suggest that at low concentrations,
these collector ions are adsorbed as individual ions in the Stern plane but that at higher con-
centrations, they associate at the interface into two-dimensional aggregates, which have
been termed hemimicelles (Gaudin and Fuerstenau 1955).
Adsorption in the aluminaalkyl sulfonate system has been studied in considerable
detail. Figure 10 presents the effect of the concentration of dodecyl sulfonate on the electro-
phoretic mobility (zeta potential), adsorption density, and contact angle on alumina at pH 7.2
and at an ionic strength of 2 103 M controlled by NaCl. From this figure, it can be seen
that the adsorption isotherm can be divided into three distinct regions. At low concentra-
tions, adsorption of sulfonate ions occurs by exchange with chloride ions in the double layer;
during the exchange, the zeta potential (and ) remains constant. In this region, only elec-
trostatic adsorption potential is active. In the second region, the adsorbed ions begin to asso-
ciate, with adsorption increasing markedly because of the enhanced adsorption potential as
G CHo becomes effective. The third region is reached when the zeta potential reverses. At
concentrations higher than this, the electrostatic interaction opposes the specific adsorption
effects, resulting in a decrease in the slope of the adsorption isotherm. Using data published
by Somasundaran and Fuerstenau (1972), Dick (1972) evaluated G ads o for the adsorption

of sodium dodecyl sulfonate on alumina at pH 6.9 and his results are plotted in Figure 11.
The onset of hemimicelle formation is accompanied by the standard free energy of adsorp-
tion becoming sharply more negative. When the zeta potential reverses, G ads o again has

much less dependence on the bulk concentration of sulfonate.

By means of the SternGrahame model of the double layer, the contribution of the
cohesive energy per mole of CH2 groups to the adsorption potential can be quantitatively
evaluated. If the standard free energy for removing 1 mol of CH2 groups from water is
through association , then the total contribution is n if n is the number of CH2 groups in the
chain. Thus, the contribution from hydrocarbon chain association to the adsorption process is
G CH = n (EQ 59)

The adsorption density, , of collector ions in the Stern plane in the absence of chemisorp-
tion will be given by
o RT ) = 2rC exp [ ( vF n ) RT ]
= 2rC exp ( G ads (EQ 60)

From the results of Wakamatsu and Fuerstenau (1968), has been evaluated to be
about 1.0 RT (about 0.6 kcal/mol of CH2 groups) in agreement with values obtained from
solubility data and micelle formation. Because of the role that CH2 groups have in control-
ling the adsorption free energy in these systems, collector chain length will significantly
affect flotation behavior (Wakamatsu and Fuerstenau 1973). 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 0.6 RT (for micellization) to 2.0 RT (for

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109 Cosine
Adsorption Density
Electrophoresis III
0.2 40

II 30

Adsorption Density, mol/cm 2

Zeta Potential, mV

of Zeta
Reversal +20

1012 +30

Alumina +40
2 103 N Ionic Strength
pH 7.2
241C +50
105 104 103 102
Equilibrium Concentration of
Sodium Dodecyl Sulfonate, mol/L
Source: Wakamatsu and Fuerstenau 1973.

FIGURE 10 Adsorption density of sodium dodecyl sulfonate, the electrophoretic mobility, and
the contact angle of alumina as a function of the equilibrium concentration of sodium dodecyl
sulfonate at pH 7.2 and ionic strength 2 103 M controlled with NaCl


22 25C =0

Gads, kJ/mol



14 2 103 N Ionic Strength
pH 6.9

105 104 103
Equilibrium Concentration of Sodium Dodecyl Sulfontate, mol/L
Source: Dick 1972.

FIGURE 11 Variation of the standard free energy of adsorption of sodium dodecyl sulfonate
on alumina at 25C and 45C for the isotherms given in Figure 13

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In many mineralcollector systems, chemisorption occurs. 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. In terms of the
concepts of Equations 57 and 58, chemisorption occurs when G chem o has some finite value.
In flotation systems, chemisorption is of primary interest because selectivity may be
obtained if there is a specific collectormineral adsorption reaction rendering a single min-
eral or group of minerals to be air avid. In nonmetallic flotation systems, several examples of
chemisorption may be cited. Hexanethiol chemisorbs on the surface of zincite (ZnO) and
willemite (Zn2SiO4), forming a strong zincmercaptan bond. Oleate chemisorbs on fluorite
(CaF2), forming strongly adsorbed films that are difficult to remove, and on hematite and
numerous other minerals. Hydroxamates strongly chemisorb on chrysocolla and hematite.
A different approach has been taken by Cases and his associates, who consider the
adsorption process as a condensation process on either a homogeneous or a nonhomoge-
neous surface similar to that of gas adsorption. 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; Predali and Cases 1974)

f -+A
kT ln x = k ln W a a + kT ln --------- (EQ 61)
where x is the mole fraction of adsorbate in the bulk, 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), a is the differential energy of desorption per molecule, k ln f/ (1 f ) is
the configurational entropy of an adsorbed molecule, k is the Boltzmann constant, T is the
temperature, and A is a constant. On assuming a to be independent of surface coverage,
Equation 61 can be rearranged to give the familiar Langmuir isotherm:

f = ------------------------------------- (EQ 62)
1 G
x + ------ exp ------a-
A2 kT

where A2 = exp (A/kT), and Ga is the free energy of adsorption per molecule = (a kTlnWa).
Langmuir isotherms have been widely used for estimating the free energy of adsorption
from adsorption isotherms. If a is assumed to be a function of surface coverage, f, one can
obtain the well-known FrumkinFowler isotherm. To derive an equation for thermody-
namic equilibrium, Predali and Cases (1974) assumed (1) a = ao + f, where ao is the
normal binding energy between one adsorbed molecule and the surface, and f represents
the lateral interactions between the adsorbed species in the adsorbed layer; (2) in the
adsorbed layer, the number of coordinations and the lateral interactions are the same as in
the plane of the lattice of the micelle, which leads to the expression o = oo + /2, where o
is the energy to dissolve a molecule from half-crystal position in the micelle and oo is the
half of normal binding energies in micelle per molecule from half-crystal position; (3) the
entropic functions are the same in the adsorbed layer and in the micelle; and (4) k T ln xo =
k T ln Wo o + A where k ln Wo is the sum of all entropic terms for a molecule in the
half-crystal position, and xo is the mole fraction of the adsorbate (collector) in solution at
saturation (i.e., in equilibrium with micelles of collector). Predali and Cases obtained the
following relation for thermodynamic equilibrium between an adsorbed layer and a dilute
solution of the same substance:

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kT ln ---------- = ( ao oo ) ---- ( 1 2f ) + (EQ 63)
1f 2
where = k T ln x/xo and is a measure of undersaturation of collector in the aqueous solu-
tion. A plot of f versus for two cases, namely, < 4 kT (e.g., C8 alkylammonium chlo-
rides) and > 4 kT (e.g., C12 surfactants) is given in Figure 12a. From the figure, it can be
noted that when < 4 kT, the slope of the isotherms on homogeneous surfaces at f = 0.5 is
finite. It is possible to calculate the lateral binding energy between hydrocarbon chains from
the value of the slope at f = 0.5. On the other hand, when > 4 kT, the slope of the iso-
therms is infinite at f = 0.5. 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. Cases (1970) studied the adsorption of dodecylammonium chloride on
homogeneous surfaces and found the isotherm to exhibit a constant slope up to f = 0.015,
followed by an infinite slope up to f = 0.985. This corresponds to a case where > 4 kT.
Cases suitably modified Equation 63 for nonhomogeneous surfaces, and this modified
equation predicts a constant slope for adsorption isotherms (f versus C plot) up to a value of
f close to 1. 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. The first has a finite slope, and, according to their developed theory, this
is due to the condensation on a nonhomogeneous surface. The second branch has an infinite
slope, which is considered to be due to condensation on a homogeneous surfacethat is,
onto the first adsorbed layer (see Figure 12b).
Though the theoretical isotherm of Frumkin, Fowler, Hill, and Halsey fits the experi-
mental data, as claimed by Cases (1970), there is one serious assumption underlying this
approach, that is, the entropic effects involved in the adsorption from solution are similar
and equal to that involved in the adsorption from gaseous state. This assumption is highly
questionable because water structure at a solidliquid interface plays a key role in adsorp-
tion, and any water molecules released on adsorption of the collector would significantly
increase the entropy of the system. Furthermore, the utility of the Cases approach is somewhat

* Chlorides
Fractional Surface Coverage, f

C18 C16 C14 C12

< 4 kT

f I
0.5 > 4 kT 1.0 C10


106 105 104 103

Equilibrium Concentration, mol/L

Source: Predali and Cases 1974.

FIGURE 12 (a) Schematic FrumkinFowler isotherm on a homogeneous surface, and (b)

adsorption isotherms of alkylammonium chlorides of different chain lengths on biotite at pH
5.5 and 25C

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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.
Finally, plotting results in the form of fractional surface coverage versus concentration masks
the very important effects encountered at low surface coverages.

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.g., hydroxamic acids on hematite or chryso-
colla, oleate on fluorite or calcite, xanthates on sulfide), and (2) long-chain ionic surfactants
that adsorb physically as counterions in the electrical double layer. The second class of col-
lectors is characterized by strong hydrocarbon chainhydrocarbon chain interaction in the
Stern layer (e.g., dodecyl sulfonate on alumina or hematite, dodecylammonium chloride on
quartz). The interaction of long-chain carboxylates with oxides might be considered as an
intermediate category.
Measurements of the heat of adsorption of collectors may be able to shed some light on
the following aspects of the collection process:
1. Nature of the interaction with the substrate (For example, by analogy with the heats
of chemisorption and physisorption of gases, it may be expected that type 1 reac-
tions will be more exothermic than type 2.)
2. 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, London. Mellgren (1966)
investigated the heat of xanthate adsorption on galena samples as ground or previously
treated with potassium carbonate, sulfate, or thiosulfate solutions. 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. This was as expected
because thiosulfate was found to be the oxidation product on the galena used. Mellgren
measured rather erratic and large H values at high pH values and concluded that second-
ary reactions were involved at these high pH values. Heat of adsorption measurements on
samples treated with carbonate, sulfate, and thiosulfate gave values equivalent to those
obtained when ethyl xanthate was reacted with lead carbonate, lead sulfate, or lead thiosul-
fate. These findings suggested that metathetical reactions between the xanthate and the oxi-
dation products on the surface of galena were involved. The quantities of xanthate adsorbed
on the carbonate- and sulfate-treated galena surfaces were equivalent to the quantities of
thiosulfate released into the solution after the treatment. This led to the conclusion that an
ion exchange mechanism might be involved in the adsorption process.
Mellgren and Rao (1968) performed similar experiments with potassium diethyldithio-
carbamate instead of xanthate and obtained similar results. Gochin (1972) carried out an
elaborate thermochemical study of the flotation of sphalerite and pyrite along similar lines.
In addition, 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+, which takes
place according to the following reaction:
ZnS + Cu 2+ = CuS + Zn 2+ ; H 298 K, theor. = 63kJ mol

Gochins measured values agreed quite well with the theoretical value stated previously.

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Two systematic studies on the heat of adsorption of type 2 collectors on oxides have
been reportedone by Roy and Fuerstenau (1968) and the other by Mellgren et al. (1974).
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. Both types of interactions involve
the removal of water in the vicinity of the surface. Roy and Fuerstenau (1968) studied the
heat of immersion of alumina in aqueous solutions containing sodium dodecyl sulfonate at
various pH values. They found that as the sulfonate ions begin to adsorb (associate) in the
Stern layer, the heat of immersion begins to become more negative than the heat of immer-
sion of Al2O3 in water, reaching a value of 1,100 ergs/cm2 at monolayer coverage. At
higher coverages, the heat of immersion remained at about 1,100 ergs/cm2. They did not
detect any measurable heat effect when the sulfonate ions occurred only in the diffuse part
of the double 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. By this model, they estimated an integral heat of adsorption of 5.0 kJ/mol.
Mellgren et al. (1974), working with the hematitedodecyl sulfate system, found that
the heat of adsorption (5.7 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. They
measured a heat close to the heat of micellization of sodium dodecyl sulfate. (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.) Mellgren and colleagues found
evidence for sites of different adsorption energy on powdered natural hematite, the propor-
tions of which depend on the method of grinding (or heat treatment) of hematite.
An indirect method for determining the heat of adsorption is to measure the amount of
collector adsorbed () as a function of concentration (C) at a given solution pH at two or
more different temperatures. From a ClausiusClapeyron type of equation:

H ads o
ln C
------------ = -----------------
- (EQ 64)
T RT 2

This heat of adsorption is the same as the isosteric heat of adsorption, Q st. The heat of
adsorption is calculated from adsorption isotherms obtained at two different temperatures.
For collectors such as amines, sulfonates, and so forth, which do not chemically react with
the surface, Q st is the heat of adsorption in the real sense of the word. On the other hand,
collectors such as salicylaldehyde (Rinelli, Marabini, and Alesse 1976) and xanthates
(Mellgren et al. 1974) chemically react with the surface and form metalcollector complexes
both on the surface and in the bulk. In those cases, Q st is not the real heat of adsorption but
represents a heat intermediate between heat of reaction and heat of adsorption. From mea-
surement of isotherms for the adsorption of sodium dodecyl sulfonate at two temperatures
(Figure 13), Somasundaran and Fuerstenau (1972) evaluated the enthalpy and entropy of
the adsorption process. Their results show that the adsorption decreases with increasing
temperature, indicating the exothermic nature of the process.
Ball and Fuerstenau (1971) used a different approach for evaluating the heat of adsorp-
tion. Taking the logarithm of the adsorption density given by the SternGrahame equation,
they obtained
o RT )
ln = ln 2r + ln C ( G ads (EQ 65)

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Adsorption Density, mol/cm 2


pH 6.9
1012 3
2 10 M Ionic Strength


106 105 104 103 102
Equilibrium Concentration of Sodium Dodecyl
Sulfonate, mol/L

Source: Somasundaran and Fuerstenau 1972.

