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The Scientific Basis of Flotation

NATO ASI Series


Advanced Science Institutes Series

A series presenting the results of activities sponsored by the NATO Science


Committee, which aims at the dissemination of advanced scientific and technological
knowledge, with a view to strengthening links between scientific communities

The series is published by an international board of publishers in conjunction with


NATO Scientific Affairs Division

A Life Sciences Plenum Publishing Corporation


B Physics London and New York

C Mathematical and D. Reidel Publishing Company


Physical Sciences Dordrecht and Boston

D Behavioural and Martinus Nijhoff Publishers


Social Sciences The Hague/Boston/Lancaster
E Applied Sciences

F Computer and Springer Verlag


Systems Sciences Berlin/Heidelberg/New York
G Ecological Sciences

Series E: Applied Sciences - No. 75


The Scientific Basis of Flotation
edited by

Kenneth J. Ives
Professor of Public Health Engineering
Department of Civil and Municipal Engineering
University College, London, U.K.

1984 Martinus Nijhoff Publishers


The Hague I Boston I Lancaster
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Study Institute on
The Scientific Basis of Flotation, Cambridge, England, July 5 - 16, 1982

Library of Congress Cataloging in Publication Data


NAi'~ ArJvan.:pd Study Insti t.ll'.. ': or. the Scientific
Bacir. of Flotation (1982 : Cambridge, England)
Th~ c,cientific basis of flotation.

(NATO Advanced science institutes series. Series E,


Applied sciences ; no. 75)
"Proceedings of the NATO Advanced Study Institute
On the Scientific Basis of Flotation, Cambridge,
England, July 5-16, 1982"--
"Published in cooperation with NATO Scientific
Affairs Division."
Includes index.
1. Flotation--Congresses. I. Ives, Kenneth James,
1926- . II. Title. III. Series.
TN523.N39 1982 622'.752 83-23685

ISBN-13: 978-94-009-6928-5 e-ISBN-13: 978-94-009-6926-1


DOl: 10.1007/978-94-009-6926-1

Distributors for the United States and Canada: Kluwer Boston, Inc., 190 Old Derby
Street, Hingham, MA 02043, USA
Distributors for all other countries: Kluwer Academic Publishers Group, Distribution
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All rights reserved. No part of this publication may be reproduced, stored in a


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publishers,
Martinus Nijhoff Publishers, P.O. Box 566, 2501 CN The Hague, The Netherlands

Copyright © 1984 by Martinus Nijhoff Publishers, The Hague


Softcover reprint of the hardcover 1st edition 1984
TABLE OF CONTENTS

Acknowledgement VI
K.J. Ives
Introduction 1

J.A. Kitchener
The Froth Flotation Process: Past,
Present and Future - In Brief 3

G.J. Jameson
Physics and Hydrodynamics of Bubbles 53

E.H. Lucassen-Reynders and J. Lucassen


Thin Films, Contact Angles, Wetting 79

P.L. de Bruyn
Some Aspects of the Physical Chemistry
of Solid/Water Interfaces 111

G.J. Jameson
Experimental Techniques in Flotation 193

H.L. Shergold
Flotation in Mineral Processing 229

G. Barbery
Engineering Aspects of Flotation in the
Minerals Industry: Flotation Machines,
Circuits and their Simulation 289

T. Zabel
Flotation in Water Treatment 349

H.H. Hahn
Wastewater Treatment 379

Index 415

Appendix 425
List of those attending the NATO Advanced Study
Institute of Christ's College, Cambridge (UK)
5-16 July, 1982
VI

ACKNOWLEDGEMENT

This book would not have been possible without the support
and cooperation of the Division of Scientific Affairs, NATO,
Brussels, and the particular help given by its Director Dr. C.
Sinclair, and his staff, which is gratefully acknowledged.

Kenneth J. Ives
1

INTRODUCTION

K.J.Ives

Professor of Public Health Engineering


University College London

Industrial application of the use of bubbles to float fine


particles in water began before the beginning of this century, in
the field of mineral processing. Such bubble flotation was
applied very little outside mineral processing, until about 1960
when the dissolved air process, which has already had some
success in the pulp and paper industry, was applied to water and
wastewater treatment. The subsequent two decades saw not only a
growth development for water and wastewater treatment, but also a
growing cognisance of the similarities that existed with mineral
processing flotation.

Therefore the time seemed ripe in 1982 for a joint meeting


between experts in these two major fields of flotation to put
together the Scientific Basis of Flotation in the form of a NATO
Advanced Study Institute. Attended by about 60 specialists,
mainly post doctoral, from 17 countries, this Study Institute in
residence for two weeks in Christ's College, Cambridge (UK) heard
presentations from several international experts, principally the
8 co-authors of this book. The integration of the various
scientific disciplines of physics, physical chemistry, colloid
science, hydrodynamics and process engineering showed where the
common basiS, and occasional important differences, of flotation
could be applied to mineral processing, water and wastewater
treatment, and indeed some other process industries (for example:
pharmaceuticals, and food manufacture).

After an historic review, with a small glimpse of the future,


this scientific basis reviews bubble behaviour in water, the
details of the bubble - particle - water interface including the
physical chemistry of many of the solid particles which are
attached to bubbles in flotation. Then the investigative
2

techniques of the laboratory are described, followed by the


applications of flotation in the mineral industry, and the water
and wastewater fields. Each chapter is self-contained, both in
style and nomenclature, for any attempt to harmonise these across
such diverse fields as surface chemistry and wastewater treatment
would have produced an unnatural marriage, pleasing no one.
Nevertheless, the book has been deliberately structured to
proceed from the most fundamental to the applied topics, and each
author was well aware of this structure and of his fellow
authors contributions.

It is assumed that the reader has a certain level of scientific


knowledge, particularly in chemistry, physics, mathematics and
fluid mechanics. Each chapter has a reference list so that
further reading is possible, to increase the reader's background
knowledge.

This book has been prepared in a similar format to the companion


volumes "The Scientific Basis of Filtration" (1975), and "The
Scientific Basis of Flocculation" (1978), published in the same
NATO - ASI Series in Applied Science.
3

THE FROTH FLOTATION PROCESS:PAST,PRESENT AND FUTURE-IN BRIEF*

J.A.Kitchener

Department of Mineral Resources Engineering,


Imperial College London.

FOREWORD

It is not easy to convey, in a few words, the enormous


importance of the froth flotation process to the economy of the
whole industrial world. It may suffice, for the present
article, to quote rough estimates of the quantity of crushed
ore which is treated annl1ally by flotation - 2 x 10 9 tonnes -
and the proportion of base-metals nowadays won by this process
- 95%. Certainly, without flotation many familiar metals and
inorganic raw materials would be exceedingly scarce and costly;
for the high-grade ores, which could be processed by simple
physical and mechanical methods, have long since been used up.

Here, then, is a remarkable and invaluable bit of technology.


Yet the general public (in Britain, at least) has scarcely
heard of flotation; and few scientists or technologists have
any knowledge of how it developed [1].

HOW IT BEGAN

The basic step in flotation - namely, the capture of small


mineral particles by bubbles and their collection in the form
of a froth - is obvious enough and was doubtless noticed, from
time to time, throughout the ages. According to Schulze [2],
there is mention of enrichment of copper carbonate by flotation
in the East during the 15th century; but flotation did not
figure as an established process in the Middle Ages, judging

* copyright J.A.Kitchener
4

by the great book of Georg Agricola (1490-1555), the "father of


metallurgy". It emerged as a workable process only late in the
19th century and can rightly be called a consequence of the
Industrial Revolution. Steeply rising demand for materials of
construction resulted in imminent exhaustion of supplies. This
provided the incentive to find new methods of working ores of
low grade.

It is impossible to pin down the "invention" of the process to


any single person or date (any more than the first cuckoo
triggers the arrival of Spring). A Victorian inventor, William
Haynes (1860), patented a process in which oil was mixed with a
crushed ore containing a metal sulphide mineral, which then
floated up with the oil when the mixture was stirred in water.
A similar process was patented in Germany in 1877 by the Bessel
brothers for recovering graphite. But this stage can only be
described as proto-flotation. In the first monograph to be
written on flotation proper, in 1912, T.J. Hoover [la] made the
following very pertinent remark:

"A new meallurgical 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".

He then named 57 people who had made significant contributions


to flotation - up to 1912! A few of these might be classified
as industrial researchers - notably the staff and consultants
employed by Minerals Separation Ltd. in London; but most were
individual inventors whose contributions were sometimes the
result of chance observations shrewdly followed up.

There is a pleasing story in Hoover's book of one of Miss


Carrie J.Everson' s several inventions, patented in 1885. This
lady school-teacher is said to have washed some ore sample bags
which had become greasy in her brother's laboratory, and, in
agitating them in the wash-tub, she noticed that the dark
sulphide mineral was concentrated in the floating scum, whereas
the gangue was not. Following up the observation, she found
that the separation was improved if the slurry was faintly
acidified before agitation. Everson's procedure contained some
of the essential elements of the later froth flotation process,
but it seems to have been shelved until modified by others in
1894. What a pity that this whole story of the discovery was
apparently a journalistice fabrication-according to Rickard
[lb].

Hoover reviewed 140 patents in his 1912 nomograph, and re-


marked that it was impossible to find among them 140 new ideas.
Apart from the invention of machines, the principles employed
5

up to that time were few. Most patents were based on ad hoc


observations, and it is difficult to trace any line of logical
development in successive patents; for inventors in differenct
parts of the world were simply trying out new ideas for
treating lower grade ore deposits or for reworking the huge
tailings dumps rejected at old mines.

However, despite the lack of logical progression or theoretical


comprehension, these early patents do reveal some interesting
principles. The main concepts are listed below:-

1. Whereas most minerals ware water-wetted, certain sulphide


minerals (e.g. antimonite) can be caused to float on water
if they are gently dusted over the surface. (Bradford,
1885). This procedure has been called "skin flotation".(Talc
and graphite are also naturally floatable minerals).

2. When sulphide minerals are agitated with oil and water they
are preferentially wetted by the oil, in contrast to the
common gangue minerals (oxides, silicates, carbonates etc.)
which are hydrophilic rather than oleophilic (Bradford,
1860).

3. Often the selectivity of the oil for the sulphide minerals


is improved by acidifying the pulp. Here is the first use of
chemical reagents to facilitate a physico-chemical
separation of mineral grains.

4. The oleophilic preference could be exploited in various


ways. If sufficient oil was added, the sulphide grains would
be buoyed up and could be skimmed off (oil flotation). Or,
with less oil, they would form dense agglomerates, from
which the hydrophilic particles could be elutriated off; or
the oiled particles could be caught on a greased belt (as
has been used much later for catching diamonds). The same
principle was used again 60 years later in the "spherical
agglomeration" process, in which oil-wetted grains are made
to clump together by under-water peletizing. The can then be
separated off by gentle sieving.

5. After an oil-selection step, sulphide minerals can be parted


from the oil by shaking with alkaline solutions, so that the
oil can be used again. Furthermore, by raising the
alkalinity (pH) in steps, certain sulphides can be separated
from one another (Cattermole, 1902) - a valuable innovation,
this, because sulphide ores commonly contain several
distinct heavy metal minerals, such as galena (PbS),
sphalerite, (ZnS) and pyrite (FeS2).

6. Finely-divided sulphide particles("slimes") can be caused to


6

clump together by adding dissolved soaps,followed by mineral


acid (which would liberate the free fatty acid)(Cattermole,
1902). This appears to be the first example of "selective
flocculation"; for there would surely be gangue slimes also
in the pulp and these were evidently not coagulated along
with the sulphide slimes. ---

In the same patent, Cattermole recommended adding coarse


oiled particles to the pulp to facilitate collection of the
coagulation slimes - employing a sound principle, nowadays
known to colloid chemists as orthokinetic flocculation. The
use of a hydrophobic mineral carrier for collecting slimes
was re-invented and patented 60 years later under the name
of "ultra-flotation". One wonders whether such a patent
would stand up in a court of law- it seems an obvious
extension of the same idea. (But scientific logic does not
always hold sway in legal arguments, which sometimes
resemble games played to Alice-in-Wonderland rulesl)

7. If air or CO2 is also introduced into an agitated ore-oil-


water pulp, it assists in collecting and raising oleophilic
grains. (Froment, 1902). A conglomerate of oiled grains and
entrapped air bubbles is what floats. Here may be discerned
the beginning of modern flotation.

8. It was a simple but significant and patentable step to


establish that the amount of oil can be reduced if plenty of
air bubbles are injected (Sulman and Picard,1903).

9. Gas bubbles for flotation can also be generated


conventiently by electrolysis (Elmore. 1904). This is the
first appearance of "electroflotation". Another way is to
reduce the air pressure above the pulp. causing the
dissolved air to nucleate and grow bubbles on the oiled
mineral grains (Elmore. 1904). Although a heavy cast-iron
cell was needed. Elmore's "vacuum flotation" method was used
successfully for several years. (Nowadays vacuum flotation
is used only as a quick laboratory test for flotability).

10. The time was now ripe for the key invention. According to
T.A. Rickard [lcI. the efforts of the Minerals Separation
Ltd. research team in London were rewarded when "suddenly
they happened upon the particular combination essential to
the froth flotation process". The simplest and cheapest way
of floating sulphide minerals is to vigorously agitate the
finely-divided ore in water with entrained air. together
with only a very little oil ("a fraction of 1% of the weight
of the ore") for a period of 1 to 10 minutes. This is the
crux of the classic British Patent No.7803 (Sulman.Picard
and Ballot. 1905). The use of a very small proportion of oil
7

took the process away from agglomeration, as there was


insufficient to form a continuous oily film around the
particles; but a few parts per 1000 was sufficient to bestow
good flotability on the sulphide grains. A machine for
providing the vigorous agitation and aeration of the pulp
was developed by T.J.Hoover for Minerals Separation Ltd.
Except for size, IIlOdern cells are not much different from
Hoover's, for although many alternative schemes have been
patented, they have not been widely adopted.

11. Yet another way of getting bubbles into a slurry is to


pressurize it with air, or inject super-saturated water, and
then rely on the gas evolved when the pressure is released
(Sulman, Picard and Ballot, 1905). This is easier to
engineer than using a vacuum. By supersaturating water with
air at several atmospheres pressures and then injecting it
through a nozzle into a tank of pulp, H.Norris (1907)
obtained "infinitesimally small nascent bubbles of air"
which are ideal for floating slimes. Here is the invention
of the "dissolved air flotation" process, nowadays being
increasingly used for clarifying effluents.

12.To improve the frothing, without upsetting the selectivity


of the flotation, it is advantageous to add small smounts of
phenols (Higgins,1908) or water-soluble alcohols (Sulman,
Picard and Ballot, 1908). (Later, pine oil, a complex
mixture of slightly soluble oils, was most widely used).

13.With certain ores containing several sulphide minerals it is


possible to first collect them all jointly by flotation and
then subject the concentrate to low-temperature roasting;
Pyrite and galena oxidize first (and are thereby rendered
unfloatable) before the sphalerite, which can be extracted
by a second flotation (Horwood,1910). Previously, such
sulphide mixtures, provided they were coarse enough, could
be separated only on shaking tables.

By 1912 froth flotation was already successfully launched in


Australia and U.S.A. In the former, some 5,000,000 tons of
tailings dumps, from which the galena has been extracted by
gravity methods, were being re-worked by flotation for their
sphalerite. The first flotation plant in the U.S.A., at the
Basin Mill, Montana, stated up in 1911 to treat the slimes
(defined as 92% passing 150 mesh) containing a "finely-divided,
widely disseminated" sphalerite from the ore. In 1912 also
laboratory trials revealed that the copper minerals,
chalcopyrite and chalcocite, can be floated - a discovery which
soon opened up huge, low-grade, porphyry ore deposits,
previously uneconomic to work.
8

The heyday of flotation invention(1910-1915)was characterized


by intense rivalry between mining groups,secretative test-
work,even what is now called industrial espionage, and finally,
long-drawn-out and bitter litigation over patent infringements.
An indefatigable American mining-journalist, T.A. Rickard, (a
graduate of the Royal School of Mines, London) recorded the
saga in detail lId].

THE FOUNDATIONS

It is interesting to consider how much basic science of this


flotation process was understood in 1912: suprisingly little!
(i) It was clear that flotation requires a contact angle,
by means of which particles become attached to air bubbles
and so are carried up into the froth layer by the forces
of surface tension.
(ii) It was recognized that hysteresis of the contact
angle favours retention of the particle-bubble contact, by
providing give-and-take under impacts.
(iii) Physicists certainly knew why alcohols act as
foaming agents; indeed, the thermodynamics of reversible
adsorption and the phenomenon of dynamic surface
elasticity were clarified in the late 19th century. (It is
doubtful whether the flotation men gave a thought to the
theory of foaming!)
(iv) Slimes were known to undergo coagulation
(flocculation) when treated with soaps prior to flotation,
and it was noticed that strong flocculation generally
correlated with strong flotation. (A sound observation -
but why?)

The most crucial question - what property of a solid determines


its contact angle with water, and, hence, its flotability? -
remained unanswerable for many years. As a matter of fact,
thinking on this problem was strangely muddled by prevalence of
a misleading concept of "attraction for air", whereas the real
key is "disliking for water" (hydrophobicity).

CLASSIC DEVELOPMENTS

Uninhibited by its shaky foundations, flotation continued to


develop healthily during the second decade of the century. The
chief advance was the introduction of various simple chemical
reagents which were added to the pulp to modify the "response"
of different minerals to the flotation oil ("collector"). In
1912 L. Bradford in Australia patented the use of copper
sulphate to "activate" the flotation of sphalerite. It is not
recorded how he came to discover this treatment; but its
independent discovery by J.F.Myers in U.S.A. in 1914 makes a
good story. At that period ores were commonly acidified before
9

flotation, and Myers obtained good results on an acidified


calcereous sphalerite ore when he tested it in a brass bench
float-cell. However, when a full-scale plant was constructed in
wood, the flotation failed until a copper sheet liner was
installed. Myers claimed to have realised that a very small
concentration of CuSO'+J formed by acid attack on the brass or
copper, explained the difference; and certainly it worked when
added deliberately.

The problem with the mixed sulphide ores was that pyrite (FeSZ)
also 'floated, especially in acid conditions. Myers (1915)
recalled that they had never been troubled with pyrite when
floating a naturally alkaline ore. Sure enough, raising the pH
proved effective in preventing pyrite floating ("depressing"
it). For no obvious reason lime, Ca(OH)2, was found to be more
effective than NaOH - so i t wasn't just the pH that caused
depression.

Soon other activators and depressants were discovered. In


Australia, Bradford (1913) found that S02 depressed sphalerite,
which is liable to be unintentionally activated by heavy metal
salts present in an ore - not only copper, but lead and silver.
In such ores the sphalerite is liable to float along with the
galena. Some years later, sodium cyanide or sodium sulphide
were used to eliminate activating metal salts by complexing or
precipitation, respectively.

The importance of these modifying reagents was two-fold.


Firstly, they drew attention to the phenomenon of surface
reaction on minerals - a new concept; secondly, on a practical
level, they provided methods of differential flotation of two
or more sulphide minerals from a mixed ore, by successive
additions of depressants and activators.

Meanwhile, until 1924, the primary flotation reagent - the


"collector" - was still a crude natural oil of vegetable or
animal origin (e. g. eucalyptus in Australia, wood creosote,
coal tar or impure oleic acid).

Coal tar and creosote contain phenol and mixed cresols


(CH3.C6HIt0H), which were patented by Minerals Separation Ltd.
in 1910 as "soluble" flotation reagents. How these various oils
worked was not understood; but the search went on for
alternatives, partly to circumvent the patents by Minerals
Separation Ltd. A petroleum hydrocarbon such as kerosene could
be used as an adjunct, though alone it was not a satisfactory
collector. It is evident, in retrospect, that a slighly polar
oil is better.
10

CHEMICAL REAGENTS

The outcome of this search was the introduction of an entirely


new class chemical collectors based on organic sulphur
compounds. Whether this important development should be called
a discovery or an invention - the former implying something
found by searching, the latter a logical application of guiding
principle - is not clear. In 1921 C.L. Perkins patented the use
of compounds containing carbon, nitogen and sulphur, such as
thiocarbanilid, S==C(NH.C6H S)2. Hwever did he hit upon such an
out-of-the-way compound? The patent gives no clue.
Thiocarbanilid is a white crystalline solid, only slightly
soluble in water, which is prepared by heating together CS 2 +
C6H s .NH 2 (aniline) + KOH. At one time it was used as a rubber
vulcanizing accelerator. Why should it serve as a flotation
collector for sulphide minerals? In fact, thiocarbanilid was
one of several solid organic compounds which were discovered to
have collector asction during the course of some sponsored
research at the Mellon Institute over the period 1914-1921.
(The sponsors, Metals Recovery Co. of New York, were rivals of
Minerals Separation Ltd).

Thiocarbanilid had the disadvantage of needing a solvent to


disperse it. A series of structurally related, but water-
soluble, collectors followed. The most important of these
proved to be the alkylxanthates, patented by C.H. Keller in
1925. Xanthates are alkyl ethers of dithiocarbonic acid. They
are easily prepared; for exa~~e, potassium ethylxanthate,
which has the formula C2HsO.CS2 K , is made by heating together
ethanol (C2HSOH), carbon disulphide (CS2) and potassium
hydroxide (KOH). Alcohols with longer alkyl groups (e. g.amyl)
yield xanthates with "stronger" collector action. They are
water-soluble on account of their ionic charge.

Again the patent gives no indication as to how xanthates were


hit upon. In fact, they were only one type of many claimed by
Keller and assigned to Minerals Separation Ltd. (As a matter of
fact, even simple mercaptans, thio-alcohols, have collector
properties, but their foul smell is intolerable!) As a rival to
xanthates, dithiophosphates were later patented by
F.T.Whitworth in 1926 and assigned to American Cyanamid Co.
According to one authority, "literally thousands of substances
have been tried in flotation tests and experiments" and 100
were "specifically described in U. S. patents up to December
30th 1925".

This is not the place to discuss how the thio-collectors work.


Certainly the patentees did not know, though the insolubility
11

of heavy-metal xanthates was on record in the chemical


litera.ture. Many years later the remarkable complexity of the
interaction of xanthates with sulphide minerals has been
exposed, though not yet fully elucidated.

The practical merits of xanthates were quickly recognized-


cheapness, water-solubility, superior selectivity and
particularly - the improved control they provided when used in
conjunction with a separate frother, depressants and activators
for differential flotation. Many schemes were worked out to
suit different ores. A classic example was the winning of
galena, sphalerite and pyrite from a siliceous gangue. By
depressing the pyrite with lime and activating the sphalerite
with copper sulphate, a first float with ethyl xanthate and
pine oil as frother collected the galena + sphalerite; on
depressing the sphalerite with sodium cyanide and zinc
sulphate, a second float brought up the galena alone. If
recovery of pyrite was required, it could be floated by
lowering the pH and adding some amyl xanthate.

The devising and optimizing of such schemes was largely done by


trial and error, once the key ideas become known. No doubt
there were crude notions as to how the· various recipes and
modifying reagents worked, but it was neither possible not
necessary to study the chemical mechanisms. It was many years
before academic research took up these questions and,
surprisingly, it is still too early to see much impact of this
work.

During the second quarter of the century practical mineral


separation continued to develop by the same empirical route
that characterized its rise during the first quarter. New
features were (a) the treatment of a great variety of non-
sulphide minerals and (b) the use of conventional surface-
active agents as flotation collectors.

In the early years of flotation, when metallic sulphides were


being floated with crude fatty acids, any calcareous gangue was
liable to cause poor selectivity, because it floated too. In
fact, many common minerals, besides the calcium salts (calcite,
fluorite, apatite, dolomite. scheelite, etc.) can be floated
with oleic acid or soaps including "oxidized" metallic
minerals such as malachite and many oxides such as hematite.
pyrolusite and chromite. Even quartz and alumino-solicates,
which normally do not respond to soaps (if pure). may be
activated. deliberately or adventitiously, by traces of
hydrolyzing metallic salts such as Cu4-.Fe 3+,Mg4-. Soaps on
their own are evidently altogether too unselective for many
ores.
12

Ways to get round this lack of selctivity have been invented


for various mineral combinations; adjustment of pH and the
addition of inorganic depressants (such as sodium silicate) or
organic depressants (such as dextrin) can sometimes be made to
yield economically acceptable concentrates of non-sulphide
minerals. Here again, the science has followed practice, never
led it. And, naturally, the closer two minerals are in chemical
type - e.g. calcite and dolomite - the more difficult it
becomes to find conditions under which they can be separated by
flotation.

The 1930's saw the spectacular rise of synthetic surface-active


agents, mostly derived from petroleum, for use in place of
soaps, as wetting agents, detergents, emulsifying agents, etc.
Cheap petroleum sulphonates have been used for many years as
flotation collectors. Literally hundreds of surfactants are
potential collectors; but as they seem to work mainly by
electrostatic attraction of their polar groups to any surface
of opposite sign of electrokinetic charge, they show little
selectivity, and separations depend largely on arranging to get
the minerals themselves differently charged by adjustment of pH
etc. Negatively charged minerals, such as quartz and silicates,
can be floated with cationi~ s~rfactants - typified by salts of
dodecylamine (e.g.C12H2SNH3 Cl ), which were first used in 1935
to float mica and talc from an impure limestone. Incidentally,
a quite surprising application of dodecylamine acetates is for
the flotation of sylvite (KCl) away from halite (NaCI), with
starch being used to depress any clay slimes. The liquid phase
here is, of course, a saturated brine! (whoever thought of
trying this separation?).

The list of minerals known to have been either recovered or


purified by flotation is now a long one. Some of the better
known examples are given in the table below, together with
their "values" in brackets. But it should be emphasized again
that there is nothing remarkable in so many different species
having been floated - for virtually particulate solids are
amenable to flotation. What is remarkable - and the present
brief account cannot do justice here - is the achievements of
innumerable flotation men who, by skill, patience and
craftiness, have devised the methods of working economic
separations, given only a very imperfect inderstanding of the
basic science.

apatite (P) kaolinite (china clay)


arsenopyrite (As,Au) kyanite (Al.sil.)
azurite (Cu) magnesite (Mg)
barite ( BaS04) magnetite (Fe)
bauxite (AI) malachite (Cu)
beryl (Be) molybdenite (Mo)
13

boric acid (B) perovskite (Ti)


bornite (Cu) phosphorite (P)
cassiterite (Sn) pitchblende (U,Ra)
celestite (Sr) pyrite (S)
cerussite (Pb) pyrochlore (Nb,etc)
chalcite (Cu) pyrrohotite (FeS gangue)
chalcopyrite (Cu) quartz
chromite (Cr) rhodochrosite(Mn)
chrysocolla (Cu) rutile (Ti)
cinnabar (Hg) scheelite (W)
coal sillimani te (AI. silo )
colemanite (B) smithsonite (Zn)
covellite (Cu) sphalerite (Zn)
felspar spodumene (Li)
fluorite (CaF 2 ) stibnite (Sb)
galena (Pb) sulphur (S)
gold sylvite (K)
graphite talc
halite (NaCl) witherite (Ba)
hematite (Fe) wolframite (W)
ilmenite (Ti) zircon (Zr)

HOPEFUL IDEAS

Looking back over almost "blind" development of flotation in


the past, it is understandable that nowadays research tends to
search for more "specific" chemical reagents which might show
strong chemisorption on the particular minerals. For the
heavymetal compounds this result is already obtained with thiol
(-SH)- type collectors. It would be valuable to discover other
principles. One hopeful idea, advanced by G. Gutzeit (1946), is
to find appropriate complexing agents. For example, some of the
colorimetric reagents used for identifying metallic elements
can function as flotation collectors; e. g. cassiterite (Sn02)
can be floated with cupferron, or salicylaldehyde or
alkylhydroxamic acids. Gutzeit correctly pointed out that all
such reagents, which form stable complexes at very low
concentrations of particular elements, do so by chelation
reactions (that is, they form closed ring complexes of
exceptional stability). The idea is fascinating; but
unfortuna tely there are snags. Today, 35 years af ter Gutzei t,
the dream of highly specific collectors is unfulfilled.

An alternative to chelation is the "fitting" of the functional


group to the lattic sites on the exposed faces of the mineral
particles, as Sorenson [3) speculated for calcite, fluorite,
etc. - a fascinating concept, though built on the dubious (and
certainly unproven) assumption that collector action depends on
monolayer adsorption.
14

Selective flotation demands a delicate balance of surface-


chemical condi tions, perhaps not to be achieved by simple
'magic' reagents. But surely here is a technological problem
which ~ be resolved by determined research I

NON-MINERAL FLOTATION

It has been known for many years that various particulate


solids besides minerals can be extracted from water by
flotation. Miscellaneous patents can be found in the literature
from the early 1920' s onwards, though whether they were ever
used is difficult to ascertain; and, curiously, the history of
this branch of flotation seems not to have been researched.
Apparently, flotation has been successfully used for a long
time in Scandinavia for recovering wood pulp from the effluent
of paper-mills - serving the dual function of saving cellulose
and minimizing pollution.

Since the second World War, there has been a flood of articles
describing the use of flotation for purifying effluents. most
of them read as though the authors had just invented the
process, whereas in truth many applications had been patented
(if not actually used) before 1945. A scan of the Chemical
Abstracts for the period 1917-1946 under "Flotation" reveals
applications to a wide range of materials, including the
following:-

bacteria pea cleaning


cereal grains petroleum from wastes
clays proteins from milk
colloids, from legumes proteins and glue
coal resins
corn root leachates
earthy impurities in diatomite rubber
ergot from rye seed hulls
fat, from animal wastes serum
fibres, from pulp mills sewage
grease, from sewage starch
ink,removal sugar juices,
from newspaper pulp purification of
laundry wastes sulphur dyes
oils and proteins from seeds water purification
oxalates, from plant material wool grease
paper wastes

The list bas grown further in recent years to include such


diverse materials as:-
15

brown-coal metallic salts


cane sugar(removal of impuri from plating baths
ties by "flocco-flotation") plastics, separation
carbon from blast-furnace of polyolefins,
flue dusts polyesters, polyvinyl
fruit juices,clarification chloride
glass recovery (from municipal pyrite, separation
wastes) from coal
waste battery
components

For many of these applications, flotation is best carried out


by the dissolved air method, rather that the dispersed air
cell, as used for minerals; alternatively, electro-flotation or
vacuum flotation are feasible. The distinguishing feature is
that, where extremely small (or even colloidal) particles have
to be floated, micro-bubbles are required. Furthermore, what is
floated is often an aggregated colloid, rather than a dispersed
one, and consequently high shear rates must be avoided to
obviate destruction of the aggregates. This factor is
particularly important in the clarification of potable water
supplies from rivers and reservoirs,where the proportion of
suspended solids is far lower than in the treatment of
effluents. Thus the flotation of colloids introduces distinct
problems not previously encountered in mineral flotation.

It is a matter for definition whether "flotation" should or


should not be deemed to include what some authors call
"adsorptive bubble separation" [4] - that is, the extraction of
soluble compounds by bubbles. If a solution yields a foam when
gas is bubbled through it, there must be adsoption of surface-
active substance at the gas/water interface, and this substance
becomes concentrated in the foam. If the solute is highly
surface-active-for example, a soluble protein, soap or
detergent foaming may continue down to great dilutions;
consequently, such substances can be effectively extracted and
concentrated by a bubbling column technique analogous to
fractional dis illation.

A neat example is the extraction of biochemical preparations of


bile acids, for these compounds are both surface-active and
sparingly soluble, with result that, when their solutions are
foamed, the collapsing foams actually precipate out the micro-
crystalline compounds (Schutz, 1942).

In principle, the adsoption of surface-active molecular solutes


at the air/water interface is brought about by the same forces
that cause flotation of mineral particles; and there is no size
of "particle" from a 1mm grain of coal down to Inm alcohol
16

molecule which cannot be extracted by means of bubbles,


provided it has the right balance of hydrophilic-to-hydrophobic
character. Only the mechanism of capture changes radically with
the size. Colloidal particles are no exception.

The scope of the adsorptive bubble separation process has been


greatly widened by use of reagents which will render the
desired solute surface active. For example, complexing agents
can be found which will react with trace metals and carry them
to an interface. Similarly, a weakly surface-active electrolyte
can be combined with one of opposite sign to form a highly
surface-active (and maybe, insoluble) complex. These schemes
are sometimes called ion flotation [4]. Whether they are going
to prove widely economic is another matter.

RESEARCHING FLOTATION

What needs to be investigated

As flotation is very much a "going concern" any review of its


operation must begin with a brief look at how it is worked
today. That will provide the possibility of analyzing the steps
involved, and then these can be considered in more detail.

At first sub-division must be made into dispersed-air (coarse-


bubble) flotation, as used for minerals, and dissolved-air
(micro-bubble) flotation, which is favoured for effluents and
water treatment. The division is actually not clear-cut because
there is probably some nucleation of micro-bubbles in mineral
cells (in the low pressure zones behind the impeller
blades)and, conversely, there are some coarse bubbles in
dissolved-air cells. However, a broad division into macro- and
micro-bubbles is useful for mechanistic considerations.
Electro-flotation obviously comes into the latter group.

Mineral flotation starts with grinding of the ore, with water


and reagent, down to a chosen average grain size to secure
"liberation" of the discrete mineral particles. This step
raises a difficult mineralogical question; as perfect
liberation is rarely achievable without excessive over-
grinding, what defines the economic compromise? The problem
will not be considered further here.

The "pulp" (i.e. mineral-water slurry after grinding) is


commonly passed through a hydrocylone to concentrate the
"sands" and reject the "slimes" (the finest size fractions,
say 20~m in diameter). the slimes are objectionable in several
respects: they are slow to float, the consume a
disproportionate share of the reagents, and they may seriously
spoil the selectivity of flotation of the sands by "slime-
17

coating" them. There are sound arguments, in any case, for


processing coarse and fine fractions separately [5].

The pulp is "conditioned" for a few minutes with reagents


designed to accentuate differences of floatability of the
various mineral species. An appreciable time is required to
achieve good distribution of the reagents and to allow give-
and-take competition between different mineral particles.
Dissolution, chemisorption, and precipitation take time, as the
concentrations are quite low. In 5-10 minutes a quasi-steady
state is reached, probably not full thermodynamic equilibrium.

The conditioned pulp is run into a flotation cell, which is


crudely a box with a stirrer, and a means of introducing air.

The whole contents are beaten together vigorously (Fig.1)

MOTOR

....
,
./'

.
r /'~~~'
c. )
fI
••. 66 c)
'.
Ci ..

Fig. 1. Schematic diagram of a dispersed air flotation


machine as used for processing minerals.
18

Typically, the cell might contain 15-30% by volume of entrained


air with bubbles ranging mainly from 0.1 to 5mm in diameter;
the "pulp density" might be 25-40% of solids having a particle
size ranging from 10-100pm. The flotation grains are caught by
bubbles and carried to the top of the cell, forming a froth,
which is automatically scraped off over the "lip" of the cell,
where it collapses and flows away in a launder. The frothing
action is quite important. A moderate depth of froth is
necessary to allow some back-drainage to take place, with
release of non-floated particles which have been, unavoidably,
entrained to some extent between the bubbles. Here is another
reason why "slimes" are a nuisance - they remain too long in
the water between the bubbles and so reduce the "grade" of the
floated product.

The first stage of flotation of the pulp amounts to a quite


short average "residence time" in the "rougher" cell before it
passes out, largely depleted, from the bottom of the cell. In a
conventional flotation plant no attempt is made to engineer a
perfect separation in one stage. Instead, both fractions
leaving the rougher are re-treated at least once in "cleaner"
and "scavenger" cells , respectively. Scavenger cells, in
effect, prolong the flotation time, while competition for
bubble surface is reduced. The net of the recycling and re-
treatment is improvements in the separation ("grade") and
proportion of valuable minerals obtained ("recovery"). As the
latter is usually a minor component of the ore, it is
preferable to float it, in preference to floating the much
greater proportion of gangue; but in some cases the gangue is
floated ("reverse flotation").

It is a characteristic feature of flotation plants that the


cells are comparatively small, but rows and rows of them are
run in parallel to increase through-put and in series to
improve grade. If more than one mineral is to be extracted, the
pulp is re-conditioned with other reagents and further stages
of flotation are operated. The engineering is simple,
continous, amenable to adjustment, and needs little operator
attention. But by modern chemical-engineering standards it is
frankly crude.

The final waste pulp of non-floated "gangue" is pumped to


lagoons, where - it is hoped - the solids should settle. If the
pulp contains colloidally stable slimes, there will be problems
from the turbid over-flow and further flocculation and
prolonged periods of settlement may be needed. In some plants,
the waste water may contain objectionable, even toxic,
chemicals [6]. So the disposal of wastes from flotation plants
is becoming a serious problem, as communities become
increasingly pollution-conscious. And it is not only the waste
19

water (which has ultimately to be discharged to a stream);


there is also the solid waste, which may contain small
proportions of finely-ground, harmful minerals, and these could
continue to impregnate any vegetation growth on filled-in
lagoons for many years afterwards.

The "concentrates" from flotation are generally filtered,


washed, dried and bagged for transport as powders.

Dissolved-air flotation whether it is for treating organic


waste slurries or for clarifying potable water from rivers,
lakes or reservoirs, needs a different engineering. Generally
the particles to be floated are smaller and less dense than the
grains in mineral flotation; and consequently smaller bubbles
provide sufficient lifting power. Often there are colloidal
particles to be removed and these must first be coagulated
(flocculated). The density of flocs is very low and they must
not be subjected to intense shear, otherwise they disintegrate.
There is, therefore, every reason for providing the air for
flotation in the form of micro-bubbles, say with 100 ~
diameter, or even smaller if possible. For clarifying drinking
water, where economy is important and the amount of suspended
solids (coagulated) is very small, there is also every
advantage to be gained by employing the smallest bubbles
obtained [7,8).

The usual plant for carrying out dissolved-air flotation is


shown schematically in Fig.2. Part of the treated water is
pumped back, under pressure, together with compressed air, into
a saturator vessel - such as a cylindrical column loosely
packed with open objects to expose a large air water
interface. The final water stream reaches practically 100% of
the equilibrium solubility of air at the pressure of the
saturator. Typically, 5-10% of the water leaving the flotation
tank is recyled at a pressure of 3-4 atm, and when the pressure
on the water is released the excess of dissolved air, above
that in equilibrium with the atmospheric pressure, becomes
available as bubbles.

Generating small enough bubbles presents problems. In


laboratory researches, micro-bubbles are sometimes produced by
forcing compressed air through a sintered disc of fine pore
size. However, experiment shows the bubble size distribution
formed in pure water is too coarse, the reason being that
colliding bubbles in surfactant-free water rapidly coalesce.
One way to prevent this is to add a smal amount of a soluble
surfactant (frother) [9). Some waste liquors already contain
sufficient surfactant to yield foams. Even sea-water shows a
certain foaming and surface elasticity, which is due partly to
traces of organic matter and partly to the effect of the
20

dissolved salts. (Pure inorganic salts do not yield any


persistent foam but they do discourage coalescence of bubbles,
through a dynamic surface elasticity, as Scott [10] has shown.)

feed
slurr~~~.~.'~.~I~··~.1."~IE~~DlIIIIIICliiaialli
air -
- ---
- -
recycle water
Fig.2.Schematic diagram of a dissolved air flotation
plant

In industrial practice the super-saturated water is forced


through needle-valves or special orifices, and clouds of micro-
bubbles are produced just down-stream of the constriction. The
mechanism by which they are formed is of interest in view of
the advantages to be gained by getting extremely small bubble
size. Experiment shows that a certain minimum velocity of flow
through an orifice is needed to produce any bubbles at all
(otherwise the water remains super-saturated). At or above the
minimum velocity the hydrostatice pressure in the neck of the
orifice, calculated on the basis of Bernoulli's equation, is
approximately zero; nevertheless, micro-bubbles are not
generated by the brief passage of super-saturated water through
this low pressure zone, for the water can be passed through a
smooth Venturi-form orifice, which has been cut off at the low-
pressure end, without any bubbles being formed. A correctly
operating orifice can be heard emitting a "sizzling" sound,
which is due to cavitation and high-frequency oscillation of a
vapour cavity just below the neck. It seems that the micro-
bubbles are formed by vapour pockets being torn off this
cavity, and they grow from the water stream as they are carried
along.

The emerging stream of water, milky with micro-bubbles, is


injected into the slurry which is to be treated. The micro-
bubbles attach themselves to particles by collisions and a
floating scum forms. This scum is gently skimmed off while the
clarified water flows out near the bottom of the tank, at the
far end. The floating sludge may be dumped or allowed to
thicken for transport and disposal, according to its nature.
21

Before a particular slurry can be subjected to flotation,


chemical pre-treatment may be necessary. For example, dilute
clays, sewage sludges, etc. need to be flocculated with alum
(or ferric salt) or polymeric flocculant (or both). \Jhen the
slurry contains organic matter, a "collector" reagent (so
essential in mineral flotation) may not be needed, for
aluminium and ferric coagulate readily forming hydrophobic
coatings in presence of lipids, and bubbles attach themselves
stongly to such surfaces. However, a surfactant of appropriate
type is needed for floating inorganic solids, such as
precipitated copper carbonate from plating-bath wash-water[ll].

In most of the current application of micro-bubble flotation


the object is total flotation of the suspended solids, and for
many purposes the technique offers advantages over filtration
or slow settlement. There is not then the requirement to float
some species while rejecting others, as in mineral flotation.
Nevertheless, the same principles apply-hydrophobic particles
are captured by micro-bubbles, hydrophilic ones are not - and
consequently separations of slimes-grade minerals ~ be
effected, with possible advantages, by means of dissolved air,
provided always that the surface properties of the different
species can be properly controlled [12]. There is also the
problem of entrainment in the froth.

For further information on the technical aspects of dispersed-


air and dissolved-air flotation, the reference can be made to
monographs (e.g.[ld,13].

From the above, very brief, summery of how the flotation


processes are actually worked, it will be realised that certain
basic principles lie hidden "behind the scenes". In fact, some
of these have already received a substantial amount of research
in recent years. That is not to imply that everything is now
sufficiently understood for perfect exploitation of the full
potential of flotation. On the contrary, much remains to be
investigated before that dsirable situation is reached.

RECOGNIZED PRINCIPLES IN FLOTATION

The following prominent scientific problems seem to be


important for a fuller understanding of how flotation works:-

A. Physical aspects
1. What makes some solids readily floatable, others
poorly floatable, and some not at all?

2. The kinetics of capture of particles by bubbles.


22

3. The overall operating kinetics of flotation cells.

B. Chemical aspects

4. The surface chemistry of minerals (and other relevant


solids) in water.

5. The mechanism of action of flotation reagents.

6. Schemes for separating various mineral combinations.

In addition, there remain, of course, other large areas for


research - notably, the mineralogical, engineering, economic
and environmental aspects; but these are outside the scope of
the present article. In what follows the salient features of
the scientific problems 1-6 will be briefly - and, inevitably,
very superficially - considered.

1. Flotability: thermodynamic aspects.

Until recently it has been universally accepted that particles


are never captured by bubbles unless a finite angle of contact
( e) is formed agains t water. A large angle is not necessary,
for the particles hang on the outside of the bubble and their
weight is supported by the meniscus, which "sticks" at edges on
the particle. (Theoretical calculations based on perfect
spheres, with no allowance for contact angle hysteresis, are
wide of the mark). In general, the larger the contact angle the
better the flotability, though there is no simple correlation
between e and flotation rate.

There is a recent exception to unanimity on the supposed


necessity for a contact angle. In a review article by Derjaguin
and Dukhin [14], the possibility of "contact-less flotation" of
very small particles is mooted. The hypothesis is that under
certain circumstances such particles might be attracted by
surface forces to the air/water interface and retained there
against gravity and dynamic impacts, without the intervening
wetting film actually rupturing. This would require appropriate
long-range forces of attraction, but also short-range forces of
repulsion a rather peculiar requirement. As no specific
examples have yet been published, judgement on this hypothesis
must be reserved, and the remainder of the present discussion
will deal only with more familiar materials.

Experiment shows that if a certain solid forms no contact with


air when a bubble is pressed against it under water, then
discrete particles of that solid are not floated. It is true
that very small particles, whatever their nature, are entrained
by hydrodynamic forces in the wake behind rising bubbles, but
23

they are not attached to it. Captured particles are attached by


the forces of surface tension and remain attached when the
bubble stops at the froth layer, whereas entrained particles
fall away when motion ceases. Quite a small contact angle
(e.g.20 0 ) may be enough for capture.

The key to flotability and non-flotability is therefore whether


the solid is hydrophobic or hydrophilic, in static tests,
respectively. (No other liquids than water need be considered).
A finite contact angle means that the work of adhesion of water
to the solid is less than the work of cohesion of water-to-
water. That principle, in turn, leads to the question of the
nature of the intermolecular forces which bind water molecules
to one another or to solid surfaces. Following this clue, the
well-known American flotation expert, A.M. Gaudin, discovered
the key to flotability (see below).

An alternative approach to the problem has been explored


particularly by Russian scientists, who direct attention to the
special condition of the very thin "wetting film" which is
formed when a bubble collides with a particles. As the film
thins, the so-called "surface forces of the second kind" come
into play -that is to say, there is interaction at a distance
between the S/L interface and the G/L interface, which appears
as a force normal to the interfaces, named by Der jaguin a
"disjoining pressure". Of course, it is a function of the
thickness, h, of the liquid film. Such disjoining pressures
have been ~easured experimentally for example, in the
silica/water/air .system, and they account very satisfactorily
for the observed fact that solids such as quartz are strongly
hydrophilic and tenaciously retain a wetting film. Furthermore,
relatively thick wetting films of this kind are quantitatively
in reasonable agreement with calculations based on the
interaction of electrical double layers on the two interfaces.
If the ionic strength of the solution is raised, the film
thins. If the surface potential is lowered towards zero, by
adjustment of the potential-determining ions, again the film
thins, and even collapses. If the potential on the air/water
interface is increased to a high value with the same sign as
that of the S/L interface (e.g. by adding a suitable
surfactant) the film is thickened; conversely, surfactant of
the opposite sign can cause collapse (analogous to
heterocoagulation). These effects are undoubtedly caused by
electrical double-layer forces.

On the other hand, it has been shown by a simple thermodynamic


argument that if a solid is hydrophobic - defined as forming a
finite contact angle - very thin water films on it would be
unstable. Experiment shows that such films spontaneously
rupture and shrink into a series of droplets, leaving dry areas
24

between them. Evidently such water films must be subject to a


negative disjoining pres.sure; and, consequently, when a bubble
is pressed against a hydrophobic solid under water, the
intervening water layer at first thins down under the influence
of hydrostatic forces until a certain critical thickness is
reached at which surface forces of attraction between the two
interfaces become dominant. Then the film rapidly ruptures, a
contact line is formed, and the meniscus runs back until the
equilibrium contact angle is reached. Schulze [2] has directly
determined some apparent values of the critical thickness for
collapse of wetting films for example, far very dilute
solutions of cationic surfactant on quartz. Values of the order
of 30nm were obtained.

Thus, with hydrophilic solids the repulsive force gets stronger


as the film thins, whereas with hydrophobic solids the
attraction between the interface gets stronger as the film
thins.

The crucial question now is what is the or~g~n of negative


disjoining pressures? One possibility is electrostatic
attraction, where the S/L and G/L interfaces carry electrical
double layers of opposite sign; interaction between them would
result in an attraction, as in heterocoagulation. Two possible
examples have been described by Schulze [2].

1. Quartz in extremely dilute solutions of aluminium salts


acquires a positive zeta-potential (through adsoption of
hydrolyzed AI-species) whereas air bubbles remain weakly
negatively charged. 2. Quartz in very dilute solutions of a
cationic surfactant remains negatively charged while air
bubbles acquire a small positive charge by physical adsorption.
In both cases collapse of wetting films was observed. It should
be mentioned, hwoever, that experiments of this type, involving
experimental surfaces of low zeta-potential and very small
area, are terribly sensitive to traces of organic matter. In
any case, the situation is rather exceptional, for the majority
of cases of hydrophobicity are definitely not due to + -
attraction of oppositely charged interfaces. For example, with
graphite in pure water both interfaces carry weak negative
charges, yet the contact angle is large.

Another theory is that a particle of high negative potential,


interacting with a bubble of low negative potential, would
experience an attraction; i t would, if one accepts the commonly
assumed model of constant potential surfaces. Actually, this
assumption is hard to believe for a water/air interface,
because it implies that some ionic mechanism keeps the
potential negative and low even when a strongly negative
surface gets close to it; and to do that the interface would
25

have to acquire a positive charge. No plausible mechanism has


b~en seriously proposed. It would have to involve adsorption of
H , or other cations, or negative adsorption of anions.

In fact, this theory is disproved by wetting-film experiments


on quartz in pure water. Here is precisely the situation of a
strongly negatively charged S/L interface (e.g. -70mV) and a
weakly negatively charged air/water interface (said to be about
-10mV).Experiment shows that a positive disjoining pressure
exists at all thickness ranges, and this pressure agrees with
that calculated on the assumption of no charge on the air/water
interface. The experiment proves that the air/water interface
does not maintain a constant potential.

Some researchers have jumped to an alternative conclusion -


that if electrical double layer interaction does not explain
hydrophobicity, the dispersion force component must be
responsible, that being the only other component recognized in
the celebrated DLVO theory of colloid forces. But this idea is
nonsense - firstly, because there are other forces (e. g. the
"structural component"), and secondly, because it can be shown
by a simple and general argument that the dispersion force
component for practically all solids is a positive contribution
to the disjoining pressure [15,16].

A simple and perfectly satisfactory explanation of hydrophobic


solids was given many years ago by A.M.Gaudin in his classic
monograph on "Flotation" (1932, 1957). Water is a liquid of
high cohesive energy because it is "associated" , i. e.
internally crosslinked by double hydrogen-bonding. Hydrophobic
solids are all structures which present non-polar groups to the
exterior - or, as Gaudin put it, no "broken bonds". For
example, graphite's planar structure has its valencies fully
satisfied; the basal plane presents only dispersion forces.
Sulphur consists of closed S8 rings. Talc presents, on its
cleavage plane, uncharged siloxane rings. Molybdenite, MoS2,
behaves as a molecular compound. Boric acid (R3B03) has a layer
structure in which all potential hydrogen-bonding OR are
internally satisfied, leaving none to hydrogen-bond on to
external water. The boron atom has 3 valencies in a plane.
(Amazing that B (OR) 3, which is appreciably soluble in water,
is hydrophobic! Contrast Si (OR)4' whose tetrahedral units are
bound to present outward-pointing SiOR groups: so hydrated
silica is hydrophilic, but when dehydroxylated it is not.)

In short, non-polar molecules interact with water only through


dispersion forces and these are weak compared with the cohesive
forces of water-to-water. Rence the work of adhesion is smaller
than the work of cohesion - and a finite contact angle is the
inevitable result.
26

At present there is simply no evidence about the range of


negative disjoining which result from the true hydrophobic
effect. The plane of weakness at which the water tears away
from the solid may be within one molecular diameter of the
solid, or the effect of the discontinuity of water-structure
may be propagated further - but presumably, at most, to only a
few water molecule diameters. The same explanation of
hydrophobicity applies, of course, to collector-coated
hydrophilic minerals; their polar groups are largely eliminated
by adsorbed surfactant.

2. Mechanisim of capture of particles

Flotation is rightly viewed as a stochastic event in which the


chance of a given particle arriving at the froth level is the
product of three probability terms:

chance of probability of probability probability


flotation particle-bubble x of x of retention
collison attachment of attachment

There is no means of calculating all these terms from basic


theory, but a partial analysis is illuminating.

The first term is obviously controlled by the hydrodynamic


conditions in the cell: the second depends of surface forces:
the third is a question of the hysteresis of meniscus contact
and the bombardment of the laden bubble by liquid turbulence
and impacting free particles.

For real flotation cells, with a dense pulp containing a


mixture of mineral species, all with their own ranges of
particle size, a range of bubble sizes, and the whole subjected
to violent turbulence, it would seem hopeless to attempt any
quantitative theory. However, three broad regions can be
perceived for the first term.
(a) With large particeles and large bubbles, collisions
will depend greatly on inertial effects.
(b) With small particles and medium-size bubbles, particle-
bubble collisions will occur by the sedimenting
particles encountering rising bubbles.
(c) Extremely small particles will be carried along in the
stream-lines and will not make a close encounter with a
bubble unless they cross the stream-lines by executing
Brownian motion - that is, by diffusion.

As regards region (a) an excellent survey is to be found in the


monograph of Schulze [2] (which also deals admirably with (b».
For regions (b) and (c) theoretical expressions have been
derived - albeit, for highly idealized models, namely, very
27

dilute suspensions of monodisperse spherical particles and


larger, monodisperse, spherical bubbles. The hydrodynamic
theory of collisions between these model particles and bubbles
has been developed particularly by Derjaguin and Dukhin (1960),
Flint and Howarth (1971) and Reay and Ratcliff (1973).
28

The quantitative results from Schulze's experiments appear to


be in agreement (within the limits of experimental error) with
the modern hydrodynamic calculations, for example, for the
parameter called the "collision efficiency" - essentially the
fraction of the particles starting nominally "above" the bubble
which come close enough to collide with it.

Whether or not a colliding particle sticks to a bubble is a


question of the surface forces which come into play when the
aqueous film between the two has thinned sufficiently. If a
positive disjoining pressure develops, thinning will be
,retarded; if a negative, it will be accelerated. By assuming an
interaction law - for example, DLVO theory - it is possible to
calculate the rate of thinning of the residual film. Model
experiments which have been carried out on wetting films
between small captive bubbles and smooth polished plates have
clearly shown that hydrophilic solids, such a quartz, retain an
elastic water layer which repels the particles from the bubble,
whereas hydrophobic solids show a sudden collapse of the
aqueous film at a certain "critical" thickness. This critical
thickness should be understood as a nominal, average, thickness
related to the dimensions of the bubble, and the roughness of
the solid, rather than the theoretical thickness at which the
disjoining pressure becomes negative; for the sudden rupture of
the wetting film probably comes about by local fluctuations of
the film.