FIGURE 13 Adsorption density at 25C and 45C of dodecyl sulfonate on alumina as a

function of its equilibrium bulk concentration at pH 6.9 and ionic strength 2 l03 M

Differentiating this equation with respect to temperature yields

o RT ) o
d ( G ads ln C d ln r ln H ads
- = ------------ + ----------- -------------- = -----------------
---------------------------------- - (EQ 66)
dT T dT T C RT 2

If the radius of the adsorbing ion is assumed to be independent of temperature,

ln C ln
------------ H ads
-------------- = -----------------
- (EQ 67)
T T C RT 2
Under conditions of constant adsorption density, H ads becomes the isoteric heat of
adsorption and is given by

ln C
------------ Q st
= ---------
- (EQ 68)
T RT 2

The values of isoteric heat of adsorption can be calculated from the slope of the plot of
(log C) against temperature. Because G ads o can be obtained as a function of temperature

from the adsorption data using Equation 65, S ads o can be computed easily as
o o
S ads = d ( G 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. Their calculations indicate large entropic effects that have been attributed to the
phenomenon of hydrophobic bonding.

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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. Systems in which the collector exhibits physisorption characteristics
2. Systems wherein the collector chemisorbs onto the mineral
3. Systems in which the collector seems to chemically react at the mineral surface with
ions derived from the mineral surface. This is actually a borderline category and, for
all practical purposes, could be classified under category 2.
For any adsorption process, the free energy change is given by

G ads = H ads T S ads (EQ 69)

If the process occurs spontaneously, then G ads is negative. This can be achieved by
the adsorption process being exothermic or by its being accompanied by a large entropy
increase. Not much is known about entropy changes in collector adsorption processes. On
the one hand, there will be an entropy decrease because of the more ordered structure of col-
lector ions or molecules at the interface, but on the other hand, 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. Particularly for longer-chained col-
lectors, this could result in S ads having a large positive value.
Type 1 systems are characterized by an exothermic heat and, as a consequence, adsorp-
tion decreases with increase in temperature. A good example of this type is the alumina
dodecyl sulfonate system investigated by Somasundaran and Fuerstenau (1972). Figure 13,
which demonstrates their results, shows such a decrease in the adsorption density. Although
no one has yet analyzed the results in such a manner, 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. Another example is the work of Ball and Fuerstenau (1971) on the aqueous
dodecylammonium acetatequartz system. 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, which
points indirectly to a decrease in adsorption with increasing temperature.
Of the chemisorbing systems investigated, the temperature dependence of the adsorp-
tion of soaps on mineral surfaces has been investigated in some detail. Falconer (1949),
referring to a 1938 French patent, wrote in 1949 about the value of using high temperature
for the conditioning of nonsulfide ores for flotation with soaps. Specifically, he mentioned
conditioning above 35C, and preferably above 60C. In 1950, Cook and Last conducted an
interesting investigation of the effect of conditioning temperature on the flotation of fluorite
with oleic acid. Figure 15 presents their results on the flotation of a fluorite/calcite/barite ore.
Below 40C, the recovery of fluorite is very low, but raising the conditioning temperature
causes the recovery to rise sharply, to 90%95% at temperatures of 70C or greater. 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 45C60C. Because of an
activation energy, raising the temperature causes the chemisorption reaction rate to proceed
reasonably rapidly during the conditioning period.

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40 pH 7


Zeta Potential, mV




1 2 3 4 5 6 7 8 9 10
Dodecylammonium Acetate Concentration, M 104

Source: Ball and Fuerstenau 1971.

FIGURE 14 Zeta potential of quartz as a function of dodecylammonium acetate concentration

at different temperatures


Flotation Recovery or Grade,%



20 Fluorite

0 20 40 60 80 100
Conditioning Temperature,C

Source: Cook and Last 1950.

FIGURE 15 Effect of conditioning temperature on flotation recovery and concentrate grade for
the flotation of a fluorite ore, which had been conditioned for 5 minutes with oleic acid,
quebracho, and sodium carbonate

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Amount Adsorbed



FIGURE 16 Schematic representation of an adsorption isobar, showing the transition from

physisorption to chemisorption. Only in the transition region should the adsorption increase
with increasing temperature.

In conditioning at elevated temperatures, activating the adsorption process for chang-

ing it from physisorption to chemisorption is illustrated schematically in Figure 16. The
change from one type of process to the other could begin at about 40C in these systems.
Kulkarni and Somasundaran (1975) found that the adsorption of oleate on hematite
increases as the temperature is raised from 25C to 75C at low ionic strengths, but the con-
verse was observed at very high ionic strengths (due to salting-out effects at lower tempera-
tures). Figure 17, after Somasundaran and Kulkarni (1977), shows that the flotation
recovery at low ionic strength increases as the temperature is increased, with maximum
recovery always occurring at about pH 8. This implies marked increase in collector adsorp-
tion with increasing temperature.
Raghavan and Fuerstenau (1975) have investigated the effect of concentration, pH, and
temperature on the adsorption of octylhydroxamate on hematite. Optimum adsorption
always occurred at about pH 8.4; they considered the adsorbing species to be the hydrox-
amic acid molecule. Using Equation 55 in the following form:

G ads o
f - = ------------
--------- exp ----------------- (EQ 70)
1f 55.55 RT

where f is the fraction of the surface covered by the collector, and C is the collector concen-
tration in solution, they found G adso to be approximately 32 kJ/mol and nearly indepen-

dent of pH and surface coverage (for f < 0.8). For a chemically adsorbing species, the
observed value of G adso is rather small. Their results on the effect of temperature, which
are presented in Figure 18, show a marked increase in adsorption with increasing tempera-
ture. However, the isotherms for 41C and 60C given in Figure 18 exhibit adsorption den-
sities that exceed monolayer (7 1010 mol/cm2) coverage. This indicates possible
formation of ferric hydroxamate by surface reaction. Thus, one effect of the temperature
might simply be to increase the solubility of the mineral, thereby giving rise to a larger num-
ber of Fe ions for reaction at the surface. In an investigation of the flotation of iron oxide
with octylhydroxamate and oleate as collector, Fuerstenau, Harper, and Miller (1970) found
enhanced flotation with increasing temperature. Their conclusions were that the chemisorp-
tion process definitely involves increased mineral solubility as the temperature is raised. In

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3 103 M KOI


Flotation Recovery, %






3 4 5 6 7 8 9 10
Flotation pH

Source: Somasundaran and Kulkarni 1977.

FIGURE 17 Effect of temperature on the flotation of hematite with 3 l05 M potassium oleate
as collector


Amount Adsorbed, mol/cm 2 10 10



pH 5.5
2 103 M KNO3

0 2 4 6 8 10 12
Hydroxamate Equilibrium Concentration 104, mol/L

Source: Raghavan and Fuerstenau 1975.

FIGURE 18 Effect of temperature on the adsorption density of potassium octylhydroxamate

on hematite

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an earlier study, while working with octylhydroxamate and various other chelating agents as
collectors for chrysocolla, Peterson et al. (1965) clearly showed that raising the temperature
can markedly increase flotation response. The optimum pH for chrysocolla flotation always
occurred at about pH 6.
In an interesting study of the flotation characteristics of pyrolusite, Fuerstenau and Rice
(1968) found that flotation decreased slightly with a sulfonate when the temperature was
raised from 23C to 60C. On the other hand, with oleate as collector for the same mineral,
flotation increased markedly upon raising the temperature from 23C to 60C. However,
the pH for optimum flotation was reduced from 10 at 23C to about 8 at 60C. On the
other hand, Yousef, Arafa, 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.
Cooke, Iawasaki, and Choi (1960) conducted a detailed investigation of the effect of
temperature on the flotation of hematite. With a series of collectorsstearic, elaidic, oleic,
linoleic, and linolenic acidsthey observed only a very slight increase in flotation and in
contact angles by increasing the temperature from 25C to 70C, except for stearic acid,
which exhibited a strong increase due to its increased solubility. They also found that con-
tact angles of calcium-activated quartz at pH 11 decreased with increasing temperature,
indicating diminished calcium adsorption. On the other hand, flotation under the same
conditions increased with increasing temperature, but this was probably due to rather
unusual frothing characteristics at pH 11.
As has already been discussed at length, pH has a marked effect in flotation because of
its effect on collector ionization, surface charge, and mineral solubility. Thus, 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).
In conclusion, the flotation process, as a consequence of its being a multiphase hetero-
geneous system, is quite complicated to analyze thoroughly by simple thermodynamic
approaches. What this chapter attempted to do is bring out a few salient features of the
application of thermodynamic concepts to the understanding of flotation.

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de Bruyn, P.L. 1955. Flotation of quartz by cationic collectors. Trans. AIME 202:291.
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Gaudin, A.M. 1957. Flotation. 2nd edition. New York: McGraw-Hill.
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Institute of Mining, Metallurgical, and Petroleum Engineers.
Lai, R.W. 1970. Surface charge, adsorption of ionic surfactants and wettability of oxide minerals.
Ph.D. thesis, College of Engineering, University of California, Berkeley.
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Lin, I.J., and P. Somasundaran. 1971. Free-energy changes on transfer of surface-active agents between
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Wada, M. 1960. The wetting of solid in solutions of surface-active substances as a function of solute
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The Nature of Hydrophobic

Attraction Forces
Jan Christer Eriksson and Roe-Hoan Yoon

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, such as surface and colloid science, biochemistry, and mineral processing. The forma-
tion of surfactant micelles and biomembranes, for instance, 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. In addition, many enzymatic reactions take place while the
substrate is locked in a hydrophobic pocket. In the field of flotation, on the other hand,
long-range hydrophobic attraction forces contribute to establishing the mineralparticle/
airbubble attachment necessary to achieve selective ore enrichment.
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. 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.
Derjaguin and Churaev (1974) and Derjaguin, Churaev, and Muller (1987), referring to a
large body of experimental results, 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), developed by Tabor and
Winterton (1969) and Israelachvili and Tabor (1972) (Figure 1); the atomic force micro-
scope (AFM) (Figure 2); 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, Ninham, and Stewart (1996).
This particular research area, which focuses on thin, aqueous films between hydropho-
bic surfaces, 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, 1984). They established that in addi-
tion to the normal DLVO (DerjaguinLandauVerweyOverbeek) forces due to disper-
sion and electrostatic interactions, a long-range attractive interaction force operates as a
consequence of the hydrocarbonwater contact. Hence, they identified this surface force as
the hydrophobic force, a term originally coined by Blake and Kitchener (1979).
Several years later, Claesson and Christenson (1988) and Christenson and Claesson
(1988) experimented with mica surfaces that had been modified by LangmuirBlodgett
(LB) deposition of dioctadecyldimethylammonium (DODA) bromide or, alternatively, a
double-chain cationic fluorocarbon surfactant. For these cases, the hydrophobic attraction
was considerably stronger and of longer range than observed by Israelachvili and Pashley

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Piezoelectric Coarse
Tube Separation

Curved Double-Beam
Mica Cantilever

Clamp to
Adjust Spring
NOTE: The interacting (mica) surfaces have cylindrical shape, and their separation is determined optically by means of an
interferometric technique. The lower surface is attached to a cantilever spring, the deflection of which serves to determine the
interaction force (Flinn 1997).

FIGURE 1 SFA based on the original design by Tabor and Winterton (1969) and Israelachvili
and Tabor (1972)

Laser Beam

Flat Plate


NOTE: The top portion shows a drawing of a triangular cantilever with an attached glass sphere. The distance between the
sphere and flat plate (sample) is measured by monitoring the deflection of the cantilever spring using a laser beam. The deflec-
tion of the cantilever of a known spring constant gives the force at a given separation distance (Flinn 1997).

FIGURE 2 Schematic representation of AFM

(1982, 1984)about 100 times stronger than the van der Waals attraction; decay length
about 15 nmand measurable up to about 80 nm. Independently, measurements were also
conducted in Moscow by Rabinovich and Derjaguin (1988) using silanated silica filaments,
which yielded mostly equivalent results (Figure 3).
Subsequent control experiments employing a variety of prepared hydrophobic surfaces
have only partially confirmed the previous findings and perceptions. An abundance of
biased and bewildering results have been presented by many investigators, making it difficult

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h, nm

0 10 20 30 40 50 60 70 80

Rabinovich and

F / R , N m1



NOTE: The points demark experimental values measured by Claesson and Christenson (1988). The solid line represents
Equation 56, obtained by inserting B = 0.6 mJ/m2 and b1 = 15.8 nm from Equation 31. For comparison, the dotted line shows
the surface force function determined by Rabinovich and Derjaguin (1988) for silica filaments immersed in 0.1 mM KCl (potas-
sium chloride) solution. The corresponding experimental points are scattered around the dotted line within a factor of about 3.

FIGURE 3 Plot of the attractive surface force, F/R, vs. the surface separation, h, for DODA-
covered mica surfaces in contact with pure water

to summarize the current status of research. Nevertheless, Christenson and Claesson (2001)
presented a detailed account of the scientific state of the art from an experimental perspec-
tive. They classified the non-DLVO attractive forces observed between hydrophobic sur-
faces into the following classes:
1. A fairly short-range but strongly attractive force, much stronger than the van der
Waals force, between stable hydrophobic surfaces
2. An attraction of variable strength and range caused by the presence of small bubbles
sporadically adhering to hydrophobic surfaces
3. A very long-range attractive force with exponential decay operating between a variety
of hydrophobic surfaces, in particular those hydrophobized by means of Langmuir
Blodgett deposition on mica or silica, or adsorption from solution of an ionic

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Spalla (2000) presented a complementary paper, primarily dealing with the theoretical
understanding of the hydrophobic force. Furthermore, papers by Tsao, Evans, and Wenner-
strm (1993) and Craig, Ninham, and Pashley (1998) incorporate illuminating discussions
about the possible origins of the hydrophobic force. More recently, Israelachvili and co-workers
have begun to critically re-examine the entire issue, and extensive reference lists are included
in their papers (Meyer, Lin, and Israelachvili 2005; Lin et al. 2005).
At this point, the chapter focus is on some typical results obtained for the main hydro-
phobic surfaces investigated so far, and in particular, for hydrophobic surfaces that are of
superior quality. The ultimate purpose is to scrutinize whether there is enough evidence
today in support of the existence of a true hydrophobic force (i.e., a surface force of long
range that is related to the structural response of a thin water film between hydrophobic sur-
faces). First, some recent findings as to the molecular organization of water interfaces and
hydrophobic interactions in general are discussed. After dwelling on the thermodynamics of
the surface force experiment, the concept of an ideal hydrophobic surface is introduced, thus
providing a frame of reference for judging experiments with real hydrophobic surfaces that
usually exhibit many deficiencies. 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.

Because of the advent of novel spectroscopic and computational methods in recent years,
considerable progress has been made in the probing and modeling of the molecular state of
bulk as well as of surface water. These novel methods include sum-frequency generation
(SFG) spectroscopy, X-ray absorption spectroscopy (XAS), and X-ray Raman scattering
(XRS) (Miranda and Shen 1999; Wernet et al. 2004). Hence, it has been established that
about one-fourth to one-fifth of the water molecules in the top monolayer of the waterair
interface have a non-hydrogen-bonded OH group as a unique feature.
The dangling OH group spectral peak for a hydrocarbonwater interface remains
essentially the same as for the free water surface toward air, and can be rationalized on the
notion of oriented oxygen double layers similar to those present in the ice Ih lattice (Figure 4).
Evidently, a large part of the comparatively high surface energy of water is connected with
the excess of broken hydrogen bonds in the surface, compared to the situation in bulk water.
Rather surprisingly, however, 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), resulting in rings and chains of water
molecules. On this point, one may note that according to Hills small-system thermodynam-
ics, 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. In the absence of any long-range forces, a mechanism of this thermodynamic nature is
decisive for the formation of elongated, rod-shaped surfactant micelles. A similar scheme
can be applicable even for chains of water molecules and might be at the root of water effects
of long range. It remains to be assessed, however, 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).

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FIGURE 4 The ideal ice Ih structure, characterized by stacked oxygen double layers. The
numbers represent dimensions in picometers.

Thus, when considering hydrophobicity and hydrophobic surface forces, bear in mind
the ongoing endeavors to probe and to simulate interfacial and bulk water by means of
molecular dynamics, which may result in a substantially revised basis for a comprehensive
theoretical treatment of these phenomena (Cavalleri 2004). The classical simulations of Lee,
McCammon, and Rossky (1984), which are often referred to in this context, may have been
based on a simplistic water potential (of ST2 type). This has already been indicated by the
fact that the predictions of the melting point of ice using water models of this kind are, for
the most part, grossly in error. Moreover, to only explore density changes in a thin water film
might not be sufficient because minor, although thermodynamically significant, structural
rearrangements can occur without sensible volume changes.
Speaking in broad terms, an atomically smooth, 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, as would actually be the case
for any liquid, and
Force the hydrogen bond network to rearrange in its vicinity so as to limit the num-
ber of broken hydrogen bonds, thus forming a clathrate-resembling contact mono-
layer of water molecules.
On average, this would result in a roughly tangential alignment of the water dipoles. In
a cooperative fashion, such a contact monolayer, in turn, imposes bonding constraints on
the successive layers of water molecules beneath it so as to generate a surface-induced net-
work. A crucial and much-debated question arises: How deep toward the bulk may such a
network prevail? Interestingly, 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,
whereas a more disordered water structure prevails for the waterair and waterhexane
The previously mentioned simulations by Lee, McCammon, and Rossky (1984) and
similar ones by other researchers (Forsman, Jnsson, and Woodward 1996) indicate that a
significant surface effect is noticeable only for short distances in liquid water, on the order of

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1 nm. In contrast, many surface force measurements (detection limit 10 Nm1) are
indicative of non-DLVO attractions extending as far as 50 nm and, occasionally, even
longer. Eventually, 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.

The concept of hydrophobicity stems from the common observation that many substances,
such as oil and hydrocarbons, do not mix with water. Yet, for entropic reasons, there is
always a slight solubility, even for hydrocarbons, that reflects the local energetic conditions
of a single hydrophobic solute molecule surrounded by water molecules. By analyzing the
(molefraction-based) solubility in water of a number of straight-chain hydrocarbons,
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. These thermo-
dynamic quantities are necessarily positive and of the following magnitude at room temper-
ature (per methyl or methylene group):
CH = 3.548k B T
(EQ 1)
CH = 1.492k B T

where kB = R/NAvogadro and is the Boltzmann constant and T is the absolute temperature.
With sign reversed, CH 0 0
and CH determine the driving force for aggregation of
3 2
hydrocarbon chains present in water, provided that the concentration of the chains exceeds
the normal water solubility of the bulk hydrocarbon, a condition that can easily be realized
by attaching a polar group to the hydrocarbon chain, thus forming an amphiphilic molecule.
Generally, the solubility of a hydrocarbon in water is nearly temperature-independent
at about room temperature. Referring to the thermodynamic GibbsHelmholtz equation
for the case under discussion,

d ln x hc h hc 0
- = ----------
- (EQ 2)
d( 1 T ) kB

where xhc denotes the mole fraction of dissolved hydrocarbon. As xhc is approximately inde-
pendent of temperature within the room-temperature range, this relation implies that the
enthalpy change for the process

hc (bulk hydrocarbon) hc (water) (EQ 3)

is small, which in turn means that the difference between the standard state chemical poten-
tials is given by
0 = h 0 T s 0 T s 0
hc (EQ 4)
hc hc hc

0 is largely determined by the (negative) entropy change, s 0 ,

In other words, hc hc
accompanying the hydrocarbon dissolution in water.

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According to Frank and Evans (1945), and Shinoda (1978), these thermodynamic
results can be understood in the following way. To insert a hydrocarbon molecule into water,
it takes a certain amount of energy to form a nano-cavity where the hydrocarbon molecule
can reside. At room temperature, however, 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, h structure . What is left, then, to obtain an estimate of hc
largely the concomitant entropy change:
0 s
s hc structure h structure T (EQ 5)

that pertains to a process similar in nature to a freezing phase transition and is, hence, a neg-
ative quantity. The last approximate relation in Equation 5 follows because for such a phase
transition, there is almost no net change in Gibbs energy.
Conversely, T s structure may be identified as being the main driving force for hydrocar-
bon association in a water environment at ordinary temperatures. In other words, the overall
excess free energy due to the water structuring can be reduced by hydrocarbon association.
In this way, one can readily rationalize why, for example, ordinary surfactant micelles start to
form in solution (and hemimicelles on surfaces) at some fairly low critical surfactant con-
centration (i.e., the critical micelle concentration).
A few decades ago, the negative thermodynamic quantity s structure discussed above
was often attributed to iceberg formation that was considered to be the general cause of
hydrocarbon association in water, the prevailing belief being that release of structurally con-
strained water molecules furnishes the free energy required to accomplish the association.
The similarities with clathrate formation for inert gases in water were also frequently men-
tioned as supporting evidence. The full experimental picture is, however, somewhat more
complex; compare Figure 5, which shows that water exhibits normal liquid properties at
high temperatures where the solubility of a hydrocarbon increases with temperature but spe-
cial, structurally related properties at lower temperatures. This behavior can, thus, be traced
back to the formation of hydrogen-bonded clusters and networks in water.
Basically, much the same explanation accounts for the relatively low surface entropy of
liquid water. On a molar basis, this entropy amounts to about 10 J/Kmole, whereas for normal,
non-hydrogen-bonded liquids, a value of about 25 J/Kmole (approximately one-fourth of
the entropy of vaporization) is typical (Eriksson 1966).
Moreover, at ordinary temperatures, the surface entropy of water increases with temper-
ature, as appears from the following experimentally determined surface tension function for
pure water (Cini, Loglio, and Ficalbi 1972), recalling that the surface entropy is determined
by (the negative of ) the temperature derivative of the following function:

w, air = 75.653 0.1379t 0.2717 10 3 t 2 ( mNm 1 ) (EQ 6)

where t denotes temperature in centigrade.

Because the surface entropy is an excess property relative to the entropy of water in the
bulk state, for an ordinary liquid the surface entropy is expected to be practically T-independent.
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. This conclusion is
supported by the temperature dependence observed for the SFG spectrum of the pure
watervapor interface that indicates a relative loss of ordered water as the temperature is
raised (Miranda and Shen 1999).

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200 180 160 140 120 100 80 60 40 20

log X 2



Extrapolated Experimental
Solubility Solubility
Curve Curve

2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.5

1/T 103

NOTE: Typically, the solubility passes through a flat minimum at about room temperature. The effect of water structuring is
related with the vertical distances to the corresponding extrapolated lines.

Source: Data from Shinoda 1978.

FIGURE 5 Diagram displaying how the solubilities of alkylbenzenes in water vary with

For the case of a planar geometry, however, 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. There-
fore, it can be assumed that the hydrophobic free energy is a curvature-dependent quantity,
being less for a strongly curved droplet of a hydrocarbon fluid than for a planar hydrocarbon
water interface.
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. 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

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measurements indicate attractive hydrophobic forces for water films as thick as 100 nm.
Hence, in an attempt to bridge the gap between theory and experiment, pertinent questions
to consider are as follows:
1. 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. To what extent do the experimental hydrophobic surfaces employed actually mimic
an ideal hydrophobic surface?
The questions presented in no. 1 above are currently being pursued by means of novel
spectroscopic and computational methods. Certainly, the difficulties encountered along this
fundamentally oriented route are rather formidable. 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.

It is common practice to quantify the hydrophobicity of a solid surface 1 by means of mak-
ing contact-angle measurements, usually employing pure water 3 as the contacting liquid.
Assuming the solidliquid interfacial tension (13), or more precisely, the reversible cleavage
work in water (compare Eriksson 1969) to be 13 = 51 mJm2 (i.e., the same as for an entirely
fluid hydrocarbonwater interface); taking the hydrophobic surface against air 2 to have a
corresponding interfacial tension value of 12 = 21 mJm2; and invoking 32 = 72 mJm2, fol-
lowed by using the Young equation, one can readily predict the contact angle of the hydro-
phobic surface to be
1 1
= cos [ ( 12 13 ) 32 ] = cos ( 30 72 ) = 114.6 (EQ 7)

where the term 12 13 (= 30 mJ m2) is referred to as the superficial tension of water in

contact with the hydrophobic surface. This particular tension, introduced by Gibbs,
accounts for the tendency of water to contract on a solid surface. A prerequisite for the
above identification is that no, or just minute amounts of, water vapor adsorbs at the hydro-
carbonair interface. According to Equation 7, a contact angle of 90 is reached when the
superficial tension equals zero, whereas a completely water-indifferent, polar solid surface
resembling ice, with 13 = 0 mJm2 and 32 = 72 mJm2, would exhibit a contact angle of 0.
Based on discussions in the previous paragraph, 1 and 13 have been plotted as func-
tions of contact angle (cos), as shown in Figure 6. It is expected that 13 = 36.0 mJm2 at
= 90 and 18.0 mJm2 at = 60. Thus, one realizes that even surfaces exhibiting a contact
angle substantially less than 90 are presumably capable of exerting a structural hydrophobic
effect on water.
The interfacial tension, 13, between solid 1 and water 3 can be considered to consist of
apolar and polar components. Thus,
13 = 13 (EQ 8)

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50 13

, mJm2




120C Hydrophobicity = 90C Polarity 60C

0.5 0.4 0.3 0.2 0.1 0.0 0.1 0.2 0.3 0.4 0.5

cos ()

FIGURE 6 Diagram showing how, in theory, the cosine of the contact angle of water (cos )
and the solidwater (13) and solidair (1) interfacial tensions depend on the polarity/
hydrophobicity of a solid surface

where LW refers to Lifshitzvan der Waals (i.e., apolar) interactions, and AB refers to acid
base (polar) interactions. Good and Girifalco (1960), and Fowkes (1963) showed that
LW =
13 LW LW (EQ 9)
1 3

where 1LW is the LW component of the surface free energy of solid, and 3LW is the LW
component of water. For the acidbase interactions, van Oss, Chaudhury, and Good (1987)
showed that

AB = 2
13 + + (EQ 10)
1 3 1 3

where 1+ and 3+ are the acidic components of the surface free energy of the solid and
water, respectively; and 1 and 3 are the basic components of the same.
Inserting Equations 9 and 10 into Equation 8, one obtains

13 = 1LW 3LW + 2 1+ 3+ 1 3 (EQ 11)

From the following fundamental relationships:

i = iLW + iAB (EQ 12)

where the subscript i refers to phases of interest, and

iAB = 2 i+ i (EQ 13)