Rupture of a very smooth surface might require activation


energy, because the creation of a hole in any liquid lamella
involves an initial increase of surface area. Scheludko and his
co-workers [16] have also emphasized the possible role of line
tension in the creation of a hole and have shown that a
limiting factor in the probability of capture may be the speed
at which the 3-phase line can run across the surface of the
solid; for the meniscus has to obtain a sufficient "hold" on
the particle, during the short period of collison, if the
particle is not to be lost again and swept away by the stream-
lines. There are two reasons. however, why these considerations
appear, at present, rather hypothetical. Firstly. the magnitude
and range of the indispensible hydrophobic force (negative
disjoining pressure) are unknown. Perhaps. it would provide the
necessary activation. Secondly, ideally smooth spherical
particles may be too unrealistic, because actual mineral grains
are neither smooth not spherical. It seems essential, at this
point, to enquire what evidence is available from experiment on
the probability of contact being formed.

Experiments with the bubble-and-plate model, in dilute


dodecylamine solutions to render the quartz plate hydrophobic
[2]. showed times for contact ranging from 10 seconds in. 10-7M
29

solution down to about 1 s in 10-4M. With mineral particles


instead of a smooth plate, the "induction time" (so-named by
Sven-Nilsson in 1935) is much shorter. Eigeles (1950) and
Glembotsky (1953) described an improved automatic apparatus for
pressing a bubble for short, measured periods against a bed of
powder, the criterion being whether any particles are picked
up. Times down to 5 ms are said to be obtainable. In tests with
various grain sizes and collector concentrations, induction
times range from 10 to 10- 2 seconds. Of course, such times are
still not comparable with to 1-3 ms avaiable for real bubble-
particle collision; but the test has some merit in revealing
significant trends which do correlate with practical flotation
tests. A relatively long induction time corresponds to a low
probability of capture, and hence a "slow float". Experiment
also reveals that probability of capture does not entirely
correlate with final contact angle, showing that kinetic
factors intervene.

Although numerous laboratory test-cells have been described for


comparing flotation rates for example, the well-known
Hallimond tube none measures absolute rates in defined
conditions. This is not easy to do. What is believed to have
been the first measurements of this kind were carried out at
Imperial College, London by J.F. Anfruns for his Ph.D. research
[17]. Single bubbles of measured diameter were allowed to rise
through extremely dilute suspensions of single-sized particles
of quartz or Ballotini glass beads, and the number caught by
each bubble was determined microscopically. The bubble sizes
and particle sizes were chosen to be appropriate for treatment
by the theory of Reay and Ratcliff. The rate of rise of the
bubbles indicated that their surfaces were substantially
immobile, as they are in practical flotation cells where
frother is used [18]. The particles were rendered strongly
hydrophobic by pre-treatment with trimethylchlorsilane, a
reagent which covalently bonds -si( CH 3) 3 groups on to silica
(or glass). The static contact angle was about 90° and the
particles were so strongly hydrophobic that, once caught by a
bubble, they were retained indefinitely.

The results obtained with this rather realistic model system


showed several interesting features:

(a) With the hydrophobic quartz particles, the rate of


flotation, agreed, within experimental error,with the
calculated rate of collision, both in the absolute
values and in their dependence on particle size and
bubble size.
30

It seems safe to conclude both that the hydrodynamic


theory is substantially correct and that the capture
probability on collison is 100% (for this system).

(b) With the glass beads, which had the same surface
properties as the treated quartz, the flotation rate
was appreciably lower than with quartz particles. The
difference can be ascribed, with fair confidence, to
the effect of angularity (roughness) on the rupture of
wetting films.

(c) The influence of long-range electrical double-layer


forces was clearly revealed, most prominently with the
smooth beads; additions of KC1 increased the rate of
flotation, though never above the calculated collision
rate, whereas small additions of sodium
dodecylsulphate (which is adsorbed at the air/water
interface) decreased the rate of flotation.

Obviously, the double-layer repulsion between silica /water and


the air/water interfaces has the greatest opportunity to reveal
itself during the slow, regular, thinning of the film on the
smooth particles. The existence of a substantial electrostatic
energy barrier on these surfaces - despite their hydrophobicity
- had prev.iously been established in static measurements of
equilibrium film thickness [19]. Although, in the latter
experiments, metastable wetting films could be demonstrated on
smooth plates in an apparatus carefully protected from
vibrations, in a dynamic system and with angular particles
(which, incidentally, also rotate as they traverse the edge of
a bubble) there is virtually 100% chance of film rupture and
particle capture, provided the particles are strongly
hydrophobic.

These results incidentally indicate that the realities of


practical mineral flotation should not be forgot ton when
indulging in theoretical treatments of flotation!

No comparable measurements have yet been published for


particles of less pronounced hydrophobicity (small 6). No doubt
capture probabilities much less than 1 would be obtained; after
all, with clean (hydrophilic) quartz flotation is zero.

It is interesting to note that in Anfruns's system the effect


of double-layer repulsion was measurable, but not so powerful
as to repress flotation greatly (except when much anionic
surfactant was added). However, with much smaller particles,
the influence of double-layer forces becomes very much greater,
as Collins and Jameson [20] have shown with latex particles.
31

As regards the effects of particle size and bubble size on


flotation rates, there is a good deal of empirical observation,
which can now be linked with appropriate, if approximate,
theory. Several valuable reviews on the physics of the
collection process are available [13,2,20,21,22]. Factors to be
considered include the following.

(a) Large particles, of course, need large bubbles (or


many small ones) to raise them.

(b) Very small particles need very small bubbles, both to


prolong residence time and to improve collision
efficiency. Large bubbles simply cannot collect a
useful mass, even when fully coated.

(c) With sparse floatable solids, the collection rate will


approximate to first-order kinetics, whereas in a
crowded pulp the rate must falloff because of
limitation of available bubble area.

(d) With ordinary pulps of mixed sizes and variable


flotability interference between the various
consitituents will greatly influence the collection
rate.

(e) Experiment seems to show that even a nominally uniform


batch of "pure" mineral of narrow size range is likely
to exhibit a considerable range of kinetic
flotability. (In the jargon of control theory, one
must introduce a "distributed parameter" to fit the
kinetic data.)

(f) Very small particles, when collec tor-coa ted for


flotation, are likely to be considerably coagulated
(unless the pulp is subjected to a high rate of
shear). Aggregates are then the species most likely to
be captured in flotation; and aggregation also occurs
on the bubble's surface.

3. Overall operating kinetics of flotation cells.

It will be obvious from comments in the previous section that


there is no prospect of theoretically predicting the
performance of a flotation cell from first principles.
Consequently, flotation cells are invented, not designed.

The best that can be done is to treat a cell as a magic box, to


be studied empirically. This is the control engineer's
approach. He installs numerous meters on all the likely
variables and runs the cell with small, controlled, changes of
32

the operating conditions, measuring the resulting outputs,


residence times, etc. If the job is correctly carried out,
changes in the overall performance of the flotation cell will
be firmly linked to changes in the control variables, and a
mathematical ''model'' can be established, which can be valuable
for control of the plant. No "explanation" need be - or can be
- offered for the inter - relationships. The "model" is only as
good as the experimental study. It cannot be extrapolated
outside the studied range. It cannot indicate mechanisms, point
to improvements, or cope with changes of the ore.

A surface chemist turns, with relief, to more interesting lines


of research!

4. Surface chemistry of the mineral/water interface

If the flotation process were confined to narurally-flotable


minerals it would be very limited - though flotation of coal
fines has become a large and worthwhile operation. Here i t is
only necessary to add to a slurry of crushed coal and shale a
small proportion of some cheap, slightly, polar, oil such as
creosote to enhance the hydrophobicity of the coal particles
(by its displacement of water) and to provide a transient
froth. The ease of flotation of different types of coal
increases with their geological "rank" i.e. extent of
conversion from plant residue to non-polar carbon - while
conversely any weathering and oxidation, by adding polar groups
to the exposed faces, detracts from the contact angle and
notability.

Similarly, graphite, which sometimes occurs as a gangue in


metalliferous ores, can be readily removed by flotation with
oil and frother. Certain gold ores contain considerable
proportions of a carbonaceous material, which can be floated
and burnt to recover any combined gold.

However, the vast majority of minerals are hydrophilic in


varying degrees and need treatment with a "collector" to render
them floatable. Any ore can be rendered hydrophobic by
chemisorption of appropriate surfactants, whereby the polar
groups on the surface of the mineral are eliminated and covered
by non-polar group. This principle has two corollaries: (a)
33

of this question is a reminder that what matters for this


research is no necessarily what might be observed by a surface
physicist, examining a freshly cleaved crystal in a high
vacuum, by some modern spectroscopic technique! Obviously, the
science of "the surface chemistry of minerals" is absolutely
basic to flotation research. Yet it is a partially developed
science, still growing - though not fast, for want of research
workers. A definitive monograph is needed.

Of the hundreds of distinct minerals known, so far only a few


have been investigated for surface properties; but,
fortunately, some general principles can be perceived which
simplify the task. The principal clarification comes from
classifying the commoner, simpler, minerals into a number of
crystal- chemical types. Their surface properties then become
more readily comprehensible. At this stage i t is perimissible
to consider· only "ideal" crystal-chemical principles.

The following main mineral types are commonly distinguished in


this context:-

I. Elemental minerals
II. Sulphides
III. Oxides (simple,single or dual cations)
IV. Silicates and alumino-silicates
V. Salt-type minerals

I. Elemental minerals: (e. g. gold, sulphur. graphite,


diamond.)

Having internally covalently bonded atoms, these structures are


insoluble per se. But at the surface they present unsaturated
atoms ("broken bonds") which are invariably reactive, for
example, with oxygen in the atmosphere. (Even gold is believed
to carry chemisorbed oxygen). The detailed interaction of these
surfaces with water has to be studied case by case. Anisotropic
structures, such as graphite, naturally have different
"chemistry" on their faces from on their edges.

II. Sulphide minerals: (e.g. galena, PbS: sphalerite,


ZnS: chalcocite, CU2S: pyrite, FeS2: chalcopyrite,
CuFeS2: molybdenite, MoS2).

Textbooks of inorganic chemistry state that such compounds are


predominantly covalently bonded. These sulphides are of very
low solubility, though each has theoretically a definite ionic
solubility product in water. For example,
34

PbS(c) -H20+Pb2+(aq) + S2-(aq): K =[Pb 2+][S2-]_10- 28


s
If that were the whole story, such minerals could be dismissed
as chemically inert; but it is not, for sulphides are
intrinsically unstable in presence of water and oxygen. By
successive oxidation steps, the S2- ion passes. to SO(elemental

sulphur), S °z
x y
('sulphoxides', such as S202: thiosulphite;
3
SH062- ,tetrathionate)and finally sulphate S042- .The so called
"Pourbaix diagram" (E - pH) shows what products are possible
or thermodynamically s~able, but gives no information about the
mechanism or rate at which the reactions occur. In dry air the
oxidation is very slow, but in water it proceeds by a mechanism
similar to the corrosion of metals; for the sulphide minerals
are electrical semi-conductors, and "local cells" are found
between spots on the surface which are relatively anionic and
others which are relatively cathodic. A scan over the surface
of a sulphide mineral with a micro-electrode reveals these
heterogeneities of electrochemical potential.

The products of these so-called "tarnishing reactions" depend


on the metal ion, the solution pH and the intensity of
oxidation. For example, whereas in neutral or acidic solutions
Sa may be stable, in alkaline media it dissolves to for~
thiosulphate. Similarly with th.f metal ion: for example, Pb 2
may pass into solution as Pb 2 (aq) or i t may hydrolyze and
precipitate as Pb(OH)2' or, i f CO 2 is present, as basic
carbonate. The oxidation products of PbS are a great deal more
soluble than PbS itself and consequently a slurry of ground
galena+in aerated water shows readily detectable concentrations
of Pb 2 (aq). Analogous, but not identical, reactions are found
with all the sulphide minerals. Each mineral needs specific
investigation. The response of a sulphide mineral to chemical
reagents is therefore the response of its oxidation
productions I Furthermore, impurities have a large influence on
the courses of the reactions.

In recent years modern electrochemcial methods have been used


to investigate the mechanisms of oxidation of sulphide minerals
and their reactions with flotation reagents. The problem turns
out to be extrodinarily complicated; and although these
researches are of fascinating interest to specialists, it is
not feasible to summarize them usefully in brief. Reference
must be made to review articles [24,25].

III. Oxide minerals

Many important metallic ores are either simple oxides (e. g.


hematite, Fe203: magnetic Fe304: cassiterite, Sn02: corundum,
35

Al203:rutile. Ti02) or "mixed" oxides (e.g.ilmenite, FeTi03:


chromite, FeCr204: spinel; MgAI 2 0 4 ). These solids are ionic
crystals which can broadly be regarded as composed of more-or-
less close-packed Oz- ions with the (smaller)metal cations
inserted regularly in interstices.

Silica, SiOz, is exceptional in that the Si-O bond is


classified as semi-covalent, the "bonds'~ being tetrahedrally
disposed disposed around each nominal Si 4 atom. This gives an
open packing, as in quartz (p=2.65: compare corundum 4.02).

Oxides are not soluble as such in water because the Oz- ion
reacts to form 2 OH • The same reaction occurs on the surface
of all oxides listed, but generally only to the extent of a
monolayer. In principle, oxides "ought to" change into
hydroxides; periclase, MgO, does change extremely slowly to
brucite, Mg (OH)z; but corundum, AlZ03' seems not to get beyond
a monolayer, although gibbsite, Al(OH)3, is the thermo-
dynamically stable phase in water.

The formation of hydroxide groups on the surfaces of the


"insoluble" oxides is readily demonstrable by infra-red
sppectroscopy and by gain of weight, which is reversible only
by heating to high temperatures, chemically, the hydroxylated
surfaces of the oxides behave like hydroxides. In particular,
the -OH groups have acid-base properties, most of the
hydroxides being amphoteric - that is, capable of combining
with acids or alkalis. Taking alumina as an example, the
corresponding surface reaction are

-AIOH + HCl ~
+ -
-AIOllzCl, and
-AIOH + NaOH ~ -AIO Na + HzO
The OH group behaves as a weak acid or a weak base, the actual
dissociation constants depending on the metal cation. The
insoluble oxides can therefore be titrated electrometrically.

Two comments are worth making here. Firstly, it is not possible


to convert all the surface groups into either of their salt
forms, because the increasing electrostatic surface potential
weakens the acid or base strength. Furthermore, at very high or
very low pH_the oxides dissolve~ (e. g. surface -AIOH groups go
to Al(OH)zO (aq) anions or Al3 (aq) cations respectively). A
corollary is that the titration curve does not follow the
simple Henderson-Hasselbach equation, and the apparent pK of
the surface groups cannot be evaluated in any simple way.
Secondl1, the +titration reactions involve the counterions
(e.g.Cl or Na) because these ions become attached to the
surface, somewhere in the outer part of the double layer. This
situation is quite different from the titration of weak acids
or bases in dilute solution, where the counterion is fully
36

dissociated; in that case, added salts have only a minor effect


on the titration curve (via activity coefficients), whereas in
surface titrations they have virtually a mass-action effect on
the titration, as with ion-exchange resins.

The counterions are readily exchangeable, although not


necessarily all situated in the diffuse part of the double
layer, for a certain proportion may be held close to the solid
in the Stern layer. Their attachment is at least by
electrostatic attraction, and in some cases by "specific"
adsorption for example, sulphate ions are specifically
adsorbed by alumina.

This aspect of the surface chemistry of oxides has been


considerably explored not only by titrations but also by
electrokinetic studies, which clearly reflect adsorption of
acid or alkali by development of a positive or negative charge
respectively on the solid. pH is thus said to be "potential-
determining". Every amphoteric oxide has one particular pH at
which the potential is zero because the density of positive
sites is equal to the density of negative sites. This is the
so-called z.p.c. (zero point of charge) in older
literature,p.z.c. (point of zero charge) nowadays or i.e.p.
(iso-electric point). (Pundits make a fine distinction between
p.z.c. and i.e.p., but the two are the same i f no specifically
adsorped species are present. In any medium, i.e.p means zero
electro-kinetic effect).

It is an experimental fact that the p.z.c. of oxide minerals is


rather variable, from sample to sample, and hydrated surfaces
show appreciably different values from anhydrous. Nevertheless,
there is a good spread of values, which is important for
flotation technology. The table below shows some approximate
values, which at least reflect the varying basicity of the
oxides.

Oxide Si0 2 Mn°2 TiO Z A1 Z03 MgO


pH of p.z.c. 2 4 5-6 7.5-9.1 12

Silica is exceptional in showing only weakly acidic properties


in ordinary dilute media. If it has any basic properties they
develop only at pH 2, a region difficult to investigate and
probably not relevant to flotation. At pH 2 the surface is
uncharged. Base-binding increases with pH, but significant
dissolution sets in above pH 10, because silica also has a
definite solubility in the form of orthosilicic acid,
Si(OH)~(aq), and this species itself dissociates in two stages
as the pH is raised. The solid dissolves further to maintain
[Si(OH)~aq] constant.
37

An extensive and quite complicated literature has grown


uparound the quantitative theory of ionization of oxide
surfaces. The challenge is to account for titration curves
(with different counterions) and electrokinetic data. I t has
been done, by elaborate computer-fitting with sundry adjustable
parameters; but the exercise is beyond the scope of the present
article [26].

IV. Silicate and alumino-silicates

As these minerals account for the bulk of the rocks of the


earth's crust, they commonly form the unwanted gangue from
which the more valuable species have to be separated in
flotation. Consequently, their surface chemistry is just as
relevant as that of the "values".

Although silicates and alumino-silicates are combined oxides,


they differ from the simple oxides in containing "continuous"
structures (excluding the orthosilicates). The structures are
chains,ribbons, sheets or 3-dimensional networks of oxygen,
linked+throu~h Si ~r Al atoms, which may be partially replaced
by Mg2 , Fe 2 , Fe 3 , etc.

The following short list exemplifies some of the classes. The


formulae quoted are idealized; actual mineral specimens vary
considerably in composition because of iso-morphous
replac~ments.

Single chains Ribbons Sheets


networks
silicate ( 8i03)n (8i'+°11)n
Si0 4 units
Zircon pyroxenes amphiboles micas felspars
e.g e.g. e.g e.g.
spodumene tremolite muscovite orthoclase
ribbons serpentines zeolites
(linked) e.g.chrysotile e.g.
palgorskite talc clay chabazite
minerals
e.g.
kaolinite

The crystal chemical structures of many minerals are now well


established - and they make a fascinating study [29]. But, for
the present purpose the essential points are (a) that - SiOSi -
structures are intrinsically insoluble and rather stable to
hydrolytic break-down, and (b) they are also generally
negatively charged structures which are accompanied by
balancing monovalent or divalent cations, not themselves parts
38

of the network. Consequently, the dominant feature of their


surface chemis try, apart from cation exchange, is the
preferential leaching out of bases (Na, K,Ca,Mg, Al,etc). This
is not a reversible dissolution of the crystal; it is a
degradative hydrolysis, which depends kinetically on
temperature, time,pH of the medium, etc.

An extreme example of silicate leaching is provided by the


asbestos mineral chrysotile. It consists of magnesium silicate
sheets, rolled into exceedingly thin needles. In water or
dilute acids magnesia is preferentially leached out until
eventually the needle is transformed into a "pseudomorph" of
silica gel. Essentially similar, if less drastic, events occur
with all the silicate structures. Therefore their surface
condition and surface composition depend critically on their
history. It is futile to discuss, for example, "the zeta-
potential of orthoclase" without closely defining the chemical
composition of the original sample and the chemical history of
the specimen after its crushing to expose fresh surface.

v. Salt-type minerals

Many minerals consist of sparingly-soluble ionic salts. There


are all the various valence-types; for example

halite calcite fluorite apatite monazite

ea 2+ F (Ce,La,Th)(PO )
2 It

In principle all salts have definite solubility products


because their ions are hydrophilic. But dissolution takes time
and is complicated by hydrolytic reactions which may lattice-
ions undergo when in water. In partic¥lar wak-~se cation~
hydroly~e by taking up OH ions (e.g. Pb 2 + Pb(OH) + fb(OH)2
+ PbH02 ) and weak-acid anions take up H ions (e.g. coj + HC03
+ H2C0 3). A whole set of reversible equilibria is often
involved and the final equilibrium depends greatly on the pH. A
mineral chemist's first concern, therefore, is to calculate the
theoretical "species diagram", and many examples of this
esoteric science can be found in the literature and in
monographs on aqueous chemistry [28].

According to classical ideas, the partial dissolution of an


electrically neutral salt would be stoichiometric, leaving the
crystal still neutral; but in practice the surface layer may
depart very slightly from neutrality, with the result that the
solid/liquid interface may show a zeta-potential, either
positive or negative. Consider, for example, the rare mineral
39

iodyrite, AgI, which, in its pure synthetic form, has been much
studied by colloid chemists as a model. Its solubility product
is about 10- 16 (mol R.-1)~ wh~ch sho~s that_ in pure water i t
would dissolve until [Ag ]=[ I ] = 10 Bmol i 1. (Neither ion is
greatly hydrolyzed.) Yet electrophoresis experiments show that
AgI adopts a negative zeta-potential in pure water. To bring it
to its p.z.c. one must add a slight excess of some soluble Ag-
salt; the concentration required is only about 10- 6 , which
corresponds, of course, to [1-] = 10- 1°. In the region of the
p. z. c. the potential approximates to that given by the Nernst
equation, and the lattice ions are said+ to be _"potential-
determining", whereas other ions such as Na and NO 3, which may
happen to occur in a pulp, have little influence. It is correct
to regard both the lattice ions as being "specifically
adsorbed" by the solid, and therefore competing to fix the
surface potential. On this vief' 1- ions are adsorbed by AgI
10 4 times more strongly than Ag ions.

A similar principle applies to other salt-type minerals, though


commonly they are also sensitive to pH changes because one or
other of the lattice ions is hydrolyzed. Few solids, however,
are so well behaved as AgI. Barite, BaS04, shows a zeta-
potential which is almost independent of pH between 4 and 10
and small additions of sulphates render it more negative
whereas barium salts render it positive; but its p. z. c. is
variable from sample to sample, perhaps because of variable
impurities.

There is an old rule, ascribed to Fajans, which states that a


"foreign" ion is strongly adsorbed on an ionic lattice only if
it forms an insoluble salt with the lattice ion of opposite
charge and provided that the surface potential of the solid
(which is primarily set by the potential-determining lattice
ions) is such as to attract it. For example, one would expect
HPof to be adsorbed by calcite, espe~ial1y in media which
initially contain a slight excess of Ca2 ions such as to make
the calcite positive. This point is of vital interest to
flotation, because chemisorption of a reagent is often
essential. But now there arises the fundamental question as to
what distinguishes adsorption of a reagent from precipitation,
if a sparingly soluble product of product of reaction is
possible. Well, in principle, a precipitate - a new phase -
cannot form until its solubility product is exceeded in free
solution; and, on top of that, a considerable supersaturation
is commonly needed to nucleate a new phase. Consequently, the
switch-over from adsorption (which might occur before
precipitation is possible or is started) to frank precipitation
of new phase may be unsharp. Certainly, i t is difficult to
identify one or the other when the amount of reagent involved
is very small, and presumably this explains the lack of
40

experimental studies of this transition region. (Nevertheless,


absence of data did not inhibit proponents of the adsorption
and reaction theories from engaging in protracted polemics in
the 1930s!)

Certainly, our present knowledge of this aspect of surface


chemistry is not very sophisticated.

5. Mechanism of action of flotation reagents.

Of the many reagents which are added in mineral flotation, some


are simple "regulating agents" - to control the pH,+to complex
undesirable ions (e.g.cyanide to knock out Cu Z ), sodium
sulphide to compete with xanthate, carbonate to precipitate out
hardness, etc.

More interesting are the "collectors", "activators" and


"depressants" which control the degree of hydrophobicity of the
various minerals by direct surface-chemical action. That is a
long story, derived from many years of spasmodic research. Even
now only broad explanations can be offered for most systems.
Much of the evidence is reviewed in a recent monograph [29],
and only a brief summery is given below, linked again to the
clasification of mineral types. Class I can be omitted because
no chemical specificity is needed for the hydrophobic minerals.

II. Sulphides

The principle collectors are thiol compounds - alkyl xanthates


or dithiophoshates - which are strongly chemisorbed by slightly
oxidized sulphides. It is still not settled whether the product
which does the job is a monolayer or consists of patches of
insoluble xanthates and whether or not significant amounts of
organic oxidation products (like dixanthogen) are formed under
practical conditions. Undoubtedly there are also complicated
side reactions and from the researcher's point of view there
are great difficulties in identifying the molecular state of
the actual flotation surface.

In several respects the chemisorption of xanthates resembles a


metathetical reaction. For example, ZnS does not float well
with ethyl xanthate unless it is previously "activated" wit!!
CuSO~, which produces CuS by precipitation (some say CUzS); Cu
xanthate having a very low solubility, whereas zinc xanthate is
moderately soluble. Conversely, sodium sulphide acts as a
depressant in xanthate flotation because the sulphides of the
heavy metals are even less soluble than the xanthates, and the
concentrations require for depression seem to correspond to
those required for the competitive reactions [30].
41

However, a simple metathetical reaction, forming an insoluble,


hydrophobic, product is not a sufficient condition for
satisfactory collector action. The product must adhere to the
mineral and at the same time effectively elminate pre-existing
polar groups. If the mineral is too soluble or too hydrophilic,
the insoluble xanthate which is formed comes away as a
colloidal precipitate. This happens, for example, with
chrysocolla, a hydrous copper silicate. Similarly, an excessive
amount of oxidized coating on a sulphide mineral is harmful to
collec.tor action. This seems to be the explanation for the
depressant action of high pH on pyrite (FeS2) flotation, where
a precipitate of Fe(OH)3 inhibits formation of dixanthogen,
which may be instrumental in generating hydrophobicity.

One surface-chemical consequence of the chemisorption of


xanthates is that the uptake of the reagent appears to be
irreversible - for example, it does not come off again on
washing or dilution of the supernatant. Consequently, there is
no sense in presenting sorption data as supposed "adsorption
isotherms", for the consumption of xanthate is progressive and
depends on access of oxygen, formation and accumulation of bye-
products, etc.

Only a minority of the many complications of the sulphide +


xanthate problem have been mentioned. Many more are touched on
in a review by Poling [31].

III. Oxides

There are two conditions to be met for a surfactant to operated


as a flotation collector for oxides; firstly, it needs to have
about 10 or more carbon atoms in its hydrophoic moity and,
secondly, its polar group must carry a charge of opposite sign
to that borne by the oxide (in the prevailing medium). The
electrostatic mechanism of adsorption of ionic surfactants has
been thoroughly investigated by D.W. Fuerstenau and his co-
workers, and subsequently by J.M.Cases and others. A recent
paper gives a useful overall view [32].

Amphoteric oxides adsorb cationic surfactants above the p.z.c.


and anionic below. The adsorption is reversible and gives a
characteristic form of isotherm. From extremely dilute
solutions the surfactant ions are simply exchanged with
counterions. with little sign of specificity and little effect
on the zeta-potential. At somewhat higher concentration -
perhaps only 1/100th of the c. m. c. of the surfactant - there is
a remarkable feature in the isotherm, namely, sharp increase in
affinity, which is undoubtedly due to favourable lateral
interac.tion of adsorbed molecules or a form of condensation.
The effect is related to micellization and has been named the
42

formation of "hemimicelle". Hemimicellization is accompanied by


charge neutralization and then reversal of charge. Evidently,
the bonding force is chain-chain interaction ("hydrophobic
association"). The surface is at its most hydrophobic in the
concentration region around the point of charge reversal, where
the adsorption amounts to about one monolayer. An excess of
surfactant reduces the contact angle, eventually to zero; and
the isotherm, of course, flattens off at the c.m.c., at which
point the total adsorption corresponds to about a bilayer.

At least five complications should be mentioned. 1. Oxide


surfaces can be readily "activated" towards ionic surfactants
by adding dmsll amounts of hydrolyzing metal salts, which are
themselves strongly adsorbed by oxides and shift the effective
p.z.c. of the surface (e.g. quartz can be activated for anionic
surfactants by pre-treatment with a trace of ferric salt in
faintly acidic media, the surface becoming positive in
potential.) 2. pH often has a complicated effect because it
affects both the oxide and the surfactant, if the latter is a
weak acid or base. 3. Under certain conditions, what is
adsorbed is probably a physical mixture of ionic surfactant and
its unionized form. 4. Added non-ionic surfactants, such as
long-chain alcohols, may participate in such a mixed film. 5.
The fatty acid soaps for products of low solubility with
various metal ions, and so may be precipitated or deposited.

Here again there is quite complicated literature to be explored


[33].

IV. Silicates and aluminosilicates

These minerals accept ionic surfactants in much the same way as


oxides; and, as silicate networks are generally negatively
charged, amine-type collectors are commonly suitable. The main
difference is that the exposed surfaces are, in effect,
mixtures of basic and acidic oxides, and therefore their
surface potentials depend on the conditions of leaching. For
example, an aluminosilicate leached in acid tends to lose more
Al than Si and therefore drifts in potential towards the
negative. A change of pH+may pr~duce peculiar results - such as
initial leaching of A13 , Fe 2 , followed by precipitation of
their hydrated oxides on the surface. Fluorides produce
activation effects, sometimes ascribed to surface complexes but
perhaps related to enhanced leaching. Separations are mainly
empirical rather than based on theory. A useful survey has been
published on silicate flotation [34].

V. Salt-type minerals

A considerable amount of research has been devoted to the


43

mechanism of collector adsorption on minerals such as calcite,


fluorite, barite and apatite. Much of it is reviewed in an
article by Hanna and Somasundaran [35].

Part of the evidence fits the electrostatic model - anionic


surfactants are adsorbed "heads down" on the positively charged
surface and cationic on to negatively charged ones. However,
the favourite collectors are the fatty acid soaps, such as
sodium oleate, and for these there is a good deal of evidence
in favour of the deposition of sparingly soluble metal soap.

The main problem over soaps is to identify the form of the


product, which, in this case, seems very unlikely to-conform to
the naive 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 [36] has shown that supposed
"adsorption isotherms" for such systems are almost certainly
abstraction-by-precipitation curves. Incidentally, practical
conditioning times are too short for attainment of full
equilibrium, and consequently kinetic factors may have some
influence on the flotation response.

Once more it has to be recognized that present understanding of


the surface chemistry involved is inadequate for a science-
based technology.

Organic depressants

"Inadequate" is also the appropriate word for current knowledge


of how depressants, such as starch, dextrin, quebracho, gum
guar, etc. work - or, more precisely, why they of ten improve
selectively of collector action. Of course they "work" by being
adsorbed on the minerals and by providing a hydrophilic
coating, in opposition to the collector's hydrophobicity. But
until the mechanism of attachment is better understood than is
indicated by the usual vague suggestions of hydrogen bonding,
it will not be possible to predict, for example, whether starch
would improve the separation of calcite and fluorite. Yet
recipes based on trial and error are in successful everyday
use.

"Real" minerals are not so simple

For basic flotation research it is usual to obtain notionally


"pure" samples of minerals for study. It should never be
forgotton that this strategy is a pious hope rather than a
logical necessity. There is no such thing as a perfect mineral,
44

only endless var.ieties. Real minerals, as they occur in ores to


be processed, depar.t from ideality in various respects, such as
the following:-
(a) They are more or less chemically impure. Different surface
regions and different speciemens have significantly
different properties, such as zeta-potentials.

(b) Mineral grains in a crushed ore are physically imperfect.


Some parts are strained and carry disturbed material,
which is preferentially soluble and reactive.

(c) Crushed ore generally contains a substantial proportion of


"middlings" - i. e. particles of one mineral stuck to
grains of another. Such particles obviously have patchy
flotation response.

(d) "Slime-coating" is common, generally produced by


heterocoagulation of very small fragments of one mineral
on to larger grains of another, whose flotability is
thereby seriously affected.

(e) Surface-chemical interactions within the pulp are also


common - for example, the transfer of traces of copper
salts (say malachite) on to quartz.

(f) Flotation pulps are not fully equilibrated systems and


surface properties may change during the conditioning.

(g) The up-take or adsorption of reagents on to even single


mineral grains is probably almost always non-uniform.

For all these reasons, what is actually floated is of varied


composition and physical condition because the real particles
have patchy properties. The effective contact angle is an
averaged property. The separation obtained by flotation is not
a sharp cut but a statistical up-grading, and inevitably there
is an inverse relationship between the grade of the cut and the
% recovery of the "values".

6. The design of separations

The fundamental, systematic, way of planning a flotation


process for a given ore ought to be - hypothetically - to first
establish the surface chemistry of all the mineral
consitituents separately, along with their responses to all
relevant reagents; then to determine likely interferences
between the various species; and finally to plan the best
conditions for securing a large difference of hydrophobicity
between reagent - treated minerals.
45

This counsel of perfection is wishful thinking. In practice,


previous experience with not-too-different ores is the usual
starting point. Ingenuity and systematic testing may lead to a
workable procedure. Obviously, this approach has led to many
economically valid operations. While expressing admiration, one
must wonder whether the separations could not be better, if
seriously researched; and whether many other ores, not yet
amenable to separation by flotation, would become so with the
benefit of improved basic understanding.

FUTURE PROSPECTS: RESEARCH, DEVELOPMENT AND INNOVATION

Nowadays the flotation process is so well established that it


has become a vital link in the mineral processing industry that
could hardly be dispensed with. There is simply no rival for
cheaply sorting particles in the size range 0.1 - O.Olmm.
Nevertheless, improvements and new developments seem quite
likely, though any specific forecast can only be
conjectural. The basis of these views is briefly outlined below.

Improvements

When any technical process has been in used for many years and
has not had the benefit of renewed, adequately-funded, R. and
D., there is a very good chance that its efficiency could be
improved. The following case of an old-fashioned mineral
treatment process - lime-burning - will illustrate the point.

The calcination of limestone has been practised for centuries,


mostly in small kilns. By the 1940's huge "modern" kilns, each
costing around one million pounds, were in use by large
companies. But they were inefficient monsters, at one
particular works, because some of the lime lumps were "over-
burnt" and some under calcined. Output from the kilns had to be
inspected and any pieces unsuitable for making plaster-grade
lime were removed by hand! When a research team was let loose
on the problem, their first question had to be "what is the
temperature distribution inside the kilns?". The plant
engineers admitted that no one knew - because one couldn't
measure it on account of the lumps. But one new Ph.D. knew that
a very similar problem had been solved for the iron blast-
furnace. The same method was tried, successfully, on the lime
kilns. (Transfer of ideas or techniques is often fruitful). The
measurements showed that much of the interior of the kilns was
too cool to decompose calcium carbonate while the hot zone near
the centre was too hot. The engineering solution to the problem
was to redesign the air and gas supplies to produce a more
uniform hot zone. Within 18 months the throughput of the kilns
was doubled and wastage practically eliminated. (Quite
46

incidentally, the resulting competitive price of lime had


disastrous consequences for the less efficient lime-producers
in the district).

Flotation is a more sophisticated process than lime-burning and


it has not gone entirely without research these past 50 years.
So one can only surmise how much improved efficiency could be
gained by determined research. Nevertheless, there are several
areas of mineral flotation where the science seems weak. For
example:-

(a) Crushing and grinding of the ore for liberation is largely


by trial and error. Attempts are now being made to rationalize
the definition and measurement of degree of liberation. Then it
should become possible to investigate more critically different
methods of comminution. Grinding is expensive in power and
overgrinding should be avoided. But how is comminution to be
optimized?

(b) At present the choice of reagent suites to secure


selectivity seems to rest on a very unsatisfactory basis - past
experience and trial and error, guided by a sketchy knowledge
of the surface chemistry. Over the past 40 years a good deal of
research - though mostly spasmodic, arbitrary, and academic -
has gone into this problem, but there is still a great deal
more needed. To a physical chemist this area seems ripe for
further development.

(c) Flotation cells seem never to have been seriously


researched. Admittedly, there are many ingenious inventions in
the patent literature; but they were not the fruits of a deep
knowledge of the hydrodynamics and the relation of collection
efficiency to power consumption. (What is the energetic
efficiency of conventional cells?) Some very fundamental
research into the physics of particle capture by bubbles is
being pursued in several Eastern European countries, presumably
in the conviction that a better understanding of flotation
kinetics will lead to practical improvements, through a
combined physico-chemical plan.

(d) Measurement and plant control pose complex problems. A


mineral flotation plant is not in a constant steady state, for
there are day-to-day fluctuations in the ore, temperature,
water supply, etc. In some cases the sale values of the several
concentrates coming from the plant change with economic fluctu-
ations in the market. Work is therefore going on - notably in
Australia - to develop automatic analyitical sensors which will
record levels of various reagents in the pulps along with
analysis of the product streams, so that the data can be fed to
47
a computer-controller to continuously optimize the overall
performance of the plant. Of course, this refinement will not
take the place of improvements (a),(b) and (c).

Extensions

The only reasonable basis for forecasting is extrapolation of


recent trends! And even this is a dubious speculation, for it
presuposes that economic, social and political changes will not
radically affect the operation of the technology during the
timespan of the extrapolation. Hith this reservation, several
developments can be expected:-

i.Flotation will be adapted to ores of increasingly poor grade


and decreasing grain size. Even with particles of l~m,
flotation is theoretically still economic in competition with
total dissolution followed by wet chemical processing.
Nevertheless, there are severe problems to be overcome. Quite
apart from the grinding costs, there is the poor kinetic
capture rate of slimes, their entrainment in the froth, and the
prevalence of slime coating or mutual coalulation. Possibly a
combination of selective flocculation and floatation will come
into use ("floccoflotation"). Perhaps slightly hydrophobic (and
therefore surface-active) polymeric flocculants will find use
here.

ii.Some complex ores which at present have to be treated by


leaching may come within the scope of flotation with
improvements in reagents science.

iii. Research on new regulating agents (especially depressants -


which have been unaccountably neglected) could lead to improved
selectivity.

iv.More sophisticated flotation cells may be introduced.

v. Flotation will be adapted to more non-mineral separations,


such as the recovery of glass, metals and plastics from wastes.

vi-Dissolved air flotation will be adapted to more industrial


problems, for concentrating and purifying materials such as
biochemical products; for recovering metals from dilute
solution; for purifying all manner of effluents to an ever
improved degree, so that the water can be largely recycled and
any excess returned to rivers, crystal-clear, aerated, and fit
for trout!

Innovations, probable but unpredictable

During the past 2 centuries scientific research and


48

technological invention have obviously advanced on similar


graphs, both convex to the time axis. Their relationship is a
matter of opinion. Conventional philosophy maintained that pure
research proceeds as a disinterested search for knowledge ,and
subsequently this knowledge opens up possibilities for useful
applications.

Nowadays the opposite view is aired by some writers - the


contention that social "needs" (real or artificial) generate
incentives for research and invention.

It is certainly true that research, for the most part, is no


longer a private activity. Even university scientists can
rarely "follow their bent", for they must first win substantial
funds for student maintenance and for equipment; and so, in
effect, the community cometimes assesses their worthiness on
the basis of supposed relevance to social needs.

In some quarters, however, this trend has gone to the point of


nonsense. Grant-giving committees have been known to seriously
demand forecasts of the likely future benefits of long-term
projects. That goes contary to the very nature of innovations;
they cannot be planned or predicted - a truism which has been
repeatedly demonstrated in modern books on the subject [37,38].

Furthermore contrary to popular myth the majority of


scientists, including experience researchers, ar not inventive.
Perhaps their training makes them content ~ study, to
experiment, accumulate data and generalize (cautiously); or in
industry, to tackle problems logically. The flair for seeing
new uses for scientific information seems to be rare, highly
personal, and difficult to foster. Even the research
laboratories of large companies are said to rarely generate
highly original inventions, though they are strong on
development work.

According to Kingston [38] "In a study of a large number of


recent innovations in Britain, it was found that in almost
every case the influence of one individual was of paramount
importance". And it is frequently an "outsider", rather than a
specialist, who spots new outlets for established techniques.

On the basis of these ideas, it can be anticipated with fair


confidence that research into the mechanism of flotation will
lead to improvements and extensions of the process; but, by
"the principle of the unpredictability of innovations", there
is simply no foreseeing what new uses for small bubbles will
emerge when we know more about the science of flotation.
49

REFERENCES

1. The early history of flotation can be traced in the


following books:-
(a)Hoover.T.J. Concentrating Ores by Flotation. Mining
Magazine. London, 1912.
(b)Rickard.T.A. (Edit.) The Flotation Process. Mining and
Scientific Press, San Francisco, 1916.
(c)Rickard,T.A.(Edit.) Concentration by Flotation. Wiley and
Sons, New York, 1921.
(d)Fuerstenau, D.W.(Edit.) Froth Flotation: 50th Anniversary
Volume. Amer.lnst. Min. Met Pet. Engrs. New York, 1962.
(e)Woodward, O.H. A Review of the Broken Hill Lead-Si1ver-Zinc
Industry. Australasian Inst. Min. Met., Melbourne, 1952.

2. Schu1ze,H.J. Physika1isch-chemische E1ementvorgange des


F1otationsprozesses. VEB Deutscher Verlag der
Wissenschaften, Berlin. D.D.R.1981.

3. Sorensen,E. On the adsorption of some anionic collectors on


minerals. J.Co11.Int.Sci., ~ 601-607, 1973.

4. Lemlich, R. (Edit.) Adsorptive Bubble Separation Techniques.


Academic Press, New York, 1972.

5. Trahar, W.J. A Rational interpretation of the role of


particle size flotation. Int. J.Min.Proc. 8, 289-232. 1981.

6. Read, A.D. and Manser, R.M. Residual flotation reagents:


problems in effluent disposal and watter-recyc1e. Proc.13th
Int.Min.Proc.Congress (Cag1iari) 1975. 1323-1344.

7. Co11ins,G.L. and Jameson,G.J.Experiments on flotation of


fine particles, Chern. Engng. Sci. 31, 985-991, 1976.

8. Kitchener,J.A. and Gochin,R.J. The mechanism of dissolved


air flotation. Water Research, 15, 585-590, 1981.

9. Me1vi11e,J.B. and Marijevic, E. Micro-bubbles: generation


and interaction with colloid particles. in Akers, R.J.
(Edit.) Foams, Academic Press, London, 1976.

10.Scott,J .C. The role of salt in whitecap persistence. ~


Sea Research, 22, 653-675, 1975.

1l.Pearson,D. and Shirley, J.M. Precipitate flotation in the


treatment of metal-bearing effluents. J. App1, Chern.
Biotechno1.23, 101-109.
50

12. Solari,J.and Gochin, R.J.to be published cf. Solari,


J • Selective dissolved air flotation of fine mineral
particles, PhD, thesis Univ. London,1980.

13. Bratby,J. and Marais, G.V.R. Flotation. in Purchas, D.B.


(Edit.) Solid-liquid Separation Equipment Scale-up. Uplands
Press, Croydon, England, 1977 (deals with dissolved air
flotation).

14. Derjaguin,B.V. and Dukhin, S.S. Kinetic theory of the


flotation of fine particles. Proc. 13th Int.
Min. Proc. Congress (Warsaw). Elsevier, Amsterdam, 1981,
pp.21-62.

15. Laskowski, J.and Kitchener, J.A.The hydrophilic-hydrophobic


transition on silica. J.Coll.lnt.Sci •• ,~ 670-679, 1969.

16. Hough, D.B. and White, L.R. Calculation of Hamaker


constants from lifshitz theory with applications to wetting
phenomena. Adv.Coll. Int. Sci.,~, 3-41, 1980.

17. Scheludko, A., Toshev, B. and Bogadiev, B. Attachment of


particles to a liquid surface.
J.Chem.Soc.Faraday Trans. I •• ~ 2815-2828. 1976.

18. Anfruns, J.F. and Kitchener, J.A. Rate of capture of small


particles in flotation. Trans. Instn.Min.Metal., C, ~ 9-
15, 1977.

19. Blake,T.D. and Kitchener,J.A. Stability of aqueous films on


hydrophobic methylated silica. J. Chem. Soc. Faraday
Trans. ,~, 1435-1442, 1972.

20. Collins, G.L. and Jameson,G.J. Double-layer effects in the


flotation of fine particles. Chem.Eng.Sci.,32, 239-
246,1977.

21. Laskowski,J.Particle-bubble attachment in flotation.


Minerals Sci. Engng. , .h 223-235.1974.

22. Trahar,lJ.J. and lJarren,L.J. The flotability of very fine


particles - a review. Int.J.Mineral Sci., ~ 103-131, 1976.

23. Jameson,G.J., Nam, S. and Young,M.M.Physical factors


affecting recovery rates in flotation. Minerals Sci.Engng.,
.2.., 103-118,1977.
51

24. Woods, R. Electrochemistry of sulfide flotation, in


Fuerstenau, M.C. (Edit.) flotation: A.M.Gaudin Memorial
Volume, A.I.M.M.P.E., New York, 1976, pp.299-333.

25. Hornsby,D. and Leja,J. Selective Flotation and its surface


chemical characteristics in Surface of Colloid Science,
Edit, Matijevic, E. vol.12, Plenum Publ., New York,1982.

26. Westall,J. and Hohl,H.A.comparison of electrostatic models


for the oxide/solution interface. Adv.Coll.lnt. Sci.,~
265-294,1980.

27. Bragg,L. and Claringbull,G.F. Crystal Chemistry of


Minerals. Bell and Sons, London,1965.

28. Stumm,W. and Morgan,J.J.Aquatic Chemistry. 2nd edn., John


Wiley and Sons, New York, 1981.

29. Leja,J. Surface Chemistry in Flotation. Plenum, New York,


1982.

30. Du Rietz,C. Chemisorption of collectors in flotation.


Proc.13th Int.Min.Proc.Congr.(Cagliari), 1975, 375-403.

31. Poling,G.W. Reactions between thiol reagents and sulfide


minerals, in Fuerstenau, M.C.(Edit.) loc.Cit.Ref.24,
pp.334-357.

32. Scamehorn, J.F. ,Schechter, R.S. and Wade, W.H. Adsorption


of surfactants on mineral oxide surfaces from aqueous
solutions. J.Coll.Interface Sci., ~ 463-478, 1982.

33. See Ch. 3,5,6,7 in Fuerstenau, M.C.(Edit.) loc.cit.Ref.24.

34. Manser, R.M.Handbook of Silicate Flotation. Warren Spring


Laboratory, Stevenage, Herts, 1975.

35. Hanna, H.S. and Somarsundaran,P. Ch.8 in Fuerstenau,M.C.


(Edit.) loc.cit.Ref.24. pp.197.272.

36. Atademir,M.R.Kitchener,J.A. and Sherfold,H.L. The surface


chemistry and flotation of scheelite. II Flotation
collectors. Int.J.Mineral Proc., 3, 9-16, 1981.

37. For examples -


(a)Jewkes,J.,Sawers,D. and Stillerman,R, The Sources of
Invention. Macmillan, London, 2nd edn., 1969.

(b)Kingston,\J. Innovation: The Creative Impulse in Human


Progress. John Calder, London,1977.
53

PHYSICS AND HYDRODYNAMICS OF BUBBLES

G.J.Jameson

Department of Chemical Engineering, University of Newcastle,


N.S.W., 2308, Australia

INTRODUCTION

J.F.Harper began his comprehensive review of this subject, with


the memorable words: "Chemical engineers, metallurgis ts,
geologists, brewers and cooks all try to understand processes
in which bubbles or drops move through liquids". He might also
have added mineral processing engineers to the list, for
bubbles are an essential part of the flotation process, and it
appears likely that further study of the interaction between
bubbles and particles could give results of practical
importance in the design of flotation cells

A bubble is a region in space occupied by a gas, and enclosed


by a gas-liquid interface. The equilibrium shape of the bubble
is determined by stress balances at the interface. Thus a
finite volume of gas injected into a liquid, will rise at such
a velocity, and assume a corresponding shape, so that at every
point on the interface there is a balance between the normal
and tangential stresses in each phase. The hydrostatic pressure
acts on all bubbles - i t is after all, the pressure gradient
which causes them to rise. Other effects which contribute to
the stresses include viscosity especially with small bubbles,
the surface tension, and gradients of surface tension which may
be induced on the surface of bubbles by adsorbed surface
agents. Often however, there is no shape for which these are in
static equilibrium, so the bubble's form may be constantly
changing.

In one sense, a bubble is not the coherent entity which is is


54
usually assumed to be. Thus it is sometimes misleading to talk
about "the force on the bubble" as i f the whole system of
stresses acting on the bubble could be replaced by a single
force acting at a point, which could certainly be done i f the
bubble were a solid particle. But this fine distinction need
not cause us any difficulties.

The earliest review of the topic is that of Haberman and Morton


[2) and the recent book of Clift, Grace and Webb [3) has
provided fresh insights, especially into methods of correlating
data.

EXPERIMENTAL RESULTS FOR AIR BUBBLES In WATER

The velocity of bubbles rising freely in a large body of water


has been the subject of many investigations. There was a great
deal of conflict and misunderstanding in early studies because
the results of various workers did not necessarily agree.
Possible reasons are associated with the "wall effect" - some
early workers studied bubbles rising in tubes where the tube
diameter was not sufficiently large to have a negligible effect
on the results; or in the influence of surface active agents.

Figure 1 represents a composite of the available experimental


data compiled by Clift et al [3). The graph represents the work
of many authors, and data points are not shown, for clarity.
For bubbles in the range 0.3 to O.8mm in diameter in pure
water, the figure has been amended to incorporate the recent
results of Anfruns and Kitchener, [4) which probably represent
the best available data for bubbles which have aged more than 5
to 10 seconds. Recent data on "new" bubbles gi ve higher rise
velocities than shown in Figure 1, and are discussed later.

The most obvious effect here is that of surface active


materials, usually in very small proportions, dissolved in the
water. In principle, it should be possible to produce very
small bubbles in pure water which have a higher rise velocity
than given by the line below O.2mm in Figure 1, but in practice
it is very difficult to remove the last traces of surfactants
from even the purest water, and the large surface to volume
ratio of small bubbles results in traces of adsorbed materials
having a large effect on the rise velocity of such small
bubbles. As the bubbles grow in size, the surface effect
becomes relatively less important but still observable. Between
bubble diameters of O.5mm and 20mm, it is not difficult to
produce "clean" water in which the small amounts of surfactant
which may be present have no apparent effect on the rise
velocity. Clearly though, addition of surfactant decreases the
rise velocity.
55

100

Spherical

40
III
.......
E
u
~ 20
>-
I-
......
U
0
....I
lJ.J
10
>
lJ.J
V')
......
0::::
lJ.J
....I 4
CXl
CXl
:::>
CXl
2

1 4 10 40
BUBBLE DIAMETER, mm
Figure 1. The terminal velocity of air bubbles in water at
20 0 C, after Clift et a1. [3]

Very small bubbles, less than lmm in diameter, are spherical in


appearance, and rise with a steady rectilineal motion. Beyond
lmm, the vertical motion appears to become unstable, with two
observable modes. Either steady motion up a helix with a
vertical axis, or zigzagging in a vertical plane on either side
of a vertical axis, is seen [5,6]. Authors do not agree on the
conditions under which the two modes are seen, but it is clear
that the instability in the motion has an effect on the
apparent rise velocity - if only because the bubbles have
further to travel than if they rose rectilinearly.

The other effect that is seen with these bubbles. is that they
are no longer spherical, but resemble flattened spheroids or
ellipsoids. Small bubbles are held in the spherical form by
surface tension, whose effect diminishes inversely as the
56

radius approximately. As the bubble radius increases, the


inertia of the oncoming liquid tends to flatten the bubble
against the restraining surface tension. The inertial effect is
in turn influenced by the particular shape adopted by the
bubble, especially over the nose, so there is a constant
interaction between the shape, the rise velocity and the local
surface tension pressure-difference. It is not surprising that
these bubbles rise in an unstable fashion.

It is in the ellipsoidal region too that the effect of


surfactants on the rise velocity is so apparent. The
surfactants arrive at the surface by diffusion from the bulk
fluid, and the surface concentration is not usually uniform -
the adsorbed molecules are usually swept toward the rear of the
bubble by the liquid, causing surface concentration gradients
and hence changes in surface tension with position. The
gradients in surface tension can be very large and hence in any
circumstance where the local surface tension is important in
maintaining a balance of normal stresses at the interface, the
adsorbed molecules are bound to have a strong effect on the
shape and hence the rise velocity of the bubbles. Furthermore,
a gradient in surface tension acts on the surface as if the
bubble had an internal viscosity, which would naturally oppose
the motion and reduce the rise velocity to be expected from a
simple gaseous body.

The third clearly-defined region occurs with large bubbles


beyond about 3cm 3 in volume. \lith these, surface tension ceases
to be important. The upper face of the bubble is defined by
local balance between hydrostatic and inertial effects, which
gives them an appearance of having been sliced off the top of a
sphere - hence the name "sperical-capped bubbles". The base of
such bubbles is roughly planar, although in viscous liquids,
skirts of air are sometimes dragged downwards into the wake.
These bubbles were first noticed mathematically by Davies and
Taylor [7] who derived an approximate formula for the rise
velocity by very simple means.

THEORY FOR A SPHERICAL BUBBLE

The basic equation which must be solved to determine the


terminal velocity of bubble is the Navier-Stokes equation. No
exact solutions are known for any case of translational motion,
but for some ranges of the Reynolds number, approximate
solutions give good results. Reference may be made to Harper
[1) Clift et al [3) and the text of Batchelor [8) for the
mathematical details.
57

Low Reynolds number

At small values of the Reynolds number Re=pUd/~, the motion is


dominated by viscous effects. Assuming that the bubble is held
in a spherical shape by surface tension, the problem becomes
similar to that posed by a solid sphere moving steadily through
a viscous liquid, the only difference being the form of the
boundary conditions to be applied at the surface of the bubble.

If the bubble is assumed to behave like a solid, in that its


surface can sustain a finite shear stress, the tangential
velocity of the surface is everywhere zero relative to the
centre of the bubble, and the conventional Stokes solution
applies. Thus a force balance yields

(1)

and, when the gas density p is negligible compared with the


liquid density p, the termindl velocity is given by

(2)

This equation is valid strictly for Re«l J and gives excellent


results up to Re -0.1 J which corresponds to bubbles of about 60
~m in diameter in water.

Another way of representing the force balance is in terms of a


drag coefficient So
defined by

C = Force on bubble = ,+&d_ (3)


D tpU z.nd z/ 4 ~
noting that the force on the bubble is simply the Archimedean
buoyancy. This coefficient is the force per unit cross-
sectional area J made dimensionless by the dynamic pressure
tpU2.
Substitution of (2) yields:

CD = 24/Re. (4)

The other boundary condition which could reasonably be applied


at the surface of the bubble J is that expressing equality of
the tangential stresses inside and outside the sphere. If K=
~./~ is the viscosity ratio, the result for the rising velocity
i~:
58

(5)
u = 11>.8!!..2 [ l:!:.K ] ,
3lJ 2+3K
a result known as the Hadamard -Rybczynski equation.
When K~, the result for a solid sphere, eq.(2), is recovered.
For a bubble, K+O and the equation predicts that the rise
velocity should be 1.5 times that of solid sphere of the same
density.

As far as the author is aware, the Hadamard - Rybczynski


behaviour has never been observed with bubbles, insofar as it
could strictly only be applied to very small bubbles, less than
40 lJm in diameter in water, when even slight traces of surface
active agents are sufficient to immobilise the surface of the
bubble.

The drag coefficient for a Hadamard - Rybczynski bubble would


be

(6)
c =~ [ 2+3K ].
D Re l+K
It is interesting to note that in a true Stokes regime with
Re+O, surface tension is unnecessary as a means of maintaining
sphericity. As Batchelor [8] points out, the pressure around
the surface due to the viscous stresses varies in exactly the
same way with angular position as the hydrostatic pressure, so
that at every point, it is possible to obtain exact equality
without the need to invoke surface tension as the balancing
component.

Large Reynolds number.

Uhen Re »1, it could be expected that inertia.L effects would


predominate over viscous, and providing the bubble is
maintained in the spherical shape by surface tension, then the
velocity field around the bubble could well be given by the
potential flow theory for an inviscid irrotational fluid. Near
the surface of the bubble however, it would be necessary to
apply a correction to the flow field, to allow for viscous
effects at the boundary.

This approach, developed among others by Levich [9] and Hoore


[10] is a reminiscent of laminar boundary layer theory over a
solid sphere, where the potential flow solution is adjusted to
permit the no-slip boundary condition at the wall. The
difference with the bubble is that 'slip' as such is permitted;
the viscosity of the bubble is assumed to be zero. However, it
turns out that the velocity field predicted by the inviscid
59
flow theory does not give a zero tangential shear stress in the
liquid at the surface of the sphere. Accordingly, a
perturbation of a boundary - layer type must be added to the
potential field to permit the tangential shear stress to be
zero at the surface of the bubble. When this is done, a drag
coefficient can be calculated. Moore's method [10] was to
equate the rate at which the buoyancy of the bubble does work
with the rate of viscous dissipation in the liquid surrounding
the bubble. The result is:

c = ~ [1 - 2.211 ] (7)
D Re ----r-.
2
Re
This equation should be expected to hold for "large" Reynolds
numbers, whenever the bubble is spherical. Harper [1] suggests
Re = 50 as the lower limit, corresponding to an air bubble of
diameter 0.5mm, and experimental evidence is that bubbles in
water remain spherical for diameters up to about 1mm. As will
be seen later, it appears that between 0.6 and 1mm diameters,
eq. (7), overpredicts the rise velocity. Beyond 1mm the rise
velocities predicted continue to increase with increasing
diameter, contrary to observation.

ELLIPSOIDAL BUBBLES

Air bubbles in water remain spherical up to about 1mm diameter.


Beyond this, they begin to distort becoming flattened and
ellipsoidal in shape. A curious phenomenon then occurs - the
rise velocity in pure water reaches a maximum of about 34 cm/s
at a diameter of 1.4mm, and thereafter declines until the
bubbles become considerably larger. At around 6mm the rise
velocity begins to increase again, Fig.1.

It might be thought that the explanation for the maximum in the


veloci ty should be sought in the helical or zig-zag motions,
but it appears to arise simple from the change in shape. Moore
[11] developed a theory for dis torted gas bubbles, allowing
them to adopt the form of oblate ellipsoids described by the
ratio of the major to the manor axis, x. The theory is very
complicated because of the interrelation between X, the Weber
number and the Reynolds number. In Figure 2, terminal
velocities calculated from Moore's theory, with the aid of
functions tabulated by Harper, [1] are shown, together with the
experimental curves for "pure" water, including the data of
Anfruns and Kitchener. [4] The agreement between the two is
remarkably good; Moore's theory predicts a maximum in the rise
velocity at a diameter of 1.75mm, compared with the
experimental maximum at 1.4 to 1.5mm. At the maximum, the
distortion as gauged by X, is 1.9. Moore considers that the
theory should be reasonably accurate up to X=2 approximately.
60

Shown in the figure are the values of X at selected points and


it can be seen that the theory predicts that a 10% change in
sphericity occurs at about 0.9mm increasing to X = 4 at 3.4mm.
By this point, the theory should have broken down, but the
trend agrees with the data. However, after the maximum in the
velocity, spirals and zig-zags are seen experimentally, which
would tend to reduce the rise velocity.

60

VI 40
'-
E
u

- --
ft 30
>-
I-
......
U
0
-l
l.LJ
:::- 20
l.LJ
V)
......
~

10
0.4 1 2 4 5
BUBBLE DIAMETER, mm

Figure 2. Terminal velocity of air bubbles in water at 20°C.


predicted by Moore.[II)j
smoothed experimental data from many sources,
for "pure" systems.

As will be discussed later, it appears that even in the purest


water, sufficient traces of surface active material remain to
retard the rise of the bubbles if they are allowed to age more
than a few seconds in the experiment. The behaviour of "new"
bubbles appears to be closer to Hoore I s curve, although the
number of data points is quite limited.

SPHERICAL-CAPPED BUBBLES

The bubbles discussed so far have been more-or-less rounded in


shape, whether or not they be ovaloid, spheroid or ellipsoid.
As the bubble volume increases however, the bubble shape
changes radically, adopting a smoothly-curved profile over the
front, with a rear or base which is almost flat, perhaps with
internal ripples or rocking from side to side.
61

For volumes greater than about 3 cm 3 , corresponding to a


spherical diameter of 18mm, the bubbles are described as
"spherical-capped". Although not strictly spherical in shape,
the radius of curvature is so large that the bubble subtends a
relatively small angle at the centre, and may be regarded as a
slice off the top of a sphere. In water, the half-angle
subtended by the base is very close to 500 and is virtually
independent of size.

The velocity of rise of spherical capped bubbles may be


predicted by a very simple theory. The Reynolds number of the
flow is large, and surface-chemical effects are not expected,
so the motion over the front of the bubble should follow
inviscid flow theory. Applying Bernoulli's theorem to the front
surface, assumed to be part of a sphere (see Figure 3) we have

2
P + !PV 8 + pgy = constant (8)

on the streamline constituting the surface of the bubble,


noting that at the nose of the bubble (8=0) the angular
velocity of the fluid is zero relative to axes moving with the
bubble, and the pressure at the surface equals the pressure
inside the bubble which is constant. Thus i f the hydrostatic
datum y is set equal to zero at the nose stagnation point, we
have:

g R(l-cos8). (9)

" ""
" ""
"
" ""
""
o
Figure 3. Flow around a spherical-capped bubble rising in a
liquid.
62

Now from potential theory, the velocity at the surface of a


sphere is

3
Va = 2" U sin a (10)

where U is the free stream velocity. Provided the angle a is


small, we can approximate the angular functions by sin e~e and
cos e~ l-e 2/ 2 ,to give,

2 .1
U ="3 (gR) 2 (1l)

This equation has been experimentally tested many times and


found to be quite accurate. In terms of more accessible
variables.

U 0.792 (g Vl/3)!

0.71l (gd) t, (12)

where V is the volume and d the equivalent diameter of the


bubble. These results are due to Davies and Taylor [7]

These results are valid for large bubbles provided the bubble
Reynolds number is greater than 40 [3]

BUBBLE BEHAVIOUR IN VISCOUS LIQUIDS

When we move away from the air-water system, we move into the
area of generalised variables. Apart from the Reynolds number
Re and the drag coefficient CD' the relavent dimensionless
groups are:

M gl1 it /pa 3 (13)

y pu 2d/a (14)

F U2/gd (1S)

and E B2 = gd 2 p/a (16)

The Morton number M contains only the fluid properties. Since


the density and surface tension of fluids do not vary much, the
main variable in M is usually the liquid viscosity. In Haberman
and Morton's experiments,[2] M for various liquids was give as:
63

Liquid M

\-later (21°C) 2.40 x 10- 11


(49°C) 3.07 x 10- 12
Corn Syrup, 68% 2.12 x 10- 3
Olive Oil 7.16 x 10- 3
Syrup (180 poise) 9.2 x 100

The Weber number \1 is a measure of the importance of the


dynamic pressure (t pU 2 ) induced by the motion, to the pressure
increment 4o/d across the vapour-liquid interface comprising
the surface of the bubble. At low Weber numbers, \/«1, the
bubble would behave as a sphere but as H increases, deformation
would be expected.

The Froude number F relates the dynamic pressure tpu 2 to the


total hydrostatic pressure change pgd across the vertical
height of the bubble. It is particularly relevant for spherical
capped bubbles at high Reynolds numbers, where the rise
velocity and shape are a balance between the two effects.

The Eotvos number E is related to the Bond number B. It is


proportional to the ratio of the hydrostatic pressure
difference pgd which tends to flatten the bubble, to the
surface-tension pressure 4o/d which tends to hold it spherical.

The numbers are related to each other. Thus

W (4 M Re lf /3 C ) 1/3 (17)
D

F 4/3 ~, (18)
3
B2 =-W
E ~, (19)
4

When the Eotvos number exceeds 40, bubbles are usually


spherical-capped, except when M is large and the Reynolds
number is low. As explained earlier, as Re+O, the viscous
stresses generated by the motion have a symmetry about the
equator which is the same but opposite to the hydrostatic
pressure. Hence there is no need to invoke surface tension, and
the bubbles remain spherical.

Despite the complexity of the wider problem, the behaviour of


bubbles in viscous liquids is very similar to that in water, in
that the shapes of the terminal velocity curves are similar,
even if the absolute values are different. Spherical.
ellipsoidal and spherical capped bubbles are seen in all
liquids, but of course the velocity-diameter relationship may
64

be quite different. Because of the similarity, attempts have


been made to correlate the appropriate dimensionless groups. A
comprehensive compilation of such correlations is presented by
Clift et al [3].

EFFECT OF ADSORBED SURFACTANTS

If a vapour-liquid interface is created in a solution of


surface-active material, the molecules of surfactant will
adsorb preferentially on the surface. The surface tension of
the interface will be altered by the adsorbed substance, and
the relation between the surface tension and the surface
concentration r is given by integrating the well-known Gibbs
equation to give:

a
p
a = II = RTr (20)

where a, a are the surface tension of the pure and


contaminfted surfaces respectively and II is the surface
pressure. This equation is approximate only and is applicable
only to ideal films. There is an extensive literature on
adsorption at the gas-liquid interface to which the reader is
directed for further details.

A consequence of adsorption is that i f bubbles are introduced


into the base of a column containing surfactant, they will
carry adsorbed material with them to the top of the column and
concentrate it perhaps in a foam. Thus the liquid becomes
depleted in the surfactant, a factor of some consequence in
mineral flotation where the collector may be removed into the
foam to the detriment of the process. The phenomenon has been
much studied, and forms the subject of a useful review [12].

Gas bubbles of course are no exception to the general behaviour


of interfaces, but when bubbles are rising through a surfactant
solution, the adsorption is not steady state. Surfactant
molecules are brought to the interface by convection and
diffusion and the local surface concentration r is therefore
related to the Reynolds number and the Schmidt number Sc=v/D,
or more generally through the Peclet number Pe=Re Sc. A further
complicating factor is that if the local surface concentration
r varies, there will be corresponding variations in surface
tension around the surface which will tend to distort the
bubble and influence its rise velocity which will in turn
influence the rate of diffusion etc. It is no surprise to find
that surface active materials in water can have a drastic
effect on the rise velocity, especially with the air-water
system, which is particularly susceptible given the large
surface tension of pure water.
65

In Figure 1, the extensive range of experimental data have


already been presented and discussed. Figure 4 shows data from
Anfruns and Kitchener [4] who conducted very careful work with
different types of solutions. Bubbles were made singly in a
rotating cavity device. The data show that.

(1) for air bubbles less than 200~m in diameter, it is


impossible with existing technology to make water
sufficiently pure to escape the influence of trace
quantities of surface active materials in this type of
experiment. The Hadamard-Rybczynski effect has never been

14
//
A// B
,'1
12 ,'1
,/ o

,'/ o
10 '
VI
...... ,'/
//
E
u
8
E/ 1/
~

>-
t-

/1
........
U
a I

/ / I.
...J
w 6
:>
w
U')
........
I It'
0::: / /. 00
W 4
...J
co
co
::::>
co
2

o 0.2 0.4 0.6 0.8 1.0


BUBBLE DIAMETER, mm
Figure 4. Experimental results of Anfruns and Kitchener,[4]
showing effect of contaminants on the rise velocity
of bubbles. (A) ultra -cleaned water, (B) distilled
water, (C) pine oil solution (lmg/R.), (D) pine oil
solution (5mg/R.). The results of Bachhuber and
Sanford [13] for "new" bubbles are also shown (E). -
Calculated for solid sphere.
Tube diameter 0 O.Scm • 3.3cm
66

observed in the bubble size range to which it is


applicable, i.e. less than about 40~m in diameter.

(ii) when the diameter is in the range 400 to 1000~m, it is


possible to obtain sufficiently-clean systems to approach
closely the free surface theory of Moore as shown in
Figure 2. Addition of even small quantities of pine oil
(5ppm) are sufficient to reduce the terminal velocity by a
factor of 2.

In this apparatus, the column of liquid up which the bubble


rose was about a metre, and trace impurities, if any would have
had an opportunity to collect on the surface of the bubble.
Bachhuber and Sanford [13) designed an experiment deliberately
to test the hypothesis that if the rise velocity of a bubble is
measured soon after its release, insufficient time will have
elapsed for the surface to be coated with surface impurities,
so the rise velocity should be that of a fluid sphere rather
than a solid, which is given more or less by the lower envelope
in Figure 1. Their bubble sizes ranged from about 200~m
upwards, and the velocity was measured within a distance of 50
bubble radii i.e. a minimum of- lOmm for the smallest. The rise
velocities obtained in this fashion were higher than_ predicted
by Moore's theory, [10) and higher also than those of Anfruns
and Kitchener [4] - they are shown in Figure 4. Bachhuber and
Sandford also measured velocities of similar bubbles in a long
tube, with water of the same quality; the results were similar
to those predicted for solid spheres. Their water was described
as "singly distilled in glass equipment".

Bachhuber and Sandford's results are rather disappointing -


they suggest that no matter what precautions are taken, it is
impossible at present to make water which is pure, in the sense
that it contains no detectable amounts of surface active
material, detectable that is by its effect on the rise velocity
given sufficient time for equilibrium. Anfruns' water was
prepared and collected under the most stringent precautions to
preclude or remove trace contaminants and yet the rise
velocities of the bubbles (with a long rise distance) are still
below those of Bachhuber and Sanford (for newly created
surfaces).

The effect of surface age has been investigated in greater


depth by Detwiler and Blanchard [14), who were able to measure
the terminal velocities of bubbles with a lifetime between 1
and 70 seconds. "Old" bubbles behaved like solid spheres, while
bubbles newly formed had rise velocities close to the
predictions of Hoore' s theory. [11] The results are shown in
Figure 5~ With a 3 percent NaCI solution, the rise velocity of
a 780~m bubble decreased by about 40 percent within 12 seconds
of formation, thereafter showing little change. However, the
authors noted that with their best distilled water (distilled,
67

deionized, redistilled, then bubbled with tiny bubbles in a 1


metre tall column) there was less than a 10 percent change in
rise speed over the first two minutes of bubble age.

The theory of diffusion of surfactants to bubbles is dealt with


by Harper, [1] who has taken the subject about as far as it can
be taken, with manageable perturbations on the theory of pure
systems.

1.0
0.8 SOLID
SPHERE
0.6

Co
0.4
"INVISCID"
SPHERE
MOOR~I]
0.2
...,,-
J,

0.1
60 80 100 200 400 600 800

Re
Figure 5. Experimental results of Detwiler and Blanchard [14]
showing the effect of bubble age on the drag
coefficient. Each straight line represents one bubble
size (950,1010,1080,1270 and 1310pm respectively),
with the rise velocity determined at various times
after formation. The newly-formed agree closely with
Moore's theory [11] but with increasing age they
approach solid-sphere behaviour.
68

CHARGE EFFECTS AND FLOTATION

If surface-active ions are preferentially adsorbed on the


surface of the bubble, it is obvious that the bubble surface
can become charged, with important consequences for the capture
of small particles, which may well be charged also, in the
flotation process. That bubbles could acquire a net charge has
been known for many years, and a number of attempts have been
made to obtain accurate measurements of the electrophoretic
mobility or zeta potential. It is only in recent years that the
formidable experimental difficulties have begun to be overcome
however, and the results so far obtained are only reliable for
very small bubbles.

The idea that assorption phenomena and flotation are linked was
developed in Russia by Derjaguin and Dukhin, the broad outlines
being published in 1961. [15] They suggested that a bubble
could be considered to be surrounded by three zones. Close to
the surface of the bubble is a region in which any particle
which finds itself will be under the influence of the "surface"
forces - the London - van der Waals and double-layer attraction
or repulsion. Further away, there is a region where "diffusio-
phoretic" forces are important, where the conetration gradients
of ionic species and hence the gradients of electrical
potential, may interact with the small charged solid particles
approaching the surface of the bubble. Finally, outside the
range of the double-layer and the mass transfer boundary layer,
the interaction between particle and bubble is dominated by the
prosaic viscous and intertial effects of conventional fluid
mechanics.

The weakest effect in this system is probably the second one -


the diffusio-phoretic effect. In conventional flotation work,
the concentration of collector on the bubble surface is usually
so high the diffusion rate to the bubble is very slow.
Diffusion will only occur, if simultaneously, adsorbed species
are being washed off the bubbles in the wake, an unlikely
occurrence with the "condensed" films usually formed by
collectors.

The concepts of Derjaguin and Dukhin have been very thoroughly


investigated in recent years by workers in a related area - the
collection of small particles in gas or liquid streams. by
spherical or cylindrical solids. Another related area is in the
coagulation of emulsions, or flocculation of small solid
particles in suspension. Capture of particles from laminar
flows has been reviewed by Spielman [16].
69

The importance of charge effects in flotation was first


demonstrated by Collins et al. [17,18] They floated polystyrene
latex particles with C TAB (cetyltrimethyl-ammonium bromide) as
collector, modifying the double-layer thickness with sodium
sulphate to vary the charge on the particle and the bubble. By
changing the concentration of sulphate ion by one hundred-fold,
the charge on both the particles and the bubbles was reduced
from about 65 to 40mV, and the rate of flotation increased by
an order of magnitude.

It would seem desirable to try to control flotation systems


involving fine particles so that the charge on the particles
and the bubbles was opposite in sign. This would be difficult
to achieve in practice however, because the collector ions
usually used to render the particles hydrophobic adsorb
similarly on the surface of the bubbles. There may be scope
however for charge modification via control of pH or ionic
concentration.

It was pointed out by Collings and Jameson that it would be


undesirable to float near the point of zero charge, because
this could lead to coagulation of values and gangue. Their
results showed that the flotation rate was not severely
affected when the particle charge was low, and suggested a
charge of 20 to 30 mV as a practicable minimum which would give
reasonable flotation rates but prevent flocculation.

The technique used by Collins et al. to measure bubble charge


has been described [19], and more recent papers have
appeared. [20-23]

BUBBLE FORMATION AT ORIFICES

Much work has been done on bubble formation at orifices. For


simplicity, we consider here the simplest theoretical models
which usually give reasonable results. The gas flowrate forming
the bubble will be assumed to be constant, as would occur for
example i f a gas is being forced through a small orifice or
frit which has a high intrinsic resitance to flow. For further
refinements, review articles may be consulted.[3,24]

Low flowrate - small orifice

At vanishingly small flowrates, when the orifice diameter is


small, the bubble volume at detachment is determined by a
balance between surface tension and gravity. If the diameter of
the orifice is d , the surface tension holding the bubble is
nd cr, and the buo~ancy is nd 3 ~pg/6, assuming the bubble to be
spHerical. Thus at the point of detachment with this simple
model,
70

nd a = nd 3 g~p/6
o
or d = (6d a/g~p)1/3. (21)
o
This simple equation is not particularly accurate; predicted
bubble volumes may be in error by a factor of up to 2. This is
not surprising because the bubbles do not usually detach as
spheres, but have elongated necks. Corrections can be made
using the factor of Harkins and Brown, [25] well known for its
applicability to pendant drops.

Inviscid liquids - surfaces tension neglected

If surface tension can be neglected, the formation of the


bubble is governed by the hydrodynamic forces in the liquid. As
the bubble accelerates from the orifice, part of the liquid
displaced by the bubble accelerates with it - the "added" and
"virtual" mass of the bubble. The fraction of added mass is
11/16 of the mass of the fluid displaced, pV. While the bubble
is accelerating away from the orifice, it is still attached to
the source of gas so its volume is also increasing like V =
Qt,so the radius r is also increasing.

The analysis of Davidson and Schuler [26] envisages a bubble


growing as a sphere, Figure 6; the centre of the sphere is
rising with velocity dr/dt. Simultaneously, the sphere is acted
upon by gravity, so it is subjected to an upward force pVg.
Ignoring the density of the gas, which tends to accelerate the
bubble upward, the equation of motion is then

(a) (b) (c)

Figure 6. Davidson and Schuler's model for a spherical bubble


forming at an orifice. (a) Underside of bubble moving
down; (b) bottom point of bubble at rest in lowest
portion; (c) bottom point of bubble reaches gas
source.
71

pVg =d- [11 ds]


- pV -
dt [16 dt. (22)

This equation can be integrated with boundary conditions t=O,


s=O and at detachment, the bubble radius r equals the height of
the centre of the bubble above the orifice, s, to give

(23)

a remarkably simple result which agrees quite well with


experiments.

Highly viscous liquids

If the fluid is very viscous so that the Reynolds number


associated with the growing bubble is small, viscous drag
replaces the inertial term in the equation of motion, i.e.

ds
pVg 611}.lr dt ' (24)

with V Qt 411r 3/3. Integrating as before,

V (411/3)1/3 (15}.lQ/2g)3/~ (25)

which again gives good results at low flowrates. At high


flowrates the virtual mass can be added but the result is
rather complicated. [27]

BUBBLE FORMATION IN FLOTATION CELLS

A conventional flotation c~ll contains a rotating impeller


which serves two functions: it circulates the contents of the
cell and keeps the particles in suspension, and it provides a
means of sucking air down into the cell and dispersing it in
the form of small bubbles. Usually, either the impeller shaft
itself or the shroud surrounding the impeller is hollow,
allowing air to pass downward to the region of low pressure
near the eye of the rotating impeller.

Despite the importance of bubbles in the flotation process,


little attention had been paid to the details of the mechanisms
by which bubbles are formed and dispersed in the medium.
Practical systems are very difficult to study of course because
the presence of particulates in suspension prevents the use of
optical methods, which have proved so useful in other problems
involving bubbles. But the difficulties are not insurmountable.
Grainger-Allen [27] photographed bubbles being generated behind
the turbine blades in a small flotation cell. Most of his
72

experiments were conducted with water alone, although he used a


suspension of natural cryolite particles, which have a
refractive index close to that of water, to test the effect of
suspended solids. He reports that the fine solids present did
not materially affect the cavity shape or bubble generation
mechanism.

Grainger-Allen experimented with a range of impeller shapes - a


disc with flat vertical blades, a circular disc with steps in
the periphery, and various types of horizontal flat bars, of
different cross-section - circular, elliptical etc. The latter
were hollow and air could pass into the liquid through slots.

The mechanism of bubble formation seen by Grainger-Allen was of


a single type. Gas filled cavities would form behind the
obstruction to the flow, whether it be a vertical blade on the
periphery of a disc, or a flat blade rotating about the axis.
The trailing edge of the cavity would then be drawn downstream
into a thin film or, in the case of blunt bodies, into a wake.
The cavity would then break up into bubbles. Some sketches from
his work are shown in Figure 7.

Flotation cells are not the only equipment in which bubbles are
generated with rotating impellers. Such devices are widely used
in biochemical engineering to provide oxygen for the growth of
micro-organisms. For this reason there have been several
detailed investigations into bubble generation which show that
other mechanisms are at work in addition to the simple
ventilated cavities seen by Grainger-Allen.

Van's Riet and Smith [28-31] have shown that, at least at low
air rates, trailing vortices develop at the corners of the
turbine blades, and air is drawn into the centre of the vortex;

,,
(b)

Figure 7. Bubble formation behind a turbine impeller, (a) with


baffles, and (b) without baffles.

the filament of air then breaks up into bubbles. At higher gas


73

flowrates, the vortices are suppressed but the gas forms


sheets, as shown in Figure 8, which is taken from Brauer· [32].
At higher gas rate still the sheets fill the entire region
behind the blade, and eventually the system floods.

The photographs and drawings in this series of papers [28-32]


will repay detailed study for anyone interested in controlling
bubble sizes and the aeration process in flotation cells.
General conclusions which may be of interes tare (i) for any
particular blade configuration there is a gas flowrate at which
"flooding" is seen, when large cavities form behind the blades
and large bubbles are formed; (11) increasing the number of
blades increases the capacity of the impeller, i. e., a larger
gas flowrate is obtained before flooding occurs; (iii) a larger
number of blades (up to 18 were tested) [32] increases the
radial velocity component of the fluid, and hence the pumping
capacity. This latter effect is important because the bubbles
are thereby ejected further into the liquid away from the
impeller, reducing the opportunities for collision and
coalescence.

./
./

(a) (b)

Figure 8. Vortex formation behind a turbine impeller blade.


(a) Bubbles are generated from line vortices.
(b) At higher gas rates, vortex sheets occur.
74

NOTATION

a bubble radius (m)


d bubble diameter (m)
D molecular diffusivity (m 2 /s)
g acceleration of gravity (m/s 2 )
Q gas volumetric flowrate (m 3 /s)
r,e polar coordinates
R radius of curvature (m)
distance moved by centre of bubble (m)
time (s)
rise velocity of bubble (m/s)
velocity in e-direction (m/s)
volume of bubble (m 3)

surface concentration (kmol/m 2 )


ratio of viscosity of internal to external fluid
viscosity of continuous, bubble phases resp.(pa-s)
kinematic viscosity, (m 2 /s)
surface pressure (HIm)
density of liquid, gas (kg/m 3 )
surface tension (HIm)
ratio of major to minor axis of ellipse

Dimensionless groups

B Bond number,eq (16)


CD drag coefficient. eq.(3)
E Eotvos number, eq.(16)
F Froude number, eq.(15)
M Morton number, eq.(13)
Pe Peclet number, ReSc
Re Reynolds number, pUd/~
Sc Schmidt number, vlD
W Weber number, eq.(14)

REFERENCES

1. Harper,J.F., "The motion of bubbles and drops through


liquids", in Advances in Applied Mechanics (ed.C.S. Yih),
Academic Press, New York, Vol.12, 1972.

2. Haberman,W.L. and Morton,R.K., An experimental


investigation of the drag and shape of air bubbles rising
in various liquids. u.S. Navy Dept. David W.Taylor Model
Basin Report No.802, 1953. Also Trans.Am.Soc.Civil
Engrs.,121, 227-252, 1956.
75
3. Clift,R., Grace J.R. and Weber,M.E., Bubbles, Drops, and
Particles, Academic Press, New York, 1978.

4. Anfruns, J.F. and Kitchener,J.A., Rate of capture of small


particles in flotation, Trans.I.M.M., C9-C15, March 1977.

5. Saffman,P.G., On the rise of small air bubbles in water,


J.Fluid Mech. J:.., 249-275, 1956.

6. Hartunian, R.A. And Sears, W.R., On the instability of


small gas bubbles moving uniformly in various liquids,
J.Fluid Mech.,1L 27-47, 1957.

7. Davies,R.M.and Taylor,G.I., The mechanics of large bubbles


r~s~ng through extended liquids and through liquids in
tubes, Proc.Roy.Soc. A 200, 375-390, 1950.

8. Batchelor, G.K., An Introduction to Fluid Dynamics,


Cambridge University Press, 1967.

9. Levich, V.G.Physicochemical Hydrodynamics, Prentice-Hall,


Englewood Cliffs, New Jersey, 1962.

10. Moore D.W., The boundary layer on a spherical gas bubble,


J.Fluid Mech. l.h. 161-176, 1963.

11. Moore D.W., The velocity of rise of distorted gas bubbles


in a liquid of small viscosity, J.Fluid Mech., 23, 749-766,
1965.

12. Lemlich, R., ed. Adsorptive Bubble Separation Techniques-,


Academic Press, New York, 1972.

13. Bachhuber, C. and Sandford, C., The rise of small bubbles


in water, J.Appl.Physics.~, 2567, 1974.

14. Detwiler,A. and Blanchard D.C., Aging and bursting bubbles


in trace-contaminated water, Chem.Eng.Sci. ll,9-13, 1978.

15. Derjaguin,B.V. and Dukhin S.S., Theory of flotation of


small and medium size partieles, Tralls.I.M.M. , 2.2.,1961

16. Spielman,L.A., Particle capture from 10\01 speed laminar


flows, Ann.Rev.Fluid Mech., ~,297-319, 1977.

17. Collins,G.L.and Jameson,G.J., Experiments on the flotation


of fine particles - the influence of particle size and
charge, Chem.Eng.Sci. ,31, 985-991,1976
76

18. Collins,G.L. and Jameson,G.J., Double-layer effects in the


flotation of fine particles, Chem.Eng.Sci. ~ 239-246,
1977 •

19. Collins,G.L., Motarjemi,M. and Jameson,G.J., A method for


measuri.ug the charge on small bubbles, J. ColI. Interface
Sci. Q, 69, 19780

20. Usui,So and Sasaki Ho, Zeta potential measurements of


bubbles in aqueous surfactant solutions, J. ColI, Interface
~~36, 1978.

21. Fukui, Y. and Yuu S., Collection of Submicron particles in


electro.flotation. Chen. Eng. Sci. ,J2..,1097-1105, 1980.

22. Sato Y., Murakami,Y., Hirose,T., Yamamoto,H.and Uryu, Y.,


Removal of emulsified oil particles by dissolved air
.flotation, J.Chem.Eng.Japan,1b 454,1979.

23. Usui,S.Sasaki,H. ,and Matsukawa,H., The dependence of zeta


potentia 1 on bubble size as determined by the Dorn effect,
J.Coll.Interface Sci., ~ 80, 1981.

24. Kumar,R. and Kuloor,N.R.,The formation of bubbles and


drops, in Advance in Chemical Engineering, ed. Drew,T.B.,
Cakelet,G.R.Hoopes, J.W. and. Vermeulen, T., Vol. 8, McGraw
Hill, ijew York, 1970.

25. Davidson,J.F.and Schuler,13.0.G.,l3ubble for.mation "it an


orifice in an inviscid liquid, Trans. Inst. Chem. Engrs., 1!h.
144,1960.

26. Davidson,J.F.and Schuler,B.O.G.,Bubble formation at an


orifice in a viscous liquid, Trans. Inst. Chem. Engrs. ,]!,335,
1960.

27. Grainger-Allen,T.J.N., Bubble generation in froth flotation


machines ,Trans. I.M.M.,C15-C22, 1970.

28. vau't Riet,K.,Turbine agitator hydrodynamics and dispersion


performance, Ph.D. thesis Delft Technological University,
1975.

29. van't Riet,K. and Smith,J.M., The behaviour of gas-liquid


mixtures near Rushton turbine blades, Chen. Eng. Set. , ~
1031-1037, 1973.

30. van't Riet,K.and Smith,J.M.,The tr.ailtng vortex: Ryste'Q


prod'lced by Rushton tur.bi'le >l~ t t>il.:or>:l. Che,Q. E'l~. Sel.) 1Q.,
1093-1105, 1975.
77

31. Bruijn,W.,van't Riet,K.and Smith,J.M.,Power consumption


with aerated Rusntofl tnrbl. 'les > 'l'ri-lr1>;. l'l" t. Chern. Engrs. ,52,
88-104,1974.

32. Brauer,H., Power consumption in aerated stirred tank


reactor systems, in Advance in Biochemical Engineering,
Vol.13, Springer, Berlin,l979.
79

THIN FILMS, CONTACT ANGLES,WETTING

E.H. Lucassen-Reynders (1)


J.Lucassen (2)
(1) 6 Kingsway,Heswall,Wirral,Merseyside, L60 3SW
(2) Unilever Research, Port Sunlight Laboratory, Bebington,
Uirral, Merseyside.

INTRODUCTION

Flotation,being the technique of removing selected solids from


aqueous suspension by attachment to a second fluid phase, pres-
ents the physical chemist with a complex web of problems.No fewer
than three interfaces are involved in interplay with thin liquid
films,and the time scale of the process virtually ensures that
conditions are far from equilibrium.

One condition for successful attachment of solid particles to a


second fluid phase,such as air or oil,is that the particles
should be wetted more readily by the second fluid than by the
aqueous phase,i.e.that the particles should be hydrophobic rather
than hydrophilic.Without surface alteration most minerals of
practical interest are not hydrophobic enough to be naturally
floatable.Flotation science addresses the problem of re:ndering
hydrophilic solids hydrophobic by the adsorption of surface
active materials.A quantitative measure of the wettability of a
solid is the contact angle, i. e. the angle under which the fluid-
fluid interface meets the solid(see Figure l).This angle depends
on the interfacial tensions of all three interfaces. Considerable
attention has been paid over the years to the effect of surfac-
tants on interfacial tensions and contact angles under equili-
brium conditions. The importance of equilibrium contact angles
should not be overemphasised, however. The time of contact of
solid and bubble in flotation has been estimated as being of the
order of milliseconds [1,2] ,far too short for adsorptions,
interfacial tensions and contact angles to reach their equili-
brium values. Information on the effect of adsorption kinetics on
contact angles is relatively scarce ,unfortunately. The main
results of contact angle studies in surfactant systems are
80

reviewed in the next Section.

a.
A w

b.
A

CD
81 / \
/ \
/ \

w
I \

1
/
\\

Figure 1. a. Schematic representation of interfacial tension of


forces acting on three-phase contact line solid
(S)/water(W) air/(A).
b. Wetting of solid spheres as a function of contact
angle e in gravity-free system.

Of more recent date [3,4] is the recognition of film rupture as a


possibly rate-determining step in flotation. Obviously, before
successful establishment of contact between a solid particle and
an air bubble rising through the aqueous suspension there must be
81

thinning and rupture of the intervening aqueous film. This step


depends on the dynamic properties of the two interfaces bounding
the film, on the interaction forces between them and on the
hydrodynamics of liquid motion. Section III is devoted to the
thinning and rupture of thin films, which is regarded by some as
the most important stage in flotation.

CONTACT ANGLES AND WETTING

Equilibrium Contact Angles

Wetting of a solid (S) by and aqueous phase (W) and a second


fluid phase,say air bubble (A) ,is quantitatively expressed in the
angle 9 of the three-phase contact line, conventionally measured
in the water phase (see Fig.l). This angle is linked to the
properties of the three-phase system by means of Young's equation
[5] :

o - 0
SA SW (1)
cos 9
o
WA

where 0 stands for the interfacial tension of the interface


indicated. The free energy of the system is at a minimum when the
solid is submerged for the greater part in the liquid against
which it has the lower value of 0. Thus, the lower the value of
(OSA-OSW)' i.e. the higher the contact angle, the more readily the
soird 1S wetted by air, as indicated in Fig. lb.

Eq.(l) can be derived in two equivalent ways. One is a balance of


forces argument in which two opposing forces per unit length of
three-phase contact line are (OWA cos 9 + 0 ) to the right and
0SA to the left in Fig. lao Alternatively, a ~ee energy argument
can be applied in which the total free energy of the three-phase
system is minimised after a virtual displacement of the contact
line along the solid surface. Without going into any detail, the
following points are worth emphasising in view of much
controversy that has surrounded the equation:

(i) The quantities 0 in Eq(l) are interfacial tensions, defined


by

(2)

They are not specific interfacial free energies, which are


numerically equal to 0 only in one-component systems. This
point was clarified in a classical paper by Johnson [6], in
which Eq(l) was rederived by rigorous Gibbsian
82

thermodynamics for a solid surface which is homogeneous and


continuous but not necessarily rigid and plane.

(ii) The derivation does implicitly assume that variations in


the system's free energy F can be achieved by variations in
the volumes of phases and in the areas of two-phase contact
surfaces, but not only by variations in the length of the
three-phase contact line. This means that the curvature of
the contact line must be sufficiently small for the effects
of line tension [7] to be negligible. For extremely small
particles or bubbles a separate term must be included [2,8]
to account for line tension effects:

o - 0
cos a SA
o
SW
- --
0 r
T (3)

WA WA

Line tension can only make itself felt if the wetting


perimeter is highly curved; its effects will be considered
later.

(iii) The angle a is the macroscopic rather than a microscopic


contact angle. A recently advanced theory [9] on contact
angles has aimed at accounting for the effect of molecular
interactions in the three-phase contact region. It has been
pointed out (10) that the resulting equation may be
applicable to a microscopic angle i.e. the angle that
pertains within an area of the size of a few molecular
diameters, but that the operationally defined macroscopic
angle is governed by Eq(l).

(iv) Gravitational effects play no part in Eq(l). They can alter


the shape of bubbles and drops but not their contact angle.

Experimental proof of Young's equation is frustrated by the


inaccessibility of the two solid-liquid interfacial tensions to
direct measurement. However, the equation can be seen as verified
by contact angle measurements on solids just above their melting
point and on mercury [11].

Another problem has traditionally been seen in the common


occurrence of contact angle hysteresis. In practice the ideal,
i.e. homogeneous and continous, solids envisaged in point (i) are
few and far between. In homogeneities (12), either geometrical
(surface roughness [13,14,15]) or energetic [16,17] lead to
hysteresis, i. e. to contact angles which are larger when the
liquid is advancing over the solid surface than when it is
receding. A third possible cause of such hysteresis lies in
physical and/or chemical changes induced in the solid by the
83

liquid wetting it [14]. In the first-and last-mentioned examples


a case can be made out for regarding both advancing and receding
angles as equilibrium values, referring to parts of the surface
with different a-values [18,19]. For flotation the receding angle
would appear to be more relevant, as the aqueous phase must
retreat from the solid, but there is a tendency in contact angle
studies to use the advancing angle as the better reproducible
quantity [20,21]. Up to a pOint, the method of interpretation can
be the same for both angles.

In terms of the interfacial tensions the condition that the solid


should not remain wetted by water means that the three-phase
system should obey the inequality:

aSA - a SW < aWA (4)

Flotation, therefore, should be favoured by relatively low aSA


and high a SW • Such solids, which have been termed low-energy or
hydrophobic solids, have a nonpolar character. Also, the liquid
interfacial tension alrlA, should be relatively high, as illustrated
by Zisman's work [:l:lJ on the "critical surface tension of
wetting".

In surfactant-free systems, wide variations in a are easily


obtained with homologous series of organic liquids (L) rather
than with aqueous phases W. Within such series there is a
critical value a of the surface tension a~ separating liquids
cr
that completely wet a given solid (aLA <; a from those that do
not (aLA> a ): cr
cr
acr = aSA - a SL (5)

Obviously, acr cannot be equated to aSA unless a SL is negligible.


Negligible a SL can only be expected for purely-nonpolar solid and
liquid phases which interact only through Van der Waals
dispersion forces. A very good approximation for interfacial
tensions between many pure condensed phases is Fowkes' semi-
empirical theory based on the following assumptions [23,24]:

(i) the interfacial tension is the sum of the surface tensions


(against saturated va-pour) as and aL and a correction term
for interactions across the ~nterface;

(ii) each of the surface tensions as and aL is the sum of a


polar and nonpolar contribution, which contribute to the
interaction term through their respective products [25];

(iii) the effect of vapour adsorption is negligible.


84

If only Van der Waals dispersion forces act between Sand L, i.e.
if polar contributrions are absent in at least one of the phases,
the result is:

(6)

and a similar equation for the interfacial tension water/nonpolar


fluid. This gives for the contact angle of a water/nonpolar fluid
interface on a nonpolar solid [26):
d d
oWL cos 6 =- oWL + 2(/oW )(/oL - loS) (7)

Evidently 1£ the nonpolar fluid L is air, °in Eqs(6), (7) is


zero. The great attraction of Eq(6) is that Itpredicts contact
angles for both air and nonpolar liquids in tElfIDs of dthe same
parameters, i. e. the disJersion contribution.!! Os and oW. Yflues
reported [25,26) for °are around 22mNm 1, whereas ° for
various solids ranges [2~) between 20 and 45 mNm- 1 • Substrtuted
into Eqn(7) these values lead to a maximum contact angle of about
120 0 for water/air, but values close to 180 0 for water/oil
interfaces on nonpolar solids, in agreement with experimental
results. (The ultimate reason for the much lower contact angles
of water/air interfaces is the absence of dispersion interactions
in air.) For such nonpolar solids 0SL is negligible according to
Eq(6) and the critical surface tension ° is equal to 0SA. The
lowest reported value is about 20mNm-1 cr for solids such as
polytetrafluorethene [26).

The conclusion so far is that nonpolar solids are not wetted by


water because their surface tension is too low, and that they
should be naturally floatable. Minerals falling in this category
are molybdenite, stibnite, sulfur, coal, amoung others [19). For
high-energy surfaces, on the other hand, where polar interactions
do play a substantial part, the critical surface tension a is
much higher. To a certain extent its value depends on the li~tids
used [27,28), and it can no longer be equated to 0SA' as 0SL can
no longer be neglected. Within these limitations -the critical
surface tension a is a useful empirical parameter to express
cr
wettability and floatability.

The category of minerals like clean metals, oxides and quartz,


for which ° exceeds the surface tension of water are, by
definition, 'i:1>mpletely wetted by water. They require surface
modification by surfactant adsorption in order to develop a
finite contact angle and so become floatable.
85

Effect of Surfactant Adsorption at Equilibrium

Surfactant adsorption is capable of changing a high-energy


hydrophilic solid into a low-energy hydrophobic one and vice
versa. Adsorption alters the values of any of the interfacial
tensions in Eq(l) according to Gibbs' adsorption law:

do
i r (i SA,SW,WA) (8)
dll i

where 11 is the thermodynamic potential of the surf ac tant, and r


its surface excess at the interface indicated. In the simplest
case of ideal solution behaviour

dll = RTdlnc (9)

if c is the surfactant concentration in one of the phases. At


equilibrium the thermodynamic potential \.I is uniform throughout
the system, regardless of solution ideality, and so is the
variation d\.l caused by surfactant addition. The resulting
adsorption of surfactant can alter the contact angle only if i t
alters the ratio between (OSA - 0SW) and 0WA in Eq(l). Therefore,
the effect of surfactant 1S most conven1ently represented in
terms of the quantity 0WA cos e (=OSA - 0SW), which is known as
the adhesion tension, as a function of 0101A' In such plots, any
straight line through the origin is the locus for a particular
contact angle value, from 0 0 for point on the +45 0 line up to
180 0 for points on the -45 0 line (see Fig.2). One advantage of
such a representation is that it yields direct information on
the adsorptions without prior knowledge of solution ideality,
because the slope of such a line is given by [29):

d(o - ° r - r
SA SW SA SW
do r
WA WA (10)

Thus a positive slope of an adhesion tension ~ interfacial


tension curve immediately reveals that r SA must exceed rSW' This
is a situation often found in flotation systems, as was firs t
noted by De Bruyn et al [30). In systems where surfactant is
confined to one of the liquid phases - in flotation this is
invariably the aqueous phase Eq(10) provides a means of
evaluation the adsorption at the interface between the two other
phases, i.e., r SA ' provided the other two adsorptions are
measured independently.

The experimentally measured effect of surfactant adsorption on


the contact angle is determined largely by the polarity of the
86

aWA COS e /~}ocus


+40 (mNm-I ) // e =0
///

o
aWA (mNm-I )

-40

Figure 2. Adhesi.on tension .y.!. interfacial tension 0WA for solid


paraffin/water/air.
* surfactant-free system; 0 with Aerosol OT [31];
• with Tergitol [31]; with butyric acid [32].

solid surface. Nonpolar surfaces have been studied most


extensively, and their contact angle behaviour is now
quantitatively understood. Typically, surfactants produce a large
decrease in contact angle on nonpolar solids for the air/water
interface but hardly any effect on the angle for oil/water
interfaces. For example, the addition of surfactants--to the
system solid paraffin/water decreases the contact angle from
about 120 0 to nearly zero at the concentrations where the surface
tension reaches its lowest value. (For 1lIOre detailed information
on similar systems the reader is referred to a recent review
[33]).Quantitatively, the adhesion tension 0WA cos o.y.!. 0WA
function in such systems has two remarkable feacures:

(1) 0WA cos e is a linear function of 0WA over the entire range
of surfactant concentration from zero up to the limiting
concentration [33-36]

0WA cos e= - 0WA + C (ll)


87

(ii) experimental results for different surfactants all coincide


on one single line, described by Eqn(ll}, even though both
the O'WA ~ c curves and the e vs c curves are widely
different for different surfactants.

Both points find a surprisingly simple explanation [36) in the


behaviour of the adsorptions which determine the slope according
to Eqn(10}. The -1 slope in Fig. 2 is explained by the
adsorptions r SW and rWA- being approximately the same while the
adsorption r SA is neg~igible, as one might expect for an
interface between two completely nonpolar phases. The coincidence
of results for different surfactants on a single line means that
the equali ties r SW = r \rIA and r SA = 0 are valid regardless of
nature and amount of surractant added.

A change of line can be obtained only by changing the composition


of the surfactant-free system. For example, replacing air by
nonpolar oil shifts the adhesion tension line downwards (because
the surfactant-free system has a lower value) while preserving
the -1 slope (see Fig.3). This simple parallel shift of the
adhesion tension line represents a very different effect of
surfactant: in the system with oil the contact angle changes very
little from its value of nearly 1800, while in the system with
air it decreases from 1200 to nearly zero. In both cases Eq(ll)
is obeyed, and the adsorptions are the same, only the value of C
is different. It is the value of C, i.e. the adhesion tension
extrapolated to 0'=0, which determines whether the contact angle
decreases (C > O) or increases (C < O). As the surfactant-free
system is included in Eqn( 11), in both cases the value of C can
be estimated [35) from Fowkes' theory by means of Eqn [7):

(12)

where L once again stands for the nonpolar fluid. In case L is an


oil, all three parameters in Eqn(12} have roughly similar values
of about 20mNm- 1 , leading to very low values of C, i.e. to nearly
constant contact angles. This is confirmed by the experiments in
Fig.3, and a120 on other nonpolar solids, yielding values of
about 0.1 mNm 1. This means that surfactants have very little
effect on the contact angle until the interfacial tension O'LW
reaches extremely low values, where an abrupt decrease takes
place with the contact angle going through 90° for O'LW = C.

On the other hand, when the nonpolar fluid L is vapour or air, 0L


in Eqn(l2) is replaced by zero and this results in appreciable
positive values of C( .. 30 to 50 mNm- 1) and hence to decreasing
contact angles. This is confirmed by the experiments in Fig.2 and
many other nonpolar solids [29,33).
88

+40

80
o
a (mNm-I)

-40

Figure 3. Adhesion tension vs interfacial tension for


polytrafluorethene/water/paraffin oil.
experimental results for oil-water [36]
~ experimental results for air-water [22].

The simplicity of this picture is progressively lost when the


polarity of the solid is increased,i.e. for increasing values of
the adhesion tension in the surfactant-free system [33].
Surfactant addition now produces non zero r SA ' increasing
differences (rWA - r ) and, as a result, an increasing slope of
the adhesion tension~ine according to Eqn(10), as illustrated in
Fig.4. As long as the solid is not too hydrophilic., i.e. as long
as 8 > 0 in the pure system, the slope is still constant and the
value of C positive, hence the contact angle is decreased by the
addition of surfactant.

For most hydrophilic solids, with 8 close to zero in the pure


system, the slope is no longer constant, as illustrated in Fig.5
for magnetite [19] and platinum [37]. In both cases the contact
89

aWAcos8
(mNm- I )

+40

-40

Figure 4. Adhesion tension.!.!. interfacial tension (\lA for solids


of increasing polarity. From experimental oata [33]. ~
solid paraffin; • talc [32]; cellulose; 0 nylon [99]

angle passes through a maximum with increasing surfactant


concentration, i.e. with decreasing 0YA' The curve for platinum
illustrates a double reversal of wetting. First, at high o\lA' r Sf!
is much larger than both r sw and r WA' which means a very hig
value of the slope and an increase 1n a from 00 to 93°. In this
stage the solid is being made hydrophobic by a first layer of
surfactant molecules. Onto this hydrophobic surface a second
layer of surfactant can be adsorbed, leading to the usual pattern
of hydrophobic solids: a -1 slope and a return of the contact
angle to low values. In such polar systems the initial adsorption
can have the chartacter of chemisorption, which is highly
specific, and the adhesion tension function is no longer the same
for different surfactants. For example, the well-known dewetting
of silica and clean metals by cationic surfactants (Fig.S) is the
result of the particularly high SA adsorption for these
surfactants. Such high adsorption requires a densely packed
monolayer, which is more easily formed with straight-chain
surfactants than with branched chains. Hence a curve like b in
Fig.S is readily obtained with primary amines but not with
secondary ones, a factor which favours the primary amines in
flotation.
90

aWAcos8
(mNm- I )

+40

o
aWA(mNm-I )

Figure 5. Adhesion tension ~ interfacial tension a WA for highly


polar solids with alkylammonium salt solutIons.
a: curve for hematite [19] with C12 salt; b: curve for
platinum [37] with CIO salt at pH = 9.3;
o nonequilibrium data for quartz with C12 salt at pH>
9 (see Section Cl).

Similar specificity of hydrophilic solids has been noted [19] in


contact angle studies with oil/water interfaces. Contact angle
changes in these systems generally appear to be smaller than for
air /water, although Aronson et al find large increases in e in
the system silica/water/tetradecane, withouty a maximum [38].

To summarise, the effect of surfactant adsorption on equilibrium


contact angles is quantitatively understood for nonpolar
surfaces. Adsorption is non specific in these systems, being the
same at the two interfaces sw and WA (or WL) and virtually zero
at the third interface. This results in a single adhesion tension
line for different surfactants described by Eqns(lO)-(12),
representing large decreases in e (wetting reversal) for
air/water but almost constant e for oil/water (Fig.3). With
increasing polarity of the surface both r SA and (r WA - rSW)
91

increase. The linearity and non specificity of the adhesion


tension function are preserved as long as the solid surface is
not too polar (1. e., as long as 6 > 0). For the most polar
surfaces (Le.6 = 0 in pure system) adsorption can be highly
specific, and the adhesion tension function highly curved as a
result of double reversal of wetting (Fig.5b).

A final remark on equilibrium contact angles must be that,


although there is a general agreement that 6 should be finite for
flotation to be possible, opinions ·differ on which function of 6
correlates best with flotation recovery. Such a correlation has
been sought both with 6 itself and with the adhesion tension and
with "work of adhesion" functions (O'JolA. [I-cos 6] for vapour and
O'WA [1 + cos 6] for water) [19]. Tlfe various expressions all
contain the same basic information on 6 and O'WA but the criteria
derived from them do not always lead to the same predicted effect
of surfactant addition. For example, in systems obeying Eqn(ll)
the work of water/solid adhesion is constant, hence in terms of
this criterion floatability should be indifferent to surfactant.
In terms of the other three quantities, however, surfactant
addition should be bad for flotation in these systems. The lack
of conclusive experimental evidence in favour of any criterion
reflects the importance of factors other than the equilibrium
contact angle. One other factor arises from the non equilibrium
conditions under which flotation is inevitably conducted,
resulting in interfacial tensions and contact angles being unable
to reach equilibrium values.

Nonequilibrium Contact Angles

Considerable deviations from equilibrium values have been


attributed to either nonequilibrium adsorption, hence non-
equilibrium tension at any of the three interfaces, or to
movement of the three-phase contact line over the solid surface.
Both mechanisms are likely to operate Simultaneously in
flotation, but they have only been studied separately so far.

Nonequilibrium adsorptions

Large effects of surfactant equilibrium have been observed in


flotation studies, with dy,namic contact angles far exceeding the
equilibrium 6 in some cases and being much smaller in others. In
a quantitative example quoted by Finch and Smith [19] the contact
angle of an air/surfactant solution interface on quartz decreased
from 80 0 to zero in a period of minutes after attachment of the
air bubble, and this decrease was correlated with the decreasing
value of the dynamic surface tension O'WA. These data have been
includ~d in Fig.5, where they appear to De surprisingly close to
the equilibrium adhesion tension line of platinum. The equil-
ibrium adhesion tension line for the quartz system is probably
92

not too dissimilar from that for the platinum system, so the
proximity of the nonequilibrium points to the equilibrium line
strongly suggests that the dynamic surface tension O'UA alone
determines the contact angle in this case. This sugges-Uon is
less surprising when it is considered that in the circumstances
of these experiments the adsorption rSU is probably close to its
equilibrium value, and that the interfacial tension O'SA is
practically constant in the ascending part of the platinum curve,
where Eq(ll) is obeyed. Hence the dynamic contact angle is
probably determined by the kinetics of adsorption at the
air/water surface alone.

Such simplifying circumstances will greatly facilitate the


interpretation and the prediction of dynamic contact angles.
Time-dependent or dynamic surface tension is a fairly well-
documented topic [39], and a recent review [40] presents a
quantitative treatment of the relaxation mechanisms responsible
for it. These include diffusional interchange between solution
and surface, exchange with micelles and structure formation in
the surface. Characteristic time scales for these mechanisms vary
from a fraction of a second to many minutes, depending on
concentration and type of surface active ateria.!. Particular
attention is paid to ultra-low tension « v.1 mNm 1) which can
persist for long times in compresseo parts of oil/water
interfaces. This may lead to interesting possibilities for oil
flotation, since contact angles in many solid/oil/water systems
exhibit the most drastic changes when the interfacial tension is
almost zero. Uetting reversal from 00 to 1800 for desirable
compounds of a slurry (and from 1800 to 00 for undersirables)
might thus be achieved in non-equilibrium systems where the
equilibrium contact angle is hardly affected at all.