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one can rewrite Equation 11 to yield the following expression:

13 = 1 + 3 2 1LW 3LW 2 1+ 3 2 1 3+ (EQ 14)

The values of 1+ and 1 of many hydrophobic substances (e.g., Teflon, polypropylene,

and dodecane) are zero and therefore have high interfacial tensions. Surfactants are used to
render various solids hydrophobic. Because the acidic ( 3+ = 25.5 mJ/m2) and basic compo-
nents ( 3 = 25.5 mJ/m2) of water are fixed under most experimental conditions, the major
role of a surfactant would be to decrease 1+ and 1 by blocking the hydrogen donor or
acceptor sites of the solid surface. 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.
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. The results are given in
Figure 7, in which K (of Equation 35) represents the magnitude of a hydrophobic force
measured. As shown, K increases with increasing advancing contact angle (a) of the silica
surfaces. The sharp increase in K at a close to 90 may represent a change in orientation of
the OTS molecule from flat to vertical orientation (Flinn, Guzonas, and Yoon 1994). As the
contact angle increases in excess of 90, cavitation may occur and cause a strong, additional
non-DLVO attraction, providing an explanation for the change in slope of the K versus a
plot. 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. It is
important to note here that K increases with decreasing 1+ , 1 , and 1LW , as suggested by
Equation 14. These findings are consistent with the work of Ederth (1999), 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 (1 and 13) and cos shown in Figure 6.
The interfacial tension (13) can be used to obtain the free energy of hydrophobic inter-
action (G131) between two solid surfaces 1 in water 3 as follows:

G 131 = 2 13 (EQ 15)

Hence, from Equation 11, one obtains the following expression:

G 131 = 2 1LW 3LW 4 1+ 1 + 3+ 3 1+ 3 1 3+ (EQ 16)

in which the first term is small for hydrophobic solids (e.g., hydrocarbons or alkanes adsorb-
ing on a solid surface), because the values of 1LW and 3LW are close to each other. If 1+
and 1 are small (i.e., a solid is apolar), the free energy of the hydrophobic interaction arises
predominantly from the 4 3+ 3 (= 102 mJm2) term. On the other hand, if the value(s)
of 1+ and/or 1 is large, G131 becomes positive (i.e., the hydrophobic interaction van-
ishes), which means that water molecules form hydrogen bonds with the surface hydroxyl
groups and render the surface hydrophobic. If a solid is basic (i.e., 1+ = 0, and 1LW =
40 mJm2, the free energy of hydrophobic interaction vanishes at 1 > 28.3 mJm2 (van Oss

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Surface Free Energy, mN/m


K, Joules
20 1



50 60 70 80 90 100 110 120

2 (Water)

NOTE: K is a parameter of a power law (Equation 35). 1LW and 1AB are the nonpolar and polar components of the surface ten-
sion of the solid surface, 1, whereas 1+ and 1 denote acidic and basic components, respectively, of 1AB.

FIGURE 7 Changes in surface free energy of OTS-treated silica plate in air contact as a
function of the advancing water contact angle, and the changes in hydrophobic force constant,
K, as a function of the water contact angle




55 60 65 70 75 80 85

Solution Fraction C16, %

Source: Ederth 1999.

FIGURE 8 Advancing ( ) and receding ( ) contact angles of water with surfaces prepared
from mixtures of C16 and C16OH-thiols of various mixing ratios

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Thus, the hydrophobic interaction is seen to be related to the strong cohesive energy of
liquid water. 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, eventually caus-
ing the water film tension to diminish as the thickness shrinks, which in turn is manifested
as a hydrophobic attraction or a negative disjoining pressure. A question remains then as to
how the hydrophobic force decays with the distance separating two macroscopic particles.
Laskowski and Kitchener (1969) suggested that the multimolecular water layer on the sur-
face of a hydrophobized silica is unstable, which is ascribed to a less favorable state of molec-
ular association at a certain distance from the surface than in ordinary (bulk) water. These
investigators were the first to recognize the existence of a long-range, non-DLVO hydro-
phobic force and to suggest that the long-range character arises from the structural proper-
ties of water.

Consider an idealized thin film/surface force experiment using two plane-parallel, atomi-
cally smooth, laterally homogeneous hydrophobic surfaces with a thin water solution film
between them (Figure 9). The thermodynamic variables of prime interest as determined in
the adjacent bulk water solution are the temperature T and the solute chemical potential
S(or the concentration cS of solute).
To establish equality of the chemical potentials everywhere, a lateral tension f develops
in the film which at large thicknesses of h will be equal to twice the interfacial tension of the
hydrophobic surfacewater solution interface (i.e., about 100 mNm1). In order to keep the
film at a certain thickness h, an extra pressure, positive (repulsive) or negative (attractive),
the so-called (Derjaguin) disjoining pressure has to be applied. This pressure, D, has alter-
natively been called surface interaction pressure.

Water Solution f

NOTE: The excess (interaction) pressure operating perpendicular to the film is, using Derjaguins terminology, the disjoining
pressure, D. In lateral directions, a film tension, f, is acting. The surface force is defined as 2 times the difference in film ten-
sion between a thin film with interacting film faces and an infinitely thick film.

FIGURE 9 Schematic of a thin liquid film between two planar, solid surfaces

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At constant temperature and pressure, the thin film system obeys the following thermo-
dynamic fundamental equation to a very good approximation:

d f = sf,ex d s + 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).
The film thickness may most conveniently be defined as the separation between the
hydrophobic surfaces devoid of any loosely adsorbed solute. 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.
Furthermore, n sf,ex A sf,ex (where A denotes the area of the film) is an excess quantity
in the following sense:

n sf,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,
respectively, and cs and cw are the corresponding bulk phase concentrations. In other words,
n sf,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.
From Equation 17 it can be seen that the disjoining pressure D is generally related to
the film tension by the derivative

------ = D (EQ 19)
h T, p, s

Hence, an attractive surface force, characterized by D < 0, will result when the film ten-
sion f decreases as the thickness diminishes, whereas D > 0 means repulsion and a film ten-
sion that increases with decreasing h. In addition, Equation 17 includes an interesting
Maxwell relation,
s D
------------ = --------- (EQ 20)
h T, p, s s T, p, 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.
The film tension f is formally an -potential per unit area,

f = A G f,ex A = G f A wf w sf s (EQ 21)

Thus, when equilibrium prevails at constant T, p, and, s, the film tension f is necessarily at
a minimum.
To derive the film tension change, f, arising because of diminishing the thickness
from h = where D = 0 (i.e., beyond the range of the surface forces), Equation 19 can be
integrated as follows while assuming that the bulk phase state will remain the same:

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f = f ( h ) f ( ) = D dh (EQ 22)

In practice, it is not feasible to employ a plane-parallel experimental setup as that indicated

in Figure 9. Instead, one has to resort to spheresphere, sphereplane, or crossed cylinder
cylinder configurations. At this point, the amazingly powerful Derjaguin approximation
(1934) takes place that, in effect, constitutes a geometrical integration of Equation 19 (com-
pare Figure 10), yielding an additional geometry-dependent factor such that the measured
surface force F becomes equal to F = 2Rf or sphereplane and crossed cylindercylinder
geometry and F = Rf for spheresphere geometry. These simple relations effectuate the
transformation from a curved to a planar geometry. 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. 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, it has become common practice to report
surface forces normalized in the form F/R, corresponding to 2f and f for these two
standard geometries.
Next, consider a pure water film between hydrophobic surfaces. Because of the unfavor-
able waterhydrocarbon contact combined with the necessity of attaining a uniform value
of the water chemical potential everywhere, the local tangential pressure pT will have to

h1 = h + r 2/2R

r Sphere

Ring of Radius r
Volume 2 drdh



FIGURE 10 Diagram of the geometrical disjoining pressure integration involving the Derjaguin
(1934) approximation

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assume a variable negative value, corresponding to tension for each water layer located at x
outside the solid surface. Hence

p p T ( x ) = [ p p T ( 0 ) ] exp ( x D ) (EQ 23)

Here, pT(0) denotes the tangential pressure next to the hydrophobic solid surface,
whereas p represents the atmospheric pressure of the surroundings. 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, at least when the outer part of the surface zones begin to
overlap (compare Marcelja and Radic 1976).
Moreover, 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, integrate Equation 23 to yield (crossed cylinders):

F ( 2 R ) = f = const. exp ( h 2D ) (EQ 24)

Hence, for the large separation part of a surface force versus thickness isotherm on this
admittedly oversimplified basis, an exponential behavior of the (attractive) surface force
with respect to the film thickness h can be predicted. Physically, this means that upon
diminishing the film thickness, 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, thereby lowering the overall free energy of the film.
Essentially the same mechanism (i.e., replacement of surface-located water) is responsi-
ble for the adsorption of surfactant and polymers at the airwater interface in the dilute
Henrys law region (Kumpulainen et al. 2005). In the following paragraphs, 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.
Diminishing film thickness from infinity to h = 0 will yield the adhesion force, as given
by the DerjaguinMullerToporov relation (for nondeformed interacting cylindrical sur-
faces, compare Israelachvili 1991):

F adhesion R = 2 f ( h = 0 ) 4 hc,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. Accordingly, the maximal adhesion
force between fully hydrophobized solid surfaces in water is estimated to be 640 mN m1.
Evidently, 2hc,w represents all the free energy per square meter that is gained in the planar
case upon eliminating the hydrocarbonwater contact area. The additional 2R-factor in
Equation 25 originates from the Derjaguin approximation.
However, when surface deformations are significant, the JKR ( Johnson, Kendal, Rob-
erts) theory instead applies, which predicts a pull-off force equal to

F adhesion R 3 hc,w (EQ 26)

that is, a maximal pull-off force of about 480 mN m1 for two crossed-cylindrical, hydrocar-
bon-covered surfaces (compare Israelachvili 1991). Pull-off forces refer to the forces mea-
sured when two surfaces in contact with each other are separated.

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The Ideal Hydrophobic Surface Versus Real Hydrophobic Surfaces

For experimental purposes, an almost-perfect hydrophobic surface and, hence, an ideal
hydrophobic surface in the theoretical, philosophical sense is often realized. The question
immediately arises about the most desirable properties of such a surface as to smoothness,
hydrophobicity, molecular constitution, motional state, fluidity, stability toward water solu-
tions and other media, and so forth.
Regarding smoothness, the answer seems simple: a minimal roughness at the atomic
level is desired, on average approaching 0.1 nm in peak-to-valley distance. First of all, this
requires a smooth enough substrate; mica, silica, or glass is usually preferred. In addition,
however, the hydrocarbon chains used as modifying agents must be attached in such a man-
ner that the smoothness is maintained. 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.
Smoothness is likely to be a crucial factor for the occurrence of a long-ranged hydro-
phobic attraction force, and for this reason, it should be fully verified. The main experimen-
tal difficulty encountered in this context involves obtaining a sufficient degree of stability
for the hydrophobic layer attached, and at the same time preserving surface smoothness at
the atomic level.
Concerning hydrophobicity, the answer may seem almost self-evident at first: maximal
hydrophobicity calling for fluorocarbon rather than hydrocarbon chains. By making such an
extreme choice, however, one may easily end up with studying the effects of vapor/air cavi-
ties and bridging bubbles rather than the hydrophobic attraction per se. For this reason, one
might well prefer surfaces exhibiting a contact angle against water slightly less than 90 for
which capillarity phenomena of this extraneous nature, in principle at least, should not
As to the molecular constitution, one would preferably desire the hydrocarbon chains
employed to be sufficiently long ( C16 ), and have them fairly densely packed on the surface,
to make up a certain minimum thickness of the resulting surface-modifying layer. Yet, 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, one might prefer the hydrocarbon chains to be in a
semifrozen solid (rather than close-packed crystalline) state, having a packing density
between 0.22 and 0.25 nm2 per single chain. For a less crowded amphiphile monolayer in a
liquid-expanded state, one runs the risk of the thermal motions making the waterhydrocar-
bon phase boundary fuzzy.
Clearly, when ionic head groups are attached to the bonding sites of opposite charge on
a solid surface for which the thermal amplitudes are small, the chains may end up in some
frozen gel state, hampering the equilibration of the adsorbate, or at least making equilibra-
tion times exceedingly long. For mica and silica substrates, there seems to be a big difference
between C16 and C18 cationic surfactants in this regard, the latter approaching adsorption
equilibrium at an amazingly slow rate (Zhang et al. 2005).
In summary, an ideal, stable, hydrophobic surface would exhibit an advancing contact
angle against water of about 110, and would in some solid state maintain a certain degree of
molecular mobility but nevertheless be smooth on the atomic scale. 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. If properly balanced in terms of its
mechanical properties to withstand mechanical loads, and if smooth enough from the