Movement of three-phase contact line

This mechanism includes both the impaction of fluid drops with


the solid [41] and any subsequent movement of the contact line
across the solid surface [42]. Drop impaction effects can include
bouncing of the drops or bubbles [43] and the parallel phenomenon
of bouncing of solid particles from bubbles [1]. These effects
are of obvious importance to flotation, and large variations in
contact angh have been reported [43] within very short time
intervals « v.1 sec). Detailed studies of the process have only
just started thanks to the development of high-speed
cinephotographic techniques [41].

The effect of contact line movement after impaction has been


studied more extensively [44,45,46] and appears to be parti-
cularly significant on heterogeneous solids. Even on nominally
smooth surfaces contact angles can change virtually from 0° to
93

180 0 with increasing velocity of the contact line. The limit of


1800 has been observed [45] for velocities so high that viscous
forces alone control the interface shape, with negligible effects
of interfacial and inertial forces. This will occur at very high
values of the capillary number Ca (=nv/o) combined with low
values of the Weber number. Of empirical relationships put
forward the simplest applies to very low capillary numbers [47]:

cos e = cos eeq - 2/(nv/o) (13)

Basically, theories proposed [44,47,48] regard the dynamic


contact angle as corresponding to a nonequilibrium curvature (r),
and hence to a noneequilibrium Laplace pressure 6P:

£
6P = r (14)

and link the excess Laplace pressure to viscous flow of the


liquid. Thus the rate of line movement is limited by viscous
resistance of the liquid flowing out of the wedge-shaped corner
region where the three phases meet [48]. Quantitatively, however,
the hydrodynamics of liquid flow near a three-phase contact line
is extremely complex [49], and these are no prospects at present
for anything better than extremely simplified models.

The relevance of these phenomena to flotation lies in the


possibility that solid/air contact may be lost if the newly
created contact area cannot expand sufficiently rapidly. If
liquid retreat from the solid is not fast enough because of
viscous resistance to contact line movement, then the hole
initially created in the wetting film may close up again (50].
This point is futher discussed below.

THINNING AND RUPTURE OF WETTING FILMS

In systems with a finite contact angle the liquid layers


separating solid and sir or oil will eventually break because
such rupture decreases the free energy of the system. The
question is whether the processes of thinning and rupture of the
wetting film can take place in. the time available for it. The
time of contact of bubble and solid in a typical flotation cell
has been estimated [1,2,51,52] as of the order of a few
milliseconds for particles of ~ 100~m size. Obviously, i f the
time needed for film thinning and rupture exceeds this contact
time, flotation is impossible in spite of a favourable contact
angle [3,4]. In fact, Blake and Kitchener [4] found metastable
films to persist for considerable periods of time on hydrophobic
surfaces with air/water contact angles of up to 100 0 , and Aronson
and Princen (53] observed the same phenomenon in solid/water/oil
systems.
94

Recent years have seen such attention paid to the mechanism and
the kinetics of film thinning and rupture, which is regarded by
some [2,54-55] as the most important stage in flotation.
Mechanisms of film breaking have been identified for both the
early stages of a film's life, at relatively large thicknesses
where the spheres of influence of the approaching interfaces do
not yet overlap, and for the later stages where the film has
thinned down to dimensions where interaction forces across it
determine the behaviour. These two stages merit separate
consideration.

Instability of Thick Films

Gradual and uniform thinning of liquid films thicker than roughly


O.l~m in general occurs by drainage under the influence of
gravity and/or suction from the Plateau borders, i.e. the curved
transition regions separating thin films from the bulk liquid.
This drainage is a viscous flow of liquid between two walls, one
of which is solid in flotation systems. Depending on the
properties of the air (or oil)/water interface bounding the film
on the other side, films are either fast or slow draining. In
slow-draining films, adsorbed surfactant causes the air/water
surface to be virtually incompressible and to behave like a solid
wall at which liquid velocity is zero. Thinning of such slow-
draining films is governed by Reynolds' equation, which for a
circular film takes the form [57].

(15)

where P is the effective pressure responsible for thinning.


e
Squeezing out liquid from between two incompressible walls is far
too slow a mechanism to effect a decrease in film thickness down
to molecular dimensions in the available contact time. The only
possibility of speeding up drainage from relatively thick films
occurs when the air-water surface is mobile and can move along
with the draining liquid. Not only does this lead to uniform
drainage being faster because of the appearance of an extra
factor of four in Eq(15) but it can also give rise to non uniform
drainage caused by surface tension gradients along the moving
interface. Such gradients produce a tangential stress in the
surface, which makes the adjoining liquid move in the direction
of the higher tension (Marangoni effect). Several examples are
known of destabilising surface tension gradients induced by
transport of surface tension lowering compounds across the film
surface into the film [58-62]. Diffusion of acetone from oil
droplets into aqueous film has been shown to promote attachment
of glass to oil [62]. The explanation is that the central part of
95

the film is more sensitive to such transport because it is


thinner than the periphery, so its surface tension will be
decreased more and the resulting Marangoni flow destabilises the
film. The process is schematically illustrated in Fig. 6.
I I
I I
I I
<THIGH HIGH

"
LOW

SOLID
Figure 6. Response of liquid film to transport of compound which
lowers the surface tension
------ direction of transport
direction of Marangoni flow

Quantitatively, the effect is governed by the resistance of the


surface against deformation, which can be expressed in terms of
the Gibbs elasticity [63] of the film .Most of the work on Gibbs
elasticity has been done in connection with the stability of
foams, where thin films are bounded by two identical fluid
interfaces [64-69] The Gibbs elasticity Ef of such free films is
defined as:

(16)

This equation reflects that local variations in area A of a film


element lead to variations in 0, simply because after extension
by an amount dA there must be redistribution of surfactant
leading to variations dc and dr which produce variations do. If
such re-equilibrium between surface and film liquid is the only
process happening it is possible to express E in terms of film
thickness and derivatives of the equilibrium relationship between
o,r and c:

-do~lnr
tE = ---::;~ (17)
f l+th dc /dr
Gibbs elasticity has long been suspected of being an important
parameter in stabilising thin films and foams [70]. The relation-
ship between stability and Gibbs is an indirect one. however.
96

a.
1

0.1

0.01

0.1 1 10 100
h/ho
E (mNm- I ) b.
30

20

10

o~------------~-------------L--------~
0.05 0.10
C(mol m- 3)
Figure. 7. a) Thickness dependence of Gibbs elasticity according
to Eqn(17). t E in units E = - da/dlnr; h in units
h = 2dr/dc 0
b) C8ncentration dependence of Gibbs elas ticity;
numerical examples calculated for Langmuir
adsorption, from data of ref.69.
97

Both the earliest [63] and the latest [69] theories hold that
Gibbs elasticity can impart stability to a film only if it
increases when the thickness of the film decreases: it is the
thinnest part of a film which is in most danger of rupture and in
need of resitance against further deformation. In conditions
where Eq(17) applies, i.e. in films undisturbed by processes
other than re-equilibration of surfactant in the film, it is
clear that at given concentration Gibbs elasticity is always
higher in the thinner parts, thus tending to stabilise the film:
see Fig 7a. However, in a draining film with mobile surfaces,
continued surface expansion means that both the surface and the
film liquid will suffer depletion of surfactant, i.e. the
concentration c will decrease. A typical example of the
concentration dependence of E is given in Fig. 7b. Numerical
values here were calculated assuming a specific relationship
between o,r and c, but the occurrence of a maximum in the curves
is general [66]. It is only on the left-hand side of the maximum
that surfactant depletion in a thinning film can lead to a
decrease in E, and hence to destabilisation of the film, as
argued in a recent review (69). In this region, i.e. at fairly
low concentrations, films are liable to rapid disproportionation
into thinner and thicker parts, as the thinner parts offer less
and less resistance to further thinning.

Thus, the criterion for destabilisation of films by the Marangoni


effect is that during film thinning the elasticity should obey
the inequality

(18)
~ '> 0
dh

For films obeying Eq(l7) this means that the elasticity must be
some distance to the left of its maximum in the E vs c curve:

dh
de (19)

Much greater scope for such destabilisation is found in films


which are disturbed by mass transfer across the surface, as in
the example of Fig.6. It has been argued [61] that such mass
transfer under certain conditions leads to negative film
elasticity, i. e. to a negative resistance against further
extension, and to extremely rapid thinning of the film.

The quantitative description of surface tension gradients and


their effect on film destabilisation is far from complete as yet.
Surface elasticity has only recently been introduced [71,72] into
classical hydrodynamic instability theory, and developments are
continuing.
98

Instability of Thin Films

When films have survived the danger destabilisation described


during the early stages of thinning and have reached thicknesses
of a few hundred nm, interaction forces between the two
approaching interfaces come into play and drainage can no longer
be regarded as caused by gravity and/or capillary suction alone.
At this stage films often appear to exhibit a "critical
thickness" at which they become unstable and break suddenly [73].
It is the mechanism of this sudden rupture which has become much
better understood.

Interaction forces in thin films vary with thickness in a


generally complex fashion because attractive and repulsive forces
falloff with increasing distance between the surfaces in
different ways. In classical colloid stability theory [74,75] the
attractive force is usually the Van der Waals dispersion force,
while repulsion results from the overlap of similarly charged
double layers. In flotation sys tems, however, both these forces
can undergo role reversal because the thin film separates two
different phases. Electrical attraction instead of repulsion is
found when solid and bubble are oppositely charged, as
demonstrated by Bleier et al [76] for oxide and quartz/amine
flotation. It has been suggested that a main function of
surfactants in flotation is to decrease, if not actually reverse,
the surface charge. Van de Waals forces, too, can change sign in
three-phase systems, turning from attractive into repulsive, and
in flotation this is likely to be the rule rather than the
exception [52,78]. A detailed discussion is given by Aronson and
Princen [52] with reference to oil flotation. (Some more data on
Van der Waals repulsion are in a recent review [79]). A detailed
discussion of interaction forces is outside the scope of this
review.

Whatever the character of the forces, all possibilities can be


covered in terms of the concept of disjoining pressure defined by
Derjaguin [80]. According to this concept, interaction forces
make the film behave as if there were an excess pressure, n,
acting normal to the film surface and opposing thinning. Thus, n
equals the pressure that must be applied to the film to counter
this excess and so keep the film at the given thickness. A
schematic picture of combined repulsion and attraction i f given
in Fig.8.

A condition for the film to be stable against disproportionation


into thicker and thinner parts is that the disjoining pressure
should increase with decreasing thickness. There is much evidence
[4,38,76,81] establishing a direct link between disjoining
pressure and floatability, indicating that a necessary condition
for floatability is:
99
II

Figure 8. Schematic example of disjoining pressure IT leading to


films being unstable (U) or stable (S) against
disproportionation into thinner and thicker parts.
contributions of repulsive (upper curve) and
attractive (lower curve) interactions.

(20)

Whether this condition is sufficient depends on the kinetics of


the rupture process. Once again, as in the case of the thicker
film, a gradual thinning of the film by Reynolds flow (Eq(l5»
does not account for the observed suddenness of film rupture. The
mechanics of the rupture process has long been an undeveloped
area, but recent work on the growth of spontaneous fluctuations
has provided a new impetus! Scheludko [82] was first to propose
that thin films at a critical thickness become unstable with
respect to small spontaneous surface deformation such as occur on
any liquid surface as a result of thermal motion. In films with
<SIT/ <Sh < 0 these small fluctuations do not lead to instability
because their growth would result in an increased surface area
and hence to a higher free energy of the film.

On the other hand, for films with <SIT/<Sh> 0, e.g. because of Van
der Waals attraction, the increase in surface area can be more
100

than offset by the increased attraction in the troughs of the


fluctuations. Growing surface fluctuations can thus initiate a
rapid disproportionation of the thin film in much the same way as
Marangoni effects can destabilise a thicker film.

Quantitative treatments for the initial stage of the


disproportionation describe the surface fluctuations as a sum of
Fourier waves, each characterised by a frequency and a damping
coefficient, like the macroscopic waves that can be generated on
a free liquid surface. The dispersion relation of these waves is
found by solving the hydrodynamic equations of motion with
boundary conditions incorporating both the elastic resitance of
the surface and the disjoining pressure of the film. In its most
general version [83,84J the theory is very complex; the reader is
referred to these papers for details and references to earlier
simpler versions. Some qualitative aspects worth mentioning are:

(i) Of all possible thickness fluctuations in the film those


with a wave length smaller than a critical value A , are
cr
unable to grow because for these smaller waves the gained
attraction is not enough to offset the increase in
interfacial area. This means that very small films,e.g.
films formed on very small particles, cannot be ruptured by
this mechanism.

(ii) Of the fluctuations that do grow spontaneously there is one


which can be predicted to grow faster than all others. This
is because fluctuations with a wavelength smaller than the
wavelengths of maximum growth, A , have a smaller driving
force while for wave lengths largermax than Amax 1°1qu1°d mus t
be transported over larger dis tances, which takes longer.
The wavelength of maximum growth depends only on the ratio
between 0 and OIT/ oh , reflecting the competition between the
surface forces promoting damping and the interaction forces
promoting growth:

A
max
= A"'n12 = 2n (21)

It is the growth coefficient of this fastest-growing


fluctuation which has been equated to the inverse of the
rupture time of the film:

t 24 no
rupt .. h 3 (oIT/6W- (22)

for films with incompressible surfaces bounding by a gas


phase. Rupture times calculated [84J for films on solid
support were higher by a factor or two, because
fluctuations act only on one side of the film. Not
101

surprisingly, the presence of a viscous medium on the other


side of the film was also found to increase rupture time
[85].

(iii) The effect of surface elasticity caused by adsorbed


surfactant is to increase rupture time by a factor of up to
four, the transition from mobile to rigid surface behaviour
taking place in a range of quite low values of the
elasticity E defined by:

do
E
dlnA (23)

This means that very small amounts of surfactant are


capable of rendering the surf ace virtually incompressible.
It should be noted, however, that this applies only to the
intial stage of the disproportionation process. It is
possible that higher elasticities become crucial in the
later stages of catastrophic growth of the fluctuations.
These later stages have proved inaccessible to theory so
far.

(iv) Rupture times calculated from Eqn(22) are extremely


sensitive to thickness h. In the simplest case, where only
Van der Waals attraction is accounted for, n varies
according to h- 3 , implying a h5 dependence for the rupture
time.(Donners & Vrij[86] have extended the theory to
include electrical repulsion in n). To complicate matters
further the film must be presumed to continue uniform
drainage according to Eq(l5) , which means that the
condition for fluctuation growth changes with time. Methods
have been proposed [86,87] to evaluate the total life time
of a film under the influence of both uniform drainage and
instability growth. With these methods it should be
possible to estimate the critical thickness at which the
film become unstable under the influence of an applied
pressure, such as border suction and/or gravity, and
ultimately the total life time of a film.

Summarising, the parameters governing the rupture of thin films


at thickness where interaction forces are active are the
disjoining pressure n, its derivative on/ oh ' the surface tension
0, the surface elasticity E and the viscosities of film liquid
and surrounding media. The rupture mechanism requires the
development of waves with a wavelength given by Eq(21) and,
therefore, cannot be operative for solid particles smaller than a
critical size.

A final problem can occur after rupture of the film. The hole
102

formed in the film when i t breaks is likely to be smaller than


the particle size. This means that the three-phae contact line
may initially have such high curvature that growth or
diappearance of the dry spot formed is governed by line tension:
see below.

Instability of Holes after Film Rupture

Two mechanisms have been proposed which may thwart successful


attachement of solid to air by preventing growth of the three-
phase contact line.

The first mechanism was originally described [70] for holes in


foam films, where there is no three-phase contact, but it should
also apply to holes in solid-supported films where there is. De
Vries demonstrated that the initial growth of holes with a
diameter smaller than the film thickness is opposed by an energy
barrier because growth in this stage requires an increase in
interfacial area. Fig.9 illustrates the simple geometrical model
used and the analogous situation for a film on solid support. The
argument is easily put in terms of the Laplace pressure AP at the
edge of the hole where the surface has two principal radii of
curvature of opposite sign:

AP = P
WAh
- P = a (1. - l......)
r (24a)
h
For holes sizes 2r h < h the Laplace pressure is negative,
promoting closure of the hole, while for 2r > h i t changes sign
and promotes growth. The model is a gross oversimplification of
reality in assuming the cross section of the film edge to be
semi-circular and in neglecting the effects of disjoining
pressure on AP, but in a more refined model the two principal
radii of curvature will still be of opposite sign, and this must
lead to a critical hole size at which AP changes sign. The
analogous situation for a film on a solid surface in Fig.9b is
described by:

AP =a ~ 1 - cos a _ 1_ )
h rh (24b)

Critical hole size for these films depends on the contact angle:

h
rcr 1 - cos 6 (25)
confirming once again that holes cannot be formed in wetting
films i f 6=0

The argument of critical hole size size is reminiscent of that


presented in Instability of Thin Films, above, for the growth of
103

a. ). 2fh
.( jh
AIR

b.
\ ~ ]h
.. 2fh
..
SOLID

Figure 9. Simple model for holes in free films (a) and films on
solid support (b).
------ film before rupture.

surface disturbances in films for wave lengths smaller than the


critical wave length (cf Eq(21».

The mechanism proposed by Scheludko et al [2] in their capillary


theory of flotation relies on the existence of a linear tension
of the three-phase contact line. Line tension, a concept first
mooted by Gibbs and also taken up in recent years by Princen
[88], de Feijter and Vrij[89] among others [90,91], is defined in
a way formally analogous to surface tension in Eq(2):

T = (26)

Thus T is the force required for an increase in the length of the


contact line. Unlike surface tension, line tension can be either
positive or negative, and examples of both possibilities have
been experimentally found. If positive, line tension clearly is a
force opposing the formation of three-phase contact and, in fact
one experimental method [92] of measuring line tension derives
its value from the critical size of solid particles just
104

es tablishing contact with air bubbles. Particles smaller than


this critical size are not recoverable by flotation.

Not a great deal is known about line tension from either an


experimental or a theoretical point of view as yet. The
experiments [92] just referred to yielded values of about 10-10 N
(10- 5 dyn) for the system glass/air/surfactant solution (0.01 M
cetyltrimethylammonium bromide) using a critical particle size of
7~m. On the other hand, negative values of about -10-10 H were
reported for the system hexadecane/air/water [93]. Other
experimental results [94,95], bopth positive and negative, apply
to systems where the part of solid is played by very thin black
films (h of the order 10nm) in equilibrium with thicker film and
air. These not-strictly-three-phase systems are the only systems
for which a theoretical interpretation is presently available
[89], which correlates line tension with the variations in
disjoining pressure in the transition region between thin film
and bulk liquid. Line tension in these systems is closely
connected with the contact angle of the thin film. Thin films
exhibiting a contact angle with thicker liquid layers [96,97]
enjoy growing interest as model systems for the study of
interaction forces leading to disjoining pressure.

Line tension and capillary pressure have here been described as


two different mechanisms for the prevention of three-phase
contact, and also as different from the critical fluctuation
mechanism decribed in Instability of Thin Films, above. This
appearance of three different mechanisms may be deceptive. All
three describe the critical size of a disturbance/hole as
reflecting the competition between the forces of surface tension
and of interactions in thin films. In a general approach of
systems containing thin films and/or highly-curved boundaries the
parameters surface tension, capillary pressure, disjoining
pressure, line tension and contact angle are all interconnected.
It is believed that in such a general phenomenological treatment,
which is still awaited, the three mechanisms indicated here will
turn out to represent three different ways of looking at the same
phenomenon.

CONCLUDING REMARKS

This review has been incomplete and may seem to have made light
of several important aspects, such as contact angle hysteresis,
the effects of electrical charge and potential [11,98] and those
of particle shape [52]. These aspects were felt to have been more
than adequately covered in existing literature. Most of the
attention in this review has been focussed on the effect of
surface active materials on interfacial tensions, contact angles
and film thinning. Contact angles can be interpreted and
105

predicted most conveniently in terms of the adhesion tension (o~


cos e) vs interfacial tension (a\~A) relationship. An additional
advantage-of this relationship is ~hat it is the same in and out
of equilibrium, under certain conditions which appear to be
relevant for flotation systems. The fluid-fluid interfacial
tension 0l.lA is also of paramount importance in the thinning and
rupture of wetting films which must precede the establishment of
three-phase contact. The quantitative description of gradients in
0WA in terms of film elasticity and their effect on film rupture
is still far from complete, and the effect of mass transfer
through the interface in particular deserves further attention.

LIST OF SYMBOLS

A area of interface (m2 )


c surfactant concentration (mol m- 3 )
C constant in eq(ll) (Nm- l )
Ef Gibbs elasticity of free liquid film (Nm- l )
F free energy (J)
h film thickness (m)
L length of contact line (m)
p hydrostatic pressure (Nm- 2 )
r radius of curvature (m)
rf radius of circular film (m)
rh radius of hole in film (m)
R gas constant (J mol- 1 K-I)
t time (s)
T temperature (K)
v velocity of contact line (ms-I)V volume of phase (m 3 )

r surfactant adsorption (mol m- 2 )


E surface elasticity modulus (Nm- 1 )
n liquid viscosity (Ns m- 2 )
e contact angle
A wave length (m)
p thermodynamic potential (J mol-I)
IT disjoining pressure (Nm- 2 )
a interfacial tension (Nm- l )
T line tension (N)

SUBSCRIPTS

A air
cr critical value
e effective
eq equilibrium
L organic liquid
max maximum growth
rupt rupture of film
S solid
W water or aqueous solution
106

SUPERSCRIPT

d Van der Waals dispersion forces

REFERENCES

1. Philippoff,W., Trans.Amer.Inst.Min.Eng., 193,386,1952.


2. Scheludko,A., Toshev,B.V., Bojadjiev,D.T.,J.Chem.Soc.,
Faraday I, 72, 2315, 1976.
3. Scheludko,A., Kolloid-Z. 191,52, 1963.
4. Blake,T.D., Kitchener,J.A., J.Chem.Soc. Faraday I, 68, 1435,
1972.
5. Young,T., Phil.Trans., 95, 84, 1805.
6. Johnson,R.E. J.Phys.Chem., 68, 1655, 1959.
7. Gibbs,J.\J., The Scientific Papers, Vol.1, Dover, New York,
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III

SOME ASPECTS OF THE PHYSICAL CHEMISTRY OF SOLID/WATER INTERFACES

P.L. de Bruyn

Vanlt Hoff Laboratory of Physical and Colloid Chemistry,


University of Utrecht, The Netherlands

ATOMISTIC DESCRIPTION OF THE INTERFACE [1,2,3]

Creation of a solid surface as by cleavage involves the


disruption of the regualr periodicity of the crystal lattice
through the breaking of chemical bonds. The different
environement of the topmost atomic layers in a crystal compared
to that of parallel layers inside the bulk solid usually results
in a rearrangement of the surface atoms, while the special
position of these atoms and the unsaturated bonds associated with
them promote a strong interaction with various species in the
surrounding medium. This interaction between the solid surfaces
and ambient is called adsorption and will be the main topic of
this chapter.

Reactivity of the surface

The reactivity of a solid surface as expressed by its adsorption


behaviour and its electrical properties has or~g~n in the
presence on the surface of active centres to be referred to as
surface sites. The density of these sites will be of the order of
lOl9/ m2, about one site for each surface atom or ion on a clean
uniform surface. The activity of these surfaces sites will depend
on the nature of the bond between the atoms or ions in the
crystal lattice and the structure of the particular
crystallographic plane that terminates the solid.

In the bulk covalent germanium crystal, for example, each atom is


covalently bounded to four neighbors by four elctron-pair bonds.
The germanium surface atoms are incompletely coordinated and at
least one dangling bond should be directed out from the surface
per surface site.
ll2

(100)

x x x

(110)

A;
x x x

~.
----

-1 ~ r'
'..J
----

-,
r'
',,:
----

.'~-', "-~-,
\. I
~

--- (111 )

Figure 1

configuration of the low-index planes «100), (110) and (111))


of a germanium crystal after Boddy [52]
X is a monovalent species covalently bonded to the surface atoms
113

Fig.l demonstrates the surface configuration of the low index


planes of the diamond-type germanium crystal. On the (100) plane
each surface atom is bonded to two atoms in the layer below while
on the (Ill) face each surface atom is bound to three in the next
lowest layer. On the (110) face each surface atom is bound to two
neighbouring surface atoms but to only one atom in the underlying
layer. The number of dangling bonds and the number of surface
atoms per m2 surface are

(100) 1.25 x 10 19 dangling bonds; 6.25 x 10 18 surface atoms


(110) 8.83 x 10 18 dangling bonds and surface atoms
(Ill) 7.22 x 10 18 dangling bonds and surface atoms

These dangling bonds are in principle available to form strong


covalent bonds with adsorbing foreign species. With no foreign
species present (for example, in high vacuum surroundings) the
surface layer of Ge atoms distorts and the energy of the system
is lowered by reconstruction of the surface layer so that the
dangling bonds can overlap somewhat with each other.

The dangling bond or surface molecular orbital is commonly


referred to as a surface state. This concept is used to explain
the effect of the surface of a semiconducting crystal such as
germanium on the electronic properties of the solid. We briefly
recall that the electronic conductivity of solids (metallic,
semiconducting or insulating) may be explained quite
satisfactorily by the band theory. This theory which recognizes
as its basis the existence of a periodic electric field in an
infinitely large crystal. Due to overlap of atomic orbitals, the
single electronic levels (orbitals) for each atom in a crystal
may then be combined and broadened into a band of delocalized
molecular orbitals. The presence of a partially filled band of
(valence) molecular orbitals accounts for bonding and electrical
conduction in metals.

For a semi-conductor or insulator the bands of interest are the


valence band occupied by valence electrons and the essentially
unoccupied conduction band separated from the valence band by an
energy gap. Electrons must be excited into the conduction band
from the valence band were the solid to conduct electricity. The
major distinction between a semiconductor and insulator lies in
the width of the forbidden gap separating the two bands. The
width of the gap is larger in the case of insulating crystals.

Returning to the dangling bond in the surface of a germanium


crystal we note that whereas in the undisturbed periodic electric
field within the cry tal , electronic energy levels between the
valence and conduction band cannot be occupied by electrons at
the surface,atoms may exist in localized electronic energy levels
located in the forbidden energy gap. Since two electrons can
114

occupy a free orbital the dangling bond of the germanium surface


atom may also capture an electron from the conduction band and
the surface atom will become negatively charged. To preserve
electrical neutrality a positive space charge (excess of holes,
"positive electrons") arises just within the semi-conductor and
which may ext~nd into the crystal for a distance typically of the
order of 10 ~ cm. This relatively deep penetration of the
positive space charge layer into the bulk crystal is due to the
low concentration of mobile electrons and holes in the conduction
band of the semiconductor. The surface states on germanium are
said to behave as acceptor states (accepting electrons). An
acceptor state is neutral when empty and negatively charged when
occupied by an electron. A donor state is neutral when occupied
by an electron and positively charged when empty.

Surface sites on an ionic crystal will be exposed ions (cations


and anions) which are surrounded by less than their normal
complement of oppositely charged species. The activity of these
ionic sites and the strength of the bonding with species from the
ambient (water) phase will depend on the details of the bonding
between the cations and anions in the solid. Recalling again the
elementary approach to bonding between atoms we note the chemical
bond can vary from the homopolar, purely covalent bond between
two identical atoms, to the ionic bond where one of the two atoms
has a comparatively high electron affinity and the bonding
electrons are primarily in orbitals around that nucleus. When a
covalent bond forms between unlike atoms there is a slight shift
in the electron distribution leading to a "partial charge" 0 on
each of the atoms. This concept of partial charge is also
important in solids. As the partial charge increases between
unlike lattic atoms the solid changes from a pure covalent
crystal to a pure ionic crystal. One speaks of the ionicity of
the crystal which is determined by the electronegativity
difference between cation and anion. To the group of ionic
crystals belong solids ranging from highly ionic materials
(alkali halides) through decreasing ionicity (including important
metal oxides) to solids where the covalent character of the
bonding will begin to prevail.

The important point to be made is that the surface cation will


exhibit a higher electron affinity than its counterpart in the
bulk crystal. The energy of electrons in orbitals around the
surface anion will be higher than that of electrons in the
delocalized valence bond (of the ionic insulator) simply because
of the lower electrostatic attraction from the neighbouring
cations. Through adsorption a strong bond may be formed, for
example, between a cation in the solution surrounding the ionic
crystal and a surface atom if this cation has a half-filled
bonding orbital of which the energy closely matches that of the
surface anion. The formation of such a strong bond will involve
115

at least partial desolvation of the cation in the process of


becoming adsorbed. This adsorption reaction is an example of what
is known as specific adsorption.

Acid/base properties of surfaces

In studies of heterocatalytic processes involving a solid


catalyst surrounded by a gas phase, the existence of special
types of sites, socalled Lewis sites have been recognized. These
sites although not recognized as such have also been introduced
in the description of adsorption at the solid oxide/aqueous
solution interface. Two types of Lewis sites are dis tinguished,
Lewis acid and Lewis base sites. According to the acid/base
theory of G.N. Lewis a base (B) is an atom, molecule, or ion
which has at least one pair of valence electrons which are not
already being shared in a covalent bond. An acid (A) is a unit in
which at least one atom has a vacant bonding orbital in which a
pair of electrons can be accomodated.
An acid-base reaction is then written

A + :B = A:B (1-1)

By analogy a Lewis base surface site is a lattice anion on the


solid surface that has an electron pair (molecular orbital)
available at a high energy level (because of incomplet~
coordination). A major decrease in energy may be obtained il this
site shares the electron pair with an (adsorbed) acid which acts
as an electron pair acceptor. A surface lattice cation represents
a Lewis acid site which has an unoccupied orbital wit:' a high
affinity for an electron pair. A decrease in energy is obtained
when this site shares an electron pair donated by an (adsorbed)
Lewis base molecule.

The adsorption of an acid onto a Lewis base surface site or of a


base at a Lewis acid site on the surface is also described by
reaction (1-1). Most metallic cations may be regarded to be Lewis
acids and the oxide anion in solid oxides is an important example
of a Lewis base. We may write the following acid/base surface
reactions involving these species

M
s
+ :OH (aq) (M:OH-)
s
(1-2)

:0 + + (aq)
H (O:H+) (1-3)
s s
with M an acid surface site (lattice metallic cation) and :0 a
base s8rface site (lattice oxide ion). s

The surface reaction (1-2) suggests that a neutral aqueous


solution (pH=7) may be acidified on the addition of finely
dispersed solid particles with a high density of active Lewis
116

acid centres. Similarly according to (1-3) the presence of active


Lewis base sites on the solid surface will render the solution
basic. These acid/base reactions are responsible for the
formation of an ionic double layer at the solid/liquid interface.
A highly acid surface will become negatively charged and this
charge localized in the first layer of the lattice will be
compensated by a diffuse layer of (ionic) charge spreading out
into the aqueous solution. this ionic space charge will not reach
as far into the solution as does the electronic space charge into
a semiconductor solid except at very low ionic strength.

The distribution of potential Lewis sites on a solid surface will


be different on different crystallographic planes as is
illustrated in Figure 2 for the ionic oxide. rutile. On the (110)
cleavage plane Ti ions in row A are five fold coordinated with
respect to lattice oxide ions whilst those in row B are in four
fold coordination with lattice oxide ions. Per ml of surface
there are I.Ox10 19 titanium ions. The Ti ions on the (101) plane
are coplanar and five coordinate with respect to lattice oxide
ions and have a density of 7.9x10 18 per ml. The density of Ti
ions on the (100) plane is 7.4xl0 18m-2.

We also observe that the acidic or basic properties of a solid


surface may be markedly altered by exchanging lattice ions. for
example. cations by other cationic species. If the non-lattice
ion fits reasonably well in the site vacated by the lattice ion
but its "acidity" differs from that of the lost cation the
reactivity and electrical properties of the surface may be
controlled at will.

Interaction between solvent and solid surface

The surface of an ionic crystal will be the seat of intense


electric fields directed into space because of the incomplete
coordination of the surface ions. It is therefore energetically
advantageous to terminate the surface by promoting whenever
possible strong interaction with the solvent molecules of the
liquid ambient. Polar solvent molecules would become oriented at
the surface in the an attempt to neutralize the intense surface
electric fields. Stronger bonds between polar water molecules and
surface sites can form when Lewis acid sites are present because
the water molecule is known to act as a Lewis base. The HZ
molecule can then undergo chemical adsorption via an acid/base
reaction with the OH group sharing an electron pair with the acid
surface site (A )
s
A
s
+ HlO + A :OH-H + (A :OH)-
s s
+ It (1-4)

leaving the proton weakly bonded. According to this scheme water


is dissociatively adsorbed. Dissociative adsorption of water can
117

B A A B

II
Figure 2

Illustrating the surface structure of rutile according to Jones


and Hockey, Trans. Faraday Soc. 67, 2669, 1971
I Plan view of the (110) cleavage plane
II Plan view of the (101) cleavage plane
us

III
Fig. 2

III Plan view of the (100) cleavage plane and an elevation


looking along the c-axis in the line of the (100) plane
119

also proceed by reaction with a Lewis base surface site when the
water molecule acts as a Bronsted acid by donating a proton
(Lewis acid). The proton will then share the electron pair
donated by the base surface site

:B + H20 + B:H-OH + B H+ +OH- (1-5)


s s
Reactions (1-4 and (1-5) will occur in combination at the surface
of an ionic solid containing Lewis base and acid sites in high
density. The outer layer of the surface may be pictured as
follows:

OH H+ OH- H+ OH- terminal (hydroxylated) surface


I I I I I
----A B A B A --- bare solid surface
s s s s s
with Lewis acid/base sites
B A B A B

The surface group A OH acts as a base when it releases OH to the


solution bu~ it =ma:f also act as a Bronsted acid by releasing a
proton,A OH +A 0 +H .This amphoteric nature of the surface group
A OH wili depelbd on the strength of the interaction between the
o~ygen atom of the OH and the cation A.Crystal field effects due
to d-orbitals of the transition ~tallic cations may play an imp-
ortant role. The surface group B H will act as a Bronsted acid.
s
If the cation A is a strong Lewis acid site the OH anion will
be held tenaci08sly and the proton associated with the anion B
will be easily given up and the surface will become negativel~
charged. This_ charg~ng of the neutral surface containing equal
numbers of OH and H ions may be described by the reaction

H+ + OH aq = H 0 (1-6)
s 2
which also suggesEs that a negative surface charge is obtained by
adsorption of OH ions from solution. If the protoI!. is attracted
more strongly to the lattice anion B than the OH ion is attra-
cted to the cation A ,the solid wills react as a base and become
positively charged s

OH + H+ (aq) = H20 (1-7)


s
b~ removal of OH from the surface(desorption)or by adsorption of
H fr0.f solution.As already pointed out, it l:f also possible to
lose H not only from Bronsted acid sites(B H )but also from the
site(A OH-)which can also show weak aciditySdue to strong inter-
s -
action between the surface cation and the oxygen of t~e OH group.
The nature of the charge of the solid surface-positive, negative
120

or zero- will under these conditions depend on the pH of the


solution phase. At the point of .!-ero c~rge (PZC) we may then
picture the number of adsorbed OH and H to anions to be equal
with a fractional coverage of t for each charged species. There
must be a characteristic pH in the solution for which this
si!uation+is applicable. If,however, other charged species than
OH and H also compete for the acid and base sites the point of
zero charge will not be uniquely characterized by a
characteristic pH in the solution.

This picture of dissociative adsorption of the water 1OO1ecule


through aCid/base surface reactions and the subsequent charging
of the surface by selective dissociation of acid and base groups
is therefore expecially applicable to oxide solids in aqueous
suspensions. Furthermore this type of chemical bonding between
the polar water molecule and an ionic solid surface is not
expected in the case of a highly ionic crystal (high ionicity)
such as an akali halide. The sharing of an electron pair, or the
possibility of orbital overlap is the basis of such bonding. The
difference in energy be~ween the lowest unoccupied orbital of the
cation (for example, Na ) and the highest occupied orbital of the
base (H 20 or OH-) is too great so that very little electron
transfer and sharing occurs. The binding will be purely
electrostatic. The lattice is too electropositive and the lattice
anion (Cl-) is too strongly electronegative to promote electron
pair sharing with the adsorbing water species.

The surface silver ion in a AgI crystal may also be treated as a


Lewis acid site and the iodide ion as a Lew~ basetsite but there
is no evidence of strong adsorption of OH or H ions on this
ionic crystal.One would therefore not expect the formation of
acid/base bonding and dissociative adsorption of water. The silver
cation is sometimes considered as a "soft" Lewis acid and the
iodide ion as a "soft" base both of w~ich pre~er to bond with
other "soft" bases and acids such as HS and Tl • The water mole-
cule and OH- anions are considered "hard" bases and the proton a
hard acid. This distinction between hard and soft Lewis acids and
bases may explain the difference in adsorption behaviour of many
solid oxides on the one hand and silver iodide and sulfides such
as Ag2S and PbS on the other hand. Pearson [4] has suggested the
name soft bases for those Lewis bases whose valence electrons are
easily polarizable and hard bases for those valence electrons are
not. Hard acids are recognized as small, highly positively
charged, and not easily polarizable; soft acids are defined as
those possessing the opposite properties. These qualitative
classifications and concepts may serve as a rough guide also in
predicting large trends in specific adsorption at solid surfaces.

In conclusion we note that solid surfaces are not always smooth


and uniform. A rough, non-uniform surface will introduce a
121

sITe AT A CRYSTAL STEP

DISLOCATION

DIFFERENT
SURFACE CRYSTAL
PLANE

FOREIGN

Figure 3

Some sources of heterogeneity in surface sites. From [2]


122

multitude of surface sites of varying reactivity. Some sources of


hererogenity in adsorption sites are illustrated in Figure 3.

THERMODYNAMICS OF THE SOLID-LIQUID INTERFACE [5,6]

As the sphere of molecular interaction is not infinitely small a


non-homogeneous region where in the properties differ appreciably
from the properties in the interior of either phase, will
separate two homogeneous phases. This transition region
constitutes what is simply referred to as the solid/liquid
interface. There is every reason to believe that the thickness of
the surface region is very small, of the order of a few molecular
layers, although we have seen that it could extend to distances
of the order of IO-~cm as a space charge into the solid.

It is not possible to isolate the solid/liquid interface for


purposes of establishing its structures and composition. This is,
however, not a disadvantage when we consider a thermodynamic
description of the interface. The interface may be treated as an
open system always in communication with the two bulk phases. We
may therefore ascribe to it the same thermodynamic properties
introduced in the thermodynamic analysis of homogeneous phase.
Such a surface thermodynamic quantity must have a definite
operational meaning in terms of measurable macroscopic parameters
regardless of atomistic details of the interfacial structure.
Once the phenomenological basis for its definition has been
established, one may inquire into its interpretation from a
molecular point of view.

Surface work and interfacial tension y [7,8,9]

We define surface work as the formation by cleavage of an amount


of new surface under reversible conditions. Thus for the
formation of an infinitesimal amount dA of new surface we write

w ydA (2-1)
rev
where y is the reversible work to form a unit amount of new
surface under clearly specified conditions. We note that the
surface area of a solid may also be increased by deformation of
the solid. In contrast to the observations made in fluid/fluid
systems, the two types of mechanical work (surface formation and
surface deformation) are not identical. By increasing the surface
area through a deformation process such as "stretching", the
density of the surface atoms will be changed whereas it remains
constant in a cleavage operation. It is therefore unfortunate
that the intensive property y is commonly referred to as the
surface or interfacial tension. Although this connotation is
quite satisfactory when applied to fluid interfaces, it is
misleading when considering solid interfaces. Only for liquids
123
will y as defined by equation (2-1) be numerically equal to a
surface density of tensile stress.

If the conditions specified for the definition of surface work by


(2-1) remain unaltered in the creation of a finite amount of new
surface we may write

W yf:,.A (2-2)
rev
It must, however, be clearly understood that in the case of
solids this integrated expression for surface work applies only
if the crystallographic orientation of the surface and the state
of strain of the solid adjoining the surface are not altered in
the process. The former condition can always be realized and the
latter condition will require only a second order correction
especially when the solid is at all times subjected to a uniform
hydrostatic pressure.

The dependence of y on orientation for an equilibrium solid may


be derived from the Gibbs-Curie criterion. It requires the
product of interfacial tension y. of face i and its surface area
Ai when sUlllllled over the entire~ surface to be a minimum with
respect to all change in form of the interface at constant volume
of the two bulk phases and constant intensive parameters. A
mathematical formulation of this criterion states

o2(/y(~)DA) > 0 (V const., intensive properties constant)(2-3)


A

where DA is a small element of the crystal surface of which the


orientation is denoted by the unit normal d to that surface. The
integral is to be taken over the entire surface and 0 refers to
any infinitisemal variation from the equilibrium state subject to
the specified confitions.Wulff gave a geometric interpretation
of this criterion. He showed that inside the volume V of the
crystal at equilibrium there is a point, such that the
perpendicular distances \ between the equilibrium surfaces Ai
and this point are proport~onal to Yi' thus
Yr
• • • = h- = cons tant (2-4)
r
To consruct the equilibrium shape of the crystal one drops
perpendiculars to all possible bounding surfaces, marks off
segments from this point .proportional to the corresponding y
values and passes perpendicular planes through the resulting
termini. The body bounded by these planes is geometrically
similar to the equilibrium form of the crystal. In general both
plane and curved surfaces may occur in the equilibrium form.
124

The inverse procedure, the construction of a polar y plot, a plot


of the radius vector 6 in any direction with a length
proportional to y in that direction, may be constructed from a
knowledge of the equilibrium shape. This is a method for
evaluating the interfacial tension of crystalline solids.

A characteristic state function for the description of


solid/liquid interfaces [5,6)

We consider the two-phase (solid/liquid), r-component surfaces


system and assume that the liquid phase contains all r components
but that components 2,. • • , r are insoluble in the homogeneous
solid phase (component 1). The state of this system and also its
extent will be determined completely by specifying r + 3
independent thermodynamic quantities. Assuming the solid/liquid
interface to be planar, the complete differential of the energy
of this sys tem is

dU = TdS + I~idni - pdV +ydA


r (2-5)

According to this differential expression the r + 3 indpendent


variables - the entropy S, the volume V, the surface area A and
the total number of moles n. of the ith component of the system -
are all extensive quantities. Some of these variables, for
example, the entropy cannot be readily controlled in a laboratory
experiment. Variables such as temperature T and the hydrostatic
pressure p which may be easily controlled experimentally do not
appear as independent variables in the above expression. For this
reason we wish to find a more appropriate state function which is
a function of variables more readily controllable by experiment.

As the energy U is a linear homogenous function of S, V, A and


n i (i=1,2, • • • ,r) at constant intensive properties, temperature
T, pressure p and chemical potential ~ (i = 1,2, • • • ,r) we
derive from equation (2-5) the fundamental relation

r
U TS - pV + I~ini + yA (2-6)
1

This expression allows us to introduce other useful state-


functions of which the Gibbs function or free energy, G:U-TS+pV
is a familiar example. Our choice is the function A defined by

r
A _ U - IS + pV I~in. (2-7a)
3 1
125

r
A G - LJ.l.n. (2-7b)
31.1.

(2-7c)

This function has also been used by Overbeek [5]. With the aid of
equation (2-5) the following expression for the complete
differential of A is readily obtained.

r
dA - SdT + Vdp - LnidJ.l. + J.lldnl + J.l2dn2 + ydA (2-8)
3 1.

We note that the set of independent variables associated with


this characteristic function includes the r intensive variables
T,p,J.l. (i=3, • • • ,r) and three extensive thermodynamic variables
nl,n21. and A. In the discussion to follow we shall take as
component 1 the pure solid and as component 2 the solvent (water)
of the solution phase.

The state of our two phase system is then seen to be fixed by


specifying T,p and J.l. (i 3,. ,r)as the independent
intensive variables. At y is an intensive thermodynamic property
its magnitude will then be determined by the function

(2-9)

to which we shall return later on.

From equations (2-8) we deduce

_(6A)
y -(6A) nl,n2,T,p,J.l k *I,2 (2-10)

This operational definition of the interfacial tension clearly


demonstrates that it is a macroscopic property of the system and
that its evaluation does not require any information about the
structure and thickness of the interface proper. If the surface
work is performed irreversibly under conditions such that the
amount of solid and of the solvent, the temperature, pressure and
the chemical protentials of all the components of the solution
phase except for components 1 and 2 remain invariant then this
work will equal the increase in A. Integration of equation (2-10)
will then yield equation (2-2) when performance of surface work
is done under conditions of constancy of the intensive properties
T,p,J.l (i=3, • • • ,r). We note again that implicit in the
definition of y (2-10) is that during the change in surface the
crystallographic orientation be fixed.
126

Thermodynamic properties of the interface

In applying thermodynamics to surfaces it is convenient to


associate definite amounts of energy, entropy, matter etc. with a
unit areas of interface. We must however insist that these
properties be measurable. The assignment of thermodynamic
properties to the interface may be accomplished by first
considering another important thermodynamic experession for our
two-phase system.

From the fundamental equation (2-6) we deduce that

r
B =U - TS + pV - tPini - yA = 0 (2-11 )

On differentiating this expression and substituting equation (2-


5) for dU we find the important relation

r
Ady + tnidP i + SdT - Vdp = 0 (2-12)

which is recognized as a Gibbs-Duhem equation for a "surface"


system (two bulk phases and an interface). We may then subtract
from this expression the contribution of the two bulk phases to
find the surface equivalent of the Gibbs-Duhem equation.

We first write the appropriate expressions for the two bulk


phases, solid (a,component 1) and solution phase (e, components
1,2, ,r)

(2-13a)

r e
tcidP i + sedT - dp 0 (2-13b)

ne
where c~ = -i-
V
is the concentration of component i in the

solution,n e is the number of moles of i in the solution, Ve


i
is the volume of the solution and se is the volume density of
entropy in the solution phase. Similar definitions apply to the
a
solid which is assu~ed to have a volume V b On multiplying
equation (2-13a) by V and equation (2-13b) by V and subtracting
the results from equation (2-12) we find the Gibbs-Duhem
expression for the interface
127

r
Ady + L[n i _(c~a+ cfv~)]dlli + [S-(s<lv a+ sl\r~]dT

(2-14)

We may now introduce formally the following surface thermodynamic


properties

s
nl Ar 1 nl - (c<tv a+ cfv~) (2-15a)

s
n2 Ar2 n2 - c~v~ (2-15b)

s
ni Ar i n. - cfv a(i:l:l) (2-15c)
1

SS Ass S - (s\Ta + s~Va) (2-16)

VS A-r V - (Va + V~) (2-17)

where T the surface concentration (moles per unit surface) of


componen\ i is commonly referred to as the -adsorption density of
i.

These definitions of surface concentrations, entropy and volume


are of little practical value as their evaluation requires the
volumes of the two bulk phases and the thickness of the
interfacial region to be known. The only experimentally
measurable quantity in equation (2-17) is the total volume of the
"surface" system.

Meaningful, and in principle experimentally verifiable surface


properties, may be introduced, however, by returning to equation
(2-8). As dA is an exact differential we may write the following
Maxwell relations:

(2-1Ba)

(2-19a)

(2-20a)

and introduce the following meaningful surface properties


128

(1,2)
c5n
(2)
- 6A Dl,n2jint. (2-18b)

s(1,2)
s
(2-19b)

(1,2) _ c5V
T
= (c5A) nl,n2;int. (2-20b)

where the subscript into refers to the r independent intensive


variables T, P'~3' • • • ,~ and the subscript ext. to the three
extensive variables nln2 ana A. As Y is an intensive property,
the subscript ext. on the partial differential quotients with y
in the numerator is actually superfluous.

Equation (2-18b) is a phenomenological definition of the surface


concentration. Only properties characteristic of the system as a
whole enter into its description. No knowledge about the detailed
structure of the interface is required. Equation (2-18b) gives an
exact description of the ~o~dure to be followed in the
experimental evaluation of r ' •Increase the surface area of
the system at constant T,p,nl,n2 and ~.' The number of moles of
component i to be added to or substrlcted from the system per
unit increase in surface area needed to keep the (f~ical
potential Uffl~,red in the process will then equal r. ' . We
refer to r. ' as the relative adsorption density of1 component
1
i with respect to components 1 and 2.

Equation (2-18a) suggests an alternative and independent method


for evaluation the relative adsorption density. However, it is
not possible to measure the interfacial tension of a solid
directly. The utility of equation (2-18a) lies in the evaluation
of changes in y with composition from a knowledge of the
adsorption density.

Another useful property of the(ls~d/liquid interface is the


Gibbs free energy density gS, which is again defined
operationally.
gs(1,2) = (c5G) .
(2-21)
c5A nl,n2;1nt.

On making use of equation (2-7b) it may be readily shown that


s(1,2) _ +I r (1,2) (2-22)
g - y ~i i

Only for a two-component system (a solid in equilibrium with its


saturated solution) will
129

g
sO,2) =

The adsorption equation

Ue are now able to write an expression for the dependence of the


interfacial tension on the r independent intensive variables as
suggested by equation (2-9). This expression follows directly
from the set of equations (2-18),(2-19) and (2-20):

r
dy =- ss(1,2) dT + T(1,2) dp - Lri(1,2)d~. (2-23)
3 l.

I t is the basic thermodynamic relation for the discussion of


adsorption at solid/liquid interfaces and will be referred to as
the adsorption equation.

It is also instructive to show that the adsorption equation may


be derived with equation (2-12) as starting point. According to
this equation the interfacial tension is a function of (r+2)
intensive variables. But the phase rule states that when r
independent intensive variables are specified, the magnitudes of
all other intensive variables will be fixed. Any two of the r+2
intensive variables may be eliminated from equation (2-12). We
elect to eliminate the chemical potential ~_1 of the solid phase
and the chemical potential ~2 of component 7:, the solvent of the
solution phase. This elimination is readily accomplished with the
aid of the two Gibbs-Duhem equations (2-13a) and (2-13b) to yield

n c ll - n c ll
1 2 2 1
Ady [s - ( - - - - - - ) sa
a
clC2
a

\I vo ll - n c ll n
1 2 2 1 2
+ [V - II ] dp
c2

1r
-[L(n i c II)] d
i ~i
3

(2-24)

On comparing this result with the adsorption equation (2-23) we


note that the expressions inside the square brackets must be
130

equal As s (1,2), kr O ,2) and Ar i O ,2) and that in contrast to


equation (2-14) the expressions inside the square brackets
contain only measurable quantities. We have now also derived
analytical expressions which enable us to evaluate relative
surface densities etc.

nz
r. O ,2) = 1.. (n - (2-25)
1. A i c~
Z

ss(I,2) = ! [5 (2-26)

n c~ - n c~ n
T(1,2) = ! [V -
1 2 2 1
- -]
2

c~ (2-27)

These analytical expressions are relatively simple because we


have assumed the solid to be a pure one component phase.

I t is also interesting to note that equations (2-25), (2-26) and


(2-27) may be derived from the formal expressions for surface
properties, equations (2-15) to (2-17) of we let nS = nS = O.
1 2
Thus the adsorption density r (1,2) may be interpreted as the
i
adsorption density of component i when both components 1 and 2
are not adsorbed.

The most common experimental technique for measuring adsorption


from dilute aqueous solutions makes use of the analytical
expression (2-25) which on the assumption that the solvent
(component 2) is not adsorbed reduces to the less fundamental
expression.

Ar (1,2) = n - c~~ (2-28)


i i i
The relative amount of component i adsorbed is equal to the
difference between the total amount of i added to the system at
constnat surface area and the amount in the solution at
equilibrium.
131

The adsorption equation (2-23) has the same form as the more
familiar Gibbs adsorption equation

dy (2-29)

where (1)
on
ri (-2.)
oA n 1> V , T , \l k f:l

Here the set of independent variables chosen to describe the two


phase system include T, V ,A,nl' \12' , \l r and the
characteristic function is

r
X == U-TS-En. \I.
21.1.

We illustrate the application of the adsorption equation by


considering the adsorption of a solute (component 3) from an
aqueous solution at constant T and p onto the solid/liquid
interface. For the change in interfacial tension (y-yo), where yo
is the interfacial tension at the specified temperature and
o
pressure and some reference value \I of the chemical potential,
3
we then write

f\l 3 r (1,2) d
(T,p constant) (2-30)
o 3 \13
\I
3

In a liquid solution the chemical potential of component 3 is


given by \I = \lo(T,p) + RTlna 3 with a 3 the activity. To evaluate
3 3
the integral on the ri~hthand side of equation (2-30) the
adsorption isotherm (r 3 (1, ) versus a 3 ) must be known.

If we assume a Langmuirian adsorption model based on localized


adsorption of the solute at a finite number of surface sites, the
adsorption isotherm will have the form

r3(l,2)
r max c3 (2-31)
= c* + C3
132
where r is the adsorption density when all the available sites
per unftlxsurface are occupied, the constant c* represents the
concentration in solution at which one-half of the sites are
occupied. The smaller the magnitude of c* the stron~r2)the
adsorption energy. On substituting this expression for r3 ' in
equation (2-30) and letting a3 ~ c3' the integral may be
evaluated with the result.

y - y
o = = RTrmax 1n(1+ c3)
c*
(2-32)

We note that the major drop in interfacial tension will be


obtained when c3» c*, that is, when the surface is practically
saturated with the adsorbing species. This interesting
illustration suggests that when a component is strongly
specifically adsorbed the interfacial tension may approach a
value of zero and even tend to become negative. The interface
will then become unstable and the formation of thermodynamically
stable solid colloidal dispersions could be obtained in the same
way as the thermodynamically stable micro-emulsions are prepared
[10].