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outset for such a surface contact angle, hysteresis might be limited and the risk minimized
for having bubbles attaching and bridging between approaching surfaces.
Real surfaces that exhibit pronounced hydrophobic properties to a variable degree are
listed as follows:
1. Cleaved mica with a deposited LB layer of a double-chain cationic surfactant (i.e.,
the hydrophobic surfaces employed by Claesson and Christenson [1988] and, more
recently, by Meyer, Lin, and Israelachvili [2005] and Lin et al. [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 waterair inter-
face. 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 0.25 nm2 per single chain, which, by the way, matches
almost exactly the anionic site density of the mica surface (0.50 nm2). Conse-
quently, upon screening (by adding salt), there is a tendency for the surfactant to
pass over to some less strained (bilayer) state. Further, the whole ion exchange pro-
cess is prone to be facilitated kinetically by the presence of small ions.
2. 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. This
scheme was successfully applied by Tsao, Evans, and Wennerstrm (1993) and Tsao
et al. (1991), who obtained hydrophobized mica surfaces that were quite similar to
those made according to point 1. In particular, 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. Interestingly, a substantially smaller
attraction force was recorded for C16 than for C18 chains, and significant tempera-
ture effects were noted, the attraction becoming weaker and less long-ranged at
higher temperature. However, stability toward salt solutions was less satisfactory
than for the corresponding LB monolayers prepared according to point 1.
3. Self-assembling alkylthiols dissolved in, for example, alcohol are known to bind
strongly to gold surfaces, a circumstance that was utilized by Ederth, Claesson, and
Liedberg (1998) to prepare hydrophobic surfaces on borosilicate glass substrates,
which started by forming (by electron beam evaporation) a 1-nm titanium layer, fol-
lowed by a 10-nm gold layer. The gold surfaces made in this manner are slightly
rough with peak-to-through values of ~1.5 nm. The hydrocarbon chains become
tilted and are tightly packed in a crystalline state. These surfaces exhibit a hydropho-
bic attraction of medium range but have been plagued by sporadic bridging bubble
steps in the surface force curves. Stability is not a problem.
4. Glass, silica, or mica surfaces rendered hydrophobic by reaction with silanation
agents (e.g., (tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane; Parker
and Claesson 1994) and capable of reacting with surface OH groups. For mica sur-
faces, a water plasma pretreatment is necessary to introduce surface OH groups
(Parker, Cho, and Claesson 1989). As a rule, stability toward salt solutions is
obtained for this type of hydrophobic surface. Yet, to quote Christenson and Claes-
son (2001): Experimental results with silylated surfaces have shown great variabil-
ity depending on exact preparation conditions, and further underscored the critical
connection between details of surface chemistry, surface morphology and the

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measured forces. Hence, it seems hardly feasible to fully control a silanation reac-
tion scheme so as to generate a sufficiently smooth, charge-free, and laterally
homogenous hydrophobic surface.
5. 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, followed by LB deposition and
chemical grafting to a mica surface. Certainly, the surfaces obtained proved stable
toward salt solutions but laterally inhomogeneous on the micrometer-length scale.
No long-range hydrophobic attraction was observed, presumably because of the lack
of molecular smoothness required.
6. Adsorption from water solution of a cationic surfactant such as CTAB or C18TAC
(octadecyl-trimethylammonium chloride) onto mica, glass, or silica. Though easily
prepared, these types of surfaces have a major drawback: they are uncharged (or
carry a minimal surface charge) only at one particular surfactant concentration,
often denoted as the charge neutralization concentration (CNC). Furthermore, for
the most desirable chain length, C18, adsorption equilibrium is only approached
very slowly at room temperature. Hence, 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, fundamental studies are hampered
by the variable state of the hydrophobic surfactant layer. Presumably, 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. The temperature dependence of
the hydrophobic force, for instance, could perhaps be investigated in this manner by
changing the temperature, followed by adjustment of the surfactant concentration
to recover a minimal surface charge.
This listing, though certainly not complete, may serve as a ranking list of hydrophobic
surfaces based on experiences from several laboratories during the past several decades. Pre-
paring hydrophobic surfaces of sufficient quality is of crucial importance for making reliable
conclusions about the strength, range, and nature of the hydrophobic force. Although
hydrophobic surfaces prepared by adsorption of surfactants from solution are at the bottom
of the list, they are probably the most important ones in terms of applications, particularly
in flotation.

Hydrophobic Attraction Forces Under Ideal Conditions

For large separations between two interacting hydrophobic surfaces, an exponentially decay-
ing, negative tangential pressure component, pT, gives rise to a likewise exponentially decay-
ing surface force. However, for closer distances between the two hydrophobic surfaces, a
more elaborate model is necessaryin principle, similar to one by Cevs, Podgornik, and
Zeks (1982)to account for repulsive hydration forces. In this type of model, changes of
state arising in the residual thin water film itself are also considered.
A quasi-thermodynamic/structural model for hydrophobic attraction forces was pre-
sented in 1989 by Eriksson, Ljunggren, and Claesson (1989). In contrast to most of the
other tentative explanations of hydrophobic force, this model has not been properly falsified
in the Popper sense. Rather, it has been refuted by the vague claim that long-ranged struc-
tural effects are virtually excluded for (normal) liquids. However, with its ability to form a

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variety of hydrogen-bonding patterns, water is still far from being a well-understood liquid
at the molecular level. Hence, 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. After all, this model might serve as a valid
point of departure for a deeper understanding of the hydrophobic force. Alternative
attempts to fully understand the hydrophobic attraction will also be addressed. The premises
are as follows:
1. The hydrophobic solid surfaces that interact in a liquid water medium are ideal:
they are geometrically smooth to within about 0.1 nm at 0 K, they exhibit small
thermal amplitudes at room temperature, and they are laterally close to being homo-
geneous in every respect.
2. Relatively speaking, 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.
3. 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, resulting in a somewhat larger average number of hydro-
gen bonds per water molecule in the film than in the bulk. Hence, assuming only
short-range interaction forces, there is a free-energy increase arising throughout the
core of the thin film, owing to the imposed hydrogen-bond network formation.
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, unfavorable restructuring of the remainder of the film. In the following discus-
sion, these free-energy changes are accounted for by making use of a dimensionless order
parameter s(x), 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). Alternatively, it may be assumed that s(x) mirrors the local
increase of the average number of hydrogen bonds per water molecule in the film, or the
associated decrease in local density.
Now imagine that the final equilibrium state of the thin water film sandwiched
between two hydrophobic surfaces is reached in a stepwise fashion. Starting from a thin film
cut out of the bulk state, the first step involves establishing the proper molecular interac-
tions at hydrocarbonwater interfaces while retaining the average spherical-symmetric ori-
entation of all the water molecules in the film.
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 HOH bisectors of the water
The film tension attained after these first two equilibration steps are denoted by 0f .
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 f is reached.

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In an approach similar to the so-called square gradient approximation, frequently used

in the past to model liquidvapor interfaces, the model features invoked previously can be
expressed in the following manner:

f = 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, hence, the packing density) for the water layers in direct contact with the hydrophobic
surfaces, whereas the integral accounts for the free energy expense associated with structur-
ing the core of the thin water film. Inclusion of the squared gradient term is essential because
it furnishes a mechanism of energetic coupling between successive layers of water molecules.
Hence, the constant c3 reflects the (average) tendency to cooperative structure generation.
Upon minimizing the film tension f 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 )


f ( h ) = 0f ( a 2 4c 3 b ) coth ( bh 2 ) = 0f as 0 2
(EQ 29)
= 0f ( B 2 ) coth ( bh 2 )

The constant b stands for the quotient, whereas the interaction constant B introduced in
Equation 29 can also be written in the form B = a 2 8c 2 c 3 .
For infinitely large film thicknesses, a lowering of the film tension caused by the
imposed structuring due to the hydrophobic surfaces is obtained:

f ( h = ) 0f = B 2 (EQ 30)

implying that B/4 is the corresponding reduction of the interfacial tension between water
and a hydrophobic surface. It can be estimated to be 50 Nm1, that is, to just about 0.1%
of the total interfacial tension value of approximately 50 mNm1.
By taking the difference between Equation 29 and Equation 30 and making use of the
Derjaguin approximation, 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 f = B [ coth ( bh 2 ) 1 ] (EQ 31)

For sufficiently large film thicknesses, the right-hand side of this equation becomes equal to
2Bexp(bh), that is, in the (weak overlap) regime, ln (F/R) is predicted to be a linear
function of h, in line with Equation 23. Moreover, in this range, b1 has the nature of a decay length.
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. On the other
hand, Equation 31 is more general because it also accounts for the free energy changes arising

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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. 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. As a consequence, the
hydrophobic surface force increases in magnitude at an accelerating rate when the film
thickness is diminished (compare Figure 17).
Equation 31 can be placed in an approximate double-exponential form, 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. However, unlike Equation 31, Equation 32 does not extrapolate properly
down to small h-values. Hence, the common practice of making use of a double-exponential
expression entailing four parameters instead of just two is understandable, namely

F R = C 1 e h 1 + C 2 e h 2 (EQ 33)

which, in many cases, has been shown to represent experimental surface force data satisfacto-
rily in a wide separation range. The first exponent yields the largest contribution for small
separations, whereas the second one dominates at large separations. Typical values derived
are C1 = 0.2 Nm1, 1 = 2 nm, C2 = 1 mNm1, and 2 = 20 nm.
Another convenient, though somewhat less accurate, manner to represent experimental
surface force data is to invoke an expression of the same mathematical form as for the van der
Waals attraction, that is,

f = ( K 12 )h 2 (EQ 34)
resulting in the one-parameter surface force expression:

F R = ( K 6 )h 2 (EQ 35)
Obviously, 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, which is
usually on the order of joules. Typical K values range between 1018 and 1019 J.
The disjoining pressure expression, which can be derived from Equation 31 by differen-
tiation with respect to h (compare Equation 19), is as follows:
D = ( bB 2 ) [ coth ( bh 2 ) 1 ] (EQ 36)

Especially when displayed in this derivative mode, experimental hydrophobic interaction

curves may appear to belong to two distinct regimes: below and above 1020 nm, respec-
tively (Figure 11). The same holds true for the order parameter s in the middle of the thin
film (where x = 0), as derived theoretically. Below about 15 nm, s(x = 0) rapidly diminishes
with the film thickness h, whereas above about 15 nm, s(x = 0) decreases very slowly in an
almost linear fashion with h (Figure 12).
The hydrophobic surface forces arising within the large separation range are generally
rather weak, at most about 1 mNm1, as compared with 500600 mNm1 for the maximum
adhesion force at h = 0, and can thus easily be concealed (e.g., by a surface force of electrostatic

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(2)XD, Nm 2


0 100 200 300 400 500 600


FIGURE 11 Surface interaction pressures between mica surfaces modified with

dihexadecyldimethylammonium (DHDA), DODA, and dieicosyldimethylammonium (DEDA)
monolayers in water at 25C as measured by Tsao et al. (1991). Note that the surface force
curves are indistinguishable for DODA (C18 chains) and DEDA (C20 chains).






0 5 10 15 20 25 30 35
h, nm

FIGURE 12 Order parameter s (x ) in the mid-plane of a thin water film sandwiched between
hydrophobic surfaces (Eriksson, Ljunggren, and Claesson 1989)

Further, on the basis of Equation 36, 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. Typically, in the medium separation range, h 10 nm, this excess free
energy amounts to about 4 104 kBT per molecule, as compared with the energy of a
hydrogen bond at room temperature, 7 kBT, again recognizing the very minute thermody-
namic effects by means of a sensitive SFA or AFM setup.
According to the theory summarized, the strength of the hydrophobic attraction force
is determined by the interaction constant B = a 2 8c 2 c 3 , which in turn is strongly

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dependent on the constant a that is related to the free-energy change associated with the
reorganization of the contact layers of water molecules. Thus, 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.
On the other hand, the decay length b 1 = c 3 2c 2 should depend primarily on the
properties of the water in the thin film, 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), that is, when cooperativeness plays a significant role. However, if
the hydrophobic surfaces are also charged and (overlapping) electrostatic double layers are
present, 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. Such a coupling might result in a larger constant c2 and, hence, a
shorter decay length.
Salt effects for uncharged or nearly uncharged surfaces are expected to be rather minor,
provided that the hydrophobic surfaces themselves are stable in contact with salt solutions.
Generally, these features have been experimentally documented. In particular, note that the
strength of the hydrophobic attraction scales semi-quantitatively with the contact angle for
water on hydrophobic surfaces (Figure 6), and that Angarska et al. (2004) have shown that
Equation 31 applies even for thin foam films at high salt concentrations. Furthermore, 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, an inter-
esting case that has been studied experimentally by Yoon, Flinn, and Rabinovich (1997).
In conclusion, it is seen that the quasi-thermodynamic theory due to Eriksson, Ljung-
gren, and Claesson (1989), which focuses on the rather minor free-energy effects that are
associated with restructuring of water in contact with hydrocarbon surfaces, is capable of
systematizing several experimental findings concerning the attractive hydrophobic surface
force. Yet a fundamental problem related to this approach is that it does not provide an
understanding as to why the effect, in some instances, can be of such an amazingly long
range that it can be detected even for separations beyond 100 nm. One must bear in mind,
however, 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, that is, larger clusters are inher-
ently more stable than smaller ones. This may set the stage for extended water clusters of var-
ious shapes to occur, provided that the associated free-energy expenses are small enough to
be counterbalanced by corresponding size-fluctuation entropies, a thermodynamic scenario
that is familiar from the field of surfactant aggregation.
Nevertheless, 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, as well as
for novel experimental methods by which one can investigate the detailed state of thin water films.

Upon observing more or less distinct steps in the surface force curves for hydrophobic surfaces
(plasma-treated mica silylated with (tridecafluoro-1,1,2,2-tetraoctyl)dimethyldichlorosilane)
submerged in water at surface separations in the range of 100 nm, Parker Claesson, and
Attard (1994) suggested that these steps might actually demark the onset of the hydrophobic

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attraction, albeit an attraction that is totally different from the water-structure-based one
discussed thus far. Hence, they attributed the attraction to tiny adhering air bubbles that,
upon the approach of the hydrophobic surfaces, suddenly form bridging (quasi-cylindrical)
bubbles. Although the concept of bridging bubbles is, in many ways, appealing, 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.
A primary difficulty is that very small air bubbles nucleated in a water phase are surpris-
ingly short-lived. Because of the rather sizeable Laplace excess pressure, 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. It is about
10 ms for a radius of 1 m, and about 1 sec for a 10-nm bubble, whereas a bubble that is
millimeter-sized may subsist for days or even months (Epstein and Plesset 1950; Ljunggren
and Eriksson 1997). Although air bubbles, as a rule, 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, adhesion of small air bubbles is nonetheless a rare
event because of the limited life span of these bubbles.
Moreover, unlike the situation for larger air bubbles, which (because of the small excess
pressure) can be treated as if they were thermodynamically closed, very small open air bub-
bles are not expected to adhere to an ideal hydrophobic surface in a stable manner (Kral-
chevsky 1996; Eriksson and Ljunggren 1999; Ryan and Hemmingsen 1993). Most real
hydrophobic surfaces, however, contain defects that presumably play a crucial role in pro-
moting bubble adhesion to occur to some minor extent.
What remains, following the bubble-mechanism line of reasoning, is the option that a
limited number of small bubbles, which have survived (because they started out as relatively
large bubbles), happen to adhere in an irreversible, defect-dependent manner to the hydro-
phobic surfaces, and that a few of these adhering bubbles rather quickly form approximately
cylindrical air bridges to the approaching hydrophobic surface. In this way, the excess
(Laplace) pressure will be efficiently cancelled, and a bridging bubble can consequently sub-
sist for a long time. To assume irreversibility for the wetting behavior is essential here. Other-
wise, the formation of one large, air-filled cavity, eventually giving rise to a huge surface
force, would have to be inferred.
Simple calculations show that in order to account for the surface force steps observed by
Ederth (1999), which amount to about 2 108 N in terms of force (rather than surface
force), one must invoke an adhering (spherical cap) bubble that fulfils the contact angle con-
dition, having a radius of curvature of about 70 nm. The surface area covered by such a bub-
ble would be 1.3 104 nm2. Supposing the three-phase contact line to be pinned in a fixed
position on some surface defects, the curvature is likely to decrease as some air dissolves, thus
lowering the Laplace pressure and extending the expected lifetime of the bubble. Gas super-
saturation in the surrounding water phase may likewise prolong the lifetime of an adhering bubble.
As is easily confirmed, the formation of a bridging bubble out of an adhering bubble is
likely to be advantageous free-energy-wise. Nevertheless, it is significant as well as under-
standable, in view of the short lifetime and submicroscopic size of such a bubble, that it has
met with experimental difficulties to positively verify the presence of adhering air bubbles
on hydrophobic surfaces (Lin et al. 2005; Mao et al. 2004). To judge from the evidence
available today, the occurrence of adhering air bubbles depends strongly on the nature of the
hydrophobic surface. This might be anticipated, of course, because non-ideal features in the
hydrophobic surfaces themselves are likely to play a decisive role.

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rc h

FIGURE 13 Two approaching spheres with a bridging (quasi-cylindrical) air bubble

For a few years, 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. More recently, however, 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. Hence, the supposition that small
adhering bubbles which collapse into bridging bubbles is the major cause of the true long-
range hydrophobic attraction, must be rejected. Strong additional support for this conclu-
sion has recently been obtained from careful degassing experiments (Meyer, Lin, and
Israelachvili 2005; Zhang et al. 2005).
Conversely, large-scale cavity formation is a capillary phenomenon that is fairly well
understood. 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. Expressed otherwise, it is a pre-
requisite that the (equilibrium) contact angle exceeds 90. A somewhat simplified, though
still sufficiently accurate version of the classical treatment presented by Yushenko, Yaminsky,
and Shchukin (1983) is discussed in the following paragraphs.
Consider the case of two approaching hydrophobic spheres (radii = R) submerged in
water (Figure 13). Suppose a quasi-cylindrical (minimal-surface) cavity is formed that has
almost no excess air pressure associated with it. The free-energy cost of forming such a cavity
stems from forming the airwater interface, whereas the gain in free energy is due to replac-
ing the hydrocarbonwater interface by hydrocarbonair interface. For the free energy of
cavity formation, the following approximate expression is obtained:
------- = r c ( h + r c2 R ) air,w r c2 ( hc,w hc,air ) = air,w [ r c ( h + r c2 R ) + r c2 cos eq ]
(EQ 37)
where rc denotes the cylinder radius, and the r c2 R term develops because the curvature of
the spherical hydrophobic surfaces is taken into account to the first order.
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, in
principle, fulfilled) and a maximum for some smaller rc value. The barrier associated with
the maximum is present, however, only when the distance of approach, h, is greater than
zero. (compare Figure 14).
Provided that the equilibrium contact angle is large enough, the free-energy value at the
minimum (representing the formation of a fully equilibrated air-filled cavity) will have a
negative value, implying that the cavity state constitutes the thermodynamically stable state
of the system. However, the intervening barrier will usually prevent the cavity from forming

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1E 15
1.0E 09
= 105

= 115

1E 15
0.0000 0.0002 0.0004 0.0006
G/2, J

0.0E + 00
= 105

= 115

1.0E 09
0.0 0.1 0.2 0.3 0.4 0.5
rc , mm

FIGURE 14 Interfacial free-energy function according to Yushenko, Yaminsky, and Shchukin

(1983), which accounts for the thermodynamically stable cavity formation between spherical,
hydrophobic surfaces submerged in water. The inset shows the barrier at short separations
that prevents cavity formation when the surfaces are brought close, though not touching, from
a great distance.

when the thin film state is approached by gradually diminishing the surface separation. In
other words, the thin film state of water between hydrophobic surfaces is actually a metasta-
ble state, as was noted earlier by Blake and Kitchener (1979).
The cavity state can easily be realized, however, by first bringing the hydrophobic sur-
faces into contact, thus reducing the barrier to zero, then slowly pulling them apart. 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).
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. By increasing the surface
separation h, the entire G function is rotated counterclockwise. Eventually, the second
(negative) term can no longer outweigh the first term, resulting in a minimum with a positive
G value, thus providing the impetus for cavity annihilation.
In general, the experimental experience is in line with the thermodynamic description
of cavity formation as outlined here; however, lack of complete equilibration for the air dis-
solved as well as complications arising because of contact angle hysteresis must be considered.

Electrostatic Interaction Forces

To estimate repulsive electrostatic double-layer forces, the nonlinearized, mean-field Poisson
Boltzmann (PB) scheme is usually applied in some numerical version. The theory behind it
assumes an evenly-smeared-out surface charge and a laterally homogeneous counterion dis-
tribution outside the charged (geometrical) surface. These assumptions seem more and
more questionable when the surface charge density is smaller. At the same time, however, the
magnitude of the repulsion becomes less, making the problems that may arise redundant in
any case.

2007 by the Society for Mining, Metallurgy, and Exploration.

All rights reserved. Electronic edition published 2009. Page 160 Tuesday, January 2, 2007 7:36 PM


The special case of one single (noninteracting) double layer is known as the Gouy
Chapman approach, according to which can be obtained the electrostatic free energy per
charge, gel, from the following set of equations:

g el = e 0 + el a charge (EQ 38)

where el is the electrostatic contribution to the surface tension, and acharge is the area per
surface charge. This particular equation is, in fact, generally valid within the realm of the PB
theory ( Jnsson 1981; Evans and Ninham 1983). For the GouyChapman case, the surface
potential is given by the following expression:

0 = ( 2k B T e ) [ S + ( S 2 + 1 ) 1 2 ] (EQ 39)

and the electrostatic contribution to the surface tension is given by

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. Fur-
ther, the dimensionless, reduced-charge parameter S introduced previously is defined by

S = ( 2 8RT 0 r c t ) 1 2 (EQ 41)

where is the surface charge density, e the proton charge, r is the relative dielectric number
for water, and ct is the total (1:1) electrolyte concentration.
In this context, the Debye length is introduced by means of the following expression
(F denotes the Faraday constant):

1 = F 1 0 r RT 2c t (EQ 42)

Hence, the Debye length, which characterizes the extension of the diffuse part of the
double layer, according to the DebyeHckel scheme, depends on the electrolyte concentra-
tion but not on the surface charge density.
From this background, briefly consider the case of an (1:1) ionic surfactant adsorbed at
an airwater interface in the dilute Henrys-law regime. In this range, where el constitutes
the chief contribution to the reduction of the overall surface tension, the surface tension
drops linearly with the surfactant concentration. Taking this circumstance into account and
making use of the Gibbs surface tension equation, one can readily show that the gas lawlike relation

el a charge = 2k B T (EQ 43)

must hold exactly for thermodynamic reasons. Evidently, twice the kBT/acharge can be attributed
to the pressure effects of both anions and cations in the surface. On the other hand, in Equation 40,
considering S to be >>1, about 1 kBT stems from the osmotic effect of the counterions,
whereas 1 kBT stems from the polarization of the water in the electrostatic mean field
(Ljunggren and Eriksson 1988). This discrepancy immediately conveys that the current the-
oretical description of electrostatic interactions has its weak points.
Furthermore, from Equation 40 it appears that the GouyChapman theory incorpo-
rates an additional factor [(S2 + 1)1/2 1]/S, which deviates substantially from unity,
especially when S becomes less than about 10, which is the case for dilute ionic surfactant

2007 by the Society for Mining, Metallurgy, and Exploration.

All rights reserved. Electronic edition published 2009. Page 161 Tuesday, January 2, 2007 7:36 PM


layers. In other words, in spite of its many virtues, the PoissonBoltzmann description has a
serious flaw, as it does not show a correct limiting behavior for charged equilibrium (Gibbs)
monolayers. This is in sharp contrast with, for example, the FloryHuggins theory of poly-
mer solutions.
The main reason behind these deficiencies is probably related to both the mean-field
concept as such and, in addition, to the particular model feature of a geometrical (i.e., volume-
less), evenly charged surface devoid of entropy of mixing for the charged groups with water.
This latter shortcoming also shows up in the fairly low surface potentials and charge densi-
ties that are commonly derived from surface force data.
Nevertheless, in the PB scheme, the electrostatic disjoining pressure is primarily given
by the following expression (for simplicity, no added salt):

Del = c ion RT ( e e m kB T + e e m kB T 2 ) (EQ 44)

where m represents the mid-plane potential and cion for the bulk concentration (moles per
cubic meter) of positive and negative ions. In particular, in the much-employed weak-overlap
approximation that is applicable insofar as the surface potential is small (< 25 mV),

Del ( r 0 2 2 ) m2 64k B Tc s 02 e h (EQ 45)


0 = tanh ( e 0 4k B T ) (EQ 46)

By integrating Equation 45, the corresponding contribution to the surface force is easily found:

( F 2 R ) = 64k B Tc s 02 e h (EQ 47)

implying an exponential asymptotic behavior determined by the (salt-dependent) Debye

length. Thus, for large separations, there is a formal similarity (though the sign is opposite)
between the electrostatic repulsion and the water-structure-dependent hydrophobic attrac-
tion treated previously. Moreover, the electrostatic surface force contribution can readily
match the hydrophobic contribution in strength, provided that there is a significant surface
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, whereas up to this point, a firm
fundamental basis is lacking for an explanation of the hydrophobic attraction in terms of the
molecular properties of water.
In the 1970s, it was realized that correlation effects may become significant, especially
for interacting double layers encompassing divalent counterions (Guldbrand et al. 1984;
Kjellander and Marcelja 1984). An attraction of this origin is conceptually similar to the
dispersion interaction because it relies on instantaneous, laterally inhomogeneous counter-
ion distributions outside the charged surfaces. On average, the fluctuations cause more
weight to be given to attractive rather than repulsive configurations, resulting in an overall
attraction. On this basis, 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, Metallurgy, and Exploration.