ADSORPTION OF ELECTROLYTES

Our understanding of the adsorption of electrolytes from an


aqueous solution at the solid/liquid interface has been advanced
considerably by extensive studies of the silver iodide and
insoluble metal oxides and metal hydrous oxides [11,12,13]. It is
common knowledge that when a solid particle such as silver iodide
is immersed in an aqueous solution it acquires a charge on its
surface by the adsorption of ions from solution. Since the system
as a whole remains electrically neutral, the solution adjacent to
the solid surface must carry a net charge equal in magnitude but
opposite in sign. This charge sepration in the interfacial region
initiates the formation of the ionic electrical double layer
already referred to under 'acid/base properties of surfaces'.

We propose to give a thermodynamic treatment of the adsorption of


simple electrolytes at the solid/liquid interface and the
electrical double layer by considering two systems - silver
oxide/aqueous solution and the solid oxide/aqueous solution. The
similarities but also impGrtant differences in the adsorption
behaviour of these two types of ionic solids will be considered.

The Silver iodide system [11]

Consider a suspension of silver iodide particles in an aqueous


solution containing the two electrolytes AgN03 and NaN03 and
saturated with respect to the solid (AgI) , Because the solution
remains saturated with respect to the solid it follows that
133

o (3-1)

and that pAg + pI = pK (3-2)


sp
where K is the solubility (activity) product of AgI at a
specifie~ temperature,and pAg = - loga , pI = - log a-.
Changes in the chemical potential of the ~ctrolytes are related
to changes in the chemical potentials of the constituent ionic
species in the following manner

(3-3)

On applying the adsorption equation (2-24) to this two-phase,


four-component system we may immediately write that at constant
temperature and pressure

- rNaN03 d\lNaN0 3 (3-4)

The adsorption densities rAgN03 and rNaN03 are relative adsoption

densities (r0,2» where we have, for the sake of convenience,


left off the superscript (AgI, H20) which refers to the
convention r H20 = rAgI = o.

An alternative and more instructive expression for the adsorption


equation may be obtained by writing at constant T and p

dy =- r Ag+ d\lAg+ - r I - djlI_ - r


Na
+ djl + - r 3
Na NO
-d~_
. NO 3(3-5)

which may then be transformed to yield

(3-6)

bu utilizing equations (3-1) and (3-3) and the condition for


electroneutrality in the interface

(3-7)

In equation (3-6) the relative adsorption densities of the


charged species in the interface (or electrical double layer) are
explicitly introduced. A knowledge of these quantities will
enable us to build a molecular model of the structure of the
double layer. A comparison of equations (3-4) and (3-6) leads to
the following adsorption identities:
134

r Ag N0 3
- r NaNO
3 (3-8)

+ r NaNO
3

If instead of adding NaN0 3 to the solution, the electrolyte NaI


is added the adsorption equation assumes the form

(3-9)

The relative charge densities may be introduced into the


adsorption equations by using the definitions

(3-10)

CJ

where F is the Faraday constant.


On introducing these quantities in equation (3-6) we find

CJ 0 CJ+
dy =-- dll 3 - - dll 3 (3-11)
F AgNO F NaNO
If NaN03 is present in a much higher concentration than AgN03 it
will determine almost entirely the magnitude of the ionic
strength of the solution.
Equation (3-11) may be rewritten to yield

(3-12)

At constant ionic strength this expression reduces to

00 CJo
(3-13)
dy = -"FdllAg+ = 2.3 RT"FdPAg

It may be integrated to find the change in interfacial tension if


the dependence of 0 and pAg (the adsorption isotherm) is known.
It may be determaned experimentally by the potentiometric
titration of an aqueous suspension of silver iodide with AgN03
135
and NaI as titrants in the electrochemical cell

HglHg CI IKCIII solution containinglAgIIAg


2 2 AgI precipitate

The evaluation of the relative adsorption density (rAg+ - rI-)


and thus of the charge density ao ~kes use of the analytical
expressions (2-25) or (2-28) where ci is the equilibrium

concentration of Ag+ (or 1-) in the solution. This concentration


is measured in the above electrochemical cell. For details of
this experimental procedure which was perfected by the "Dutch
School" of colloid science the reader is referred to [11]. An
example of the adsorption isotherms obtained by this technique is
given in Figure 4.

An expression with the surface charge densities a and a+ (or a )


as independent variables is obtained by introduc<tng the surface
Gibbs energy density gs(I,2) (see equation (2-29)

s(1,2)
g
(3-14)

At constant temperature and pressure, differentiation of equation


(3-14) yields

dg s (I,2) - ~ d(ao/F) + ~NaN03 d(a+/F)


- AgN03 (3-15)

Another useful relation is

a+ (3-16)
~ 3 d(a IF) - - d~ 3
AgNO 0 F NaNO

where s(1,2) a+
g -- ~
(3-17)
F AgN03
As dy, dg s (1,2) and dE; are all exact differentials we find from
equations (3-12), (3-15) and (3-16) by cross-differentiation

oa
~ 0
o~aNO
3 ~AgNO
3

(3-18)
136

-6~ j.LC.cm- 2
0'0
-5 .
I
-4
-3
-2
pAg
9 10 11 12

Figure 4

Adsorption isotherm (a o vs pAg) on silver iodide in the presence


of different molar concentrations of KN03 at 25 0 C taken from [11]

10-1

10-2
11)-3
}~
11

-1
Figure 5
Ionic components of charge in the electrical double layer on
silver iodide at 25 0 C. Supporting electrolyte KN03
0+ = Frr a -FrNO -
Taken from [11] 3
137

( (
(3-19)

(3-20)

These Maxwell relations may be used to evaluate the ionic


components of charge in the interface (or electrical double
layer). Details concerning the use of these relations in
calculating eJ+ and eJ_ are described by Bijsterbosch and Lyklema
[11]. Figure 5 summarizes some of the results of such a
calculation.

The solid oxide system [14,15,16]

Adsorption expressions analogous to those for the silver iodide


system may be derived for oxide systems. The solution chemistry
of oxides is however complex because of the hydrolysis of the
metallic cation and polymerisation reactions involving the
hydrolysis products.

The equilibrium between a relatively insoluble metaloxide or a


metalhydroxide solid and the aqueous solution is described by

M °
x xz/2
(s) + ~xz)
2
H2 0(l) = xM(OH)
z
(s)
(A)

xM(OH) (s) + (xz - y)H+ (aq) M (OR) (xZ-Y)+(aq)+ (xz-y)H20


z x y (B)

(xz-y)+
where M (OIl) may be mono- and polynuclear positive or
negativeXhydlo-complexes. Under equilibrium conditions it follows
that regardless of the solid phase

The solubili ty of the oxide or hydroxide will be determined by


the sum of the equilibrium concentrations of all the hydroxo-
complexes and the neutral complex M(Oll) as illustrated in
z
Figs. 6-8

Although the solubility at a given pH will be different for the


various modificat?0ns (crydtalline and amorphous) of the solid
phase of metal MZ , it follows from equilibrium reaction (A) that
138

-4 -

-6

z -8 -
o
I-
~-IO
I-
z
W
~ -12-
o
u
l!) -14
o
..J

16

o 2 4 6 B 10 12 14
pH
Figure 6

Variation of solubility of amorphous Fe (OR) 3 (Curve I), goethite


(Curve II), and hematite (Curve III) with pH.
Lines A through F represent the changes with pH of the concentration
in solution of the following hydroxo-complexes in equilibrium with
hematite. The concentrations or all species shift upwards by a
constant amount when in equilibrium with the other two solid phases.
The vertical line a-a determines the pH at which [Fe(OH)~]
4+ 2+
[Fe O 2]
A Fe 2 (OH)2 C FeOH E Fe0 2

B Fe 3+ +
D Fe (OH)2 F Fe (OH) 3
Taken from [1 7]
139

2 3 4 5 6 7 8 9 10 11 12 13
pH

Figure 7
Variation of so lubi l i ty of a.-AI (OH) 3' gibbsite with pH
3+ -
1,0 Al 1,4 Al (OHJ
4+
1,1 Al (OH) 2+ 2,2 AI 2 (OH)2
+ 5+
1,2 Al (OH)2 3,4 AI 3 (OH)4
0 7+
1,3 Al (OH) 3 13,32 Al 13 (OH)32

Taken from Baes, C.F. and Mesmer, R.E.: The Hydrolysis of Cations,
John Wiley & Sons, New York, 1976

Figure 8
The equilibrium solubility diagram of ZnO.
Taken from dissertation of L. Blok, University of utrecht, The
Netherlands, 1968
140

the solubility curves will be displaced parallel to on another by


an amount equal to AG*/2.303RT where AG* is the standard energy
for this reaction. The pH of the minimum solubility (see Fig.6)
will of course, remain unchanged because At fixed temperature and
pressure reaction (A) is independent of the pH of the saturated
solution. We also remark that the pH of the minimum solubility
will in many instances be determined by that pH at which the
univalent mononuclear complexes M(OH)t:land M(OH)i;l are present
in equal concentrations.

Consider, for example, a suspension of gibbsite (Al(OH) 3) in an


aqueous solution containing HN03' Application of the adsorption
equation yields.

(3-22a)

or, on addition of the base NaOH

(3-22b)

where, in view of equation (3-21),

r~+ - r~H_ = [(r H+ -rOH_)+1/3rAl 3+ + E~xz:y)rAl (OH) (3x-y)+]


x y (3-23)

On introducing the charge density

(3-24)

and assuming the ionic strength of the suspension to be


determined by concentration of the indifferent electrolyte NaN03,
we may write

RTa
o
dy 2.3 -F- dpH

a
o dlJ _
F OH (3-25)
141

This result is to be compared with the analogous expression,


equation (3-13) for adsorption onto silver iodide. The adsorption
isotherm (0 versus pH) may again be determined experimentally by
means of pcftentiometric titraton of an oxide suspension with an
acid and base as titrants

HglHg Cl IKCllloxide suspensionlglass electrode


2 2

This technique for determining the ads~rption _density cannot


distinguish between the adsorption of H or OH ions and the
adsorption of the metal-hydroxocomplexes, therefore what is
measured is the relative adsorption density (r~+-r~H-). Part

of the added base or acid is also consumed by the hydrolysis and


polymerization reactions. A correction must therefore be applied
for changes in the solubility of the solid during the titration.
This correction may be negligibly small when the oxide is highly
insoluble. According to Fig.6 in the pH range 4 <pH <10- the pH
range in which reasonably accurate measurements may be done - the
change in solubility of hematite or goethite is negligible a~
well as the expected concentrations of the metallic cation Fe 3
and all hydrolysis products. This is not true for ZnO and it has
been found necessary to correct for the amount of added base or
acid consumed [15]. Such corrections will limit the pH range over
which meaningful adsorption measurements can be made. It is also
possible that when the oxide phase is not stable at the
temperature at which the adsorption measurements are performed, a
thin interfacial region develops of which the composition and
structure is different from that of the bulk phase [17]. To avoid
complications by dissolution reactions de Bruyn and associates
introduced a fast titration technique [17].

Some examples of 0 -pH curves are collected in Figs.9 and 10.


These adsorption is8therms differ significantly from those on AgI
and on Ag2S [18] in that for an equivalent change in pX (pAg,pH)
a much higher adsorption density is measured.

ELECTROCHEMISTRY OF THE ELECTRICAL DOUBLE LAYER

General features of the electrical double layer at the


solid/liquid interface

An electrical potential difference usually exists between two


phases. If one of the phases is a liquid ionic conductor, part of
this potential difference is located in an electrochemical double
layer, in which ionic charges are displaced perpendicular to the
interface, so as to create two regions of space charge equal in
magnitude but of different sign.
142
~
I
~
~

Jl
5.

-
,
••
~

-6

'0 60 70

Figure 9
Adsorption isotherm ([r H+ - r OH -] vs pH) on rutile in NaCl04
solutions of varying ionic strength at 25 0 C. The results of the
pH drift technique for establishing the pzc are plotted in top
half of diagram. Supporting electrolyte, 0.01 M NaCl0 4 •
Taken from [14]
<70

-9 I'C/cm2 IN
lO-I N
-6
1O- 2 N
-3 1O- 3N

pH
0
11
+3

+6

+9

+12

+ 15

+18
Figure 10

Surface charge of hematite as a function of pH in presence of


different KCl concentrations.
Taken from doctoral dissertation of A. Breeuwsma, Landbouwhogeschool
Wageningen, the Netherlands, 1973
143

Figure 11 2 3 .5 pH 6 7 8 9

Surface charge for CAB-O-SIL M-7 in KCl as a function of pH and


ionic strength.
Taken from Abendroth, R.P., J. Colloid Interface Sci., l!, 591, 1970

0'0

CHARGE SOLUTION

t DISTANCE

POTENTIAL

o t
Pigure 12

a) Charge density vs distance and potential vs distance curves for


a double layer consisting of a geometrical surface charge layer
and diffuse layer in the adjacent solution.
144

t
CHARGE

SOLID SOLUTION

POTENTIAL-

I SOLUTION

Fig. 12
b) Charge density vs distance and potential vs distance in a double
diffuse double layer with surface charge.
c) Charge density and potential vs distance at the pzc. The space
charge inside the solid is exactly balanced by the surface charge
density.
145

In many instances one of the space charge regions may be


approximated by an atomic surface layer to be referred to as the
surface charge layer (Fig.12a). This model would be a good
approximation if one phase is a metal which has a high
concentration of mobile charge carriers (electrons). We have
already suggested that a surface charge may be established by
preferential adsorption or desorption of one of the constituent
ions of the solid lattice or of ions closely related to the
lattice ions in chemical properties and in size. Here only the
outermost layer of the crystal is involved in the ion exchange
with the solution phase. A surface charge is also obtained by
dissociation of uncharged surface sites (see section 1.2). The
other layer (in the liquid) will practically always have the
character of a space charge. This picture of the double layer is
almost exclusively used in describing the electrical properties
(charge versus potential or capacity versus potential) of the
double layer on slightly soluble inorganic crystals and sols
(silver iodide and metallic oxides).

Another less simple model of the electrical double layer is the


double diffuse double layer which, as the name signifies,
consists of two space charges, one in each bulk phase. In
addition to the two space charges a surface charge layer may also
be present (Fig.12b). The components of the two spaces charges
may be quite different or some of the components may be found on
both sides of the interface.

In a pure ionic crystal lattice defects of atomic dimension may


consist of cation and anion vacancies (Schottky defects)and
interstitial cations and anions(Frenkel defects).These species
when present in the interior of a large crystal will occur in
pairs so that electrical neutrality is preserved. According to
Grimley [19] unless the free energy change accompanying the
transfer of an ion from the interior of the liquid to the solid
is zero, lattice ions will pass either from the crystal to the
electrolyte or in the opposite direction until equilibrium is
established. If the crystal contains Schottky defects i t will
acquire a charge through the presence of vacant cation and anion
sites in unequal numbers.If vacant cation sites are in excess the
solid will carry a negative charge spread out as a space charge
near the surface. Consider a pure stoichiometric crystal
containing Frenkel defects of cations.A space charge is again
developed by transfer of ions between solution and crystal when a
net amount of either vacant cation sites or interstitial cations
is present. The space charge due to defects in the ionic solid may
also be formed by a process not involving exchange of lattice
ions between the two bulk phases[20,21].Frenkel[20]was first to
point out that point defects can form independently of the
corresponding defect of opposite charge at the surface of an
ionic crystal.This suggestion was later exploited by Lehovec[21].
146

Imagine a perfect crystal without any lattic defects. If the


energy of formation of interstitial cations is less than the
energy of formation of interstitial anions at the solid surface,
initially more interstitial cations will form and migrate into
the interior than interstitial anions. This will lead to a
positive space charge layer and leave a corresponding negative
charge at the surface of the crystal. A cation vacancy at the
surface is equivalent to an "adsorbed anion". The potential
difference established between the surface and the bulk solid
phase will obstruct migration of cations from the surface into
the interior but enhance migration of anions which is necessary
to obtain equilibrium throughout the solid. According to this
Frenkel-Lehovec model vacancies and interstitia1s forming the
space charge layer are in dynamic equilibrium with charged
surface sites. In general one would expect both the Grimley-Mott
and Frenkel-Lehovec charging mechanisms to be operative in the
solid in forming a double diffuse double layer (Fig.12b) with a
surface charge layer. The surface charge will consist of surface
sites which become charged in the formation of the Frenkel-
Lehovec solid space charge and of adsorbed lattice ions from the
solution phase.Trautwei1er (22) has pointed out that a (III)
surface of AgBr would have 10 1S cm- 2 Br- ions sites. Of these
sites about 5xl0 14 cm- 2 may be shown to be occupied in the
formation of the space charge in the solid mainly through the
Frenke1-Lehovec mechanism. If in addition I014cm-2 sites are
occupied by adsorption of Br- ion from solution (a reasonable
estimate) then by adsorption the ratio of filled to empty surface
sites will change from 1:1 to 3:2. There is always competition
for the surface sites between these two ways of charging the
surface layer. Interaction between the solid space charge and
adsorption from solution is to be expected. We also note that at
the pzc (no net surface charge due to adsorption of lattice ions
from solution) the space charge in the solid will not be nece-
ssarily zero. The net charge of the solid will, however, be zero
as the space charge will be exactly balanced by the surface
charge (Fig.12c).

The model of a double diffuse double layer with a surface charge


is also applicable to the interface semiconductor/solution (23).
The mobile carriers in the space charge in the solid are
electrons and holes and will be present in unequal concen-
trations. The surface charge in the case of a semiconducting
metal oxide will be formed by capture of a mobile carrier in an
uncharged surface state and by dissociation of surface OR groups
(see 1.2).

Thermodynamics of the electrical double layer [5,24)

The point of departure in a thermodynamic treatment of the


147

electrical double layer is the concept of the electrochemical


potential ~j of the charged species j (electron or ion). In
dealing with a material phase which is homogeneous and
electrically neutral except for its surface regions, the work of
bringing a charged particle of the given chemical component j of
the phase, ini tially at res t in a field-free vacuum, into the
medium defines its electro-chemical potential ~j. The interior of
the medium is considered to be at the potential ~, the Galvani or
inner potential of the phase (solid or liquid) with respect to
the surrounding vacuum. It is considered to be comprised of a
potential 1/1 (the outer or Volta potential) due to excess on the
phase at the free surface (solid/vacuum or liquid/vacuum) and a
potential difference X associated with the dipole layer at the
free surface due to polarization of the surface atoms.

(4-1)

The electrochemical potential is often split into two parts, a


chemical and an electrical part

llJ. = ll.
J
+ z .F~
J
(4-2)

with z. the valence (including sign) of charged species j. This


divisidn is quite arbitrary and strictly (thermodynamically)
speaking devoid of physical significance. Electrical charges
(electrons and ions) are also chemical entities and all forces
between atoms and ions are fundamentally electric in nature.
However, in practice some subdivisions have proved to be useful
when a model of the system is to be introduced.

Although the electrical potential difference ~ between a point in


a material phase and a point in a vacuum cannot be measured an
electrical potential difference can always be measured between,
for example, two pieces of metal a(l )and a(2 )of identical compo-
sition except for their electrical state. This statement follows
directly from the formal definition of ~j in equation(4-2).

(1) (2) a(l) a( 2)


z.F(~ - ~ )
J
z.F(1/Ia(l) - 1/Ia(2) (4-3)
J
This relation clearly demonstrates that it is the electrochemical
potential and the Volta potential which have an operational
significance. The Galvanic potential difference, the X potential
and the chemical potential of an ion must be obtained from a
model by theoretical calculation.

We also note that the emf AE of a reversible electrical cell is


148

measured under conditions where equation (4.3) applies. From such


measurements the electrode potential E is obtained by using the
o
convention that the standard potential EH of the hydrogen
electrode equals zero.

We are,however,interested in the potential difference ~cpae=cpa_cpe


between the solid phase (a) and. the electrolyte solution (e). For
complete equilibrium between the two bulk phases and the
interface(s) the transfer between the phases of a charged species
j common to both should proceed unhindered. The condition for
thermodynamic equilibrium may then be formulated by writing

a s
].lj (4-4)

On introducing the formal expression for the electrochemical


potential (equation (4-2)) we derive

ea
~
z.F (4-4)
J
The Galvani potential difference is lrus determined by the
difference in chemical potential ~].lea =].l - ].la, of the lattice
j j
ions which can pass freely through the interface. Such species
are called potential getermining ions(p.d.i). The Galvani
potential difference ~cp a cannot be measured because it is the
electrical potential difference between two phases of dissimilar
composition. For the same reason the chemical potential
difference is not measurable. Changes in the Galvani potential
difference are accessible to experimentation
~(~cpae) = ~cpae _ ~cpae
o
(~].lea _ ~].lea )/z F
j j(o) j (4-6)

where the subscript 0 refers to some convenient reference


equilibrium state. For a pure hulk solid we may let ].la = ].la
j j(o)
at constant temperature and presure. Equation (4-6) then assumes
the form
149

(4-7)

where aa is the activity of the potential determining ion j in


j
the electrolyte solution. This equation has the same form as the
familiar Nernst equation for a reversible electrode.

E - EO = RT In
z ,F aj
J
and is therefore referred to as the Nernst equation for a
completely reversible solid/liquid interface. The change in the
Galvani potential difference is seen to be completely determined
by the change in the concentration (actively) ~f_the p.d. ion in
the solution phase. For a simple ion~c soli,5! A B the equilibrium
concentrations of the p.d. species A and B in the solution are
coupled by the solubility product thus

a a
aB-(o)
Acpaa _ Acp:a = !T In a~+ = !T In
a
aA+(o)

2.;03RT (pAo-pA) = 2.:03RT (pB-pB o )


(4-8)
It is convenient to choose as a reference stat$. the p.:>int of
zero surface charge (pzc) ; for an ionic solid XZ yZ- at the pzc

-
00 = F(z+f x

This reference stat~ will be


z_fy)
°
determined by
the activity a '( )
(4-9)

of the p.d. ions (xz or yZ-) in the solution. J pzc


By analogy with equation (4-1) we may also write

AcpaB = AX + 1/1 (4-10)


o
where the potential difference AX. not to be confused with the X
potential at the free surface. is ascribed to oriented adsorption
of the polar solvent and other polar molecules from solution and
to the deformation of the polarizable surface atoms of the solid.
The potential difference 1/1 is ascribed to the potential drop
across the electrical doubleo layer of free charges. It at the pzc
(0 =0) there is no electrical double layer of free charges
o
150

anywhere in the interfacial region then


llcj>aS and 1/1
o
=0
pzc pzc (4-11)

This situation will be met for the surface charge/diffuse layer


system of figure 12a in the absence of specific adsorption and
for the double diffuse double layer predicted by the Grimley-Mott
model discussed in section 4-1. For such systems a Nernst-like
dependence of 1/1 on the concentration (activity) of the p.d. ion
is often assumeg

= -RT 6
d1/lo
zl dIn a
j (4-12)

We note,however, that this is a non-thermodynamic postulate which


quite arbitrarily assumes llX to be constant independent of the
presence or absence of an electrical double layer of free charges
across the interface.

The Nernst equation (4-7) may also be shown to be applicable to


an ionic crystal with point defects and which, according to the
combined Grimley-Mott.Frenkel-Lehovec model, will in addition to
two space charge regions also have a surface charge layer (see
Fig.12b). Honig and Hengst[25] have shown that the thermodynamic
equilibrium between a AgBr crystal with point defects mainly of
the cationic Frenkel type implies
+ + Ag+(S)
Ag
+
in

and therefore

S
!JAg (4-13)
!Jin(Ag)

where Ag+ is an interstitial silver ion in the crystal. We have


seen tha!nthere is a potential difference between the surface and
the interior of the crystal, owing to a difference in the free
energy of formation of an interstitial ion and a vacancy in the
surface as compared to the bulk of the crystal. The space charge
of silver vacancies and interstitial silver ions need not
necessarily vanish at the pzc and therefore 1/1 will not be zero
(see Fig.12c). The net charge in the crystalO is however still
zero because the diffuse charge in the crystal is compensated by
an equal "surface charge" in the crystal. For this system
151

+ loX
pzc pzc (4-14)
<1 S
Where the potential differences • - . lies completely in the
solid phase and may in principle be evaluated. In any case the
right hand side of equation (4-7) remains unaltered when applying
the equilibrium condition (4-13).

The condition for themodynamic.equilibrium, equation (4-4) allows


one to write three equivalent expressions for the change in the
electrochemical potential, regardless of the mechanism by which
the equilibrium charge distribution is realized

(4-14a)

(4-15b)

-s s se
= d~j = d~j + ZjF dlo' (4-15c)

where lo+<1e = .<1 _ .e


Mse = .S _.e
and where .e, the Galvani potential in the bulk solution is
arbitrarily set equal to zero.

On combining equations (4-15a) and (4-15b) we recover, after


integration, the Nernst e~uation<1~4-7) which predicts that for a
univalent p.d. ion at 25 C, lo' will change by 59 mV with a
decade change in activity of the p.d. ion j in solution.

Complete equilibrium will be established by exchange of p.d. ions


between the bulk solid and solution phase. At room temperature
the diffusion coefficients Dj of lattice ions in ionic crystals

are often smaller than 10- 21 cm 2s- 1• As the diffusion length will
be proportional to 12D;t, with the diffusion time t, the depth of
penetration of these !"bns into the solid in one day will be of
the order of 0.1 nm or less, dis tances much smaller than the
thickness of the space charge region. Equilibrium of the solid
particles suspended in the solution during adsorption
measurements (changing concentration of p. d. electrolyte) will
therefore involve at most the outer surface layer of the crystal.

The diffusion coefficients for silver halides are larger than


10- 20 cm 2s -1 at room temperature. Thus the average penetration
depth for an iodide ion in one second will be of the order of 3nm
152

and the more mobile Ag+ ion in silver iodide will diffuse farther
in the crystal in this time period. When small AgI particles are
allowed to equilibrate with the solution phase, thermodynamic
equilibrium will therefore be established within a couple of
minutes not only between the interface and the solution but also
between the solution and the solid interior. The Nernst relation,
equation (4-7) should therfore be obeyed as is demonstrated by
the existence of reversible silver halide electrodes. For the
silver iodide/soplution system at room temperature we may then
write

0.059(pAg -pAg) volts


pzc (4-16)

0.059(pI-pI ) volts
pzc

and for the adsorption equation at constant ionic strength

dy

0.0590 d(PAg) (4-17)


o

Adsorption of potential determining ions and the site-binding


model [26,27]

If establishment of equilibrium between the solid surface and the


solution but not between the two bulk phases is possible then
with reference to equations (4-15a) and (4-15c)

S
sQ d\1 j RT Q
dl14> jJ
= zjF + ~F
dl n a jJ
j (4-18)

This expression will reduce to the Nernst equation if one were to


assume the chemical potential of the p.d. ion j in the surface to
be constant, independent of the composition of the solution and
of the surface. Alternatively, one may introduce an adsorption
model from which an expression for \1~ may be derived. The
J
dependence of l14>s~ and the activity of the p.d. ion in the
solution will then be fixed. We are thus again confronted by the
dilemma first pointed by Guggenheim in 1929 [28]. The splitting
of the chemical potential of an ion in a chemical part and an
electrical part when describing equilibrium between two
dissimilar media cannot give a definite and unique answer. One
must resort to models and must admit that more than one model may
fit the experimental facts.
153

We have already pointed out that spontaneous formation of an


electrical double layer featuring at most a monolayer of surface
charge and a diffuse charge in the adjacent solution phase may
result from two related adsorption mechanisms. These mechanisms
are selective adsorption or desorption of p.d.ions at the surface
of an ionic solid and dissociation of "potential determining"
surface sites. The former mechanism is commonly involved in
correlating adsorption measurements at the silver iodide/solution
interface with double layer theory. The existence of a space
charge inside the solid is either ignored or assumed to make a
negligible contribution. The origin of the double layer on oxide
solids is almost exclusively ascribed to dissociation of acid and
basic surface groups as discussed previously.

Ever since Stern [29) introduced the concept of specific


adsorption and proposed a site-binding model to analyze the
adsorption of ions at the mercury/solution interface, a variety
of site-binding models have been proposed not only to explain
quantitavely specific adsorption of non-lattice ions but also the
adsorption of p. d. ions. As the mercury/solution interface is
completely polarizable over a wide range of applied potential,
the adsorption of so-called p.d. ions is not encountered in this
system.

All site-binding models employ the formalism of Stern and


Langmuir which implies the availability of localized surface
sites for adsorption. In oxide systems the model has as its basis
the existence of Lewis base and acid surface sites which are
responsible for hydroxylation of the surface through dissociative
adsorption of the polar solvent water. There are many different
ways for specifying the adsorption sites which has resulted in a
proliferation of site-binding models.

The preferred model for the adsorption of p.d. ions (H+ and OH-)
is a three site model in which the charged sites are created by
dissociation of an amphoteric surface group MOH according to two
connected adsorption steps

..
+
MOH + H+(aq)
K+(K ) H K (K )
1 - 2
MO + H+(aq) (4-19)
The formation of a negative surface site is indicated to occur by
desorption of a proton, it may equally be regarded to form by
adsorption of an hydroxyl ion. Thermodynamic equilibrium between
the surface and the solution requires
154

Il n + IlR+ - 11+ o (a)

11 - + IlR+ - Il n o (b) (4-20)

11 - + iuR+ - 11+ =o (c)

where the subscripts n, + an~ - identify respec!ively the


uncharged (MOR), positive (MOR2) and negative (MO) surface
sites. The total (constant) number of sites per unit area is

N c + c++ 'c (4-21)


s n -
which may also be expressed as

I = 6n + 6+ + 6
-
(4-22)

in terms of fractional coverage (S=c/N). The surface charge


density may be introduced by writing s

0'0 e (c+ - c_)

Ns e(6+ - 6_) (4-23a)

or
0'
(l 0_ = 6
= __ - 6 (4-23b)
o 0' +-
max
where 0' = N e is the surface charge when all the available N
sites a~xoccu~ied by positive or negative species. s

If we consider negligible interaction among the sites, the


surface species will be randomly distributed with

N !
s
w = c !c !c ! (4-24)
+ - n
The total number of arrangements for the distribution of c ,c ,c
species on N distinguishable sites per unit area; Thi~
expression may snow be used to evaluate a configurational J30] or
entropic contribution to the potentials Iln , 11+ and 11. The
complete partition function (Q) for the surface layer ~y be
written
155

where q is the partition function of a site of type i. We make


use of ~e statistical thermodynamic relations

A kT In Q

and
lli
- = (6A/kT)
kT 6ci
T,clf:i

where A is the Helmholtz energy of the surface. The


configurational contribution to the chemical potential is
readily found

a+
-kT (Hnw) kTln
6c+ c- ,N s I-a -a
+ -

a
-kT (Hnw) = kTln
6c- c+,N s l-a~ (4-25)
+ -
where we have employed the Stirling approximation Inx! = xlnx-x.
On utilizing the results of (4-25) we write

-0 + kT a
ll+ ll+ In l-a+:e"
+ -
a
ll_ j';~ + kT In I-a :a (4-26)
+ -
-0 .
where the term II 1S the remaining part of the electrochemical
i
potential assumed to be independent of a. On introducing these
expressions for ~ and II and the appropriate expressions for ~+
+
equilibrium (equation (3-20c» we find after rearranging terms
a
+ -0 -0 -0
-In -a- + 2 In ~+ = - (ll_ + 2 llH+ - ll+)/kT
- b.'G0 /KT

In K.r~ (4-27)
156

where K+, K_ are the equi!.~brium dissociation constants for the


two steps in (4-19) and AG is the standard (electro chemical)
Gibbs energy for the reaction

MOH+ + MO + 2 H+ •
2 +

Next we introduce the electrical part (±e",) of the


o
electrochemical potential:

(jio _ ji: + 2ji;+)


kT (4-28)

as a mean electrostatic pOiential in the surface measured


relative to the potential. in the bulk solution which is
arbitrarily 'assumed zero. Equation (4-28) may be transformed to
yield with the aid of equation (4-27)

(4-29)
where
K K = exp(~+ - ~_ - 2~0 )/kT
1 2 H + (4-30)

-2F1j1 /RT
k+K_e 0

From equation(4-29) i t follows that at the point of zero charge


when "'0
= 0; 5+ 5 = 50

pH t(pK + pK )
pzc 1 2 (4-31)

The separate values of Kl and K2 may be obtained by defining a


parameter K

(4-32)

As Kl is small when the surface has a stong basic character and


K2 is large when the surface shows strong acid behaviour, pK will
be negative for reactive surfaces. From equation (4-19) we derive
157

KI 62 0-26 )2
n 0
K 6+6_ 2
2 6 (4-33)
0

therefore

1
6
2+1K IK
I 2 (4-34)

The fraction of positive or negative sites at the pzc is seen to


be related to the dissociation constants KI' K2. The more active
the surface is the larger will 6 be (see Table 1). The data
displayed in this table are based on a value of 9.4 for the pH at
the pzc [31] ,

Table 1

pK 5.6 2 0 -2.0 -5.6 -9.4

pKl 3.8 7.4 9.4 11.4 15 18.8

6 0.002 0.08 0.33 0.47 ~0.5 0.5


0

On making use of equation (4-31), equation (4-29) may be


rearranged to give the dependence of pH on the surface potential

(4-35)

This important relation shows that deviation from Nernstian


behaviour is measured by the second term on the right hand side.
r t may be shown to be a function of KI (=K2 /K) -1) and a. To
illustrate this we follow Smith [32] and consider a surfaceOonly
slightly removed from the pzc for which

a
o
6
o
Deviations from the Nernstian equation at low surface charge are
seen to be most serious when 6 is very small as would happem
when K is small (see(4-34) andtT~le 1). The exact expression for
the function f(K,a ) = (6 16) may be found by solving equations
(4-22),(4-23b) and o (4-33) +
as-was done by Dousma (31)
158

f (K, a) ~_1_ ) t f_o;;...-_ _~o;;...-_ _ _ ] (4-36)


o = 4K 1 - a
o
We may now write for the equilibrium concentration of hydrogen
ions in the solution phase (on the assumption of ideal behaviour)

[H+] = (K K )t exp(y ) f (K,a ) (4-37)


o 0

where y - ev /kT and [H+] exp(-y ) = [H] + is the concentration


of the °p.d. <ion in the solutioR immedia'lely adjacent to the
surface. Equation [4-37] serves as the a basis for calculations
of adsorption isotherms based on the three site (amphoteric)
model [31]. However, before this can be done we IIlUst find a
relation between y (V) and a (0). This would require
introducing the mode~ of ~he electr~cal 80uble layer. In the next
section we shall give a treatment of the theory if a few double
layer models.

On comparing equations (4-18) and (4-29) we conclude that for the


three site binding model the chemical potential of the p.d. ion
in the surface is determined by the expression

pSj = tkT In (K K )(6+/6 )


1 2 - (4-38)
which automatically fixes that electrical contribution to the
electrochemical potential. In a rigorous treatment of this and
also other models the mean electrostatic potential or the I~cro­
potential" equated to V should be replaced by a "micropotential"
which includes the s8lf-atmosphere or discreteness-of-charge
potentials which will differ for the positive and negative p.d.
ion [30]. These corrections will, however, only make sense once
our experimental information of such systems is in a more
advanced state than is presently the case.

We may also c~nsider a _two-site model for the adsorption of the


p.d. ions A and B from solution [31,33] where their
concentrations are related through the solubility product

We neglect non-ideal behaviour, for simplicity. The adsorption of


the cationic species may be expressed by the reaction

s + A+ + S
.. +
159

+
The adsorption of A will take place on site S and convert it
into S+ site. The charge of the surface will then increase by one
unit Whereas the difference (C+ -C_)F increases by two units.
These considerations show that

a
max
and

or
(9+ - 9_) = (29+ - 1) - a /a
o max = a 0
If we further define a equilibrium constant K3 for the reaction

S + A+ + S K3
- s + +

where [A+] = [A+] exp (-y ) is the concentration of the p.d ion
o
+ s
A next to the surface then the following relations are readily
obtained

-+ .
[B-]
K3 K pzc
[A ] pzc sp

and

We note that for this two-site model, at the pzc

9 .. t
0

It may be shown that for the three site model with 9


0
.. t [31]

[A+] = [A+] 9 t
(-±.) exp (e1jl0 /kT)
pzc 9
160

THEORY OF THE ELECTRICAL DOUBLE LAYER [5,37]

The diffuse double layer model of Gouy-Chapman

The simplest model of an electrical double layer is that of two


plane layers of smeared out charge with charge densities 0 and
o
-0 separated by a fixed distance o. For this "Helmholtz double
la~er", equivalent to a capacitor with parallel plates we may
write

e:e: (5-1)
o
ao =-0-1jIo

00 &&
C o o
-0-
<iTo (5-2)

where 1jI is the potential difference across the double layer, e:


is the 0 dialectric constant of the medium separating the two
layers of charge, e: is the permittivity of free space
(S.85xlO- 12 coulomb~/volt meter) and C is the capacitance of the
double layer.

A more realistic model for the double layer is that of Gouy-


Chapman, the surface charge-diffuse layer model dpicted in Fig.
12a. The charge density ad of the diffuse part of the double
layer which is equal in magnitude but opposite in sign to the
surface charge 0 is defined for a plane surface
o
0= t'Pdx (5-3)
d 0

where

(5-4)
is the (volume) charge density and ni(x) is the concentration of
ions of charge zi e at a point in a plane parallel to the solid
surface at a perpendicular distance x from the surface. To
evaluate 0d we make use of the Poisson equation in the form

~2~= _ p(x)
e:e:
dx o (5-5)

where 1jI is the mean electrostatic potential at position x in the


space charge region, and of the Boltzmann equation (to describe
the distribution of ions in the potential field of the double
layer)
161
(5-6)

where n. (0) is the concentration of ionic species of type i in


the bu1~ ~olution where p=O. The quantity z ew(x) represents
electric work to be performed on moving an ion from the bulk at t
x = '"' where the electrostatic potential is arbitrarily assumed
zero to a position x from the surface. On using the Poisson
equation to eliminate p in (5-3) and evaluating the integral by
applying the boundary conditions

dw/dx = 0 at x = '"'; dw/dx = (dw/dx) at x = 0


x=O

where W - W , one finds


o

°o - ££
o (5-7)

To evaluate the field strength at the surface the Poisson and


Boltzmann equations are combined to yield familiar Poisson-
Boltzmann (P.B.) equation in the form applicable to flat double
layers

~2~
(5-8)
dx

This expression may be integrated once on applying the boundary


conditions referred to above. If the solution contains a
symmetrical e1ectrolyte(z+ = Iz-I = z) with concentration no'
then

Isn
kT
(d1l1) = _ _0 _ sinh (zeW 12kT)
dx ££ 0
(5-9)
o
x=o

where 2sinhx = exp(x) - exp(-x)


and on substituting this result in (5-7) we find

0d = - 18££ kTn sinh(y 2) (5-10)


000

with y = zW IkT
o 0

For small W i.e. y 12 < 1, the hyperbolic sine can be expanded


o 0
and only first order terms to given

o KW0
00 = ££ (5-11)
162

t
where K
(5-12)

On comparing (5-11) with (5-1) we note that 11K represents the


thickness of the double layer but that in contrast to <5 it is
seen to vary inversely with the square root of the electrolyte
concentration or inversely with the square root of the ionic
strength I (=tz 2 c ).
o
The most general expression for K also referred to as the Debye-
Huckel parameter is

2", 2
e "zino(i)
K2 =--7'=~~
EE kT
o
For large double layer potentials when zeW /2kT > 5 or W > 250/z
mV (T = 250C), sinh(y /2) ~ texp(y /2) 0 0
o 0

thus
- 0d = ILEE n kT exp(y /2) (5-13)
o 0 0

The separate contributions of the cations (0+) and anions (0_) of


a symmetrical electrolyte may also be evaluated by writing

(5-14)

and a similar expression for o. After introducing the


appropriate form of the Boltzmann equation and completing the
integration we find

(2EE kTn )t [exp(-y /2) - 1] (5-15a)


o 0 0

-(2EE kTn )t [exp(y /2) - 1] (5-15b)


o 0 0

We note that the sign of the two charge density contributions


will be the same because the co-ion - the ion of the same charge
as 0 - will be repelled from the surface and thus. be present in
the ~iffuse layer in amounts less than in the bulk solution. It
is said to be negatively adsorbed. If Wo is positive then o±< 0
as well as 0 • For small values of W ~. e. for zw < 25 mV at
250C i t follOWs from (5-15) that 0 /0 0 = 1, that iso the counter
ion and co-ion contribution to 0 d + -
~s equal. For large values of
Wo the contribution of the co-ion to 0d tends to a limiting value
163

lim a+ (or a_) =(2££ kTn )t


o 0

2zen o
111 + CD =
o IC (5-16)

whereas that of the counter ion will keep on increasing


exponentially. The predictable negative adsorption manifests
itself as a slight rise of co-ion concentration measured in the
bulk solution and has been used to determine surface areas of
clays which carry a high negative surface charge [34]

The differential capacity of the diffuse double layer is obtained


by using the defining relation

da
o
d1llo
to yield

e = ££ IC cosh (y /2) (5-17)


o 0

It is seen to reach a minimum value at the pzc when 111 = 0


o
e mi = ££ IC (5-1S)
n 0

and to rise steeply and symmetrically on both sides of the pzc.

At 25 0e and with water as solvent (£=7S.49) the pertinent charge-


potential and capacity-potential relations may be summarized

a
d
=- 11.74/c
o
sinh 19.46z1ll
0

a = 5.s/c [exp(-19.46z1ll) - 1)]~e/cm2


+ o 0

lim aco-ion = 5.S7/c o


e = 22S.5 z/c cosh 19.46z1ll
o 0

where c is the concentration of a symmetrical z-z electrolyte in


moles/l~tre in the bulk solution, 111 is the double layer
o
potential in volts.

We note that the same basic treatment may be applied to the


diffuse double layer in the solid [35] and the double layer [36).

Modification of the Gouy-Chapman model

The beauty of the GC model of the electrical double layer lies in


164

its simplicity. The charge-potential relations can be calculated


with a minimum of assumption. Unfortunately, except in the
neighborhood of the point of zero charge quantitative agreement
between thoery and exper.iment is poor. There are a number of
reasons for this discrepancy.

a) The use of the Poisson-Boltzmann equation which is basic to


the theoretical treatment has been questioned. The quantity
zie1/l(x) appearing in the Boltzmann equation and interpreted as
tIle work done in bringing the ion from infinity to a point x in
the diffuse layer is not unambiguous. As the ion carries a finite
charge, its insertion at position x will cause a disturbance in
the ioaic atmosphere of the solid which is not accounted for as 1/1
refers to the mean electrostatic potential. It has been shown,
however, that for charged surfaces which carry many elementary
charges the use of the unmodified PB equation is allowed provided
the electrolyte concentration is not too high.

b) A more serious shortcoming of the model is that the charge


consituents of the .diffuse layer are treated as point charges. An
ion not only has a finite size but in aqueous solution becomes
solvated. The solvent (water) interacts with the ''bare'' ion by
electrostatic and ligand field forces and forms strongly bound
shells around it. There is normally an inner coordination sphere
of very strongly bound water molecules and an outer sphere of
polarized water molecules around the central ion. Clearly, this
ion cannot approach the charged surface indefinitely. In
addition, the solid surface itself is surrounded by at least one
layer of oriented solvent molecules.

c) Another important aspect of the solvation effect is that if an


ion were to become chemically bonded to the surface (specific
adsorption) it must penetrate the layer of the adsorbed molecules
and rid itself of part of its own inner sphere of solvent
molecules. The energy necessary for this adsorption process must
come from the strength of the solid/ion bond. Thus only the
strongest interactions can lead to specific adsorption. The
diffuse layer model also does allow for specific adsorption.
Clearly not only electrical work can be involved in moving an ion
from infinity to a position close to the surface for specific
adsorption. Other forms of work to be considered are (i)
displacement of the polar solvent molecules from regions of high
field strength to make room for such an ion, (11) crowding
together of ions already present and (iii) distortion of
displacing of the inner sphere of water molecules due to too
close an approach to the surface.

Correcti9ns based on points b) and c) were introduced by Stern


[29] in 1924 and by Grahame [37] in 1947. The modified model of
the electrical double layer which forms the basis for all
165
interpretations of experimental data is known as the Gouy-
Chapman-Stern-Grahame (GCSG) model. A problem with the
application of this theory to electrolyte adsorption studies at
the solid/liquid interface is the limited number of independent
experimental techniques available for making quantitative
measurements. This is in contrast to studies of the nercury/
solution interface for which a large number of experimental
methods have been developed [24]. The neasurements of surface
charge and especially the capacity of the double layer on nercury
provide the best check of the validity of the various double
layer models.

The Stern-Grahame modification of the diffuse double layer in the


absence of specific adsorption defines a region adjacent to the
surface which is charge-free, it is bounded on the solution side
by the outer Helmholtz plan (OHP) which defines the locus of
closest approach of solvated ions to the surface (Fig.l3). This
charge-free region wityh a thickness d of the order of the radius
of a hydrated ion is also referred to as the Stern region.

The introduction of an inner charge-free region accomplishes two


purposes. First, the potential at the origin of the diffuse or
Gouy layer is considerably reduced. This gives us more confidence
in applying the PB equation to calculate diffuse layer charge
densities. Second, the Stern region can serve as a catch-all for
all the complications introduced by the interaction of the
solvent with the surface. It is clear, for example, that the
potential difference b. (see equation [4-10] must fall in this
region. X

All the relations derived in the previous section will still


apply to the diffuse part of the GCSC model on replacing the
double layer potential ljI by the potential ljId at the OHP. Thus
for a solution of a z-z e~ectrolyte

(8££ kTn
o 0
)t sinh(zeljld/ 2kT) (5-19)

(5-20)

and

(5-21)

or
166

0'0
'+'0 o~p
I
I
I DIFFUSE
LAYER

--'l--DISTANCE

'Tl..

t ~--=~--i\.o

Figure 13

Model of double layer (GCSG) in absence of specific adsorption


a) potential- distance curve
b) concentration versus distance at low ionic strength
c) concentration versus distance at high ionic strength
167

eYO Oft
I
I I
I CYd
':HP:
I

<PO
IO:HP
I I

r
I J
I I
I I
'Pfl I
I
I
<Pd

.. DISTANCE ~

~
I
I
I
I

Figure 14

Model of double layer (GCSG) in presence of specific adsorption


a) illustrating the components of the inner region
b) strong specific adsorption at the pzc
168

(5-22)

We must however distinguish between the differential capacity of


the diffuse layer (Cd) and that of the entire double layer (C)

(5-23)

As the inner region of the double layer does not contain any free
charges, the potential will vary linearly with distance and we
may write (see equation (5-7)

(5-24)
a
o

where Ei is the dielectric constant of the medium in this region


of high electric field strength. The total differential capacity
of the double layer may now be formulated by inverting equation
[5-23]

(5-25)

This relation is analogous to the expression for the capacitance


of two condensers arranged in series. The capacity C commonly
referred to as the Stern capacitance may be defined b~tutilizing
equation [5-24] and solving for ~
o

ao
o=-+
~
C ~d (5-26)

(5-27)
An order of magnitude for C may be calculated.For water as sol-
vent we let E. ~ 10,a valuestlose to that for dielectric saturat-
ion,and choos~ d ~ 0.3nm to find C ~30~F/cm2.As C increases ra-
pidly with increasing surface char~~(equation[5-221)tthe capacity
of the double layer at moderately large values of a will be det-
ermined mainly by C .A plot of C versus a will ~ow the char-
acteristic minimum ~~lue of capacity at theO pzc(equation [5-18])
for low electrolyte concentration and rise to a plateau value
about 30~F/cm2 on both sides of the pzc. The assumption is made
here that C is a constant.Although qualitative agreement bet-
ween theory stand experiment(C vs a ) is obtained,it was assumed
that the lack of quantitive agreemen~
169

must be due to the implied constancy of C • There is no reason


to assume the thickness d of the inner reg~tn to remain constant
when the field strength varies. It may be decreased by
compression of the polar solvent with changing field strength
(electrostriction) and polarization of the nearest counter ions
and will also depend on the nature of the counter ion including
its size and degree of hydration. The choice of a value for E. is
also ambiguous, being a macroscopic parameter its introductioa to
a region of molecular dimensions is questionable. As it is
assumed that the dielectric constant in the diffuse layer is
equal to that of the bulk solvent, the abrupt lowering in its
value when entering the inner region is not defensible. This
illustrates our reference earlier to the Stern layer as providing
a catch-all for all ill defined and ambiguous structural aspects
of the double layer.

Grahame, for example, assumed C to be variable but a unique


function only of 0 • As this fuJltion could not be derived from
first principles i<t was empirically obtained from experimental
capacity measurements at high electrolyte concentration when l/Cd
approaches a value of zero. A way out of this dilemma may be
found if Wd may be evaluated by independent means. Electrokinetic
measurments give a zeta potential (~) which may be, and is often,
equated to Wd but the exact location of ~ relative to 1Pd in the
diffuse layer can never be made with certainty (see reference
32).

As pointed out by Mackor [38] one may also elect to retain the
concept of a constant Stern capacity C* and account for the
st
experimental facts by the dependence of the A potential
difference on the surface charge. Certainly the ori~tation and
polarization of the polar solvent molecules must be affected by
changing field strength. Mackor's suggestion is then to write

1 1 + .,!AX + 1
C= ~
st
do
0
Cd
(5-28)

Information about the role of neutral polar molecules on double


layer properties was obtained especially by the studies of
Bijsterbosch and Lyklema [11] and more recently by De Keizer and
Lyklema [39]. As pointed out by Smith [40] although the
adsorption of a neutral dipolar molecule cannot contribute to the
net surface charge it can affect the adsorption of p.d. ions and
thus o. For example, if such a neutral polar molecule is
introdu~ed in the solution at low concentrations so that the
activity of the p.d. ions is unchanged then it follows from
equation [4-10] that
170

d1/l - dAX
o
Suppose now that the dipolar molecules adsorb by orientating
their positive poles to the surface then 1/1 will change to more
negative values and therefore also 1/Id proviSed that 11/10 1 was not
already large. If this adsorption took place in a system
initially at the pzc this implies then that the pzc will be
restored after adsorption of the dipolar species only by raising
the concentration of the p.d. cation in the solution.

Specific adsorption of non-potential determining ions in the


inner region of the double layer

Specific adsorption may be defined generally as adsorption which


depends not only on the charge of the ion but also on its
chemical nature. One would therefore expect as a characteristic
of this type of adsorption, its occurence at the pzc. Although
this is a useful criterion for strong specific or chemical
adsorption, ions which do not adsorb at the pzc may react
chemically with the surface when 11/1 1 and 10 1 become large.
o 0

The structure of the inner region becomes more complicated in the


case of specific adsorption as is illustrated in Fig.14. A layer
of relatively immbolized, partially desolvated ions is introduced
at the inner Helmholtz plane (IHP) separated from the surface by
distance a. The condition for overall electroneutrality in the
double layer gives

°0 =- (OS + ad) (5-29)

where °
may even exceed in magnitude 0. Strong specific
adsorptiSn implies that at the pzc 0

Of:! = - °d (5-30)

The pzc is therefore no longer uniquely defined by a


characteristic pX where X is a p.d. ion, but will assume a
series of values ll~~ending on the concentration of the adsorbing
non-p.d. species. For example, in the specific adsorption of a
cation A on an oxide, the pzc will be displaced to lower pH
values with increasing concentration of A. The_ accumulation of
cations in the IHP promotes the ad~orption of OH on the surface,
hence a higher concentration of H (lower pH) is needed to make
° zero. On the other hand we note that adsorption of cation A at
tRe IHP will make 1/Id more positive and therefore the pH must be
increased to reduce 1/1 to zero. Two experimental criteria are
thus available for eva1.uating the occurrence of strong specific
adsorption; observation of the shift in pzc and the shift in the
point of zero 1/Id potential. As the zeta potential and not 1/Id has
171

an operational significance but the effect of specific adsorption


on changes in 1/1 and Z;; is identical, the second criterion for
specific adsorptfon is referred to as the shift in iep(the iso--
electric point, that is the point of zero zetapotential). It is
important to note that the shifts occur in opposite direction and
that only in the case of non-specific adsorption shall the pzc
and iep coincide.

We may also write

(5-31)

(5-32)

where CI and C2 may be taken as the capacities in the inner


regions of thicKness a and (d-a) respectively. If one assumes the
capacity per unit area of the whole inner region to be given by
the expression

e:oe: i (5-33)
Ki "'--d-
then
CI '" _a_ and C = (d-aL
Kid 2 Kid

It also follows that at the pzc

whereas at iep

1/1o -- 0
o/C I

For the charge density in the diffuse layer we may still write
for a symmetrical electrolyte

2e:e: KkT
0d '" - 0 sinh ze1/l/2kT
ze (5-34)

One might question the usefulness of this model of the inner


region of the double layer in the presence of specific
adsorption. Quantities such as £i ,Ct 'C 2 ' a, d have no operational
meaning and may only serve as ffttf"ng parameters when one tries
to describe the experimental data with this model.

An adsorption isotherm describing the dependence of the specific


adsorption density of non-p.d. ion i on its concentration in
172

solution may be derived in a manner analogous to that used for


adsorption of p.d. ions. We write the condition for thermodynamic
equilibrium between the ion i at the IHP and in the bulk solution

(5-35)

where a refers to the IHP and L to the bulk solution. Assuming


again localized ads.orp.tion at non-interacting sites then

o(a) 9
~i = Pi + kTln - -1-9
-- (5-36)

where the second term on the right hand side represents again an
entropic contribution to Pi and 9 is the fraction of the
available ~ites in the IHP occupied by the ion on the basis of
one ion per site. On applying the condition for equilibrium we
deduce

o(a) o(L)
_9_ - C [exp-(p
1-9 - -p )/kT]
i i i (5-37)

o
Ci exp (-AG-ads/kT)

o
where 6G d is a standard electrochemical free energy of
(specifier sadsorption, C is the equilibrium concentration
(neglecting activity coefdcients) in the bulk solution. Solving
for 9 we get

ri C
9
ri(max) = Ks+ Ci
(5-38)

0
where K exp (AG d /kT).
s a s

This expression for the specific adsorption of ion i resembles


the familiar Langmuir adsorption equation for gases on solids. To
illustrate the difference between ionic adsorption and that of a
(neutral) gas re
introduce now the electrostatic work of
adsorption z.e, as was done in the discussion of p.d. ion
adsorptibn: l.