All rights reserved. Electronic edition published 2009. Page 162 Tuesday, January 2, 2007 7:36 PM


For the correlation interaction between surfaces carrying mobile charges, the Ninham
Parsegian expression holds true for the disjoining pressure. At large separations, it takes on
the following limiting form:
D = kT
------------- e 2 h h 1 (EQ 48)
The magnitude of the attractive interaction pressure predicted by means of this equa-
tion is, however, on the order of the van der Waals attraction. Hence, 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. This was realized by Fors-
man, Jnsson, and kesson (1998), Miklavic et al. (1994), and Kekicheff and Spalla (1995),
who argued that more sizeable contributions of this nature can be obtained for charged sur-
faces that are heterogeneous, containing (mobile) charged surfactant aggregates of some
size, such as, for example, hemimicelles. In particular, Miklavic et al. (1994) were able to
demonstrate that at relatively high salt concentration, the correlation attraction should
decay with a decay length equal to 1/2(i.e., half of the Debye length) upon increasing the
surface separation. However, their calculations presuppose that the surface density of
adsorbed micellar aggregates is basically independent of the concentration of added salt, a
condition that for the most part is unlikely to be fulfilled.
Although these concepts about ionic correlation attractions may be of some relevance
for hydrophobic surfaces formed by adsorbing (e.g., a water-soluble cationic surfactant onto
mica, glass, or silica), 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. (1991), at least insofar as no
salt is added when making the surface force runs. The surface characterizations carried out
as well as the preparation protocols employed seem to leave little room for speculation in
this direction.
In a similar vein, it was suggested by Tsao, Evans, and Wennerstrm (1993), and Yoon
and Ravishankar (1996) that correlations among colloidal-grained, ordered dipole domains
across the thin film may give rise to sizable attractions, far stronger than the van der Waals
interaction. Although these matters, perhaps, are not yet resolved, it seems implausible that
all observations regarding the hydrophobic attraction can be accounted for on the basis of
correlation attractions alone.
Returning to the subject of hemimicelle formation, an aggregation of this kind is antic-
ipated for hydrophobic surfaces prepared by surfactant adsorption from water solution,
starting at the critical hemimicelle concentration where the hydrophobic attraction is
already high. Herder (1990) demonstrated that upon adsorbing a cationic surfactant onto
LangmuirBlodgettDODA-modified mica, the hydrophobic attraction rapidly vanishes
and is replaced by electrostatic repulsion. Furthermore, Craig, Ninham, and Pashley (1998)
thoroughly investigated the interaction between silica surfaces in dilute CTAB and cetylpy-
ridinium chloride (CPC) solutions in the presence of electrolytes, and firmly concluded
that a direct electrostatic mechanism for the hydrophobic attraction is hardly an option.
Parker and Claesson (1994) arrived at the same conclusion using the MASIF setup and
silanated glass spheres. Page 163 Tuesday, January 2, 2007 7:36 PM


After about two decades of research efforts devoted to searching for the mechanism that
gives rise to the hydrophobic attraction, it is probably time to turn back to where the
surfaceforce-based development phase startedthe measurements by Israelachvili and
Pashley (1982). 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.
In the 1960s, the mysteries of water were still fashionable topics for study. Much
inspiration came from Paulings (1960) investigations of the hydrogen bond and from the
fascinating field of clathrate physical chemistry (Franks 1973). Later, the tendency to
restrict the discussion to structural aspects onlyinstead of employing the full statistical-
mechanical machineryand the polywater affair made this research direction fall in disrepute.
More recently, however, 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.
In order to cope with the long-ranged hydrophobic attraction, a few different
approaches than the water-structure method have been rather thoroughly scrutinized. In
particular, electrostatics beyond the standard PB mean-field description have been reexam-
ined, and more trivial, though quite cumbersome, capillary effects have been investigated in
detail. The latter phenomena include the formation of cavities and bridging bubbles
between (hysteretic) hydrophobic surfaces submerged in water. In the end, however, both of
these major alternative approaches have turned out to be untenable.
To further reveal the extent to which the waterstructure-based theory of the hydro-
phobic force compares with experimental data, perhaps the most illuminating and most
well-documented experimental surface force study carried out so far will be examinedone
that clarifies the hydrophobic attraction (presented by Tsao et al. [1991]). These investiga-
tors made use of hydrophobized mica surfaces (mounted in an SFA), prepared by means of
adsorption from cyclohexane solutions of cationic surfactants of different chain lengths:
DHDA, DODA, and DEDA, with bromide or acetate as the counterions. The resulting
adsorption layers were characterized by AFM. Hence, it was verified that the double-chain
surfactant cations employed are electrostatically bonded, one to each anionic mica site,
resulting in a packing density close to 0.50 nm2 (0.25 nm2 per single chain), 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 50C. Full stability toward salt solutions
was, however, not achieved using this surface preparation method.
Moreover, the aforementioned authors demonstrated that while the DEDA monolayer
preserves a frozen chain state at 50C, this is not the case for the DHDA and DODA mono-
layers. In fact, DHDA appears to be present in a melted chain state already at 25C, whereas
DODA melts in the range between 40 and 50C.
Correlating changes were observed in the surface force curves, and it was concluded
that a well-organized, smooth hydrocarbon monolayer of frozen hydrocarbon chains causes
the strongest hydrophobic attraction. This finding was later corroborated by Rabinovich,
Guzonas, and Yoon (1993) by means of Fourier transform infrared (FTIR) measurements.
The chain length primarily matters in the sense that it determines where on the temperature
scale chain melting occurs. Moreover, for one and the same temperature, the decay length at
large separations was found to be nearly the same. Page 164 Tuesday, January 2, 2007 7:36 PM


These observations fit well into the theoretical model description presented previously
that presumes structural water effects. Accordingly, the strength of the hydrophobic force is
determined primarily by the constant a of the (linear) response function as0 , which partic-
ipates in the expression for the constant B in Equation 31:

B = ---------------- (EQ 49)
8c 2 c 3

In view of the cooperative nature of water structure generation, 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. This dependence may suffice to account for the distinctly different surface force
behaviors recorded by Tsao et al. (1991) for hydrocarbon surfaces in a frozen (larger B) or
melted (smaller B) state.
Similarly, raising the temperature should tend to make a smaller, and, in addition, make
the structuring of the film core more costly in terms of free energy, yielding a higher c2, that
should likewise tend to diminish B. Also, the decay length b1, which is given by c 3 2c 2 ,
depends inversely on c2 and should thus diminish with temperature, which is for the most
part observed. Concerning c3, just a modest dependence on temperature is anticipated.
On the other hand, the (unintentional) presence of a polarizing electrostatic field
would tend to increase c2 and hence shorten the decay length, 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, implying a smaller c2 and a longer decay length.
More importantly, however, a virtually model-independent, surface-thermodynamic
analysis of surface force data as complete as those of Tsao et al. (1991) can be carried
through. Revisit the thermodynamic fundamental equation governing the present film case
(see appendix to this chapter). For a pure water film in contact with water,

d f = ( V f,ex A )dp ( S f,ex A )dT D dh (EQ 50)

where Vf,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. The excess entropy
Sf,ex is analogously defined. For an infinitely thick film, accordingly, obtain the following:

d f ( ) = ( V f,ex A )dp ( S f,ex A )dT (EQ 51)

Upon deducting Equation 51 from Equation 50, next obtain

d ( f ) = ( V f,ex A )dp ( S f,ex A )dT D dh (EQ 52)

This equation is the appropriate thermodynamic relation for dealing with surface force data
for thin films consisting of pure water. It obviously includes the partial derivative

( f )-
--------------- S f,ex
= ------------- (EQ 53)
T p, h A Page 165 Tuesday, January 2, 2007 7:36 PM


DEDA (s) and DODA (s) at 25C
DEDA (s) at 50C
5 DODA (s) at 40C
DHDA (l) at 25C
DHDA (l) at 40C

F/2 R, mJm 2

0 50 100 150 200 250 300 350 400


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. (1991)

Thus, if the surface force increases with temperature, which in the present case means that
the attractive hydrophobic surface force becomes less negative when the temperature is
raised, it necessarily results in Sf,ex as a negative quantity. In turn, 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. 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, especially if the surfaces are solid), there will be no contribution to
Sf,ex other than the one arising in the water film.
By integrating the disjoining pressure functions derived experimentally by Tsao et al.
(1991), the corresponding relative film tensions can be obtained (compare Figure 15).
These curves display the crucial feature discussed previously, that is, upon diminishing the
surface separation, the film tension reduction is larger at room temperature than it would be
if the room temperature were greater. Consequently, as soon as the surfaces interact, Sf,ex is
always a negative quantity. Also, Equation 31 with B-, b- values generated from the measure-
ments of Claesson and Christenson (1988; who used similarly prepared hydrophobic sur-
faces), yields a reasonably good fit for the film tension curve obtained by Tsao and
colleagues for DODA at room temperature.
The relative excess film entropies per unit area, Sf,ex/A, can be quantified using Equa-
tion 53, resulting in the curves shown in Figure 16. Evidently, the excess entropy becomes
increasingly more negative when the water film gets thinner, especially for the frozen hydro-
carbon surfaces, DODA and DEDA.
Regarding the numerical values, 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. By
invoking the entropy of fusion of ice ( 22 J mol1 K1) for a 5-nm water film, estimate
S freezing = 6 mJm 2 K 1 , which is about 30 times more than the entropy reduction
quantified from the surface force measurements. In other words, the enhanced molecular
order in the thin film is equivalent to introducing about 3% of ice ordering. Page 166 Tuesday, January 2, 2007 7:36 PM



DODA (s)

S f,ex/A , Jm2K1

DEDA (s)



DHDA (l)
0 50 100 150 200 250 300

FIGURE 16 Excess film entropies as functions of the separation between mica surfaces
hydrophobized with DHDA, DODA, and DEDA. The difference between the DODA and DEDA
curves is presumably due to experimental uncertainty.

Furthermore, comparing with the relative film tensions shown in Figure 15, observe
that for every thickness h, it holds true that

f << T 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, that is,

T S f,ex H f,ex (EQ 55)

Such an enthalpyentropy compensation is perhaps the most distinguishing feature accom-
panying structural changes in water. This was briefly discussed in relation with Equation 5.
For freezing of water at 0C, G = 0, which means that a relation similar to Equation 55 is
exactly fulfilled.
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. Conversely, it
would be meaningless to propose an interaction mechanism incapable of giving rise to a sig-
nificant reduction of the water film entropy. This circumstance apparently restricts the num-
ber of alternative mechanisms and, hence, lends support to the idea that a water structuring
effect caused by the contact with hydrophobic surfaces is being addressed. 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.
The most important assumptions on which these conclusions rest are the following:
1. The disjoining pressure data recorded by Tsao et al. (1991) are representative of a
water film state where the film itself is fully equilibrated, whereas the (smooth)
hydrophobic surfaces remain in the same metastable frozen state all the time. Page 167 Tuesday, January 2, 2007 7:36 PM


2. No conceivable mechanism, other than the water restructuring mechanism, can

reproduce the strong temperature dependence and the characteristic enthalpy
entropy compensation documented for the thin water film sandwiched between
hydrophobic surfaces.
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. Point 2 is further discussed in the following paragraphs.
An additional advantage of the water restructuring model should be brought up explic-
itly. It is not necessary to assume that different physical mechanisms are operating at small
and large separations. By making use of Equation 31 and introducing two parameters (i.e.,
the surface force strength parameter, B, and the decay length, b1), the seemingly different
mechanisms observed at small and large separations can be accounted for within one frame-
work. Figure 17 shows a surface force function of the form given by Equation 31 and with
B-, b-parameter values obtained by fitting the data of Claesson and Christianson (1988),

--F- = 0.600 coth ---------- 1 ( mJm 2 ) (EQ 56)
R 15.8

(where h is in nanometers) together with the surface force data reported by Lin et al. (2005).
It is evident that the function in Equation 56 produces an amazingly good fit, especially for
short separations.
Likewise, the disjoining pressure function (Equation 36) is given by:
D = 6.04 10 3 coth ---------- 1 ( Nm 2 ) (EQ 57)


F/R, mNm1


0 10 20 30 40 50
h, nm

FIGURE 17 Surface force data points recorded by Lin et al. (2005) at 25C for DODA-modified
mica surfaces in water, compared with the surface force function (Equation 31), where the
fitting parameters of B = 0.6 mJm2 and b 1 = 15.8 nm Page 168 Tuesday, January 2, 2007 7:36 PM



(2) x D, Nm 2


0 10 20 30 40 50 60
h, nm

FIGURE 18 Comparison between the disjoining pressure data reported by Tsao et al. (1991)
and the disjoining pressure expression given by Equation 36 and inserting the parameter
values of B = 0.6 mJ/m2 and b 1 = 15.8 nm

which according to Figure 18 fairly well represents the data recorded by Tsao et al. (1991)
for DODA and DEDA at 25C.
For h values that are small enough (less than about 2 nm), the B[coth(bh/2)1] func-
tion can be approximated by 2B/bh; that is, the surface force is predicted to vary inversely
with h. The good fit in the short separation range displayed in Figure 17 is noteworthy. Still,
it is hardly conceivable that the model concepts introduced to derive Equation 31 would
apply below 2 nm; in other words, the agreement may appear reassuring but is presumably
little else than fortuitous.
For completeness, add an expression for Sf,ex, which can be derived by combining
Equations 31 and 53:

ln B Bbh ln b dT
S f,ex = ------------ f --------- ------------------------- (EQ 58)
T 4 sinh 2bh 2

where the (negative) terms on the right-hand side, primarily, are expected to contribute
about equally. Thus, approximately Sf,ex and f are expected to be proportional. This particular
feature is clearly observed in the thermodynamic surface force data (compare Figures 15 and 16).

Having recognized the significance of the strong temperature dependence of the hydropho-
bic force demonstrated by Tsao et al. (1991), and the ensuing conclusion concerning the
lowering of the water film entropy, 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.
There are no strong indications that the hydrophobic surfaces primarily referred to here
(i.e., those used by Tsao et al. [1991]) would be laterally inhomogeneous. On the contrary,
AFM studies showed that they were homogeneous over a micrometer scale. Furthermore, Page 169 Tuesday, January 2, 2007 7:36 PM


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. Consequently, it is not anticipated that the hydro-
phobic surfaces will grow inhomogeneous under the experimental conditions, thus setting
the stage for various forms of attractive ionic or dipolar correlation interactions (Tolstoi et al. 1966).
However, 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.
These areas would comprise strongly correlated water dipoles pointing approximately in the
same tangential direction in the interface. In this way, large (cluster) dipole moments may
arise at each of the interfaces, which could interact by an electrostatic correlation mecha-
nism and give rise to a strong attraction pressure. This is the key idea (in a slightly modified
version) of the hydrophobic force theory that was advanced by Pazhianur and Yoon (2003).
Making a Hamaker type of approach and assuming independent surface dipoles, one
can theoretically estimate the corresponding surface force by means of the following expression:

( m2 r 0 )2
--F- = ------------------------------
- (EQ 59)
R 32k B Th 4

where is the surface density of dipoles and m is the dipole moment. Equation 59 was
derived on the basis of the concept presented in Section 5.3 of Evans and Wenerstrm
(1999). For a surface separation of 10 nm, an average patch size 20 20 nm, and an effective
cluster dipole moment equal to 6 103 D, this expression yields an attractive surface force
amounting to 1.6 mJm2, which is the correct order compared with experiments. However,
even if a good fit to experimental data can be obtained in the middle separation range, the h4
factor in the denominator makes it virtually impossible to simultaneously generate accept-
able fits for short and large separations, respectively.
A distance dependence of h4 type is likewise obtained using the more general Lifshitz
approach, regardless of the lateral dipole interaction mode assumed within the surfaces.
Hence, it does not appear straightforward to formulate a fully satisfactory theory of the
hydrophobic force on the basis presently being discussed. Nevertheless, 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. Although it has been claimed that huge dipole moments can arise for hydrophobic
colloidal particles in water (Tolstoi et al. 1966), the implicit assumption of cluster dipole
moments on the order 103 104 D would need additional justification.
Incidentally, the K/h2 function that accounts for the hydrophobic surface force, though
evidently more appropriate than const.h4, does not yield an entirely satisfactory description
of experimental data. Primarily, 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.

Brief comments will be made on the effect of adding a solute to the water phase that is in
equilibrium with a thin film. The main thermodynamic relation governing this case is the
counterpart of the Gibbs surface tension equation, which at constant T and p reads: Page 170 Tuesday, January 2, 2007 7:36 PM


d f = sf,ex d s D dh (EQ 60)

where s denotes the chemical potential of the solute. Consequently, having access to equi-
librium data on the surface force for a certain film thickness as a function of the solute con-
centration, the change in solute excess, sf,ex , for a film of that thickness as compared with
an infinitely thick film can be obtained.
Very recently, such SFA data were published by Meyer, Lin, and Israelachvili (2005),
aiming to clarify the effect of degassing (pure) water contacted with DODA-modified mica
surfaces. Within most of the separation range below 50 nm, a reduction due to degassing of
the magnitude of the hydrophobic force is clearly seen. Hence, referring to dissolution of the
main air components N2 and O2, the derivative is

---------- = sf,ex (EQ 61)
T, p , h

has a negative sign. This obviously implies that sf,ex > 0; that is, 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.
By applying Equation 61 to films of 10 to 20 nm thickness, as examples, 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. This observation is in fair agreement with
the idea of an enhanced water structure in thin water films delimited by hydrophobic sur-
faces. The solvent properties of the water change as additional water cage volume becomes
available to the (clathrate-forming) gas molecules, similar to when the temperature is
reduced to below room temperature.
Relatively speaking, the higher content of the gas solutes for thin films will cause the
film tension to become more negative in accordance with Equation 61. Conversely, deaera-
tion should tend to diminish the magnitude of the attractive hydrophobic force, as observed
by Meyer, Lin, and Israelachvili (2005). Moreover, it seems most likely that the effects of
deaeration documented by Pashley (2003) on the stability of colloids and emulsions can also
be understood, at least in a preliminary way, on this basis.
Referring to Equation 58, an analogous equation for sf,ex is

ln B Bbh ln b d s
sf,ex = ------------ f --------- -----------------------------
- (EQ 62)
s 4 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. From this expression, an increase
in sf,ex , such as found in the case under discussion, is strongly coupled with the constant
B becoming larger as the chemical potential s is raised: the H-bond network in the film is
reinforced by introducing inert gas molecules.
Concerning the addition of alcohols and surfactants that readily adsorb on hydropho-
bic surfaces, in the dilute regime the situation is principally opposite: The surface force rises
with s, yielding a negative sf,ex that, according to the quasi-thermodynamic relation
(Equation 62), can be interpreted in terms of a smaller constant B and a diminishing decay
length b1. This is true for alcohols as well as nonionic surfactants. For a contact monolayer
mixed with such surface-active species, there is simply less free energy to be gained by Page 171 Tuesday, January 2, 2007 7:36 PM




F/R, mN/m


0.10 12.5% Ethyl Alcohol

20% Ethyl Alcohol


0 10 20 30 40 50 60

Separation, nm

FIGURE 19 Surface force isotherms presented by Ederth (1999) for water and ethanolwater
mixtures between hexadecanethiol surfaces, showing the pronounced effect on the
hydrophobic attraction of adding alcohol. The advancing contact angles are 94 (12.5%) and 88
(20%), respectively.

restructuring (smaller a). Evidently, for ionic surfactants, the electrostatic (double layer)
repulsion must also be invoked.
Surface force curves for water and ethanolwater mixtures recorded by Ederth (1999)
using C16-alkylthiolated gold surfaces are reproduced in Figure 19. It appears that the sur-
face force is substantially reduced in magnitude by adding alcohol. Using Equation 61, esti-
mate sf,ex to 4 1016 molecules m2 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 m2. The reason why the surface force diminishes as alcohol is added is that
the lowering of the film tension f is larger for an infinitely thick film than for a thinner film.
In turn, this is because adding alcohol to the thin film counteracts the favorable structure formation.
On the other hand, 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), the chief reason being that small ions do not mix with the water in the
contact monolayers adjacent to the hydrophobic surfaces. Hence, the B constant should be
left much the same, and likewise b1, insofar as the ions do not interfere significantly with
the H-bond network formation. This agrees with a multitude of observations using hydro-
phobic surfaces that are sufficiently stable.

Hydrophobic Forces in Flotation

In flotation, hydrophobic particles are selectively collected on bubble surfaces and separated
from the hydrophilic particles suspended in aqueous slurry. Thermodynamically, the bubble
particle adhesion occurs when contact angle of the particle is larger than zero. In view of
their high interfacial tensions in water, air bubbles should be considered hydrophobic. Thus,
the bubbleparticle interaction occurring during flotation may be seen as a hydrophobic
interaction, the kinetics of which is controlled by the surface forces involved, namely elec-
trostatic, van der Waals, and hydrophobic forces. The electrostatic forces are repulsive when Page 172 Tuesday, January 2, 2007 7:36 PM


both particles and bubbles are negatively charged. The van der Waals forces operating in
wetting films are also repulsive according to the Lifshitz theory. Therefore, it is difficult to
explain flotation without considering the existence of the attractive hydrophobic force dis-
cussed in this chapter. In flotation, the role of the hydrophobic force is to reduce the energy
barrier so that the bubbleparticle interaction becomes a fast heterocoagulation process.
The process can be slow if the hydrophobic force is too small to counterbalance the repul-
sive electrostatic force. It is well known that flotation rate increases with increasing particle
hydrophobicity and decreasing double-layer potentials.
In general, surface forces are weaker than the hydrodynamic forces operating in a flota-
tion cell by orders of magnitude. As a particle approaches a bubble in close proximity, how-
ever, the hydrodynamic force is much reduced because of the hydrodynamic resistance
against film thinning. 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. By assuming that the probability of the bubble
particle adhesion is determined by the hydrodynamic and surface forces, a flotation rate
equation has been developed both under quiescent and turbulent flow conditions (Schimol-
ler, Luttrell, and Yoon 1994; Yoon and Mao 1996; Mao and Yoon 1997; Do and Yoon
2005). This approach made it possible to develop a model that can predict flotation rates
using both hydrodynamic and surface chemistry parameters.
Hydrophobic forces also play a role in particleparticle interactions. Hydrophobic par-
ticles coagulate at a pH well above the isoelectric point, which cannot be explained without
assuming the existence of a hydrophobic force (Xu and Yoon 1989, 1990). The hydropho-
bic coagulation, which is driven by the hydrophobic force, also plays an important role in
flotation. In general, flotation rate decreases with decreasing particle size. Gaudin (1957)
showed, however, that the flotation rate of galena particles stayed constant at particle sizes
<10 m, which may be attributed to the hydrophobic coagulation. Thus, use of a stronger
collector that can increase the hydrophobicity of mineral particles and, hence, increase the
particle size may be conducive to improving fine particle flotation.

In Jacob Israelachvilis book, Intermolecular and Surface Forces (1991), he writes, It is the
energy (or entropy) associated with the H-bonding network and proton hopping defects,
which extends over much larger space than the molecular correlations, that is probably at
the root of the long-range solvation interactions of water. After having scrutinized the sci-
entific issues standing today regarding the origin of the amazingly strong and long-ranged
hydrophobic attraction, the authors agree with Israelachvili. No equally convincing
approach to gain a closer understanding of the hydrophobic surface force has so far been
proposed. Various electrostatic interaction mechanisms have been subjected to critical tests,
and likewise the adheringbridging bubble track. Yet, none of these approaches has been
applicable for the most ideal hydrophobic surfaces one can prepare where the hydrophobic
attraction is strongest. In the end, they have to be abandoned as possible starting points of a
more elaborate theoretical modeling.
Two decades ago, 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. After some time, however, a paradigm shift occurred within the
scientific community, and eventually the concept of water restructuring was considered to Page 173 Tuesday, January 2, 2007 7:36 PM


be nothing but a bold conjecture, maybe even too bold to be taken seriously. Today, how-
ever, a vast amount of experimental results has been accumulated. Together, these results
indicate that there is hardly any alternative route that might be fruitful when aiming at a
molecular understanding of the hydrophobic attraction.
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,
close to a real hydrophobic surface, will be difficult to make, particularly because the molec-
ular description of liquid water is still much in dispute. However, water has long been
known to be an associated liquid where three-dimensional networks play a significant role.
Furthermore, the association process is of a cooperative nature, implying that the free energy
per water molecule depends on the cluster size. Therefore, it may not be surprising that the
introduction of an (infinite) hydrophobic solid surface can promote an extensive structure
generation in the adjacent water, and that confinement of water in a thin film between two
hydrophobic surfaces might strongly promote additional restructuring.
Given the background presented in this chapter to attempt resolving the long-standing
issue about the origin of the hydrophobic force, 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; (b) probe the state of the water
next to carefully prepared and characterized hydrophobic surfaces, as well as in thin water
films sandwiched between hydrophobic surfaces, using, for example, the SFG or XAS tech-
nique; 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.


T H E R M O DY N A M I C S O F A P L A N A R , T H I N A Q U E O U S F I L M
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 f = ( S f A )dT + hdp D dh wf d w sf d s (EQ A.1)

Here, it is presupposed that the properties of the thin film are estimated by using the
equimolecular dividing surfaces with respect to the solid component, that is, by using the
(solid) dividing surfaces in the Gibbs notation. Thus, 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. In the Equation
A.1, p is the ambient pressure, D is the disjoining (interaction) pressure, and f is the film
tension. This equation is a straightforward extension of the Gibbs surface tension equation.
As considered by Gibbs (1961) and treated in more detail by Eriksson (1969), the latter
equation only holds true as long as the state of strain of the solid surfaces remains
It is emphasized that f is energetically (rather than mechanically) defined, by means of
the following relation: Page 174 Tuesday, January 2, 2007 7:36 PM


f = G f A wf w + sf s G f, ex A = f A (EQ A.2)

Accordingly, f 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. Stated another way, it corresponds to the reversible cleavage work up to a certain surface
separation h. In addition, it is formally the same as the potential per unit area of the thin film.
For the special case under discussion, however, regarding a thin film between hydro-
phobic surfaces and made out of a dilute water solution, f has also a rather clear-cut
mechanical significance. 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, the integrated
tangential pressure pT profile across the film thickness h to a good approximation corre-
sponds to f.
Next, Equation A.3 must be brought in harmony with the phase rule by invoking the
GibbsDuhem relation for the bulk phase (denoted by superscript b):

S b dT V b dp + n w d w + n s d s = 0 (EQ A.3)

Upon eliminating dw and switching to the solute concentration cs as variable from

(A.1), the following is obtained:

d f = ( S f, ex A )dT + ( V f, ex A )dp D dh sf, ex -----------
- d ln c s (EQ A.4)
ln c s T, p

where the coefficients dT, dp, and ds are given by

S f, ex A = S f A wf s wb sf s sb (EQ A.5)

V f, ex A = h wf wb sf sb (EQ A.6)


sf, ex = sf wf c S c w (EQ A.7)

In these expressions, sb and b denote partial molar volumes in the bulk solution, and cw and
cs represent the bulk phase concentrations of water and solute, respectively.
The (reversible) surface force measured in a surface force device is proportional to the
film tension difference f = f ( h ) f ( ) for which the following equation is obtained,
assuming an ideal solution of the solute and noting that D ( ) = 0 :

d f = ( S f, ex A )dT + ( V f, ex A )dp D dh sf, ex RTd ln c s (EQ A.8)

with obvious definitions of the coefficients dT, dp, and ds as the differences for the proper-
ties in question between a thin and an infinitely thick film. Because almost all residual con-
tributions from the solid surfaces to the thermodynamic film properties cancel upon
forming these differences, the constraint of a constant surface strain can be disregarded, and,
furthermore, f corresponds almost exactly to the change in overall lateral mechanical tension
of the film when comparing a thin and a very thick film; compare the equivalent equation
presented by Gibbs for the noninteracting case (Equation 678 in work by Gibbs [1961]). Page 175 Tuesday, January 2, 2007 7:36 PM


For the case of 1:1 electrolyte being the solute, the last term in Equation A.8 must be
multiplied by a factor of 2. Hence, by plotting f as a function of the state variables T, p,
and cs for fixed surface separations h, important information can be gathered as to the ther-
modynamic thin film (excess) properties Sf,ex/A, Vf,ex/A, and sf,ex . Using Equation A.2
and the free enthalpy definition results in

G f, ex A = H f, ex A T S f, ex A = f (EQ A.9)
implying that the corresponding enthalpy difference is readily derived. In particular, gaining
knowledge about Sf,ex/A and Hf,ex/A will be crucial for understanding the structural
aspects of thin aqueous films, whereas the effect of solutes on the surface force is intimately
related with sf,ex . In all likelihood, 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.

The authors wish to thank Atte Kumpulainen and Jinhong Zhang for many illuminating
discussions and for assistance with the figures. Appreciation is also extended to Per Claesson
for critically reading the manuscript and making several useful comments.

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