(5-39)
173

If the number of r. of ions of type i adsorbed per uni t area is


far less than the afuount required for formation of a monolayer we
derive [41] from equations (5-38) and (5-39),

r.~ = ei [r max exp(-~Go/kT)] exp(-zie~~/kT)

= eiB.exp(-z.e~~/kT)
~ ~
(5-40)
where Bi is an equilibrium constant, i.e. the number of ions unit
area for unity concentration of ions of type i and vanishing
potential difference. The exponential term in equation (5-40)
accounts for the difference between the adsorption of an
electrical neutral and of a charged species. Even at low surface
coverage the adsorption density of ion i need not be directly
proportional to its concentration in the solution phase.

Suppose that only univalent ions are present of which only the
cation i is specifically adsorbed. If we con~ider now the
adsorption of species i at the pzc then d~ = d~ and according
to equations (5-7) and (5-9) 0

8e kT t
_ (___0___) sinh(e~~/2kT) (5.41)
££
o

where e is the total electrolyte concentration and where w~


suppose °the simple Gouy-Chapman model to suffice. Solving for ~
and substituting the result into equation (5-40)

(5-42)

where
-1
y 2 sinh OX} (5-43)

and
174

x = r i t (5-44)
i(PXC)~2££ C kT)
o 0

If X«1. we have

(5-45)

that is. the amount of ions of type i chemisorbed per uni t area
at the pzc is proportional to their concentration in the co-
existing solution and the presence of the electrical double layer
yields only a correction of minor Wportance. This implies that
the p. d. across the double layer ill/I = ill/I is less than 25 mV at
room temperature. 0

If the argument of the inverse hyperbolic sine is greater than


two. the inverse hyperbolic sine may be replaced approximately by
the natural logarithm of twice the argument. Thus

r i(pzc)

whence
r i(pzc)-- c il/3 c 0l/3 (2Bi ££ 0 kT/e 2)1/3
(5-46)

We note that this condition which requires X>4 implies that


riC pzc )/c:>
0
8/Ko For instance if riC pzc ) be 10 13 cm- 2 and c0 =
0.6xI018cm-3 corresponding to a molar concentration of 10- 3
mole/liter then r i ( )/c = I.6xIO-Scm and 8/K - 0.8xIO-Scm.
pzc 0

Also the concentration of co-ions in the vicinity of the IHP must


not exceed a value of about 1 mole/liter (0.6x10 21 cm- 3) since
above this concentration the Boltzmann equation does not apply.
not even approximately.

If these limiting conditions (x.>4) are fulfilled then we deduce


from equation (5-46)

a) ri(pzc) - c~/3 if only cations of type i are present.

b) r - c l/3 if foreign cations are present and c is kept


i(pzc) i constant 0

c) r - c l/3 if the concentration of the specifically adsor-


i(pzc) 0 bing species is kept constant.
175

This analysis of specific adsorption at low surface coverages


should be applicable for systems containing trace amounts of
"surface active" non-potential determining ions.

We note that the above treatment of specific adsorption is


subject to the validity 8f the expression for the electrostatic
work of adsorption ziel/l introduced in equation (5-39). This
problem was also referred to in the treatment of the adsorption
of potential determining ions. The charge in the IHP consists in
reality of discrete ionic charges. When an ion is moved into this
plane discrete charges will be rearranged and this must be
allowed for in writing the electrostatic work. Levine and
associates [40,42] pointed out that the rearrangement imposes a
self-atmosphere potential on the adsorbed ion and investigated
the consequences of this for the further analysis. It is
questionable whether the accuracy of the available experimental
information allows this refinement to be introduced in the
interpretation.

The amphoteric site-binding model and the electrical double layer


at the solid oxide/aqueous solution interface

One may now combine the t~eatment _of the three site or amphoteric
model for adsorption of Hand OH ions on oxides and the double
layer theory to calculate charge-pH and potential -pH curves. The
calculations make use of three equations [31]

exp(zel/io/kT)f(K,~o)
(K 1K2 )' (4-37)

(Bee kTn )1 sinh zel/id /2kT (5-19)


o 0

,',
"'0
= "'d
'"
+ 0 / C
0 st
(5-26)

To perform the calculations


. the parameters Kf,Kl,N s (0max ) and Cst
must be specif1ed. Kl and K are eva ua ed as discussed
previously from a knowledge of plI and e (or If). It should be
noted that in equation (4-37) wg suppoge b.$s = 1/1 which of
course implies that db. = o. The calculations baseS on these
three relations assume ~he absence of specific adsorption. The
results are summarized in Figures 15, 16 and 17 which are taken
from Dousma [31]. In Fig. 15 adsorption isotherms (0 /0 )
versus pH are plotted for specified values of the four par~me~~s
K ,K2 ,N and C at an ionic strength of O.lM. We note that
wlthout S the Ste~~-Grahame correction to the Gouy-Chapman diffuse
layer model (C = m) the maximum adsorption is reached much more
rapidly than tnt the modified GCSG model. In both models we note
that saturated adsorption is reached at shorter distances
176

1.0...-------------------------r

"

.....
......
a ......
----...... .......
...... .......

8.0 10.0
pH

Figure 15

Calculated curves of cro/crmax vs pH in absence of specific adsorption,


taken from Dousma [31]
Ionic strength 0.1 M
pHpzc = 9.4 2
cr = 1.2 clm
max

Curves pK = pK2 - pK 1 Cst


a 5.6 5F/m2
b 2.0 ,,
c 0 ,,
d -2 ,,
e 5.6 00

f 2.0 ,,
g 0 ,,
h -5.6 ,,
177

d c b a

¢d (mV)

== (pH.
p. z. c.
_pH)

Figure 16

Calculated curves of ~o and ~d vs ~pH after Dousma [31].


Paramaters used in calculating the potential-pH curves are the
same as those introduced in Fig. 15
Nernst equation
TWo-si te model
178

1.0~------.,----------------....,

a:Cstern = 5 F/m 2

b:C =00
stern

p. z. c.

OL--~--~----L-_~ __ ~_~ __ ~~_~

2.0 4.0 6.0 8.0 10.0


pH

Figure 17

Calculated plots of 0o/omax vs pH according to different models


after Dousma [31]
a~photeric model pK = -5.6
- - - - - - two site model
°max = 1.2 C/m2, ionic strength 0.1 M
179

(pH -pH) from the pzc when pK is negative (K small) that is when
theOfraction of charged sites at the pzc (a ) approaches a value
of t (see Table 1). All the curves are sj>mmetrical around the
pzc. The continuation of the curves beyond pH = 9.4 is therefore
not shown in Fig.lS. A change in the pzc at c8nstant pK (a ) will
give curves displaced parallel to those shown for pH = 9~4. The
calculated dependence of land Wd on pH are ilfustrated in
Fig.l6. It is interesting toO note the deviation of the calculated
curve (W vs pH) from the Nernst equation (dashed curve) near the
pzc at Righ pK values (low a ). Except at high ~pH (pH -pH)
values when charge saturatio~ (a ) is reached the PN~rnst
equation is seen to be obeyed ratherma~ll for low pK's. A similar
behaviour is also noted at lower and perhaps more realistic
values of C (e.g.O.S F/m 2 ). It would appear therefore that only
for 0 ao st 0.08 noticeable deviations from the Nernst equation
are to be expected for the chosen set of parameters (K 1 ,K2 ,
etc.) •

We also note that the Wd versus pH curves overlap for different


values of a at low ~pH values except again when a < 0.08. Now
it would apBear from this analysis that i f a is sn&ll and if l
is assumed to equal approximately the zetJ> potential, a ana
o
therefore values of Kj and K2 can be obtained. This procedure has
been developed by SmHh [31r and the reader is referred to this
excellent paper for details of the method. This author found from
micro-electrophoresis measurements on silica samples a ~ 0.001.
A larger value of a was indicated from electrokinetic ~tudies of
rutile suggesting t~at the deviation from the Nernst equation is
less severe for this oxide.

Stumm and co-workers [43,44] claimed that pK} and pK 2 could be


obtained by an extrapolation procedure whicn is also used by
Davis et al [26]. They write correctly for the adsorption
reaction
+ !
MOH 2 MOH + H+ (aq)

To evaluate pK l the ratio (a /a ) DD.lst be known at the pzc. To


obtain this ratio these autho~s assumed that at positively
charged surfaces a = a / a = a and a = 0, which is true
reasonably far fro: the Y,zc~~om ~ plot of pH + log (a /l-a )
versus a , pK l is then obtained by extrapolation to a = 8. Th~s
extrapol~tion to find pK l is, however, not valid bec~use it is
performed through a region where the stated assumption (e = 0)
is not realistic. After all, at the pzc, e must equal e • -
+ -
180

The results obtained with the two-site model of Stol [33] are
included (stippled curves) in Figs. 16 and 17. We note that the
two-site model yields curves nearly identical with those derived
from the amphoteric model for e = 0.5. The two-site model
proposed by Stol might !1-e prefe.!ab~y applied to the description
of the adsorption of Ag and r on silver oxide. However, this
model also gives adsorption i.sotherms which are sYDDDetric around
the pzc, whereas asymmetric experimental curves are found for
silver iodide (see Fig.4). A possible model which could account
for this aSYDDDetry would be one which features four distinct
sites. Such a model was suggested by Healy and White [27]
although not in this context. This model when applied to Agr can
be described by the surface reactions [31].

SAg + Ag+ (aq) t S+ K1

(aq) t S

and in combination with the following relations

K
sp

nAg + nS NS/2
+

nr + nS N /2
s
C1 =(n - n_)F
0 +
may be solved to obtain theoretical isotherms. The sites S+ and
Sr and the sites S_ and SA are not identical as would be the
case for a two-site mOiel.g This distinction implies that, for
example, an adsorbed Ag ion is distinguishable from a surface
lattice ion.

A similar approach may be introduced to obtain aSYDDDetrical


adsorption curves with oxides. One might distinguish between two
types of IDH site as was already suggested in the discussion of
the Lewis acid/base surface structure p.!evio~sly. Some of these
sites act as Bronsted acids· ID H -+- MO + H, these are those
sites where 0 is a surface O~i~ ion; 3ther MOH sites are pred-
ominantly bas~ sites, IDH + M + OH-, the 0 in this site is the
oxygen of the dissociated water molecule and not a surface oxide
ion. This site may also show acid behaviour but not as strongly
as the MO H site. It is likely that a greater aSYDDDetry will be
introduce! in the calculated adsorption curves i f a distinction
is made between_ oxide ions and ox~en in the surface due to
adsorption of OH (or desorption of H ).
181

The asymmetry in the adsorption curves on oxides up till now has


always been introduced by an amphoteric model in the presence of
specific adsorption. This entails the addition of the adsorption
reactions [26,31]
+ - + +
MOH + As ... MO
+
-- A + Hs K3

whert A+ and B are specifically adsorbed ions in the IHP where ~


= ~ and by making use of equations [5-29], [5-31] and [5-32]
which describe the double layer in the presence of specific
adsorption. Details of the calculations needed in plotting the
adsorption isotherm for the p.d. ions (Fig.18) and the ~d versus
pH curves (Fig.19) may be found in the doctoral thesis of Dousma
[31]. Fig.18 clearly demonstrates that specific adsorption of
anions introduces asymmetry into the adsorption curves and a
shift of the pzc to higher pH with increasing ionic strength. The
~ versus pH curves in Fig.19 illustrates that specific
a8sorption of anions displaces the iso-electric point in the
direction of decreasing pH with increasing ionic strength, in
agreement with our earlier discussion. This is also in qualitative
agreement with the results of Breeuwsma and Lyklema [16] who
experimentally determined such shifts in the adsorption of anions
at the iron oxide surface. A disadvantage of this model is the
large number of adjustable parameters needed in the analysis. The
list of required parameters includes K1 ,K2 ,K3 , K4 ,C 1 ,C 2 and Ns •

COMPARISON BETWEEN EXPERIMENT AND THEORY

A limited number of experimental techniques have been used in the


study of the adsorption of electrolytes at the ionic/ solution
interface and in the correlation of adsorption results with
double layer properties. The adsorption density of p.d. ions is
measured analytically with the potentiometric titration method
and indirect information about the double layer potential is
obtained from electrokinetic measurements.

Detailed information on the structure of the ionic double layer


may also be obtained from the observed variation of the
differenctial capacity which is operationally defined as

d(z+r x - z r y ) do
o
C • d(pY.pY ) (6-1)
d(pX - pX)
pzc pzc
182

~/crmax

-0.05

8 9 10
= pH
Figure 18
Calculated plots of O%max vs pH in presence of specific adsorption
and varying ionic strength after Dousma [31]
a: 0.001 M b: 0.01 M c: 0.1 M d: 1 M
Arrows indicate position of pzc
The following parameters were used in making the plots:pKl = 5.1,
P K2 = 10.7, this fixes pzc at pH 7.9 in absence of specific
adsorption
Cl = 1.4 F/m2, C2 = 0.2 F/m2 2
0max = 1.2 C/m2 in agreement with 8 sites/nm
pK3 = 10.5, pK4 = 9.0. This choice allows for strong specific adsorp-
tion of anions. A decrease in pK3 below chosen value results in in-
creased adsorption of cations; a decrease in pK4 results in a de-
creased adsorption of anions.
183

80
IjJd
0.001 M

pH __~~---------

Figure 19

Calculated plots of ~d vs pH, arrows indicate i.e.p. (after Dousma


[31]). All physical parameters used in the calculations are the
same as those used in Fig. 18.
184

where the validity of a Nernst-type expression relating the


double f!yer potential 1/1 to the solution activity of the p. d.
ions XZ and yZ- is ass<tmed. Unfortunately this assumption is
seldom justifiable because of lack of equilibrium between the two
bulk phases. The expression for C must then be modified

C
(6-2)

where the correction term (dpY/d1/l) must be evaluated by


introduction of suitable model. 0

The pzc and iep of ionic solids

Both pzc and iep are quantities which may be determined by


experiment. A knowledge of the pzc is important and basic to the
interpretation of the adsorption of ions at the solidi solution
interface and to the description of the stability of colloidal
suspensions. We have seen that in the absence of specific adsor-
ption the intrinsic pzc will coincide with the iep.

The most reliable pzc data are obtained by two experimental met-
hods.(a)In the absence of specific adsorption the a vs pX curves
at different ionic strengths will have a commono intersection
point. If specific adsorption does occur at high ionic strength
the pzc will shift and will be determined as the intersection
point of the adsorption curve with the zero charge axis deter-
mined at low ionic strength or in the absence of the chemisorbing
ion at a fixed ionic strength. (b) Berube and De Bruyn [14] proposed
an alternative method based on the consideration that the pX of a
solution containing an indifferent electrolyte will change upon
the addition of the uncharged solid except at the pzc(see Fig.9).
I t is essential that the dry solid, for example, an oxide, does
not contain free acid or base before being added to the solution.

The iep of solids are usually observed by electrophoretic or


streaming-potential measurements and from the suspension effect
[45] as measured in the electrical cell

settled
calomel electrode A Isuspension I supernatantlcalomel
of solid liquid electrode B

An extensive review of pzc and iep values for simple and complex
oxides have been made by Parks [46,47]. This author did not
always distinguish between pzc and iep measurements. Honig and
Hengst [45] have tabulated iep values for a large number of
slightly soluble inorganic salts measured by the suspension
185

effect technique and compared their results with other types of


measurement.

Most of the accumulated data on pzc show wide variation among


different samples of the same type of oxide. This is sometimes
true even for synthetic samples prepared by supposedly identical
methods. These variations are, however, mainly traceable to
different methods of preparation and the presence of small
(sometimes trace) amounts of impurities. Heat treatment of oxide
materials has been observed to cause a drastic lowering of the pH
of the pzc at high temperature.

The effect of small amounts of impurities introduced in the bulk


solid on the location of the pzc was quite exhaustively studied
by Honig and Hengst [25] with si1¥$r brom:f..de as solid. Small
amounts of divalent impurities (Pb and S ) were 0Wrved to
yield strong shifts in the pzc. Incorporation of Pb in th~
crystal at a lattice site will create a silver vacancy or a Br
interstitial site to preserve electroneutrality. One would e~pect
the pzc to shift to higher pAg (lower concentration of Ag ) in
the solution. This was indeed found to happen. The pzc of AgBr
shifts to a lower pAg i f sulphur is incorporated in the lattice
because of the creation of interstitial silver ions in the
lattice. Only certain foreign ions can be incorporated in a
crystal, usually ions having about the same radius as those they
replace. The effect of incorporation of foreign ions in the
surface of a solid during precipitation on the pzc has also been
determined by Blok and De Bruyn [15,48]. They noted a lowering of
the pH with increasing amounts of incorporated anions.
pzc
When a particular solid consists of more than two p.d. ions
instead of one intrinsic pzc, a series of pzc's will be observed,
for example, if a solid has three p. d. ions then a "solubility"
surface may be obtained when the equilibrium concentrations
(activity) of the three p.d. ions are plotted on three mutually
perpendicular axes. The coordinates of all points lying in this
surface will satisfy the conditions for heterogenous equilibrium.
On this surface one may then locate a line or curve connecting an
infinite number of pzc' s. Saleeb and De Bruyn [49] were able to
measure several iep' s (pzc' s~ for++a numbp of alkal_ine e!rth
apatites M10(P04)6Z2 with M=Ca ,Ba or Sr , and Z=OH or F in
agreement with this hypothesis.

Attempts .have also been made to correlate the pzc of oxides with
their bulk properties. One method of predicting pzc' s of simple
oxides and hydroxides [50] is based on locating the pH of the
minimum solubility of the solid in solubility diagrams (Fig.6). A
second method due to Parks [46.47] is largely based on an
approach similar to that used to estimate the acid strength of a
186

series of oxyacids. I t utilizes physical parameters such as ionic


size. effective charge of a surface metallic cation. the coor-
dination number. and introduces an empirical correction for CFSE
(crystal field stabilization energy) in the case of transition
metals. Parks was able to find an empirical predictive relation.
largely based on the ratio Z/R. with Z the oxidation state of the
cation and R the separation distance of an adsorbed proton from
the metallic cation (diameter of oxygen + radius of metal
cation). Yoon. Salman and Donnay [51] later on proposed an
improved version of this empirical relation.

In all these attempts to calculate the pzc from fundamental phy-


sical parameters a major uncertainty arises because the surface
need not be representative of the bulk solid in stoichiometry.
structure and hydration. The condition of the oxide surface will
reflect its past history. The pzc should also be a function of the
orientation of the exposed surface as was shown by Boddy[52.53]
to be the case for hydroxylated surfaces on the semiconductor
solid. germanium.

Adsorption isotherms

The accumulated adsorption data(a versus pX)for p.d.ions point


o
to some conspicous differences between the double layer on oxide
materials and on the sparingly soluble solids. silver iodide and
silver sulphide and on liquid mercury. These differences are in
part. we believe. related to the more active role of water in the
formation of the double layer on oxides compared to its "spec-
tator" role in the other systems.In Fig.20 taken from Furlong et
al [12] adsorption curves for some simple oxides are compared
with the a -~pAg curve for silver iodide. The ~pAg scale not indi-
cated in tRis figure coincides in size with the ApH scale.In gen-
eral.exept for the silica. the surface charge of all oxides at co-
mparable displacements from the pzc are considerably greater than
that found on AgI.Ag 2S or Hg.Thus it is found that a on negative
oxide surfaces reaches values of the order of tens 8f ,-,C/cm 2 and
only few ,-,C/cm 2 on the other solids and liquid mercury.

The adsorption curves on oxides are also more symmetric in shape


compared to the other systems. Whereas the curves on oxides are
convex towards the pH axis the curves for AgI (and also mercury)
are slightly concave. For both oxides and silver iodide the
adsorption curves on positive surfaces are convex to the pX axis
but the magnitude of a on oxides again exceeds that on the other
system. For most oxidg systems the order in the specificity of
adsorption of ions belonging to a lyotropic series is the reverse
of that found on either mercury or silver iodide. Thus. for
example. the specificity in the adsorption of the alkali metals
on Fe 2 0 3 [16] and on Ti02 [54] in moderate salt
187

Figure 20
Some experimental ao vs ~pH curves for 0.1 M 1:1 electrolyte.
For comparison the adsorption zurve for AgI is included, the ~pAg
scale is the same as ~pH.
- - - - - - - - TiO iNaNO
2 3
. . . . . . . . aFe 20 3i Kcl
_ _ _ _ y-A1 2o/NaCl
_______________ Ti0 2KN0 3
_ • _ • _ . _ a-FeOOH/KCl
Taken from [12]
188

concentrations increases in the order Li+ '> Na+ ~ K+;> Cs + which


is also the order of increasing hydration of the ions. The
opposite order in specificity is observed on silver iodide [11].
Similarly the observed specificity in the adsorption of the
halide ions on Fe 2 0 3 [55J, Ti02 [541 and ZEO [48J is the reverse
of that found on mercury, V1z C1 ".> Br > I . The order of
specificity of adsorption of alkali ions for silica [56,57] and
other oxides, 6-MnO [58], W 3 ' for which pH < 3 ¥ a~a1n in
agreement with the sequence found on silver i8&fde (Cs '>Li ).

The high surface charge values measured for oxide materials


however do not manifest themselves in particularly high zeta
potential values [12]. this would imply that most of the counter
ion charge must lie inside the shear plane where the I; potential
is located. This observation is also in agreement with the normal
stability characteristics of colloid suspensions of oxides [55]
again with the exception of silica.

It may be argued[59lthat the high surface charge measured on


oxide materials results from the assumption that the adsorption
is restricted to a two-dimensional surface layer.If the adsorbing
species are able to penetrate a thin but three dimensional sur-
face region then the effective surface charge will be smaller.
Onoda and De Bruyn[17]proposed that adsorption on hematite is
controlled by a superficial shell of hydrated oxide,perhaps sim-
ilar in composition to goethite. Berube et al [60] concluded from
tritium exchange studies that the hematite surface is covered by
a surface olayer which,if goethite-like in composition,would be
about 13.3A thick.Breeuwsma estimated from differential thermo-
gravimetric analyses and assuming a goethite-like composition a
surface layer varying in thickness between 15 and 25A.Tritium
exchange studies on Ti0 2 [14]however,do not support the existence
of a thin hydroxylated surface layer on this oxide. Tadros and
Lyklema [57] proposed a porous double layer model to account for
the exceptionally high surface charge measured on precipitated
silica in contrast to the low surface charges found on non-porous
pyrogenic silica.

Curve fitting and model testing

Three basic models have been proposed to account for the


adsorption of p.dions. These models are (a) the site-binding
model discussed in some detail. The section above on Electro
chemistry of the Electrical Double Layer. (b) the patchwise
interfacial hydration model [39], an extension of the Mackor
treatment [39] and (c) the solid state model [61] or double
diffuse layer with a surface layer. The first and the second
model consider the surface charge to originate as a monolayer
through adsorption of the p.d.i. at localized sites in the solid
189

surface. The main difference between two models lies in the


explicit focus on the solute and solvent orientation at the
surface by the patchwise hydration model. This model recognizes
that the description of water and other dipoles near a surface or
interface remains one of the most difficult problems. The
hydration of the surface of a solid in aqueous solution is
treated as a patchwise phenomenon in which the orientation of the
water dipoles varies along the surface. This idea is applied to
the AgI sy~tem where besides the neutral surfa5e, positively
charged (Ag) patches and negatively charged (I) patches are
distinguished. The orientation of water dipoles near an adsorbed
iodide ion is expected to differ from that near an uncharged part
of the surface and also near an adsorbed +silver ion. The
effective orientation o.! water molecules on Ag patches will be
stronger than that on I patches and this difference is believed
to account largely for the asymmetrical location of the pzc and
the asymmetry of the pzc and the asymmetry of the 0 vs pAg
o
curves.

The solid state model which has also been applied to the silver
iodide system, emphasizes the solid state properties of Ag1 by
expecting the defect structure to play an important role in the
formation of the double layer. For the interface ionic
crystal/electrolyte solution this leads to a double diffuse
double layer, modified with in addition a fixed surface charge.
This surface charge is due to a difference in free energy
formation of intersitials and vacancies in the bulk of the
crystals compared to their formation at the surface. Honig [61)
was able to obtain a good fit with the experimental adsroption
curves by adjusting the values of two imporant parameters of his
model; the fraction if the number of lattice defects in AgI of
0.17% and the potential difference between the solid surface and
the solid interior of -53mV both at 20DC.

The performance of the site-binding model in re~roducing_ the


experimentally observed adsorption isotherms of Hand OH on
various oxides and hydroxide solids has recieved much attention.
We have seen that the three site, amphoteric model includes a
number of physical and chemical parameters. The total number of
parameters will depend on whether specific adsorption is included
in the modeling procedure. To account for specific adsorption the
GCSG double layer becomes a triple layer (surface charge, layer
of specifically adsorbed non-p.d. ions and the diffuse layer). Of
the parameters in the site-binding model the maximum number of
available adsroption sites N may be determined independently by
tritium exchange measurementSs or from crystallographic surface
analysis [12). The specific surface can also be evaluated
separately, for example, by BET gas adsorption measurements. One
may, however, ques tion the applicability of this technique to a
hydrated surface in contact with an aqueous solution. It would be
190

extremely difficult to predict by independent means values of the


equilibrium constants K!,K2 etc. for the proposed adsorption
reactions and the capac ty of the inner region of the double
layer. These quantities will depend on the degree of structure in
the water layers adjacent to the surface and therefore on the
nature of the surface. These parameters can only be "adjustable
parameters", the values of which are obtained by optimizing the
fit of the model to experimental data.

Westall and Hohl [62] developed a mathematical procedure for


parameter adjustment to obtain optimal fit of the model to
experimental data. In making these fits they have introduced five
different electrostatic models of the <louble layer, varying from
the simple Helmholtz model to .the triple layer, GCSG model for
specific adsorption. They found a wide raange of parameter values
to yield an optimal fit of a given electrostatic model and
concluded from this that there is no unambiguous way for
separating the adsorption energy into chemical and electrostatic
components. They also found that all five electro-static models
can represent the experimental data equally well, but the values
of corresponding parameters (K1 ,K2 ,c 1 ,C Z etc.) in different
models are not the same although all of the adjustable parameters
have physically reasonable values. We must therefore conclude
that the models although of the correct mathematical form to
represent the data empirically, do not necessarily give an
accurate physical description of the adsorption.

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99, 1972
50. Parks, G.A. and De Bruyn,P.L., J.Phys.Chem.,66, 967, 1962.
51. Yoon, R.H. ,Salman,T. and Donnay, G. ,J.Colloid and Interface
Sci. ,2Q.,483, 1979
52. Boddy,P.J.,J.Electroanal.Chem.l0, 199,1965
53. Boddy,P.J.,Surface Sci., 13, 5~ 1969
54. Berube, Y.G.and De Bruyn,~L., J.Colloid and Interface Sci.,
1!!., 92, 1968
55. Dumont,F.and Watillon,A., Disc. Faraday Soc.,52, 352, 1971
56. Malati,M.A., Disc.Faraday Soc., 52, 377 ,1971-
57. Tadros,Th.F. and Lyklema, J.,J.Electroanal.Chem.,17, 267,
1968; B., I, 1969 -
58. See Reference 43
59. De Bruyn, P.L., Phys. Chem.Liq. ,1., 181,1978
60. Berube, Y.G., Onoda, G. Y. and de Bruyn, P.L., Surface Sci.,
8, 448, 1967
61. Honig, E.P., Trans. Faraday Soc., 65,2248, 1969
62. Westall,J.and HOhl,H.,Adv.Colloidand Interface Sci., Q,
265, 1980
193

EXPERIMENTAL TECHNIQUES IN FLOTATION

G.J.Jameson

Department of Chemical Engineering University of


Newcastle, N.S.W., 2308, Australia

INTRODUCTION

The last decade has seen a flowering of experimental techniques


applied to flotation. Some have been no more than an extension of
modern instrumentation for chemical analysis, as applied to
specific flotation problems. But there has also been a number of
simple yet il.luminating experiments devised to shed light on
particular flotation problems.

The number of experimental techniques which have been used is as


great as the number of individual problems associated with
specific ores, minerals, oils, potable and waste waters etc. to
which flotation is applied. To reduce the field to manageable
proportions, this review is directed toward techniques which have
been devised to gain insight into the basic mechanisms of the
flo.tation process in general.

There is no doubting the difficulties usually facing an


experimentalist in the flotation field, nor can one fail to
appreciate the ingenuity and skill which has been brought to bear
on the various problems. Nevertheless, a technique is only as
useful as the progress which it affords in the subject to which
i t is applied. Accordingly in this review, the results of the
experiments will be given equal prominence with the techniques
themselves.

THE CAPTURE OF INDIVIDUAL PARTICLES

Readers of Taggart's invaluable tome [1] cannot fail to detect


the undercurrents of controversy which surrounded early
speculation about the mechanism of bubble-particle attachment.
194

One theory was that bubbles grew by precipitation from solution


on the surface of the particles, which was rivalled by the
"coursing" bubble theory, in which bubbles rising through the
pulp were held to collide and coalesce with particles if the
surface conditions of the latter were appropriate. These theories
have been discussed at length by Klassen and Mokrousov [2]. The
collision mechanism is now thought to dominate in all processes
except those in which bubbles are formed deliberately from
supersaturated solution.

Strong support for the collision theory was provided by the


experiments of Bogdanov and Filanovski, [3] Spedden and Hannen,
[4] Whelan and Brown [5] and Bennett, Chapman and Dell, [6] who
observed collis.ions taking place with high-speed photography.

The cine film of Spedden and Hannen showed that when larger
particles struck the bubble, it was possible for the bubble's
surface to deform elastically. The particle was seen to bounce
off without making contact, even if it was hydrophobic, an
observation which has been confirmed many times since. This
observation led a number of authors, notably Sutherland [7]
Philippoff, [8] Evans [9] and Eigeles, [10] to postulate that
there was an "induction time" necessary, to allow the thin liquid
layer between bubble and particles to drain away and permit
coalescence to occur. If the "induction time" were less than the
"contact time", i.e. the time available while the particle
approached the front of the bubble, then moved sideways and
travelled around the nose, coalescence could be assumed to occur.

The induction time concept is certainly valuable in that it gives


a physical explanation of the resistance which must be overcome
before bubble and particle can coalesce. Nevertheless, it has
rather limited validity. For any particular particle-bubble
combination, there is no single induction time, because the
behaviour of the couples will be strongly influenced by the
relative positions of the two bodies before the capture process
begins. The trajectory taken by the same particle will obviously
vary according to its initial position relative to the bubble in
the flow field in question, so the induction time will also vary.
The alternative approach to this concept is however much more
complex, because it involves the solution of the equations of
motion around the two bodies, which may not be possible in an
analytic form except in special cases.

An early attempt to provide a more complete analysis of viscous


effects in the interaction of particle and bubble was provided by
Flint and Howarth [11]. They solved the equations of motion, so
as to be able to predict the trajectories of particles
approaching a bubble. Their theory was tested against
experiments, using an apparatus shown in Figure 1. They did not
195

actually use bubbles and particles, but rather fixed nylon


spheres, pas.t which was circulated a stream of glycerol solution
containing a suspension of glass beads. The Reynolds number of
the system, based on the flow past the fixed nylon spheres, could
be altered in the range 4 to 250, a range considered by the
authors to be similar to that achieved in a flotation cell.

CaimllK,I and
straiQ~n9
HCtIon

Injection line

LoacIInQ
ella

WorklnQ MCtIon

Drain
Air
bleed
line

Line to initially
fill caIurM

Figure 1. Apparatus of Flint and Howarth [11] for observing


particle collisions.

Flint and Howarth did not measure "contact" between spheres in


their system, but measured the position of the glass beads
relative to the fixed spheres as a function of times, thereby
determining the trajectory experimentally, so that they could
test their theory. Their results, Figure 2. showed that at large
Reynolds numbers Re > 100. the trajectories followed almost
exactly the predictions from potential theory which had
previously been given by Sutherland.[7] while at intermediate Re.
there was some deviation toward the predictions based on Stokes'
theory, which is strictly valid only for Re <<: 1. The curious
feature of the theories is that the trajectories for particles at
low sphere Reynolds numbers, is almost identical whether a
potential flow or a Stokes flow is assumed. The termination
196

Ca)

e---e-
4

o 3 4

Ce)

Table 2. Results from Flint and Howarth (11]. The points


represent the experimental trajectory under various
conditions.: (a) Re=234, K=O.046, G=O.049; (b) Re=30,
K=O.015, G=O.l; (c) Re=5.6, K=O.0028, G=O.53. The line
is the Stokes trajectory and the dashed line is for the
potential flow theory.

point of the trajectories on the fixed sphere was essentially the


same in each case, at least for small values of the parameter

K = p d 2 U/9~ db (1)
P P
which are obtained in flotation (K « I).

A similar type of experiment, using air bubbles as the collector


sphere, was conducted by Schulze and Gottschalk. [l2] A relatively
large bubble, about 3mm diameter on average, was formed and
maintained on the end of a capillary tube, and small spherical
particles of diameter I60~m and density p = 2500kg/m 3 were
allowed to fall toward it through water; the? water could also
flow downw~rd past the bubble, so that the mean approach velocity
of the particles was about 10cm/s. The particles were made
hydrophobic using 10- 5 molar dodecylamine hudrochloride.
197

Their results were interpreted in terms of the potential flow


model of Sutherland.[7]

From photographic results, Schulze and Gottschalk were able to


show that at some distance from the bubble, the particles
followed the potential flow theory. As the particle approaches
within one or t.wo particle diameters from the bubble surface
however, discrepancies appear, and the velocity components of the
particles are markedly different from the calculations of
potential theory. For their purposes, the zone around the bubble
was di vided into a "collision" zone, extending up to about 30 °
from the axis, where particles were seen to impinge upon the
bubble but not to coalesce; a "sliding" zone where particles
would approach very close to the surface and slide around it,
perhaps sliding to the meridian of the bubble at 90° from the
axis. If attachment was to occur, it was usually seen in the
transition region between colliding and sliding, between 30° and
450 from the axis.

The collection efficiencies of single particles were also


measured, being defined as the ratio:

E (2)
c
where db is the radius of the bubble, and d is the radius of the
"tube" ahead of the bubble in the flow field, within which any
particle which is to collide and coalesce with the bubble must
initially have found itself. Any particle distant further than
(d/2) from the axis of the system will then escape collection.

The results were in reasonable agreement with the predictions of


Flint and Howarth [11]:

E
c
= G/(l + G) (3)

2
where G = (p
p
-p) d g/18~U,
f p
and also with an expression of Fonda and Herne. [13] However, the
simple result of Sutherland: [11]

(4)

tended to underpredict. There was considerable scatter in the


experimental data.

From their observations, the time of collision was no greater


than 4ms, i. e. at tachment took 1 to 4 ms to occur; the sliding
time, i f sliding without attachment took place, was 30 to 50ms.
198

Accordingly, in their experiments the induction time was not


constant but varied with the angle <I> from the axis at which
contact with the bubble was first made, i. e. the impingement
angle. The expression for the induction time

t. =n (d 3 P 112Y)! (5)
~ p p
due to Philippoff [8] and Evans [9] was found to give induction
times about one-half of those observed.

The general picture emerging from these experiments is that for


the circumstances for which they were devised, i.e. the
interaction between a bubble rising through a dilute stationary
suspension of particles, the simple hydrodynamic theories of
Sutherland, and Flint and Howarth, give reasonable predictions of
the behaviour of the particles up to the point when they make
"contact" with the buhble. From this time onward, they do not
make proper allowance for the drainage of the thin liquid film
between particle and bubble.

This deficiency was highlighted in a most illuminating way by


Anfruns and Kitchener. [14] They measured the collection
efficiencies of single bubbles which were released individually
and allowed to rise up a cylinder of water containing either
quartz or glass ballotini, of diameter about 30]Jm in each case.
The bubble diame.ters were in the range 500 to 1000]Jm. The bubbles
were caught individually at the peak of their ascent, and the
number of attached particles as seen through a microscope were
counted. The particles had previously been rendered hydrophobic
by treatment with trimethylchlorosilane. A sketch of their
apparatus if shown in Figure 3.

A very marked difference in behaviour was observed between the


glass spheres and the jagged, angular quartz particles of
essentially the same density and hydraulic diameter. as shown in
Figure 4. The results for quartz particles were in quite good
agreement with theories like Flint and Howarth I s [11] in which
attachment is assumed to occur when grazing contact is made, i.e.
when the streamline of the particle approached to within one
particle radius of the bubble I s surface. The glass spheres. on
the other hand, gave collection efficiencies very much less than
predicted by such theories, the discrepancy being almost an order
of magnitude.

Anfruns and Kitchener attribute the difference in behaviour to


the angular shape of the quartz, which can more easily rupture
the thin liquid film between the particle and the bubble. The
hydrodynamic theories have been criticised [15] as not taking
199

g.--- Microscope

Sample

.--:-:-~:qC
Vacuum '"
"'"
1rCollection
Three"'.. way
,,
ta,!s . J section

Constant
,
head water ~=.:;-,

.(I)
,::":',
Suspension
container

-- ---
Rotating tap for
bubble production

Gas waste
Figure 3. Apparatus of Anfruns and Kitchener [14] for
determination of rate of capture of particules by
single bubbles. A, bubble generator; B, inlet for
suspension; C, outlet for suspension; D, optical cell
for observing particles attached to bubbbles; E,
preparation vessel.

into account the drainage time which is necessary before two


collidi.ng spheres may coalesce. If the .drainage induction time is
substantial, one would expect collection efficiencies for
spherical particles to be much less than predicted by the
hydrodynamic theories, as has now been observed. It appears from
these experiments that the drainage or induction time for jagged
particles is very small, and that attachment occurs very soon
after impingement.

If the drainage time of the thin water film was the cuase of the
low collision efficiencies of the spheres, then Anfruns and
Kitchener argued that one ought to be able to reduce the drainage
time by removing one of the factors tending to keep the surface
of the bubble and the spherte apart, namely, the electrical
double layer at each interface. Accordingly, they added 1 M KC1
200

(0)

••
0·02

0
c: 004
0

u (b)
~
0
<...> 003

002 . ••
• •
0,01 •• • ·t

00
.• 00 0

",
0
,
0
00

,0
0 ,0

05 06 0 08 09 70
Bubble diameter, mm

Figure 4. Experimental collection efficiencies obtained with (a)


31vm quartz particles, (b) spherical .Blass partic!es
32vm diameter; 0 distilled water;e 10 ltM SDS; 010 3M
SDS; • 1 M KC1

to the solution. While the collision efficiencies of the bubbles


increased by a factor of up to about three times, they were still
only about one-half the values predicted by the hydrodynamic
theory. The results for the quartz particles on the other hand,
came into almost exact coincidence with the theoretical
predictions.

Further evidence was provided by the addition of sodium


dodecybulphate (SDS) in quantities insufficient to cause
significant changes in the contact angle either on quartz or
glass. SDS is physically adsorbed at the air-water interface, and
could be expected to influence the charge of the surface of the
gas bubbles. The results are shown in Figure 4, where it is seen
that SDS has a strong effect on the collection efficiency of the
spheres, depress.ing the values markedly. At the same time, the
quartz particles were little affected.

The conclusions drawn from these experiments are that the


201

collision step in the collection process is quite well accounted


for by relatively simple hydrodynamic theories; that the
induction time for angular particles is very much less than for
spheres, and is little influenced by electrical double-layer
forces; and that smooth particles are sensitive to double-layer
effects because of their strong influence on the rate of drainage
of the thin film between particle and bubble.

Model experiments of a different kind have been carried out by


Reay and Ratcliff [16,17] and Collins and Jameson [18,19]. In
both cases flotation took place in a cell in which bubble were
formed at a porous f.rit, so that in the absence of large-scale
convection, the collisions occurred as the bubbles rose through
the cell contents under gravity. A sketch of a flotation cell is
shown in Figure 5.

The particular emphasis in these works was on fine particles,


i.e. less than 30~m in diamater. Reay and Ratcliff [17] used 20~m
glass beads and 5.7~m latex particles. Stirring was necessary in
the case of the beads to prevent settling. They derived a theory
rather similar in some respects to that of Flint and Howarth,
[11] but with corrections, as far as hydrodynamic collision is
concerned. Put very simply, the theory predicts that the
collection efficiency of single bubhles should vary like:

- - - - Stirrer
Foam '\
suction
plate
Baffle

~~~~~m~?--
"
Porous
glass
frit

Nitrogen
Figure 5. The flotation cell of Reay and Ratcliff. [17]

(6)

where n is approximately 2. The impor.tance of this relation is


twofold: (.a.) i.t suggests a strong dependence of E on the
c
particle diameter, which can help explain the difficulty so often
observed in the flotation of fine particles; and (b) i t also
suggests a remedy in the simila~ strong dependence of E on the
c:
gas bubble diameter ~. At a constant gas flowrate, the nu~ber of
202

bubbles will vary inversely as d~, while the collection


efficiency for single bubbles varies as d;, by this equation. The
total rate of removal, will vary as the product of E and the
number of bubbles produced, and the area swept by eac~ bubble.
Hence it would be predicted that the rate constant should vary as

2 3
k a: (d/d b ), (7)

and obviously k will increase markedly as the bubble radius


decreases.

The object of the experiments was to test the values of the


exponents in this equation. Although there were minor variations,
it appears that .the exponent on d should be 1.5 rather than 2. A
limited amount of data for bubblePsize [17] suggests that ka:db-3,
for small bubbles in the range of 40 to 80~m.

These experiments are strictly for bubbles rising and colliding


with particles under gravity. There is a complete lack of
experimental data on the co.llision processes in controlled
turbulent conditions, e.g. in a stirred cell fitted with a
Rushton impeller, and, most importantly, with all variables under
control - particle and bubble size, contact angle, zeta potential
of both the particles and the bubbles.

SPECIAL PROBLEMS OF FINE AND COARSE PARTICLES

Practical mineral processors are familiar with results like those


shown in Figure 6, as quoted by Jowett. [20] The percent recovery
of various minerals is given after one-minute flotation under
standard conditions, as a function of particle size. It is seen
that the recovery is small for the finest particles, but
increases to a maximum and then declines as the diameter
increases.

Fine particles

The reasons for the low recoveries at the low and high diameter
ends of the spectrum are quite different. With small particles,
we have already seen that there is a strong dependence of the
flotation rate constant on the particle size. Equation (7),
derived for collection by bubbles rising in a stationary fluid,
predicts that the rate constant should vary as d 2 • while the
experimental data for such systems (Reay and ~cliff; [17]
Collins and Jameson)[18] suggest that the exponent should be 1.5
approximately. Traher [21] quotes results from Gaudin et al [22]
and Morris [23] which indicate that in flotation cells with
conventional impellers. the rate constant varies linearly with
d •
p
203

90

Z 80
o
;::
{) 70
~
U.
W 60
N
iii
::; 50
oa:
u.
>-
a:
w
~ 30
{)

..
W
a: 20

'0

0~'--~--~~'~0~2~0---5~0~'~00~2~00~-5~00~·100·(
AVERAGE PARTICLE SIZE (MICROMETRES)

Figure 6. Recovery of some sulphide minerals after one minute


flotation in a batch cell. Data by W.J.Traherj from
Jowett. [20].

For fine particles then, it seems that a plausible reason for the
low recovery is related to the low rate of flotation. If the
flotation time is increased, the recovery of the fine particles
increases also, but in a practical case, the quantity of gangue
entrained and removed in the froth would increase as well, giving
rise to a reduction in the grade, i.e. the proportion of valuable
material in the conce~trate.

The work of Reay and Ratcliff, and Collins and Jameson, suggest
that a way to improve the rate of flotation of fine particles,
would be to use smaller bubbles. The bubbles in conventional
flotation machines are typically 0.5 to 2mm in diameter, although
the available data are meagre. [2] For bubbles in free rise, at a
constant gas rate the rate of flotation should vary inversely as
d~, so there would be real advantages in using bubbles in the
range 50-100~m in diameter. Such bubbles are produced in
dissol:ved air flotation, such as in the nozzle developed by the
Water Research Centre, Medmenham. Rees et ale [24] show that
their nozzle gives bubbles with a mean diameter of 80~m
approximately, with air at a saturation pressure of 485 kPa.

The problem with dissolved air flotation, at least where mineral


processing is concerned, is that the volumes of bubbles produced
are far lower than with mechanical systems. In a mechanical cell,
the air use is typically 1m 3 air/(m 3 cell)-min, or with a
residence time of 10 minutes, the air rate is 10 m3/m 3 pulp. In
dissolved air flotation, the air supply rate is 8 to 10 g air/m 3
204

raw water, [24] or about 0.007m 3 air/m 3 water - or three orders


of magnitude smaller. Further, in the treatment of potable water,
the concentration of solids to be removed is very small,
typically 50 ppm or 50 x 10-1+ wt percent; in mineral processing
the mass fraction often exceeds 20 percent, (although the values
may be only I percent of this, i. e. 0.2 percent by weight of the
total pulp). The outlook for the use of dissolved air flotation
in mineral processing does not look promising.

I t would seem desirable to be able to produce large numbers of


small bubbles by mechanical means, but so far this appears to be
beyond present technology. The main reason is that bubbles formed
at orifices slow down when they leave the orifice, and are then
"caught up" by the one emerging from behind. The main problem is
to prevent coalescence of newly formed bubbles.

An alternative hypothesis has been advanced for the low recovery


of fine particles by Scheludko and co-workers. [25-27] Whatever
the validity of their own experimental work (which is far removed
from the actual flotation of fine particles), they began with a
false premise. They began from the position that "it is clear
from practical experience that particles smaller than a few
microns cannot be captured in foam flotation" (reference 25,
p. 2818), citing what appears to be anecdotal evidence for this
statement. To explain the "minimum size", these workers have
invoked the "line tension" which may exist when the radius of
curvature of a contact line is very small, for which there is as
yet little experimental evidence. There is abundant evidence that
it is quite possible to float particles less than a few microns
in diameter. Cassall et al[28] have described a range of
colloidal particles which have been successfully floated. Yuu et
al [29] describe th.e flotation of 0.1-0.2}.lm diameter MnOz
particles with small hydrogen bubbles in the absence of
collector; flotation progressed normally, albeit very slowly. The
speculation that there is some minimum size of particle which can
be floated remains an interesting possibility, but it does not
seem to justify at present the concept of the "line tension".

Large Particles

The decrease in the recovery of particles beyond a certain size


is explicable in terms of simple concepts, and has been clearly
demonstrat.edby Schulze. [29] His view of the attachment-
detachment p.rocess is shown in Figure 7, which shows the
formation of a stable three-phase contact line, and also the
possibility of rupture by the application of a force which pulls
the particle away from .the bubble. In a conventional flotation
cell, that force will arise from the stresses caused by
turbulence developed by the impeller. In the absence of these
turbulent stresses, the equilibrium configuration adopted by the
205
bubble/particle pair will be a balance between the gravitational
effects acting on the liquid and the particle, and the surface
tension forces.

The concept on which Schulze's theory is based is that work must


be done in order to rupture a particle/bubble couplet, against
the restoring force of the surface tension. The work of rupture
can be calculated by solving the Young-Laplace equation with
appropriate boundary conditions. He assumes that this work is
obtained from the turbulent field, and although the details are
somewhat obscure, it appears. that a couplet is assumed to rotate
about the centre of the bubble, the motion being sustained by the
local turb.ule.nt field.

-:::.:.- - -~~ -- ~--


~
::.-:=-=-
--~= :.:=
::.--: -
=:.-:-~
=--
--::-:-:.
--=:
:.~---.:.
~ -=:~ ~ ~=-:.
=-==~-------=-= =~~-----.:--:--===
-- - -- -----
=~-~
----
- -- - -----
-.:-~--:.~
---
(al (bl (el

Figure 7. Three fundamental processes during the attachment of


particles to bubble. (a) Approach of the particle to
the gas;""Uquid interface, (b) Formation of the three-
phase contact line, (c) Detachment of the particles
from the interface.

Thus if the kinetic energy of the particle exceeds the work of


rupture, the particle will detach. Schulze related the velocity
of the ro.tating eddy surrrounding the bubble, to the mean energy
dissipation around the impeller. Because of the spherical shape
of the particles he worked with, the work of rupture was a strong
function of .the contact angle.

To test his theory, Schulze carried out experiments on glass


spheres in a stirred flotation cell, using 10- 5 molar
dodecylamine hydrochloride as collector, and with the pH varying
from 2 to 12, presumably to alter the contact angle. A comparison
between theory and experiment is shown in Figure 8; although not
explici.tly stated, i t appears that the theoretical line was
calculated for a bubble diameter of 0.5nnn on the grounds that
this is a commo.n size in flotation cells.

Schulze's theory and experiments were conducted for spherical


particles, which are not found in practice except in oil-drop
flotation. This limit.ation was pointed out by Jowett [20] who
went on to develop a simplified theory for sharp-edged particles
206

Cp - \0 , 6 ... riable
E - ~9 -10 4 ",,2 -S-, t-----T---+----I
gF- 2,5g·",,-3
I

10~--+-+~-+--t-

I
~ u v, - 2Scm·s~ I
&. 0 v, - 37cm-s·f

-~
II
I
I
I
I
I
10 12 14
pH ... Iue

• expenmentol values for the torgest


floatable sIZe of slOgle spheres
- - theoret,cal curve
o experrmental values at v, - 2S. __ 37cm·s·'
- - - - theorerical curve

Figure 8. Comparison of theoretical and experimental upper


flo table sizes, for spherical particles in a laboratory
flotation cell, after Schulze. [29]

exemplified by right cylinders. A sharp edge acts as a sticking


point for a three-phase contact line. which will not move away
unless the contact angle forced upon the gas-liquid interface
becomes less than the equilibrium contact angle. along one or
other of the faces containing the solid angle. Jowett I s view is
that when the ac.celeration imparted to a particle attached to a
bubble exceeds a critical value. the particle will detach; the
acceleration due to rotation of turbulent eddies can be very
considerable. being of order 400 times the acceleration of
gravity. in a flotation cell. The predictions from his theory are
in reasonable agreement with practical observations for galena
particles; the maximum floatable particle size is of order lOO~m.

Interaction between species

It is natural to speculate that in the presence of a mixture of


particles of different sizes. densities and hydrophobicities,
there could be considerable interaction between one particle and
another. Even with a single species with a narrow size range,
some interaction can be postulated in that i t is possible in
laboratory conditions to load a bubble with many particles. so
that the addition of every incremental particle has an effect on
the ability of the bubble to capture the next one. However. in a
207

conventional flo.tation cell, it is not evident that bubbles pick


up more than a limited number of particles.

That species interaction is negligible in a conventional stirred


cell .has been shown quite positively by Harris and Cuadros-
Paz. [52] They floated different narrow-:-size fractions of three
different sulphide minerals singly and together in all possible
combinations. No significant interaction between the mineral
species could be observed. This result is of considerable
importance because it increases the confidence one can place on
the results of tests on single species, so often used in the
laboratory for practical reasons. These conclusions apply
strictly to phenomena within the pulp however; when the particles
enter the froth, there is considerable potential for species
interaction especially if the particle sizes are radically
diffferent.

THE EFFECT OF BUBBLE CHARGE

It is well know that colloidal particles carry a net charge as


the result of adsor.bed surfactants or collectors, and since
charged surfactant ions adsorb similarly at the gas-liquid
interface, it would be reasonable to assume that bubbles would
also carry a net charge. If this were the case, it would follow
that the s.ign and magnitude of the charge on both bubbles and
particles would have an important bearing on the rate at which
coalescence between the two could occur, i. e. on the flotation
rate. Such effects should be observable not only for colloidal
particles, but also for any particle-bubble combination where the
electrostatic force of repulsion or attraction was significant
when compared with other forces acting in the system - buoyancy,
inertia or viscous drag.

The first to show the importance of bubble charge in its effect


on the rate of flotation of small particles were Collins and
Jameson. [19] They floated spherical latex particles of mean
diameter between 6.6 and 20.8~m, using cetyltrimethyl - ammonium
bromide as collector and ethanol as frother. The charge was
varied by addi.tion of sodium sulphate, which acted by
conventional double layer theory, collapsing the double layer
progressively as the concentration increased.

The measurement of the charge, described in their work in) terms


of the measured electro h r.eti mobilit U {m s.-l V-1 m ' ~s
carr"ieii out: ~n a con~n~~ona1. apparatus E iJ.\~ wtilcn tlJle ma~n
component was a horizontal quartz cell, internal dimensions 100mm
(vertical) by 1mm (horizontal), made by Rank Brothers, Bottisham,
England.

The charge on the bubbles was measured in the same type of cell,
208

and is described in some detail be Collins et al.[30] An


elevation of the cell is shown in Figure 9, and the principle of
the method in Figure 10. Small bubbles 30 to 40J.IID. in diameter

Figure 9. Elevation of the modified electrophoresis cell of


Collins, Motarjemi and Jame.son [30] Internal dimensions
of central area 1 x 10 x 40mm.

Figure lO.The path of a bubble rising up a stationary level under


an applied horizontal potential gradient.[30]

were generated electrolytically by controlled pulses, the


position of the wire was such that the bubbles then rose up the
"stationary level" in the cell, where the streaming velocity
relative to the wall is zero. The path taken by the bubble as it
rose through the cell contents could be seen through a microscope
and the electrophoretic mobility was calculated in the usual way.

One of the concerns one must have here, is whether or not the
bubbles which are generated by a pulse of current, are in
equilibrium with the liquid, especially regarding the surface
concentration of adsorbed surfactant. Elsewhere in this volume,
experimental evidence is given which shows that the rise velocity
of bubbles created in almost pure water decreases gradually with
time as the surface of the bubble becomes contaminated with trace
quantities of dissolved materials. In the experiments of Collins
et al., however, the concentrations of surfactant were far from
209

"trace" quantities, so that the time to equilibrate is very


small. Calculations showed that in typical experiments with 30~m
bubbles, the equilibration time should be of order 0.14s; taken
with a rise velocity of 0.49nnn/s, one can see that the bubble
will be at equilibrium before it has travelled more than a few
bubble diameters from the point of formation.

This point was verified by measuring the distance moved by


bubbles in the cell, as a function of time since formation,
measurements being taken from cine film of the event. It was
observed that the bubbles took up to 100 ms to accelerate to
their terminal velocity which thereafter remained at a constant
value.

Roughly speaking, in their experiments the charge on the bubbles


and on the particles were about the same, ranging from 40 to 60mV
approximately. The effect on the flotation rate constant was
quite marked. A tenfold reduction in the rate constant occurred,
when the zeta potential rose from 30 to 60mV. Extrapolation of
the results to zero zeta potential suggested however, that in the
range of 0 to 20mV, the rate constant drops only 20 to 30
percent.

These results lead to an important conclusion. In a single


species pulp, e. g. an emulsion of oil in water, it would be
possible to maximise the flotation rate by controlling the pH for
example, to give essentially zero charge on the particle and
perhaps the bubbles too. The flotation rate would be maximum for
two reasons: the electrostatic repulsion between bubbles and
particles would be at a minimum; and the conditions would also
lead to coagulation of the oil droplets to form larger aggregates
whose flotation rate would be enhanced.

With a pulp containing mixed species however, it would be


undes.ira.ble to try to create conditions of zero charge for the
material to be floated, because conditions may then favour
heterocoagulation of values and gangue slimes. In view of the
observed effect of the particle/bubble charge on flotation rate,
i t would probably be desirable to try to maintain the particle
charge at about 20mV, thereby preventing coagulation without a
drastic reduction in the flotation rate. Hennnings [56] has shown
that slime coat.ing of galena with consequent depression of the
values, can be explained simply on the basis of electrostatic
attraction. At the correct pH, particles have large charges of
the same sign and depression ceases.

Since the work of Collins and Jameson, the zeta-potential of both


bubbles and particles in flotation experiments have been measured
by others. Fukui and Yuu [31] floated polystyrene latex particles
0.6~m in diameter, with no collector or frother, but with
210

additions of AlC13. They were able to control conditions where


the particles and bubbles had opposite signs. One curious effect
was that the flotation time increased (in batch operation) the
zeta potential of the particles increased markedly, from -lOmV to
+ 35 mV in the space of 30 mins. No explanation was given. Sato
et al.[32] described a different type of electrophoresis cell for
measurements of zeta potential of bubbles. The oil emulsion they
were floating, and the bubbles, both had a point of zero charge
at a pH of about 4.5, and it was here that the rate of removal of
the oil was a maximum, as would be expected.

The zeta potential of bubbles alone have recently been measured


by Usui et ,al [33,34]. They used the Dorn effect, or the
potential generated by small gas bubbles rising through aqueous
solutions, ,to measure the charge on the bubbles, as a function of
surfactant concentration [33] and bubble size [34]. One of the
major problems in measuring the charge on bubbles is to eliminate
bulk convection of the liquid surrounding them, and one criticism
which can be levelled at these results is that when a bubble
cloud rises, it entrains some of the surrounding liquid and
causes "gulf streaming", which may account for their observation
that the bubble charge was dependent on bubble diameter. The
results of Usui et ale should be treated with caution.

FROTH STUDIES

The froth flotation process involves two major steps. In the


flotation cell, bubbles collide with hydrophobic particles and
carry them to the top, where they enter the froth zone. In
passing between the slurry and the froth, pulp is entrained by
the bubbles, and in the froth some of the liquid and gangue
particles drain back into the cell, while the major part of the
values plus some water and gangue, are removed from the froth as
the concentrate.

The phenomena which take place in the froth probably have little
effect on the yield of values, because there is little evidence
to suggest that there is a substantial return of values from the
froth to the pul.p by rupture and disengagement from the bubbles
in the froth. However, the froth effects have a very large effect
on the grade, i.e. on the mass fraction of values in the
concentrate. This is because the practical measures which can be
taken to inc.rease the mass of values recovered from a cell, such
as increasing the residence time of the pulp, lead inevitably to
an increase in the quantity of pulp entrained into the froth and
recovered with the concentrate. Since the values normally
represent only a small mass fraction of the gangue present in the
feed, a disproportionate quantity of gangue ends up in the
concentrate as flotation time increases. This effect is shown
clearly in the graph from Hemmings, [35] Figure 11.
211
30

25

20

-.:.
CO') 15
0
~
III 10
"...
III
C)
5

100

Recovery W0 3 0/.

Figure II.Typical grade-recovery curves for slime (fine) and sand


(coarse) particle flotation, after Hemmings [35]

Despite the importance of the physical processes which take place


in the .froth, little detailed experimentation has taken place
until recently. Earlier workers placed greater emphasis on trying
to produce mathematical models to represent overall behaviour of
the froth phase, rather than in seeking explanations for the
physical phenomena taking place within them (Harris [36] has
given detailed consideration of much of the earlier work).

A significant step forward was made by Watson and Grainger-Allen


[37,38] who constructed an apparatus in which the froth could be
separated from the pulp after the desired flotation time, by
means of a thin metal slide. The total contents - values, gangue
and water - of the froth could then be analysed. A sketch of the
apparatus is shown in Figure 12. To simplify the mechanical
arrangements at the top of the cell, the impeller and air supply
entered through the ba.se. Hematite was recovered from a quartz
gangue using "petroleum sulphonate" as collector.

The results reported in the original paper were rather


unexceptionable, verifying that the mass fraction of values in
the solids recovered from the froth was from two to four times
that in the feed. However, the Warren Spring Group continued to
develop the cell and later work provide interesting insights. For
example, Cut.ting and Devinish [39} modified the cell to include
three further horixontal slides, so that the froth could be
divided into four slices. The contents of each slice were removed
by suction for analysis. The results. using hematite as the
recoverable mine.ral, Figure 13. showed that there was a very
212

SlOE ElEVATIOtI
FROTH

INTERFACE SLIDE
(IN OPEN l'OSITiON)
PULP

IMPELLER ~ STATOII

VARlMLE
SPEED
MOTOR

-CENERA1OR

Figw:e. 12.Iheearly Warren Spring Laboratory equilibrium


flotation cell; Watson and Grainger-Allen [37]
25 FIiOTH
H~IGHT(2) CURVE /3 y
A 0·12 GANGUE (I)
f! 0·31 3-4xI0- 3 HEMATITE
C 0·23 I 6010-' WATER (1)
D 0·22 1·5010-' WATER (2)
20

E
u
,.: 15
:r
!2
'"
:r
:r
b
...a: 10

O~____~____~~~~~~------
o 50
CONCENTRAnON.9 r '

Figure I3.Concentration curves for a hematite ore, as a function


.of height above the liquid level in the float cell
(Cutting and Devenish [39]). A gangue; B, hematite; C,
water; D, water, at an increased air rate.
213

strong effect of sample height above the level of the pulp in the
cell. Near the base of the froth, the mass ratio of values to
gangues was approximately 2.5, whereas at the top of the froth,
it was 4.3. In the feed, the ratio was 0.11. The water content,
measured as g water per unit volume of froth in the horizontal
slice, decreased by a factor of ten, for a total froth height of
20cm. Increasing the air flowrate increased the wetness of the
froth, and there were also small changes in the grade of the
hematite concentrate in each slice. At the base of the forth, the
grade was lowered by the increased air rate, whereas at the top
of the froth column (20cm height), the grade was actually higher.
The overall recovery was slightly higher at the increased air
rate and the overall average grade was slightly improved.

The implication here of course, is that if in a conventional


flotation cell, the froth residence time could be controlled so
that only the top layers of froth were skimmed off, the grade of
the concentrate would be much improved. The improvement is
clearly due to the drainage of water and gangue into the lower
layers and back into the pulp. Even further improvement might be
expected by "washing" the pulp, as suggested by Flint and Howarth
[40], with a spray of clean water or possibly of water containing
a froth stabilizer.

A further development of the Warren Springs cell has been


described by .Cutting et al., [41] in which the horizontal slicing
technique was dispensed with, as shown in Figure 14. A multipoint
sampling lance is used to extract froth samples for analysis. To
characterise the total froth solids concentration, a dip-tube
assembly was used to measure the hydrostatic pressure in the
froth column. The dip-tube also enabled precise location of the
froth-pulp interface to be established. The local density may be
found from the pressure gradient by integration, and to eliminate
noise due to surface tension effects at bubble boundaries, a
simple mathematical function was fitted to the data for
integration purposes.

These techniques, developed for the batch laboratory cell, were


aapplied also by Cuting et a!. [41] to continuous cells on a
pilot-plant scale. The grade-enrichment mechaanisms seen in the
batch cell were also in operation here; the grade of the
concentrate increased markedly within the froth, as distance
above the pulp increased. However, there was a high degree of
mixing in the bottom of the froth, two to four cm above the pulp,
where the entrained water/pulp concentration was quite high, the
froth density being about 400kg/m 3 • Some results are shown in
Figure 15; at high air rates, recirculating vortices were formed,
while at low air velocities, the froth moved upward and across
the cell in a regular way.
214

.... OTORISED MULTI - POINT SAMPLE TlMEA


DIP TUBE SAMPLING AND CONTAOL
ASSEMBLY LANCE UNIT

SAMPLE VACUUM
COLLECTORS SUPPLY

IMPELLEA AND STATOR

VARIABLE
SPEED
MOTOA
FLO-S TAT

AlA
SUPPLY

Figure 14 .Equili brium frothflotation test cell, modi! ied to


pe.rmit measurement of solids concentrations etc. at
various heights above the pulp (cutting et al (41).

Another variant of the Watson/Grainger-Allen cell was used by


Moys, [42] as shown in Figure 16. He floated a complex zinc-
copper-iron sulphide ore containing a siliceous gangue, with a
conventional xanthate-frother combination. The results were in
agreement with the observations of Cutting and Devenish [39] in
that there was a steady increase in the grade of concentrate as
height above the pulp increased, with concomitant reduction in
gangue. In his view however, the practical gains to made from
this observation may be limited because the well-drained froths
were generally unstable and resisted movement in the horizontal
direction. He foreshado:w.ed .further work on the removal of well-
drained froths involving verti.cal removal of the froth over the
whole cell surface.

A different type of cell was used by Bishop and White, [43] to


study the entrainment of gangue into froth in a pilot-scale cell,
Figure 17. The gangue was quite hydrophilic; no hydrophobic
particl~s were present and frother was the only reagent addition.
The design of the circuit was such that pulp and collapsed froth
could be recirculated to simulate continuous operation. A range
215

AIRFLOWRATE 2' 1.- 2 1-'

FROTH PULP DENSITy ENRICHWENT, Upd I.,


20

'0

AVER ACE PULP


DENSITY OF E
U
CELL PULP '5"1. 0
0-
PULP PULP X

";;;
X
ESTIMATED FROTH MOBILITY STRUCTURE X
5
...
It

20

..
..,
oJ

"
U
'";i
g
.,
co:
>
0

Figure 15. Density enrichment contours, and estimated froth


mobility in a continuous flotation cell. (The
enrichment Upd is the ratio of the density of the
froth pulp to the density of cell pulp).After Cutting
et al [41].

of minerals was used with densities from 2650 to 7000 kg/m 3.


Their main purpose was to find experimental constants to include
in a model for simulation of froth behaviour, and
phenomenological observations are sparse. However, they did
observe that the single most imprtant factor in drainage of
particles from the gangue was the residence time in the froth. No
details are given as to how the residence time was altered -
presumably it was by controlling the air rate and the pulp level.
Very significant improvements were seen when the residence time
increased from 4.3 to 10.3 seconds. Another significant
observation was that entrainment of fine particles was far higher
than with large, thus when quartz was entrained, the
concentration of 7-5lJID particles in the froth concentrate was
about 70 percent of the concentration in the feed whereas at
37.5lJm, the froth concentration was only about 10 percent.
216

. . ",":. : " ,':.


:·::.::::.:.:.<o.::·:::::·:~·.:·.:<-:::\··""··."·.'__--'CONCENTRATE
::; ..:: ..:.-:::::::..::-.::.. ::.::.:-:...>/::. OVERFLOW WEIR
(Verleble 1Ie....1)

+----TAILINGS OVERFLOW
SLURRY PHASE ---f-:"''' WEIR

SANDS GATE

AIR

Figure 16.The deep flotation cell of Moys,(42) for both batch and
continuous tes ts. Dis tance between sample points is
5cm.

Tailings Feed bo_


box
Concentrate
·Z-_I-T1'launder
Dual impellor
avllair110.'
IIotatian coli.

---.
~-I+-~-:::::::""--i'1
~~m+iH-~-
avila....
DUWmotar

.......

Figure 17.The continuous cell of Bisshop and White,[43] for the


study of entrainment of hydrophilic gangue.
217

The experiments of the Warren Springs group and M.H.Moys have


emphasised the importance of the phenomena which takes place in
the froth. .Tbere is a strong suggestion here that the design of
flotation cells orient.ed as it has been to considerations which
enhance the collection of particles by bubbles in the pulp, may
be misguided, a point made also by Flint [44], who suggested that
in many cases, the apparent flotation .rate may be controlled by
froth phenomena. Of particular interest is the mechanism of froth
drainage and rupture, for i f the surface zone in the cell does
not allow the froth sufficient drainage time, or if there are
factors inherent in the nature of the particles themselves which
prevent a froth from draining, or which promote premature rupture
of the liquid lamellae before the gangue has had an opportunity
to drain, the overall performance of the cell will suffer.

The critical role of the rupture thickness of the froth lamellae


in determining the grade of concentrates of fine particles has
recently been emphasised by Hemmings, [45] who had earlier
explained [35] by a simple mass balance over a lamellae
containing values and gangue, the shape of the grade-recovery
curve depicted here in Figure 11. In the later paper, he
described a probe rather like a conductivity cell which was used
to estimate on a comparative baSiS, the thickness of the lamellae
in various industrial flotation cells. The results from his
measurements indicated that, in his view, the lamella were too
thick in general to permit effective separation of ultrafine
particles, although in the light of his later observations it is
not clear just what was responsible for keeping the films
"thick". Perhaps it was the presence of large hydrophilic
particles which bridged the film and prevented collapse.

He considered the conditions for film stability and instability


in the presence of a hydrophobic sphere, and concluded that even
if the contact angle was considerable, there were conditions
where a spherical particle trapped in a thinning layer of water
between two gas-liquid interface, could enter both interfaces and
yet come to a stable equilibrium if the equilibrium contact angle
was of the correct magnitude. For this to occur, the contact
an~le should be less than 900. For contact angles greater than
90, no stabilizing influence of hydrophobic particles was
possible. This hypothesis can be put forward to explain the
results of Livshitz and Dudenkov, [46] who found that in some
cases, hydrophobic sphalerite (44-74~m) had a stabilising effect
on a froth. These matters have also been considered in another
context by Garrett. [47]

Dippenaar [48] has produced fascinating photographic evidence of


the way in which particles of different shapes and
hydrophobicity, as determined by the contact angle, can rupture
218

thin liquid films. His apparatus, which is shown in Figure 18, is


simplicity itself •.A thin liquid film in the form of two concave
me.nisci is formed and the required particle is dropped into the
upper one. The film is then thinned by controlled withdrawal of
liquid and photographs are taken of the events which follow.

Some of his results are shown in Figure 19-21. I t appears that


with spheres, if the contact angle was greater than 90 0 , the
surface of the sphere itself acted as the scene of rupture. The
contact lines on op.posite sides of the sphere simple slid around
unt.il they met at a single congruence, when they drew back
entirely from the s.olid.

When the contact angle was less than 90 0 , the two circular lines
of contact formed by the section of the upper and lower
interfaces,did not actualLy meet on the surface of the sphere,
lllumllllltion

Figure 18.Apparatus of Dippenaar [48] for the study of particle


effects in thin liquid films.

and rupture occurred only if the film was thinned by further


drainage.

With cubic orthorhombic such as galena, the contact lines pulled


back toward the sharp edges where they ruptured. Once the
particle had bridged the liquid film, spontaneous rupture
occurred as for spheres with e 90 0 •

Rough particles such as quartz and sulphur, gave an interesting


effect, because they were capable of adopting an orientation in
which the bulk of the particle lay in the air phase, rather than

° °
in the liquid. It was observed that when the contact angle was
be.tween 82 and 98 roughly, such particles did not rupture the
film, but for all other contact angles, the ability to rupture
films was identical to that of spheres.
219

Time, m.
Time, m.

40
81

13,5

68

- - 82

70 14,7

274
24,5

423

116

~---"""::::::::J 554

Figure 19.0bservations of Dippenaar [48] of the interaction of


250jlm glass beads with a liquid film. (a) Contact
angle = 740; (b) Contact angle = 1020.

Where spontaneous rupture occurred, the film thickness was of


about the same thickness as the particle. In other cases, the
film bad to thin to no more than half the particle diameter
before it ruptured.

In a second paper, Dippenaar [49] conducted experiments on the


effect of fine particles on the s.tability of foams produced by
shaking a solution of non-ionic surfactant. It was shown that the
rate-determining step was the drainage of the liquid lamellae in
the foam, rather .than the time it takes to rupture the lamellae
when they encounter a hydrophobic particle. The remarkable result
which was deduced and confirmed by the experiment, at least for
quartz, is that the ratio M/d is a constant, where M is the mass
p
220

of entrained quartz required to reduce the immediate volume of


the froth to a specified low volume (1 m1) and d is the particle
.diamet.er. Thus with quartz particles of diamet~ Slim 0.16mg had
the same effect as a froth destabiliser as 18.8mg of 54411m
particles. With the smaller particles, it would be expected that
a film would need to drain to a correspondingly small value,
before rupture occurred, but it must be recalled that the number
of particles and hence the probability of causing a rupture, will
rise like d -3 as d decreases.
p p
In mixtures of particles, the largest particles determined the
stability of the foam.

In conclusion, it can be said that the recent upsurge of interest


in froth phenomena is not misplaced, and it is probably in this
area that greatest advances will be made in the future design of
flotation machines, especially to handle fine-particle flotation.
Existing machines are well able to promote contact between
bubbles and values, but they lead to large quantities of
entrained gangue which enters the froth and is difficult to
remove. As suggested by Young, [50] it is perhaps to column

-;-~-O9-_-
A

8
---------r--~---------
w

Figure 20.0rientation of orthorhombic particles in an air-water


interface. A=air, W=water, S=solid.[48]

flotation devices that we will look for improved methods, not


leas.t, as he says,. "because conditio.ns in columns are the more
readily simulated in the laboratory, this class has a greater
probability than mechanical machines of further improvement on
the basis of experimental observations"

STANDARD TEST CELLS

A number of flotation cell manufacturers market laboratory-scale


test cells ranging from I to 20 litres in size. However, these
.cells are very operat.or.-:.dependent. Unless the froth is removed
exactly in the same way, different operators obtain different
results, so comparability between different laboratories may be
difficult to achiev.e. Further, with small samples, small
quantiUes of froth which may stick to the walls or impeller
shrouding, may induce large errors. Accordingly, from
221

Time,
ms

80

12,0

97

14,9
_101
----- 97

16,3
-103
- --- 97

17,7

19,1

19,8

Figure 21.A particle of galena rupturing a film of liquid [48]

time-to-time "standard" designs have been proposed to try to


overcome such difficulties. The first such was probably that of
Harris and Raja, [51] but since the principal author has since
deferred [52] in approving terms to the Leeds cell, we shall
begin with this design.

The "Leeds" cell described by Dell and Bunyard, [53] is shown in


Figure 22. The main features of the cell are: an impeller and air
supply of conventional design; provision for maintenance of the
liquid level at a constant height; control of the froth so that
none remains in the vessel beyond a small residual amount.

The froth is contained and directed toward the overflow lip by a


porous ceramic plate through which a solution of frother in water
222

is fed. The froth rises to meet the deflector and slides smoothly
forward on the thin liquid film on the underside of the porous
plate. Some liquid is also directed to run down the vertical
walls of the cell, so that froth does not adhere here, either.

Another Leeds design has been described by Dell and Hall, [54]
which has a bottom-entry impeller, thus leaving the top of the
cell open and unimpeded. The layout is shown in Figure 23. The
authors suggest that fro.th can be scraped off at a single rapid
stroke, and that with this arrangement, there is no need for the
sweaty porous plate in their previous model. The design would be
particularly valuable for work on the entrainment and drainage

u-tube
m",nometer

Makt:-up
water Inltt-

Horizontal

Figure 22.Schematic diagram of the Leeds cell of Dell and


Bunyard.
properties of the froth described in the section headed Froth
Studies.

The problem of reproducible handling of the froth has been


tackled in another way by Roberts et al, [55] who devised a
standard cell which CQuid be used in conjunction with many
comme.rcially available laboratory cells. Their particular
adaptation was to a Denver Laboratory Sub-A-Flotation machines
(Model D-l), and the most significant feature is a perspex
deflector block which is shaped to fit within the cell and around
the shaft housing in such a way as to direct the froth forward to
the lip as shown in Figure 24. Froth is removed with a scraper of
convenient design, and a liquid-level control device is
incorporated. The cell is very satisfactory for floats where a
large amo.unt of the feed reports to the concentrate, but it may
not be suitable for mineral flotation without a4aption, because
of the tendency of some of the froth to accumulate between the
deflector block and the cell wall.
223

Air control post

ter
Linkage
control
corner
piec(ls
000 0

Bas.
drive unit

Tochometer Drive
pick-oft bpi!

Figure 23. the leeds open-top cell (Dell and Hall. [54]

Locating hooks
Scraper
Deflector
block

Clamping
screws
Cell

Impeller

Figure 24. The modified laboratory test cell of Roberts,Firth and


Nicol. [55] The froth is brought to the front of the
cell by the internal deflector block.
224

NOTATION

db·d diameter of bubble. particle (m)


E p single particle collection efficiency, dimensionless
kC flotation rate constnat (s-l)
rb·r radius of bubble, particle (m)
t. p induction time (s)
U~ rise velocity of bubble (m/s)
Y surface tension (N/m)
)J viscosity of liquid (Pa-s)
P.Pp density of the liquid, particle (kg/m 3 )

REFERENCES

1. Taggart.A.F.Handbook of Mineral Dressing,Ores, and Industrial


Minerals. 2nd ed.New York, Wiley,1945.

2. Klassen,V.I., and Mokrousov,V.A.,An Introduction to the


Theory of Flotation, Butterworths, London, 1963.

3. Bogdanov,O.S. and Filanovski.M.Sh., Adhesion of mineral


particles to air bubbles, J.Phys.Chem. U.S.S.R.,~, 224-227,
1940

4. Spedden,H.R.and Hannen, W.S., Attachment of mineral particles


to air bubbles in flotation, Min.Technol.,~, T.P.2354, 1948.

5. Whelan,P.F., and Brown,D.J.,Particle - bubble attachment in


froth flotation, Trans. Inst.Min.Metall., ~ 181-192,1956.

6. Bennett,A.J.R •• Chapman.W.R., and Dell,C.C •• Studies in froth


flotation of coal, 3rd International Coal Preparation
Congress, Brussels-Liege, 452-462, 1958.

7. Sutherland,K.L., Kinetics of the flotation process, J.Phys.


Chem.,~, 394-425, 1948.

8. Philippoff,W., Some dynamic pheomena in flotation,


Min. Enging .. , !!.... 386-390, 1952.

9. Evans,L.F. ,Bubble-mineral attachment in flotation, INd.


Engng. Chem. ,i§.., 2420-2424, 1954

10. Eigeles,M.A.,Kinetics of adhesion of mineral particles to air


bubbles in flotation suspensions, Comptes Rendus (Doklady}de
l'URSS,24, 340-344, 1939.

11. Flint,L.R., and Howarth,W.J., The collison efficiency of


small particles with spherical air bubbles, Chem. Eng. Sci. ,
1..?., 1155-1168, 1971.
225

12. Schulze,H.J., and Gottschalk, G.,lnvestigations of the


hydrodynamic interaction between a gas bubble and mineral
particles in flotation, Proc.13th Int.Miner. Proc. Congr.
Warsaw, 1979, Par.t A,63-85; Elsevier, Amsterdam,1981.

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No. 2608, National Coal Board(U.K.), 1957. See also Herne,H.,
The classical compu.tations of the aero.dynamic capture of
aprticles by spheres, in Aerodynamic Capture of Particles,
ed. E.G. Richardson, Pergamon, London,1960.

14. Anfruns,J.F. and Kitchener,J.A.Rate of capture of small


part.icles in flotation,Trans.lnst.Min.Metall., ~ C9-C15,
1977 •

15. Jameson,G.J.,Nam,S., and Moo Young, M., Physical factors


affecting recovery rates in flotation, Minerals Sci. Engng. ,
i., 103-118, 1977.
16. Reay, D., and Ratcliff ,G.A. ,Removal of fine particles size on
collecti.on efficiency, Canad.J.Chem.Eng.,l,h.178-185, 1973.

17. Reay,D., and Ratcliff, G.A., Experimental testing of


hydrodynamic collision model of fine particle flotation,
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18. Collins,G.L •• and Jameson,G.J.,Experiments on the flotation of


the fine particles - the influence of particle size and
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19. Collins,G.L.,and Jameson,G.J., Double-layer effects in the


flotation of fine particles, Chem. Eng. Sci.. lh. 239-246,
1977 •

20. Jowett, A., Formation and disruption of particle - bubble


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particle size in flotation, Int.J.Miner,Process., 8, 289-327,
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27. Mingens, J., and Scheludko, A., Attachment of spherical


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bubble size on microflotation, Water Research, 9, 1017-1024,
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theory on the upper particle size of floatability,
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measuring the charge on small gas bubbles, J. ColI. Interface
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227

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K.V.S.,Sastry and D.W. Fuerstenau, Trans.Am.lnst.Min.Eng.,
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42. Moys,M.H., A Study of a plug-flow model for flotation froth


behaviour. Int.J.Miner.Process., 5, 21-38, 1978.

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in flotation froths, Trans.lnst.Min.Metall. (Sect. C: Mineral
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Trans.lnst.Min.Metall. (Sect. C: Mineral Process. Extr.Metall. )
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lamella thickness, Trans. Inst.Min.Metall.(Sect.C:
Miner.Process.Extr.Metall.) 1.Q.,C96-102, 1981.

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froth stability, VII International Mineral Processing
Congress, Arbiter,N., ed., Gordon and Breach, New York, 367-
371,1965.
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229

FLOTATION IN MINERAL PROCESSING

H.L.Shergold
Department of Mineral Resources Engineering
Imperial College, London,S.W.7.,England.

INTRODUCTION

Few of the metals or minerals required by modern civilisation are


mined naturally pure and ready to use. Instead they occur in
complex aggregates of up to twenty different minerals of which
only one or two will be of value. There are some two hundred of
these 'value' minerals amoung the several thousand minerals that
go to form the earth's crust. The number of combinations of
minerals that can occur with a valuable component is therefore
very large and each deposit (ore) containing nominally the same
valuable minerals will differ materially from all others.
Consequently, the best separation process for a particular ore is
closely related to its overall mineralogy and not to just the
nature of the valuable components.

During the separation procedures the minerals are separated into


distinct products by the exploitation of differences in the
chemical or physical properties of the various species. These
properties may include size, shape, colour, specific gravity,
electrical conductivity, magnetic susceptibility, surface
chemical effects, chemical reactivity, etc. Separation can only
be achieved, however, if the valuable minerals are presented to
the separating force as individual, unlocked or liberated grains.
Liberation is usually achieved by crushing and grinding the rock
so that most of the material is finer than the grain size of the
valuable minerals in the original rock.

A simplified flowsheet of a mineral processing operation is shown


in Fig.l. During crushing, the rock is reduced from about 500mm
230

to less than 101lDll following which grinding reduces the particle


size to less than 150pm if required. This is a typical liberation
size for many metalliferous minerals. Before each stage of size
reduction the material is sized and only the oversize material is
passed to the appropriate crushing or grinding stage. This
procedure minimises the breakage of already liberated valuable
particles and prevents the production of excessive amounts of
very fine material, which could have a deleterious effect on the
separation process.

reed maximum partK:lc size


approx. sOan

aperture size
about I Scm

maximum paJ1.ide
lize.boutS~m

aperture sin
about Ian
r~uent1yless
thanl~..

dilpolal of dispoOll of
.w.bIo pn>d.ds ...... pn>ducts

Figure 1. Simplified flowsheet of a mineral processing operation

Flotation is one of the most important processes used to separate


mineral particles. Over 10 9 tonnes of ore are treated by
flotation annually and flotation plants capable of treating over
100,000 tonnes of low grade material per day by flotation are not
uncommon. Judged by the scale on which it is operated, it is not
only a very important separation process but a very impressive
technical application of surface chemistry.

The success of the process depends on rendering selected minerals


in a pulp hydrophobic and hence floatable whilst keeping, or
231

making, all the other minerals hydrophilic. Air bubbles blown


into the pulp collect the hydrophobic particles and carry them to
the top of the separation cell, where they concentrate in a froth
which overflows into a launder. The hydrophilic minerals or
tailings are recovered from near the bottom of the flotation
cell. Mineral flotation processes operate IIIOst efficiently when
the particle size is between 10 and 150pm.

THERMODYNAMIC CONDITIONS FOR FLOTATION

In the flotation process an air bubble must be able to adhere to


the mineral surface so that the particle becomes floatable. The
general thermodynamic condition for three-phase contact between
the particle, solution and gas bubble is a finite contact angle
(Fig.2) at the three phase boundary. From Young's equation,
modified to take into account saturation of the gas phase with
water vapour •.

Y - Y
Cos S = sv sl
Ylv (1)

where S is the contact angle, and y , y 1 and Yiv are the


solid/vapour, solid/liquid and liquid/vlpour 'urface tensions.

The work required to separate liquid water from the solid surface
and replace it by an adsorbed water layer in equilibrium with
saturated water vapour (Wsl ) is given by the Dupre relationship.

(2)

combining (1) and (2) gives

Wsl = Y1v (1 + cosS) (3)

Therefore, for air to displace water so that a finite contact


angle is obtained with an air bubble

Ws1 < 2y1v

or WS~ < Wco where Wco is the work of cohesion of the liquid (149
mJ m- for water). Thus a the·rmodynamic condition for flotation
is that the work of adhesion of the water to the solid must be
less than the work of cohesion of water.

The work of adhesion of water to the solid is made up of


contributions from London - van der Waals dispersion forces (Wd ),
hydrogen bonding of water to polar sites (Wh ) and interactions
with ionic sites, (Wi)' When IIIOSt minerals are crushed, ionic or
covalent bonds are broken giving rise to highly reactive, charged
232

Solid

Figure 2. Water - Vapour - Solid System.

sites which readily hydrate, so that the resulting surface has


substantial Wh + Wi components. For all solids Wd is less than
W so that adhesion to an air bubble can only be Obtained if the
w~o+ Wi components are diminished appreciably. In flotation, this
is achIeved by adsorbing surfactants, referred to as collectors,
at the solid/water interface to eliminate or shield polar sites
or replace them with sites which do not ionise or take part in
hydrogen bonding.

Flotation collectors are characterised by (i) a polar group,


usually ionic, which interacts with the mineral surface and gives
the reagent solubility, and (11) a non-polar group, typically a
hydrocarbon chain, of sufficient size to impart hydrophobicity to
the mineral surface.

Although most clean mineral surfaces exhibit a zero contact angle


in water, there is evidence to suggest, that between groups of
minerals, there are differences in their degrees of hydrophil-
icity. Thus oxides and silicates have substantial W + W.
components, whereas those of the sulphide minerals are tess. It
can therefore be argued that sulphide minerals are not as
hydrophilic as oxide minerals. A manifestation of this difference
might be the fact that collectors used for the flotation of
oxides and sillicates have substantially large hydrophobic non-
polar groups (e.g •• ClZH 5-) than those used for sulphide
flotation (e.g.C 2H -). fn a few cases, e.g.graphite, talc,
pyrophyllite, molybaenite and sulphur, the minerals can be broken
so that only van der Waals (dispersion) forces are affected.
Under these conditins the W + W. component is small and
flotation is possible without t\e addition of collectors.

MINERAL/WATER INTERFACE

A successful mineral flotation process requires that at least one


of the minerals in a pulp is made selectively hydrophobic. In the
233

simplest case this is achieved by adding a collector which has


selectivity for the mineral to be floated. Normally, however,
additional reagents are required to accentuate the difference in
the surface chemical properties of the minerals. Depressants are
reagents added to prevent the flotation of unwanted minerals and
activators are used to promote the adorption of collector on a
given mineral. Both classes of reagents are generally referred to
as flotation modifiers. Frothers are surface active agents
(usually non-ionic) added to the pulp, primarily to stabilize the
froth in which the hydrophobic minerals concentrate.

A preliminary selection of the reagents and conditins required to


separate a given mineral mixture can be made by considering the
surface chemical properties of pure, idealized models of the
major minerals present. However, the real conditions required
will be dependent on the properties of the actual minerals
present which will probably differ from thos of the models. The
surface chemical properties of minerals are very dependent on the
presence of trace impurities, and their origin and previous
treatment history.

Naturally occurring minerals rarely conform to their chemical


formulae. Instead, they contain minute inclusions of other phases
of appreciable amounts of foreign elements within the lattice.
Many crystal structures tolerate a considerable degree of solid
solution. Oxides, feldspars, micas and other alumino-silicates
are particular examples where the charge compensating cations, in
what is effectively a close-packed oxygen ion lattice, are
interchanged by cations of a similar size. No two samples of
nOminally the same mineral have therefore the same bulk analysis
or surface properties.

In addition to variation in the composition of a given mineral,


there is the proibability that the same mineral from diffeent
sources, will have a different concentration of dislocations and
slip bands etc. which will give rise to heterogeneous surface
properties. These effects are likely to be increased on grinding.
This is particularly true of dry grinding where localised high
temperatures can lead to mineral decomposition e.g.C0 2 is
released in the dry grinding of Caco and malachite. Disturbed
regions of a mineral surface will inevltably have a higher energy
than the stable crystal, and will therefore dissolve and react
first. Although these changes are unlikely to influence the
thermodynamics of bulk reactions it is likely that they will give
rise to a non-uniform adsorption density of reagents.
Autoradiography studies of collectors adsorbed on minerals have
shown the collectors to be concentrated in cracks and
disclocations rather than on the clean, undisturbed surfaces.

How a mineral is stored after grinding can have an important


234

effect on its surface chemistry. In general, breakage of a


mineral results in what can be considered as a high energy
surface. Low energy contaminants in the solution or atmosphere
will readily adsorb on this surface. Furthermore, there is the
probability that ions produced by the dissolution of a sparingly
soluble mineral in the pulp, will adsorb on the surface of other
minerals and thereby change their surface chemistry. These
effects will be time dependent, so that i t is probable that the
conditions required to treat an aged pulp will differ appreciably
from those required to treat a fresh pulp.

In view of the problems associated with the study of natural


minerals, it is hardly surprising that a considerable amount of
surface chemistry research, relevant to mineral flotation, has
been conducted on carefully produced artificial minerals.

To understand the nature of the collector and the conditions


required to make a mineral in a pulp selectively hydrophobic i t
is necessary first to consider the properties of the
mineral/water interface. This is most conveniently done by
dividing the minerals into (a) oxides and si;Licates, (b) salt-
type minerals (c) sulphides and (d) molecular crystals.

a) Oxide and Silicate Minerals

(1) Simple oxides: this group includes many common minerals


such as quartz Si0 2 , cassiterite Sn0 2 , rutile Ti0 2 , hematite
Fe 2 0 3 , and ilmenite FeTi0 3 • Ionic crys""tals are formed with th~
smaller cations in the interstices of the sublattices of 0 2
ions. On addition to water the minerals do not dissociate into
the metal cation and 0 2- ions, instead water is chemisorbed to
form a surface metal hydroxide. With some oxides the
hydroxylation proceeds throught the structure, thus MgO is
converted to Mg(OH)2' but with others it is restricted to the
surface. Ionisation of the surface hydroxide gives rise to a
surface charge, the magnitude of which is dependent on the pH.
Thus

MOH sur f + MO + H+
+ surf aq
(4)

+
MOH sur f t MOH2surf
_(5)
where M denotes a surface metal site and H+ and OH ions are
potential determining. Parks and de Bruyn [1] have postulated a
different mechanism for the charging of oxide surfaces which
involves partial dissolution of the oxide and the formation of
hydroxylated metal species in solution, followed by adsorption of
these complexes. For example, for the metal oxide ~03:-
Z35

MZ0 3 solid + 3HZO t ZM(OH)3


aq
(6)

M(OH)3 + M(OH)3-m + (3-m) OH


aq +
m(aq) aq (7)

M(OH)3-m + M(OH)3-m
+
m(aq) m(surf) (8)

Distinguishing between these two mechanisms is not possible,


because both will involve the same change in pH, and in the
latter case, the soluble metal species will be below the limits
of detection in the pH range of interest.

Titration of a suspension of an oxide in water at high ionic


strength with an indifferent electrolyte such as NaCl with acid
o~ alkali_can yield the surface charge by assuming that all added
H or OH ions change the solution pH or are adsorbed at the
surface. The results of titrations against hematite [Z] are shown
in Figure 3. This figure clearly shows that the surface charge on
hematite would reverse its sign at pH 8, 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 point of zero charge (p. z. c.), since at
this point, the net adsorption of potential determining ions is
zero.

The p. z. c. of an oxide is generally considered to correspond to


the pH of minimum solubility. Provided that all the stability
data are known for a given metal oxide-aqueous sustewm, it is
possible to calculate the solubility-pH curve. However, the value
of the calculated pH at the minimum solubility usually differs
appreciably from that determined by potentiometric titrations on
natural minerals. Typical values are given in Table 1. Values
shown in Table 1 are 'typical' because variation in the observed
values are obtained depending on the origin, imputities and pre-
treatment of the sample.

An alternative method of determining the p.z.c. is to use


electrokinetic methods to determine the zeta potential as a
function of pH. The pH at zero zeta potential (the iso-electric
point, i.e.p.) should correspond to the p.z.c. provided that the
specific adsorption of ions does not occur. The most commonly
used method is mocroelectrophoresis, which gives results in terms
of the electrophpretic mobility or the velocity of the particles
migrating under a potential gradient i. e. ~ sec -l/vo l t em-I. I t
is possible to convert these values into zeta potentials using
the Helmholtz-Smoluchowski equation [4], but as the correction
236

12
10
8
IC'I
~ 6
0
E
~
4
"'0
~
2
....
-.g
c ~

11\
0
2
I
:::c
0
~
4
0
+
:::c 6

8
10
12
3 4 5 6 7 8 9 10 12
pH
Figure 3. Abstraction of H+ or OH ions by Swedish hematite in
KCl solutions [2 ]

Table 1. The point-of-zero-charge of some oxides [3]

Oxide pzc(pH)
quartz, Si0 2 1-2
cassiterite Sn02 4.5
zirconia Zr0 2 4
rutile Ti02 5.8
hematite(natural) Fe 20 3 4.8-6.7
hematite(synthetic) 8.6
corundum Al203 9.1
magnesia MgO 12

factors required are often unknown, i t is wiser to leave the


result in terms of mobilities, expecially since the mobility will
also be zero at the i.e.p ••

A note of caution must be introduced at this stage. Just because


the i.e.p. and p.z.c. value do not coincide does not necessarily
mean that there is a fundamental difference. Potentiometric
237

Number of Structural unit Structural Silicate class


oxygen atoms formula
shared
0 ~ (Si0 4 )4- Orthosilicate

6- Pyrosilicates
1 ~ (Si20?)

Metasilicate
2 ~ ~(Si03)2- chains
~ pyroxene

¢*
(Si03)~n- Metasilicate
rings

Metasilicate
2~ (S;40,,1 6- chains
(amphibole)

4 Three dimensional Framework


network silicates

Figure 4. Structure of silicate minerals.

titrations are usually conducted on a dispersion, in which the


solids have a high total surface area, so the effects of trace
impurities in the water or electrolyte are minimused, because
they are spread over a large area. In microelectrophoresis, a
dilute suspension is used and therefore trace impurities will be
spread over a smaller area. The effect of impurities will
therefore be greater on the i. e. p. than the p. z. c.. One of the
most common impurities is soluble silica, derived from the glass
containers during prolonged storage periods. Recently, it has
been shown that the i.e.p. of Ti02 moves from 5.95 to 5.75 after
storage (at pH £, for 2 months) in glass containers [4]. Storage
at higher pH values, where glass is more soluble, has a more
238

marked effect and the i.e.p. of Al203 was shifted from 9.6 to 8.8
after storage at pH 10.0 for 16 hours in glass vessels.

(ii) Silicates: Silicates are the most abundant minerals in the


earth's crust. Though they occur in the majority of cases as
waste minerals in many ore deposits, they also serve as the basic
raw materials for many important applications. The chemical and
physical properties of the silicate minerals are extemely
complex, but all silicates are built of silica tetrahedra. In
this structure, the silicon atom is surrounded by a tetrahedral
group of four oxygen atoms, and different silicate groups are
obtained according to how many of the oxygen atoms are shared
with adjacent tetrahedra. (Fig.4).

The sim~lest of the silicates are known as orthosilicates, where


the SiO 4 ions are independent and the negative charges on them
are balanced by the positive charges of multivalent cations
present in the lattice between the silicate ions. Examples
include forsterite Mg2SiOH' zircon ZrSi0 4 , topaz
AI 2 (Si0 4 )(OH,F)2. In the pyrosilicates one oxygen atom is shared
beEween two silica tetrahedra gIvIng the structural unit
(Si Z0 7 )6-. Multivalent cations link the units together, e.g.
hemImorphite Zn4Si207(OH)2.HZO. When two oxygen atoms are shared,
either two-dimensIonal cfiains of silica tetrahedra of infinite
length (pyroxenes) or closed rings are formed (metasilicates).
Enstatite (MgSi0 3 ) falls in the former category and beryl
(Be3AIZSi601S) in the latter. If two and a half oxygen atoms are
shared by rue combination of two pyroxene-like chains, minerals
like the amphiboles are obtained which include tremolite,
(OH)ZCazMgS(Si4011)Z·
When three oxygen atoms are shared, a two-dimensional sheet
structure can result. These sheet-structure minerals are made up
of layers of silica tetrahedra condensed with gibbsite, (AI(OH 3 )
or brucite (Mg(OH)Z) in a variety of ways. The most common sheet
mineral is kaolinIte, which consists of alternating layers of
silica tetrahedra and gibbsite. The condensation of two silica
tetrahedra layers with gibbsite, gives the mineral pyrophyllite
and a similar condensation, but with brucite, gives talc. In
kaolinite, pyrophyllite and t~~c, the units are electrically
ne~~ral, but if some of the Si are isomorphically replaced by
Al in the silica tetrahedra, the units must be held together by
the introductions of cations between the layers. Muscovite (a
mica) is formed by the replacement of one in four of the silicon
atoms+in the pyrophyllite structure with aluminium, and the entry
of K between the layers to neutralise the excess negative
charge.

The sharing of four oxygen atoms gives rise to a three


239

dimensional network of tetrahedra. Quartz (Si0 2 ) is the result of


the idealized sharing of each oxygen between two silicon a~~ms.
This structure~s electrically netural but if any of the Si is
replaced by Al ,cations must be introduced into the lattice to
maintain electroneutrality. The feldspars orthoclase (KAISi 3 0 S )
and albite (NaAISi 30S ) are examples where the alkali metals fiave
been introduced inco the structure.

When quartz is added to water is should dissolve at pH 7 to the


extent of 7 ppm, but the dissolution is very slow so that
saturation is never attained. The surface of quartz hydroxylates
with the formation of silanol sites -SiOH. Ionisation of these
sites gives rise to a negative surface charge, which becomes more
negative with an increase in pH. The p.z.c. of silica is
generally assumed to be about pH 2, but some controversy exists
as to whether pure silica and quartz can have positive surface
charges. Determinations of zeta potential are particularly
difficult under these conditions because of the high ionic
strength.

Although the crystal structure is of prime importance in


determining the surface properties of a silicate, it is very
difficult to classify these properties according to the
structure. This is largely because nearly all silicates undergo
some isomorphic replacement of the cations, thus making
comparisons of minerals with the ideal chemical composition
nearly impossible. However, some generalisations can be made.
When a silicate such as an orthosilicate is added to water, it is
reasonable to assume that the surface will be composed of sites
originating from the silica tetrahedra and sit$s origi~ting from
the hydrolysis of the polyvalent metal ion. Hand OH ions will
be potential determining and the p.z.c. will depend on the
relative proportions of the silanol and hydroxylated metal sites
and the p.z.c. values of quartz and the metal oxide.

I I
-Si-O- + H+
-Si-OH +
+
Isurf Isurf (9)

I + -H+ I I
-M-OH + -M-OH -M-O
12+ Isurf Isurf (10)
surf
Breakage of an orthosilicate is more likely to give rise to a
metal cation site than breakage of more complex silicates, which
should lead to higher p.z.c. values for orthosilicates than those
obtained for other silicates. The p.z.c. values shown in Table 2
suggest~ that, in general, this is the case. The p.z.c. values of
the pyrosilicates, pyroxenes and amphiboles would be expected to
be near that of quartz, because of the predominance of silanol
240
sites over those of the metal hydroxide.

With aluminosilicates the neutralising cations are mobile to some


degree and can be slowly leached by acids or partly exchanged.
Thus the minerals show a cation exchange capacity and a negative
zeta potential, which is not simply dependent on the acid-base
dissociation of surface hydroxyl grou~ but 4.l:s l~.fgely
co~~rolled by isomorphic replacement of Al for Si ,Mg for
Al etc. Mica, for example, has a negative zeta potential at
acid pH values which is essentially independent of the pH. Cation
exchange capacities range from about 6 meq g-1 for the zeolites
to 0.03-0.1 meq g-l for kaolinite; even lower values are obtained
for the aluminosilicate such as hyanite and sillamite, which fall
in the orthosilicate class. The latter minerals provide an
example of where acid washing reduces the i. e. p. because of the
removal of surface aluminium oxides [61.

Table 2. The point-of-zero-charge of some silicates [51

Class Mineral pzc(pH)


ortii'Osilicate
forsterite Mg ZSi0 4 4.1
fayalite Fe2S~04 5.7
olivine (Mg,Fe)2Si04 4.1
zircon ZrSiO 5.8
kyanite Al 2sto 5 6.2
Metasilicate
(Single chain) enstatite (Mg,Fe)Si0 3 3.S
spodumene(LiAl(Si0 3 )2 2.6
Metasilicate
(ring) beryl Be3A12(Si601S) 3.2
Sheet silicate
kaolinite Al 4 (Si 4010 )(OH)S 3.4
talc Mg6(Si8020)~OH)4 3.6
muscovife K2AI4(A12S~6020)(OH,F)4 1
Framework silicates
microcline K(AlSi 30 S ) 1.S
orthoclase K(AlSi °)
anorthite Ca(A12S!2~8)
1.7
2.0

The double layer characterisitc of the sheet minerals depends to


some extent on which crystal face is considered. Thus, along the
cleavage planes, a zeta potential essentially indepentent of the
pH might be expected, whereas at the edges the potential should
be pH dependent because of the+ presen~ of surface hydroxyl
sites. Partial dissolution of Mg2 or Al3 from the edges should
gi ve a surface which resembles that of silica. However, the
possibility of readsorption of the polyvalent cations cannot be
ignored.
241

With the exception of pyrophyllite and talc, the breakage of


oxide and silicate minerals will result in a very reactive
surface which will readily hydrate to produce hydrophilic
surfaces. Breakage of pyrophyllite and talc along their cleavage
planes, will result only in the distruption of van der Waals
bons, so that appreciable hydration of the cleavage faces will
not therefore occur, as these surfaces are inherently
hyfrophobic. At the edges, however, hydrophilic properties should
be obtained because of the presence of ~AI-OH and ;Si-OH sites.

b) Salt-type minerals

This group includes many common minerals such as calcite CaG0 3 ,


barite BaS0 4 , fluorite CaF Z ' apatite Ca S(P0 4 )3F, gypsum Cas0 4 and
scheelite caW0 4 • All are soluble in water to some extent, and the
dissolution can be represented in terms of a solubility product
and the equilibrium reactions between the lattice ions and water.
In the case of barite, the dissolution is simple can be
represented over a fairly wide pH range (3 to 11) by

(11)

but with calcite, the situation is somewhat more complex because


of the hydrolysis of the carbonite ion and the possible presence
of CO 2 from the atmosphere. The equilibria involved can be
summar1sed as [7].

CaC0 3 (s) + GaG0 3 K' =8.12xl0- 6 mole 1-1 (1Z)


+ aq

GaC0 3 (s) + Ca 2 + + 003 K =4.57 10- 9 mole 2 1- 2


+ s
(13)

+ COZ aq
COZ(g) K =3.38 x 10- 2 (14)
+

COZ aq +HZO + HC0 3 + H+ Kl =3.98 x 10- 7 mole 1-1 (15)


+

HC0 3 + H+ + C0 3 2- K2 =5.01 x 10-11 mole 1-1 (16)


+

Ca 2+ +HC0 3- + mole -11


+ CaHC0 3 K3 =6.6 (17)
+

Ca Z+ +OH- + Ca(OH)+ Kl1 =Z.S x 10 1 mole-II (18)


+

CaOH+ + OH + Ca(OH)Z aq K12 =Z.34x 10 mole -11 (19)


242

From these equilibria, it may may shown that when calcite is


equilibrated with pure water in the absence of atmospheric
CO 2 , the equilibrium pH is 9.9. However, exposure of _Sh~
suspension to atmospheric CO at a partial pressure of 10 •
atm., (as in air), reduces tfie equilibrium pH to 8.4. Clearly,
the pH of a calcite suspension is dependent on whether the
container is open or closed to the atmosphere.

10-10~_~_~_--=-_---=_-:::-----:~--=---:;!.
5 6 7 8 9 10 11 12 13
pH
Figure S. Solubility of calcite as a function of pH in a closed
container

Using equilibria 12 to 19 and mass balances on calcium and


carbonate species it is possible to calculate the solubility of
calcite, in the absence of atmospheric CO 2 , at different pH
values. Fig. 5 shows that calcite exhibits a calculated minimum
solubility at approximately pH 11. Similar calculations are not
possible for calcite suspensions in open vessels because true
equilibrium is only obtained at the pH where the dissolved CO 2 in
equilibrium with atmospheric CO~, in the absence of Caco 3 , would
be equal to that from the dissorution of Caco 3 • i.e. pH 8.4.
243

Similar calculations can be made for the other salt-type mine-


rals. Interestingly, thermodynamic considerations suggest that a
distinction should also be made here between a closed and open
vessel because, at a pH dependent on the mineral, the dissolution
of CO 2 from the atmosphere should make the metal carbonate the
stable solid phase.In fluorite suspensions,CaC0 3 should form at
pH values above 8.6 and for Scheelite the corresponding pH is
9.3. The extent of carbonate formation has not been ascertained,
and it is not known whether it forms on the solid phase already
present, or precipitates as a new phase. Either could have an
important effect on say the separation of calcite from scheelite
by flotation.

Strictly speaking, the potential determining ions for the salt-


type minerals should be the lattice ions. However, in many cases,
it has not been possible to ascertain whether this is so because
of the hydrolysis of the lattic cations and anio-¥s in solu,!ion.
For barite it is reasonable to suggest that Ba 2 and 50 4 2 are
potential determining and that the i.e.p. ~d p.z.c. will corre-
spond to a certain concentration of Ba2 and 504 2- in bulk
solution. With Cac0 3 , however, the zeta potential is not only
dependent on added concentrations of Na 2D0 3 and CaC1 2 but also on
the pH. Thus in the absence of added carbonate or calcium ions an
i.e.p. is obtained at pH 10. Below this pH the positive zeta pot-
ential can be reduced to zero and reversed by the addition of
Na 2C0 3 , Whereas above the converse can be achieved by addition of
CaC1 2 • Several authors have suggested tha.i- all ~he cal£ium an$
carbonate ~ecies in solution, such as Ca2 , C0 3 2 J HC0 3 ' CaOH+
and CaHCO should adsorb on the surface, and together with H
and OH-, ~e potential determining. In the absence of ~erimenta!
evidence it is more reasonable to assume that only Ca and 00 3 2
ar potential determining and that the role played by the pH is to
change their concentrations in the solution.

c) Sulphide minerals

The sulphide minerals which include galena PbS, sphalerite ZnS,


chalcopyrite CuFeS 2 and pyrite FeS 2 have been well studied in
connection with the flotation process because they are the major
source of non-ferrous metals. Their solubilities in water are
extremely low, but they do have solubility products deduced from
thermodynamic data. Values for PbS,CuS and ZnS are roughly 10- 28 ,
10-~S and 10- 23 (mole 2 1- 2) respectively.

Such small solubility products suggest that sulphides should be


relatively inert in aqueous solution. This is,however,not the case
because they are ~-pH dependent and as such are thermodynamic-
ally unstable in tHe presence of oxygen and altho'.!.&h bulk oxida-
tion does not occur,surface oxidation to S2-,S 0 2 and 5O~2- can
take place. The oxidation products are more solu~le than tlie
244

underlying sulphides.

As mineral sulphides are semiconductors they can act as a source


or sink of electrons, supporting electrode reactions at their
surfaces. The electrochemical phase diagram for galena presented
in Fig.6. indicates that the potential range in which galena is
thermodynamically stable is pH dependent. At cathodic potentials,
the surface of galena will be converted to lead and sulphide ions
will pass into solution whereas, under anodic conditions lead
will dissolve or form oxidised metal species on the surface
depending on the pH. Similar diagrams can be constructed for the
other sulphide minerals but the reduction and oxidation products
and the ~/pH conditions under which they form are, of course,
dependent on the mineral.
0·5,~----------------,

Eh

-0·5 Pb
+
H2S
Pb+ HS-

-1-0
0 pH 7 14
Figure.6. Electrochemical phase diagram for galena (Equilibrium
lines correspond to dissolved species at lO-4M)[35]

The electrical double layer properties of the sulphide minerals


have not been studied in any detail. Lattice ions will be
potential determining but in view of surface oxidation, pH and
redox potential will have a marked effect on the zeta potential.
Quoted i.e.p. values for galena and chalcopyrite lie at acid pH
values, for pyrite at neutral pH values and for zinc sulphide
between 2 and lOB. However, it is unclear as to which surface
phases these values apply, because the conditions have not been
adequately defined. In one of the few careful studies on ZnS,
245

Moignard and Healy [9] showed that acid or alkaline i.e.p. values
were obtained depending on whether the sample was washed with
acid or alkali. It was suggested that the ZnS was oxidised to SO
under acid conditions and to Zn(OH)2 under alkaline conditions
and that the i.e.p. values representeo surfaces covered by these
compounds.

Generally the surfaces of sulphide minerals are considered to be


hydrophilic. The notable exception is molybdenite. which has a
cleavage plane in which only van der Waals forces are present. so
that appreciable hydration does not occur. However. many of the
sulphide minerals do exhibit hydrophobic properties if the redox
conditions are adjusted so that sulphur can form on the sulphide
surface. Thus. in the case of chalcopyrite. a hydrophobic surface
is obtained under neutral to alkaline conditions i f the redox
potential corresponds to that required for the reactions [10].

+ CuS + Fe(OH)3 + SO + 3H+ + 3e (20)

Rhombic sulphur is composed of octagonal rings of sulphur bound


together by van der Waals forces. Cleavage surfaces therefore
exhibit hydrophobic properties. The general use of sulphur
formation to promote the flotation of sulphides is unlikely.
because strong oxidising and acid conditions are generally
required.

The major contribution to the hydrophilicity of sulphides must be


interactions between the oxidised groups and water. Whether or
not a less hydrophilic surface would be obtained by adjusting the
redox potential to that where the sulphide phase is stable. is
not known though is being investigated at present. Certainly the
reasons mentioned previously (Thermodynamics of Flotation)
suggest that this should be the case.

d) Molecular crystals

These include diamond. graphite and rhombic sulphur. In diamond.


each carbon atom is tetrahedrally linked to four other carbon
atoms whereas in graphite. the carbon atoms form layers of
hexagonal rings which are bound together by van der Waals
(dispersion) forces. Similarly in rhombic sulphur. the S8 rings
are held together by van der Waals (dispersion) forces. These
minerals are essentially insoluble in water. but they do have
measureable zeta potentials which are dependent to some extent on
the pH. In the case of graphite and diamond [11]. negatively
charged surfaces are obtained above pH 4. and although some of
the charge can be explained by the ionisation of weak acidic
groups. the surface charge is still negative after removal of
these groups by methylation.
246

Table 3. Structural formulae of typical collectors

Collector Structure

Non-sulphide flotation
0
II
Carboxylate R - C
\
0
+
Na

0
II
Sulphate R - 0 - S - 0 Na+
II
0

0
II
Sulphonate R - S - 0- Na
+
II
0

H
1
Hydroxamate R - C- N
II
0 0
1- Na+

Amine R NH/Cl-

Sulphide flotation

0
II
Xanthate R - 0 - C
\_+
S K

Dithiophosphate R - 0 S
\ II
p
I \
R - 0 S K+

Dithiocarbamate R S
\ II
N- C
I \_+
R S K
247

Graphite and sulphur have hydrophobic cleavage planes whereas


diamond, surprisingly, exhibits both hydrophobic and hydrophilic
properties depending on its source. Diamonds from freshly mined
kimberlite rock are generally hydrophobic whereas those from
alluvial deposits are predominantly hydrophilic. Why these
wettability differences occur has not been established.

COLLECTOR ADSORPTION MECHANISMS

The collectors used in mineral flotation can be divided into two


classes, based on whether they are used to float non-sulphide or
sulphide minerals. Typical examples of the collectors in the
first class are the long chain alkyl sulphates, sulphonates,
amines and carboxylates, while xanthates and dithiophosphates are
typical thio-type collectors used in the flotation of sulphides.
The structural formulae of some of the collectors in each class
are shown in Table 3.

In table 3, R represents the non-polar hydrocarbon part of the


collector molecule. For non-sulphide collectors, the hydrocarbon
group is generally equivalent to at least 10 carbon atoms,
whereas chain lengths of 2 to 5 carbon atoms are used in the
sulphide collectors. Collectors in the first class can be used to
float both sulphides and non-sulphides, provided that the
appropriate conditions are used. However, the short chain thio-
type collectors generally do not promote the flotation of non-
sulphides.

The mechanisms of adsorption of collectors at the mineral/water


interface can be broadly divided into three classes.

a) Coulombic attraction between the collector ion and a surface


bearing an oppositely charged double layer followed by the
formation of hydrophobic associations at high adsorption
densities, e.g., the adsorption of alkyl sulphates on
oxides.
b) Chemical interaction between the collector ion and sites in
the mineral surface resulting in the formation of a
chemisorbed layer or a new phase at the mineral/water
interface. e.g. adsorption of fatty acids and alkyl
sulphates by the salt-type minerals.
c) Electrochemical interaction between a semiconductor mineral
and a collector that readily oxidises. This applies to the
adsorption of thio-type collectors by sulphide minerals.

Coulombic attraction and hydrophobic association

Long chain electrolytes, such as the alkyl sulphates and amines,


can function as counter ions in the double layer at the
mineral/water interface. At low collector concentration collector
248

zero
zeta
potential -40
CHMC
I I -30
-10 I I
10 I I
-20>
I E
I
I -10 c;
cu I :.::c
C
E _11
, 10
I
I
I
0 cu 0-
Co

-
~ I
'Vi I
10 c
c cu
~ 10 N
20
30
40
SO
1013L--~-::--_-l----'-:----':""--L-;------I
10- 5 10- 4 10- 3 10- 2
Equilibrium concentration of sodium dodecyl
sulphonate( mole/litre)
Figure 7. The adsorption density of sodium dodecyl sulphonate and
the zeta potential of alumina as a function of dodecyl
sulphonate concentration at pH 7.2. {after Wakamatsu
and Fuerstenau[14].

ions adsorb by ion exchange with other ions present in the


diffuse layer, so that there is no net change in the distribution
of charge between the Stern and diffuse layers and the zeta
potential remains constant. At a certain critical collector
concentration, however, there is a sudden change in zeta
potential and a rapid increase in the adsorption density, which
has been attributed [12,13,14], to the formation of hydrophobic
associations between the adsorbed surfactant ions. These events
are sypified by the results shown in Fig.7 for the alumina
dodecyl sulphonate system [14]. Because of the similarity with
micellisation in bulk solution the patches of the associated
adsorbed ions have been referred to as two-dimensional micelles
or hemimicelles, and the concentration at which they form as the
critical hemimicelle concentration (CHMC).

The formation of hydrophobic associations provides an additional


adsorption mechanism, so that adsorption continues after
249

neutralisation of the surface charge. Although the CHMC is


usually two orders of magnitude lower than the critical micelle
concentration CMC, factors which effect the CMC also effect the
CHMC. Thus the CHMC can be reduced by increasing the ionic
strength and hydrocarbon chain length, and by the addition of
neutral molecules [15].

The formation of hydrophobic associations at the mineral/water


interface, is generally accompanied by an increase in the
hydrophobicity and hence floatability of the mineral. Thus the
adsorbed ions are predominantly oriented with their ionic polar
groups towards the polar mineral surface and the non-polar group
pOinting into the aqueous phase. The formation of dimer-type
groups, one ion adsorbed with its ionic group toward the surface
and another with the ionic group toward the aqueous solution,
might be expected, but presumably the opposite charge of the
mineral surface must reduce the mutual repulsion between the
collector ionic groups.

The coulombic attraction plus hydrophobic association theory can


be used as a very good model for the interaction of alkyl
sulphates, sulphates and amines with oxides and silicates. It can
be used to explain why alkyl sulphonates and other anionic
collectors promote the flotation of these minerals at pH values
below their p. z. c. values, and why amines act as collectors at
higher pH values. Furthermore, it explains the effect of
hydrocarbon chain length and various additives, on the the
flotation recovery. However, it does not provide all the answers;
it does not explain why in some cases adsorption occurs at pH
values where the mineral has the same sign as the collector, and
why calculations, using a simple double layer model, of the
adsorption density required to change the zeta potential by an
observed amount, give values much smaller than those actually
mesured. Furthermore, it assumes that the concentration of
collector at which the zeta potential changes rapidly, should
correspond to that at which the adsorption density increases;
there are a number of examples where this is not the case. The
alkyl sulphate - Ti02 system at acid pH values is an example of
where marked changes in the zeta potential and charge reversal
are obtained at alkyl sulphate concentrations at least an order
of magnitude lower than that where the adsorption dsensity
increases rapidly [16].

Adsorption by a chemical interaction with metal sites in the


mineral surface.

The long chain anionic collectors form insoluble compounds with


polyvalent metal ions. Adsorption of these reagents should
250

therefore be possible by forming a chemical bond with available


metal sites. Thus fatty acids chemically interact with the salt-
type minerals and many oxides and silicates. Although the alkyl
sulphates and sulponates interact in the same way with the salt-
type minerals, there is little evidence to suggest that they
chemically interest with the oxides and silicates.

Studies of the interaction of fatty acids with minerals are


complicated by the fact that the collector is a weak acid, and
the undissociated form has a low solubility.

RCOOH +
+
pK
a
= 4.7 (21)

and RCOOH + RCOOH pK = 5 for


s + aq
dodecanoic acid (22)

If the total solubility is defined as S = [RCOO-] + [RCboH]


aq

then S K { Ka + I} (23)
[H+ ]

which describes the solubility dependency on the pH. Using


equations 21, 22 and 23 it may be shown that around pH 5 to 7, it
is possible to have all three fatty acid species present. At high
pH values the carboxylate ion predominates, but at low pH values
the solution becomes saturated with unionised acid. Depending on
the pH at which adsorption takes place therefore, it is often
difficult to determine which forms of the collector is the
adsorbing species.

The carboxylate ion can function as a counter ion and form


hydrophobic associations at the mineral/water interface, provided
that the p.z.c. of the mineral occurs at a pH significantly
higher than the pK of the acid. Since the p. z. c. of mos t oxides
and silicates olcur at acid to neutral pH values, the
contribution of coulombic attraction to the adsorption process,
is therefore probably not significant. Some coulombic adsorption
of carboxylate might however, be obtained with alumina, calcite
and other minerals with p.z.c.'s at high pH values.

When a chemical interaction occurs, the amount of fatty acid


abstracted is often equivalent to many layers. It is therefore
difficult to ascertain whether a chemisorption followed by a
physical adsorption process is involved or a new phase of metal
soap has been formed. In the case of calcite and scheelite, there
is evidence [17] to suggest that the abstraction of fatty acid
can be accounted for by the formation of a new soap phase
251
involving simple solution reactions such as

CaC0 3 (s) + ca2+ + C0 3 2- (24)


+

K [Ca 2+] [CO/-] (25)


sCaC0 3
and ca(RCOO)2(s) + Ca 2+ + 2ROO (26)
+

K [ca 2+] [RCOO-] 2 (27)


sCa(RCOO)2
Thus the equilibrium fatty acid concentration corresponds to that
in equilibrium with solid soap. Whether the soap forms in
solution and then deposits on the mineral surface, or forms at
the surface and stays there, is not known. Microscopic
examination of the surface of calcite ofter immersion in myristic
acid solution, clearly shows crystals of calcium soap
concentrated around cracks and imperfections. A similar mechanism
has been suggested by Fuerstenau and Miller [18] for the
abstraction of alkyl sulphonates by calcite, and it seems
reasonable that it should apply to a number of other salt-type
minerals.

A number of authors [19,20] have suggested that fatty acids


adsorb on the salt-type minerals by a chemisorption mechanism.
Evidence has been obtained by infrared spectrophotometry of the
presence of a surface calcium soap. However, whether or not such
a species exists in aqueous systems is difficult to assess,
because to obtain the infrared data the samples had to be dried
prior to analysis.

The adsorption of fatty acids on the oxide minerals would appear


to be a chemisorption-type reaction. The adsorption is
particularly strong on the iron oxides such as ilmenite and
adsorption densities equivalent to several layers have been
observed. It has been suggested that first a chemisorbed layer is
formed, followed by physicial adsorption and condensation of the
unionised acid [21]. Judging by the flotation results obtained
[22], fatty acids adsorb on the orthosilicates and in some cases
the pyroxenes, but in general no adsorption occurs on the
amphiboles and framework silicates. What evidence is available
suggests that adsorption occurs via a chemisorption mechanism in
these cases.

Other systems where chemical interactions are predominant include


those between chelating agents such as the alkyl hydroxamates
with hematite and chrysocolla [23,24], 8 hydroxy quinoline and
dithizone with zinc oxide minerals [25] and salicylaldehyde with
cassiterite [26]. In all cases the interaction is a chemical
reaction rather than a chemisorption, and multilayers of the
252
metal chelate are formed.

Interaction of thio-type collectors with the sulphide minerals

The interaction between thio collectors and sulphide minerals


represents the most studied area of mineral flotation chemistry.

Despite all this attention, controversy still exists over the


nature of the hydrophobic species on the surface of the minerals
and the interaction mechanism. One of the problems has been to
deri ve a mechanism which explains the roles played by oxygen in
the adsorption process. Three mechanisms have been proposed using
ethyl xanthante and galena as a model system.

a) Chemical:

The galena surface is first oxidised to a lead-sulphur-oxygen


speCies, such as basic thiosulphate, and this reacts with
xanthate in an ion exchange process to form lead xanthate

2PbS + 202 + H20 + (28)

PbS 20 3 + 2ROCS 2- + (29)

The lead xanthate is considered to render the sulphide surface


hydrophobic

b) Mixed potential:

A hydrophobic layer of dixanthogen is formed on the sulphide


surface by two coupled electrochemical process; an anodic
oxidation of xanthate

ROCS 2- +
+
(ROCS 2 )2 + 2e
(30)
and a cathodic reduction of oxygen

t 02 + 2H+ + 2e +
+
H2O (31)

In the presence of oxygen dissolved in the solution, the


conducting mineral/solution potential adopts a 'mixed value' (El!: )
between the reversible potentials E02/H20 and
Exan/dixan/Emineral ox/red (Ea)such that cathodic oxygen
reduction occurs at a rate (which may be limited by its transport
to the mineral surface) equal and opposite to the sum of the rate
of anodic oxidation of collector and mineral, so maintaining
electron balance. The relative rates of the two anodic reactions
is pH and mineral dependent, so providing a means of achieving
253

selectivity between sulphides (see section 7.). The potential


differences (EO/H20 - E ) .. TI and (E - E ) .. TI provide the
driving forces/overpotentDtals (If,), whicYl cau~e thea cathodic and
anodic half cell reactions to depart from equilibrium and occur
at a significant rate i.e. the oxygen chemically anodically
polarised the mineral surface, the good electronic conductively
of which, 'shorts out' the two half cells as in the corrosion of
metals.

c) Semiconductor:

The reductive adsorption of oxygen changes the electron energy


levels of the semiconducting sulphide to a state where the
xanthate can be adsorbed and even dicanthogen formed. Often
mineral sulphides, such as galena, are degenerate semiconductors
i.e. quasi metallic, so that surface reactions are not limited by
the supply of carriers (electrons or holes) in the surface.

The interactions between galena and xanthate were the subject of


detailed reviews in 1972 [27] and 1973 [28]. These reviews draw
attention to the controversy over whether or not dixanthogen
formation is required to render galena hydrophobic. Mechanism (a)
is supported by spectroscopic evidence [29,30] for the presence
of oxidised lead sulphide and lead xanthate species on the
surface of galena, and thermochemical measurements of the
reaction of lead salts and galena with xanthates [31]. Mechanism
(c) was developed by Plaksin et al [32] to account for
heterogeneities in surface properties. Mechanism (b) was first
proposed by Salamy and Nixon [33] and more recently Woods and co-
workers [34,35] have extended it to other sulphides. Of the three
mechanisms this one most readily explains the experimental
observations. Furthermore, because the sulphides are
semiconductors and can be used as electrodes, the proposed
reactions can be investigated by electrochemical techniques which
for example, show that the reactions suggested by mechanism (a),
can take place under certain redox conditions.

The rest potential of an electrode provides information regarding


the possible processes taking place on its surface, since such
processes require the potential to be in a region where the rate
of reaction is finite. Allison and co-workers [36] correlated the
rest potential of a number of sulphide minerals in different
thio-collector solutions with the products extracted from the
surface. Some of their results are shown in Table 4.

In general, oxidation of the collector to its disulphide only


occurs on those minerals which display a rest potential above the
corresponding reversible potential for disulphide formation. For
those sulphides with rest potentials below this value, the metal
collector compound is formed. Covellite is an exception to this
254

rule, dixanthogen being formed even though the measured rest


potential is significantly below the reversible potential. This
was explained in terms of a reaction between cupric and xanthate
ions in solution. Whether or not the disulphide is formed,
depends not only on the sulphide, but also on the thio-type
collector. Thus with the dithocarbamates, the metal
dithiocarbamate is formed on covellite, chalcopyrite, galena,
bornite and chalcocite, but not pyrite, on which the disulphide
is formed.

Table 4. Correlation between rest potentials and the products of


interaction of sulphide minerals with ethyl xanthate
solutions.
(Potassium ethylxanthate 6.25 x 10-~M at pH 7
Reversible potential for xanthate oxidation.
= + O.l3V (S.H.E.)

Mineral Rest potential Product


(V vs. S.H.E.)
arsenopyrite + 0.22 dixanthogen
pyrite + 0.22 "
pyrrhotite + 0.21 "
molybdenite + 0.16 "
chalcopyrite + 0.14 "
covellite + 0.05 "
bornite + 0.06 metal xanthate
galena + 0.06 metal xanthate

In the case of galena it has been shown [34] that around the rest
potential, xanthate is chemisorbed by a reaction of the type

+ (32)

where (ROCS) represents the adsorption of a xanthate


radical,an ete~flon being transferred from a xanthate ion to the
metal, resulting in chemical bonding with the surface. This
reaction is preferred to the formation of lead xanthate by

2PbS + 4ROCS 2- + 3H20 + 2Pb(ROCS 2 )2 + S2032- + 6H+ + 8e(33)

because this would lead to the loss of sulphure species to the


solution, and cylic voltammetry showed that this does not occur
[34]. The chemisorbed xanthate is believed to be hydrophobic
enough to induce flotation, but a more hydrophobic surface is
obtained if the potential is sufficiently anodic for the
formation of dixanthogen. Under these conditions lead xanthate
also forms according to reactions of the type represented by
equation 33 and thio-sulphate is detected in solution.
255

Exactly how the metal dithiocarbamates and dithiophosphates are


formed oli the appropriate sulphides has not been established.
However. from data obtained with galena in dithiocarbamate
solutions [35) and chalcocite in dithiophosphate solutions [37)
it would appear that chemisorption reactions, of the type shown
for galena and xanthate occur, and that at suitably anodic
potentials, the metal compound is formed.

FLOTATION OF OXIDES AND SILICATES

Oxide and silicate minerals are floated with long chain


electrolytes as collectors. which are adsorbed either by
coulombic attraction followed by the formation of hydrophobic
associations or chemical interaction with the mineral surface.
Adsorption of alkyl sulphates and amines are examples of the
former mechanism, and adsorption of fatty acids is almost the
exclusive example of the latter. Both collector mechanisms are,
in general, not very selective because of similarities in the
electrical double layer characteristics of the pulp minerals.
Furthermore, in the case of fatty acids, the carboxylate ion not
only reacts with many different metals, but under appropriate
conditions it adsorbs coulombically on the unwanted minerals.
Where poor selectivity is obtained, modifiers are added to
enhance the differences in the wetting behaviour of the component
minerals.

One of the few examples of where selective flotation is obtained


without the use of activators or depressants, is in the removal
of iron oxide minerals from glass sands. Many glass sands in the
United Kingdom contain small amounts of ilmenite, magnetite,
hematite, .geothite and siderite. The sands are first leached with
HF plus sodium dithionite which provides a suitably reducing
medium for the removal of iron-staining from the sand grains.
Next, after removal of the slimes and dilution with water, the pH
is adjusted to 3 to 4, and the iron oxides are floated with
petroleum sulphonate based collectors. At this pH. the sand is
weakly negatively charged and the iron oxides are positively
charged. The petroleum sulphonates therefore adsorb on the iron
oxides by coulombic attraction and the formation of hydrophobic
associates.

Reference to Table I and consideration of how long chain


collectors adsorb, will suggest a number of different ways of
separating oxide minerals. In particular, it should be possible
to separate quartz (p.z.c. - 2) and hematite (p.z.c. - 7) by at
least three different methods.

(i) flotation of the hematite at pH 3-4 with an anionic


collector such as an alkyl sulphate or sulphonate,
256

(ii) flotation of quartz at pH 5-6 with a cationic collector such


as dodecylamine,

(iii)flotation of hematite at pH 7-8 with a fatty acid collector.

The treatment of artificial mixtures of minerals under these


conditions will produce a separation. In practice, however, a
number of other factors determine the conditions used. Thus, in
the case of an ore containing the iron oxide minerals, it is
unlikely that quartz will be the only waste mineral; other
silicates will be present with surface characteristics similar to
the iron oxides. the pulp will probably contain soluble
multivalent cations which might have an activating effect on the
flotation of silicates. Furthermore, one of the minerals present
might grind more easily than the others so that it forms slimes,
which unselectively coat the coarser mineral particles. Also,
there is the possibility that although the collector adsorption
is selective, it will not be strong enough under the pH
conditions suggested, to give a high mineral recovery. All of
these factors lead to the use of depressants to improve the
selectivity. For example, iron ores are separated industrially by
flotation of the silicates at pH 8 with amine, while depressing
the iron oxide minerals with starch. Alternatively, the iron
oxide minerals are floated at pH 8 to 9 with fatty acid, using
sodium silicate to depress the silicates.

The modifiers used in the flotation of oxides and silicates


include inorganic compounds, such as sodium fluoride and
hydrofluoric acid, sodium silicate and multivalent cations and
macromolecules such as starch, dextrin, gums and quebracho.

Modification by sodium fluoride/hydrofluoric acid.

Fluoride in its various forms (NaF, HF and Na 2SiF 6 ) is one of the


most widely used, and certainly the most versatile, modifying
agents in silicate flotation. The effect it has on the flotation
of certain silicates with cationic (amine) and anionic (fatty
acid) collectors is summarised in Table 5 [38].

Addition of NaF or HF to an aqueous solution will give rise to F,


HF and HF2 species at concentrations dependent on the total
fluoride concentration, pH and magnitude of the equilibrium
constants.

(34)

.. (35)
257

Table 5. Effects of HF and fluoride on the flotation of


certain silicate minerals

Cationic flotation
Mineral HF treat. Fluoride addn.
pH 3.5 - 10.0

Feldspar Strong mild activation pH 7


activation
quartz little effect little effect
beryl activation activation
spodumene no float slight activation
fosterite no float mild activation
with or without
HF

Anionic flotation
Mineral HF treat. Fluoride addn.
pH 3.5 - 10.0

Feldspar no float no float


quartz no float no float
beryl depression depression
spodumene depression depression
fosterite no float strong
with or without depression
HF

In the presence of sodium fluorosilicate, however, hydrolysis of


the fluorosilicate ion occurs.

+ (36)
+

and monosilicic acid (Si(OH)A) is formed. If the concentration of


this sEecies ex£eeds the solubility of amorphous silica (approx.
2 x 10 3 mole 1 1 Si0 2 ) [39], polymerisation of the silicic acid
and formation of colloidal silica or silica gel might occur. The
rates of these reactions are, however, pH dependent, being very
slow at acid pH values and somewhat faster at pH 8 to 9 [39].

In the flotation of feldspar from quartz with an amine collector,


at pH 2-4 fluoride is added to activate the fledspar. The double
layer characteristics of quartz and feldspar are very similar and
both have weak negative charges at pH values between 3 to 4. In
the presence of fluoride, however, the negative charge on
feldspar increases markedly whereas that on quartz is unaffected.
258

The adsorption density of cationic amine is therefore greater on


the feldspar than on the quartz, so that it is possible to float
the feldspar away from the quartz. The reason why fluoride
increases the negative surface charge on feldspar is not
completely understood.

Some dissolution or degradation of the quartz and feldspar


lattice will occur in the presence of NaF or HF at pH values
between 2 and 4. Silicic acid and the fluorosilicate ion will be
formed in solution and the extent of the reaction will be
dependent on the HF concentration, rather than the total fluoride
concentration. Not all the fluoride added will be available to
form the fluorosilic~te ion, because some will be consumed in the
com~lexation of Al3 from the dissolution of the feldspar, and
Fe 3 which is invariably present in pulps at acid pH values.
Aluminium and ferric fluoride complexes are much more stable than
the fluorosilicate ion, so that the latter will not appreciably
form unless all the iron and aluminium is complexed first.
Consideration of the concentration of polyvalent cation and
silicate found in a feldspar flotation pu12 after the addition of
a typical dose of fluoride (l.5kg tonne 1 equivalent to 0.02M
total fluoride), and the stabilities of all the complexes present
[38], shows Jhat the iron and aluminium will be present as AlF3 ,
FeF3 and FeF2 and that the predominant divalent species is SiF 26 •
It is hardly surprising therefore, that several authors have
suggested that this species is involved in the activation
process.

Smith [40] proposed that the SiF 2- ion adsorbed on aluminium


sites in the feldspar surface to gfve a negative site

\ Al - OH + SiF6 2 - ++
\ AI- -
SiF 6 + OH
/ surf / surf (37)

which would then coulombically adsorb an amine ion. Alternatively


he suggested that the fluorosilicate ion might complex with the
amine according to
SiF 2 + RNH + + RNF3 SiF 6 (38)
6 3 +

and that the complex would ion exchange with surface hydroxyl
groups

\Al - OH + RNH 3SiF 6 +


+
\AI - SiF 6RNH3 + OH
/ surf / surf (39)

Both of these mechanisms would give rise to the same surface


species, and an increase in the pH. The latter has been observed,
but it is possible that the pH increased because of exchange of
259

. + + ++ +
surface latt1ce cations (Na,K and Ca ) for H ions.

A¥other ~uggestion is that the fluorosilicate ion interacts with


K or Na on the feldspar surface to give a layer of sodium or
potass~um fluo~osilicate,and that the amine cation ion-exchanges
with ~ or Na+ ions [41]. This seems unlikely, because most ~f
the K or Na available would probably ion-!fxchang~ with H •
Furthermore, if amine could ion-exchange with K or Na , why does
it not do so in the absence of the fluorosilicate ion? The
formation of an unchanged layer of fluorosilicate, would also not
explain why the surface becomes more negative, unless SiF 6 2- is
considered to be potential determining.

Kitchener and Warren [42] considered that the SiF 6 2- ion was not
the activating species, bcause they argued that an increase in
the negative zeta potential of feldspar was obtained at fluoride
conce!!trations too low to form significant concnetration of the
SiFh 2 ion. Indeed, the concentrations used by these authors were
a ractor of ten lower than that considered by Read and Manser
[38] in their calculations of the complexes in solution. It would
therefore appear that although the SiF6 2- ion might be important
at high fluoride concentrations, some interaction between the
fluoride and the feldspar surface must occur at low
concentrations. Kitchener and Warren suggested the adsorption of
F- ions on aluminium sites. Possible reactions might be

'AI - OH + F
\
+ Al - F + OH
+
(40)
'surf 'surf

'Al - F+F +
+
\Al - F2
-
(41)
'surf 'surf

\
Al - OH + F + -AI
, OH

+
'surf \
surf F (43)

-Al
,OH

+ F + -Al
, OH

+
\ \ -
surf F surf F2 (44)
Although a lot of emphasis has been placed on the activation of
feldspar at low pH values, fluoride is also adsorbed at higher pH
260
values to give more negative zeta potentials. The presence of
fluorosilicate under these conditions is unlikely, because the
dissolution of the silicates is low and therefore an alternative
interaction mechanism is required. The most likely is that
suggested previously, where the fluoride ion interacts with
aluminium or other polyvalent metal sites in the silicate
surface. Such a mechanism would explain the increased negative
zeta potentials, and hence increased flotation with amines, and
also the depressing role that fluoride has on the fatty acid
flotation of silicates.

No detailed studies of what happens to the mineral surface when


fluorosilicate is added instead of HF or NaF, appear to have been
made. Presumably it minimises the dissolution of the silicates by
a common-ion-tr.pe e~fect, and at the same time provides
sufficient SiF6 or F to act as an activator/depressant.

10- 4
A1 3+ AI (OH)3
(5)

--
IQI
~
10-5
~

J!! 10- 6
0
E

c::
10-7

-
0
+=
c
~

c::
QI \
u
c:: 10-8 \
~
0
\AI(OH)i
\
10-9 \
\
\
10-10
0 2 8 10 12 14
Figure 8. Logarithmic concentration diagram for I x 10-~M AlGl 3

Table 6. Approximate pH rrange where positive qua~tz zeta


potentials are obtained in the presence of 10 ~M sAlt
solution [43).

pH range
2 - 7
6 - 10.5
3 - 8.5
8 - 12
11
12
261

Modification by polyvalent cations

Polyvalent metal ions adsorb on oxides and silicates in the pH


range where the ~~~ration of one of the lower charged hydroxy
complexes, M( OH) , is at a maximum. On quartz and those
silicates with a low p.z.c. value, the adsorption is
characterised by a reduction in the negative zeta potential and
charge reversal, if sufficient metal salt is added. Table 6 shows
the pH range where positive zeta potentials can be expected in
the presence of 10-4M salt solutions.

Calculations of the conce~ft!.i5~ons of metatn,!lf1~ieS in these pH


ranges, shows that M(OH) or M(OH)2 is jfesent at
higher concentrations than the unhydroxylated cation M • This is
typified by the results shows in Fig. 8. for a 10-4M solution of
AlCl 3 • The formation of polymeric aluminium complexes has been
ignored in these calculations. Comparison of Fig.8 with Table 6
shows that in the pH range where charge reversal is obtained, the
aluminium is present as a hydroxylated ion, or as precipitated
aluminium hydroxide. Similar figures could be drawn for the other
cations.

The mechanism of metal adsorption is controversial. Fuers tenau


and co-workers [43] consider that since charge reversal is
obtained, specific adsorption in the Stern layer must occur. They
suggested two possible mechanisms. In the first the hydroxylated
metal is adsorbed by hydrogen bond formation

OH OH •••• O - eu+
\ I \ I I
Si + <ll(OH)+ + Si H
I \ OH I \
OH
surf

and in the second, water is formed and removed

\ /H +
Si + <ll(OH)+ + (45)
I \
OH

Both models show why a positive zeta potential could be obtained.

James and Healy [44] have proposed that the relative hydration
energies of the hydrated cation and the hydroxylated cation may
be used to explain why the hydroxylated metal species is involved
in the adsorption process. For the highly charged parent cation,
the energy involved in removing the hydration sheath, to allow
262

the ion to penetrate the Inner Helmholtz Plane (IHP) was


considered to be so large that the overall value of AGO would
ads
be positive, and adsorption would not occur. Reduction of the
charge on the cation by hydroxylation would reduce the solvation
energy (AGO 1 ), so that a net negative free energy would be
obtained. so v

AGO +_ AGO + AGO (46)


coul i solv i chem.
l.

°
where AGadsi is the free energy of adsorption of the i th species
and AGO and AGO h ' are the contributions from coulombic and
chemicffUlnteracti'bn'i;~ James and Healy [44) assumed that AGghemi
would be independent of the cationic species so that adsorption
would not be through the OH group by hydrogen bonding, but
through the metal ion itself. Thus whether or not AGOadsi is
ne~ative, will depend on the relative magnitudes of AG80uli and
AGcouli ' These authors calculated AGOsol v . using a model in which
the aasorbing ions, with its primary h~dration sheath intact,
moves from the solvent up to the IHP, where the permittivity (E i )
is lower, and in the process losses its secondary hydration
sheath. Several approximations had to be made to estimate E., but
l.
a good agreement was obtained between the calculated and measured
metal adsorption densities.

These authors also considered the possibility that the adsorption


was an interfacial precipitation of the metal hydroxide,
occurring at a lower pH than the bulk value. Charge reversal
would therefore be obtained between the pH value at which the
hydroxide forms, and the p.z.c. of the hydroxide. In this range
the zeta potential would approach that the of the hydroxide, as
the layers build up. Although this theory explains a number of
experimental observations it does not readily show why cationic
metal species adsorb on to positive oxide surfaces [45).

Whatever the adsorption mechanism, it is clear that multivalent


cations will have a strong influence on the adsorption of
collectors by oxides and silicates. In general, the adsorption of
multivalent cations by quartz and silicates activiates these
minerals to flotation with anionic collectors, such as the alkyl
sulphates and fatty acids. Activation is obtained in the pH
ranges where charge reversal occurs, where the alkyl sulphate can
adsorb coulombically, and in the case of fatty acids, where the
carboxylate ion can adsorb either coulombically or by chemical
interaction with the polyvalent metal. In contrast to the
behaviour with the anionic collectors, depression is obtained
with cationic collectors in these pH ranges.
263

Modification by starch and gums

The hydrophilic organic colloidal materials such as gelatin,


guar, gum arabic, starch and dextrin, are used as depressants in
the flotation of oxides and silicates. All are large carbohydrate
molecules with regularly repeated structural units. The molecules
can have cation, anionic or essentially non-ionic character
depending on the pH, and whether or not the functional groups
have been modified. The compounds used in flotation are generally
non-ionic to weakly anionic.

In aqueous solution, the molecules extensively hydrogen bond with


each other and also with water, through their many alcoholic OH
groups. Their structure in water is therefore complex, which
makes it even more difficult to envisage their structure in the
adsorbed sta~e. The molecules can adsorb by coulomibic attraction
i f they have a charge apposite to that on the solid surface;
alternatively they can hydrogen bond with ~uitable sites on the
solid surface. However, invoking such mechan~ims does not readily
explain why they promote select~vity in some flotation systems.

One of the most important applications of reagents in this class,


is in the amine flotation of quartz and silicates, where starch
is added to depress iron oxide minerals. Not all starches or gums
give satisfactory results in this process, and selective
depression of the iron oxides is very dependent on the type of
starch, the extent of its branching, its mode of preparation, the
solution pH and the electrolytes present [46,47]. Why selective
depression is obtained in this system is not clear, because the
addition of starch does not appear to affect the adsorption of
amine on either quartz or hematite. Balajee and Iwasaki [48]
showed that corn starch and British Gum 9084 were adsorbed more
strongly by hematite than quartz at pH 7 and that the presence of
doecylamine increased the adsorption on quartz, but did not
affect that on hematite. The presence of starch did not affect
the amine adsorption by both quartz and hematite, the adsorption
by quartz being more extensive. Thus, it would appear that
selective flotation is obtained, although the adsorption density
of amine on both minerals does not change. Clearly, this implies
that the amine-starch layer on hematite must be more hydrophilic
than that on quartz. The structure of the adsorbed layers is not
known but Balajee and Iwasaki [46] proposed that an amine-starch
complex was formed at the mineral/water interface, though they
did not consider why the complex was hydrophobic on one surface,
and not on the other.

Starch is also used as an iron oxide depressant in the fatty acid


flotation of activated quartz and silicates at high pH values
(-pH 12).The quartz and silicates are activated with calcium
ions,which at these pH values, will be in the hydroxylated state.
264

Adsorption of the carboxylate ion then occurs via chemical bond


formation with the adsorbed calcium speicies. and/or coulombic
attraction. if sufficient calcium has been adsorbed. Iwasaki and
Lai[49] showed that the starch was adsorbed more strongly by the
iron oxides than the silicates. The same was true in the presence
of calcium ions. although the starch adsorption on the silicates
increased. The most likely reason for the latter. is that the
adsorption of calcium by the silicates reduced the negative zeta
potential. and thus lowered the repulsion between the weakly
anionic starch molecule and the silicate surface. A similar
argument can be used to explain why amine enhances the starch
adsorption on quartz.

Another application of the gums and starches. is in the


depression of naturally hydrophobic minerals such as talc and
graphite. The mechanism of adsorption in these systems is
unclear. because hydrogen bond formation would not be expected
along the cleavage planes of. for example. talc. However. it is
possible that the cleavage planes contain sufficient
discontinuities and dislocations. to expose what is effectively
end ;Si - OH or >Al-OH groups. which would be capable of
interactions with the gums. The number of sites required would
not be large because of the large size of the molecules. A
similar argument can be applied to graphite. because the edges
and discontinuities will contain various oxygen groups such as
phenolic and carboxylic groups. which would be capable of
hydrogen bond formation.

FLOTATION OF SALT-TYPE MINERALS

Flotation methods have been developed and are used commercially


for the separation of salt-type minerals such as
calcite.fluorite.barite.apatite and scheelite from oxides and
silicates. Separation of the salt-type minerals from each other
is, however,very complex and in some cases apparently
impossible. Thus, separation of calcite from fluo~te,calcite from
apatite. calcite from barite is difficult to achieve.Anionic
collectors such as fatty acids and sulphonates are generally used
to float these minerals, because of their tendency not to float
silicates and quartz at high pH values.However,because these
collectors predominantly adsorb by chemical interaction with the
cation in the salt-type mineral surface,it follows that little
selectivity will be obtained between minerals containing the
same,or a similar. cation. The use of modifying agents such as
sodium fluoride, phosphate. silicate and dichromate, and of
organic molecules such as tannin and starches. is therefore
essential to achieve selectivity. The mechanism by which these
reagents act. however, have remained obscure. mainly because of a
lack of systematic data in the literature on their use. Sodium
265

silicate, tannins and starch will be briefly considered here.

Modification by sodium silicate

Sodium silicate is used in the anionic collector flotation of


salt-type minerals to depress the silicate minerals, to disperse
the slimes and to improve the selectivity between the salt-type
minerals. Exactly how it fulfils these functions is difficult to
deduce from the studies which have been made, because of
inadequate descriptions of the sodium silicate and the
experimental conditions used.

The term sodium silicate refers to a whole family of chemicals


which consist mainly of sodium oxide and silicon dioxide in
various proportions, and whose composition can be represented by
the general formulae Na 20.rSi0 2 , where r is usually called the
'modulus' ratio of the sodium s~licate. The commercial silicates
are prepared by fusion of a mixture of sand and soda ash at high
temperatures. The resulting glass is dissolved in water under
controlled conditions of temperature and pressure, and the
solution obtained is referred to as soluble sodium silicate
(Water glass). Most commercial silicates are not true chemical
compounds but complexes of definable sodium silicate, and either
Na 20 or Si0 2 • There would appear to be only two definable sodium
silicates Na 2 Si0 3 (and its hydrates Na 2 Si0 3 .6H20 and
Na SiO .2.5~O), and Na 20 2SiO which correspond to the
metasi!icate (r=l) and the disilica~e (r=2), respectively [50].

The species present in an aqueous sodium silicate solution depend


to a large extent on the concentration of the solution in rela-
tion to the solubility of amorphous silica. For this reason it is
useful to consider the dissolution of silica in aqueous solutions
first. The equilibria involved can be summerised as [51]:

Si0 2(s) (47)

+ OH - 4.27 (48)

+ - 1.17 (49)
+

:c
SHOH) 4 + 20H + Si0 2 (OH)2 + H2O. PS2 - 5.44 (SO)
+

2-
4Si(OH)4 + 20H +
+
Si 4 0 6 (OH)6+ 6H 2O. pS24 = 14.9
(51)
266
It-
4Si(OH)4 + 40H- ...+ Si 40S(OH)4 + 8H2 0. p~44 23.6 (52)

2-
2Si(OH)4 + 20H- ...+ Si 20 3 (OH)4 + 3H 20. p~22 .. -9.9 (53)

Using these equilibria, and assuming the Si(OH) 4 concentration


remains constant throughout the pH range, it 1S possible to
construct the solubility and distribution diagram shown in Fig.9.
This diagram suggests that the solubility is independent of pH in
the pH range 5 to 9, and that under these conditions the
monosilicic acid is the predominant soluble silicate species. At
higher pH values the solubility increases because of the
formation of monosilicate, disilicate and other polynuclear
silicate species. Experimental values for the solubility of
amorphous silica in water at 298 K fall aound 1 - 2 x lO-3M SiO
[39]. The dissolution of amorphous silica in water is slow ana
long equilibrium times are required. Interestingly, amorphous
silica is metastable because the stable form of solid silica at
room temperature and pressure is a-quartz. In practice, no
detectable recrystallization occurs, except in geological times.

1
10
'I
Amorphous silicQ
~ 10-1
:=
Sit OH}t,
c
o

-
~
'-
c
OJ
w
C
o
105

\...J

t,-
10- 9 Si 4Os IOH)4
5 6 7 8 pH 9 10 11 12 13 14
Figure 9. Solubility of amorphous silica as a function of pH

Equilibrated sodium silicate solutions with Si0 2 concentrations


below the solubility of amorphous silica, can be represented by
equilibria of the type shown above. If, however, the solution is
supersaturated with respect to soluble silica, polymerisation of
silica takes place. Depolymerisation occurs when the silica
267

concentration is reduced below the solubility of amorphous


silica. The overall polymerisation/depolymerisation process can
be represented as

polymerisation
silicic acid + polyilicate ions ++polysilicic acid
+
depolymerisation
aggregation
+ colloidal silica (sol) + gel
+ +
(54)
deaggregation
Siloxane bonds are formed during the polymerisation and a
possible way of representing this is

OH OH OH OH
I I I I
Oll-Si-OH + Oll-Si-OH HO-Si-O-Si-OH (55)
I I I I
OH OH OH OH

The rate of polymerisation is very dependent on the pH, silica


concentration and the temperature. Very slow rates are obtained
at low and high +H values [39]. Thus, in acidic media the
polymerisation rate is so slow that supersaturated solutions of
monosilicic acid can exsist for a very long time. The fastest
rate would appear to occur at weakly alkaline pH values. Fluoride
and hydroxyl ions are considered to have catalytic effect on the
polymerisation process. The structure of the various polymeric
species is not well defined, but it is known that under certain
conditions the polymers or colloidal sized particles, exhibit a
considerable negative charge. Polymerisation/depolymerisation is
reversible, but depolymerisation from colloidal silica to
monsilicic acid is very slow.

The nature of the silicate species after the addition of sodium


silicate to a flotation pulp, will depend therefore on the
concentration of the sodium silicate solution, the dose rate, the
pH and the conditioning time. Addition of a concentrated silicate
solution will probably result in the formation of polymeric
species, even if the equilibrium concnetration is below the
solubility of amorphous Silica, because the conditioning time
will be too short for the polymeric silica in the concentrated
solution to depolymerise. The absence of polymeric silica will be
favoured by the addition of dilute sodium silicate solutions and
long conditioning times. The interaction of polymeric silica
species at mineral/water interface, is likely to differ
appreciably from that with monosilicic acid and other soluble
silicate species. This fact has been neglected by a number of
authors [52,53], and in some cases the presence of colloidal
268

silica has been assumed at concentrations well below the


solubility of amorphous silica.

In a recent study, Marinakis [54] showed that sodium silicates


with Si02 : Na 20 ratios between 1:1 And 3.41:1, reduced the
sOlubility of calcite, barite and fluorite and produced negative
zeta potentials. No polymeric species were present under the
conditions used. Strongest silica adsorption was obtained on
fluorite, followed by calcite, and then barite. Changing the
ratio of the sodium silicate did not significantly change the
adsorption, provided that the concentrations were expressed in
terms of the Si0 2 content. Figs. 10,U, and 12 demonstrate the
effect of pH on the silica adsorption. Maximum adsorption was
obtained on calcite at between pH 9 and 10, and on fluorite at pH
values above 7. Significant adsorption on barite was only
obtained at pH values above 10.

Small scale flotation tests showed that fluorite floated well


with oleic acid between pH4 and 12, barite floated well at pH
values above 7, and calci te at between pH 10 and 12. Sodium
silicate depressed the flotation of fluorite and barite at high
pH values, and calcite at all pH values. In general, the addition
of sodium silicate reduced the oleate adsorption in the pH
regions where depression was obtained. However, the oleate
adsorption on fluorite was so strong, that despite extensive
silica adsorption, the fluorite floated better than the calcite
and barite, especially at pH 9-10.

Marinakis suggested, after consideration of his adsorption


results and solution equilibria data, that the predominant silica
adsorption mechanism on calcite was

: ea 2+ - 0 - SiO(OH)3
surf (56)

with the formation of a surface calcium silicate. A similar


mechanism was considered to take place on fluorite and barite,
but in the former case, adsorption through the formation of
hydrogen bonds between silicic acid or the monosilicate ion and
fluoride sites, was also considered possible. This might explain
the higher silica adsorption obtained on fluorite. Another
possibility is that more calcium sites are available on a
fluorite surface than cationic sites on calcite and barite, if
the distribution of sites on the cleavage planes are considered
representative.
269

30
ro
......
)(

. .e.
. . . . . . 20 a
VI
1M
o
e

Si~frla20 Initial Si02 M


01-00:1 5-2.10- 4
0207'1 5-0.10 4
lll41 :1 5-2.10 4
121 1-00 '1 2'4 x 10-4

456 7 8 9 10 11 12
pH

Figure 10. Adsorption of silica by fluorite as a function of pH.

CD
o
20

-
)(

e
N

VI
QJ

~
"0-
QJ
10
....
.0

~
"8 o
SiOz!NazO
[J 1· 00: 1
o 2·07:1
II 3·41:1
B 9 pH 10 11 12
Figure 11. Adsorption of silica by calcite as a function of pH

The important conclusions of the work of Marinakis [54] are that


sodium silicate does selectively depress the fatty acid flotation
of calcite under conditions where no -polymeric species are
present in bulk solution, and that the depression and silica
270

5 Initial SiO 2 M
GO Siod Na 20
0
~
0 1·00: 1 4·9 x 10"4
x
"'e 4
...........
VI
C1I
<5
e 3
"0
C1I
.D
L-
0
VI
"0
2
c:I
c:I
u

Vl

o
°3~~4~S~~6~7~~8~~9~10~1~1~12~
pH
Figure 12. Adsorption of silica by barite as a function of pH

adsorption, are dependent on the total Si0 2 content of the


solutions and not the ratio of the sodium silicate. The
conclusions contrast with those of Klassen and Mokrousov [52],
and also Sollenberfer and Greenwatt [53], who claim that the
depression-effect is dependent on the sodium silicate ratio. It
is difficult to comment on this claim, because inadequate
information is available on the nature of the original sodium
silicate, how the solution was added, and the equilibration times
used.

Little is known about how polymeric silica adsorbs on a mineral


surface. It is reasonable to assume, however, that hydrogen bond
formation between silanol sites on the polymer and suitable sites
on the mineral surface, will occur. Furthermore, there is the
possibility of chemical bond formation between negative silicate
sites and surface cations. Whatever the adsorption mechanism, the
presence of a large negatively charged hydrophilic polymer on the
mineral surface will result in dispersion of the mineral
suspension and probable depression of flotation with anionic
collectors.

Sodium is more effective as a depressant when it is added with


the salts of polyvalent metal cations. The favourable effect of
aluminium salts, has been reported by a number of authors
[55,56]. Thus Abeidu [56] attributes the improved separation of
271

fluorite and calcite in the presence of aluminium and sodium


silicate, to a decrease in oleate adsorption on the calcite,
because of competition between the carboxylate ion and the
anionic Al2 Si03(OH)~- ion. Salts of zinc and chromium have been
found to improve selectivity in this system [57,58], and iron has
been added to improve the separation of calcite and scheelite
[59]. Marinakis [54] showed that barite and calcite were strongly
depressed by sodium silicate and aluminium chloride, at pH values
below 12. However, the flotation of fluorite was unaffected. He
further showed that the adsorption of aluminium by calcite and
barite was enhanced in the presence of sodium silicate, and vice
versa. Adsorption of silica by reaction with colloidal aluminium
hydroxide present on the calcite and barite surface, was
considered to occur at pH values below 9,

Al(OH)3 + 8OSi(OH)3 + Al(OH)20Si (OH)3 + ~O (57)


surf surf

and at higher pH values adsorption through the formation of


soluble aluminosilicates was thought likely.

Other inorganic reagents which are frequently used as


depressants, include chromates, dichromates, ·phosphates,
polyphosphates and fluoride. Chromates and dichromates are used
to improve the depression of barite. They are claimed to form the
more insoluble barium chromate on the surface of barite, which
then inhibits the formation of barium carboxylate [60].

It seems likely that the phosphates and polyphosphates, which are


used extensively to to depress carbonate minerals, act by
specifically adsorbing, and increasing the negative zeta
potential to the extent that it inhibits the adsorption of ionic
collectors. The formation of surface phosphates is also a
possibility.

Modification by organic molecules

Organic modifying agents such as starch, tannin and quebracho


have been used to increase the selectivity in the fatty acid
flotation of the salt-type minerals. They are particularly useful
in depressing carbonate minerals and barite in preference to
fluorite. Despite their extensive industrial application
information on their mechanism of adsorption is limited.

Hanna [61] showed that starch depressed the fatty acid flotation
of calcite and barite, although the greatest starch adsorption
occurred on fluorite. Somasundaran [7,62] showed that starch
produced a more negative zeta potential on calcite and this was
interpreted to indicate that the weakly negative starch molecules
were adsorbed on cationic calcium sites. A similar
272

effect was observed by Blazy and co-workers [63] with fluorite


and barite. Adsorption of the starch by hydrogen bond formation
is also a possibility. as suggested for its adsorption on iron
oxide minerals. This might explain why greater adsorption is
obtained on fluorite. than on calcite and barite.

The adsorption of starch on calcite is dependent on the pH. and


decreases as the pH is increased from about 8 to 12 [62]. The
presence of starch apparently increases the adsorption of oleic
acid and vice versa. In other words. a hydrophilic surface is
obtained even though the mineral adsorbs more surfactant. A
similar result was obtained in the starch-amine-oxide mineral
system. Hanna and Somasundaran [7] proposed that thse results
could be explained by the formation of a helical starch-oleate
clathrate at the calcite/water interface. with the hydrophobic
oleate chain held inside the starch helix. The exterior of the
helix would be hydrophilic and thus the calcite would remain
hydrophilic. Experimental evidence for such complexes at the
calcite/water interface is. however. lacking.

The tannin compounds differ from the starches in that their


hydroxyl groups are phenolic (pK 9.2 to 9.9) rather than
alcoholic (pK > 12). Adsorption by 2hemical interaction [64] at
moderately hfgh pH values is therefore possible as well as
adsorption by coulombic attraction or hydrogen bond formation.
Similar to starch. co-adsorption of tannin and oleic acid has
been observed on calcite. barite and fluorite. The formation of a
tannin-oleate clathrate at the mineral/water interface has been
suggested [7]. In contrast to this suggestion. Iskra and co-
workers [65] showed that quebracho has similar adsorption
affinities for calcite and fluorite. and that the adsorption of
quebracho and oleate is competitive. Thus increasing the
quebracho adsorption. decreased that of oleate and vice versa.
The decrease in oleate adsorption due to quebracho was. however.
much greater for calcite than for fluorite. presumably because
the oleate adsorption was much stronger than that on calcite. The
overall effect of the quebracho was that fluorite floated. and
calcite was depressed. Both reduction in the oleate adsorption.
and the presence of the hydrophilic quebracho molecule at the
calCite/water interface. were considered to be responsible for
the depression effect. Iskra and co-workers [65] agreed with the
biew of Schulze and co-work.frs [64]. that tannins chemisorb on
calcium minerals through ~2 ions. either in the surface of the
mineral lattice. or as Ca2 ions adsorbed on it from solution.

FLOTATION OF SULPHIDE MINERALS

The flotation of sulphide minerals from oxide. silicate and salt-


type minerals with thio-type collectors. is usually very
selective. This is because these collectors. either do not adsorb
273

'"i"_ 700
CI
PYRITE
E 600
....
0
GALENA
+-
u 500

-
CIJ

0
u
400
0

c: 300
0
:.:: CHALCOPYRITE
....0 200
+-
c:
CIJ
u
c:
0
100
w

O2
3 4 5 6 7 8 9 11
pH
Figure 13.Effect of diethyl dithiphosphate concentration on the
critical pH values of pyrite, galena and chalcopyrite
[66]

Table 7. Critical pH values in 25 mg 1- 1 K-ethyl xanthate [66]


Mineral .E!!.
pyrrhotite 6.0
galena 10.4
pyrite 10.5
chalcopyrite 11.8
covellite 13.2
bornite 13.8
chalcocite 13.8

at the non-sulphide mineral/water interface or, when they do,


they do not contain a sufficiently large non-polar group to
render the minerals hydrophobic. Selectivity between the
sulphides is, however, only achieved by the addition of modifying
agents.

Depression of sulphide flotation can occur by a number of


mechanisms - enhancement of oxidation of the mienral surface,
inhibitation of collector oxidation, inhibition of oxygen
reduction, decrease in the oxygen concentration and complexation
of surface metal sites. Selectivity is achieved in practice by
changing the pH and adding such reagents as sodium cyanide,
sodium sulphide, sodium sulphite and potassium dichromate. In
many cases the mechanisms involved have not been adequately
elucidated.
274

Thus galena is depressed at pH values above 4, chalcopyrite above


5.5 and pyrite above 7 [66]. Sodium sulphide is a strong reducing
agents, and therefore it will consume soluble oxygen, reduce
surface oxide layers and adjust the redox potential so that the
collector cannot adsorb by an anodic process.

Other reagents used to improve selectivity in sulphide flotation


include sodium sulphite and potassium dishromate. Both of these
reagents are used galena and the former is also used to depress
spaleritej they are usually added in conjunction with other
depressants. Sodium sulphite, added as sulphur dioxide, finds the
widest application and there are numerous operations where it is
used in the separation of copper sulphide minerals from galena.
Despite the fact that it is a reducing agent, its major
depressing mechanism would appear to be the formation of a layer
of insoluble metal sulphite, which inhibits the electrochemical
interaction of the mineral surface with the thio-type collector
[68]. A similar mechanism has been proposed for the depressing
effect of chromate on galena [68,69].

Activation of sphalerite

The flotation behaviour of sphalerite (ZnS), wurtzite (ZnS) and


marmatite (ZnS(FeS» is different from the other sulphides,
because in general poor flotation is obtained with the thio-type
collectors, especially the short-chain xanthates. Good flotation
is only obtained with these collectors if the minerals are
treated with solutions of copper and other heavy metal salts.
These features are exploited in the separation of zinc sulphide
from galena and copper sulphide minerals.

Various suggestions have been proposed as to why the short chain


xanthates only interact weakly with sphalerite etc. The little
reaction that does occur, would appear to produce a zinc xanthate
[70], but of insufficient quantity to render the surface
hydrophobic. It has been suggested that zinc xanthate is so
soluble that it dissolves leaving the surface hydrophilic. A more
reasonable explanation, however, is that zinc hydroxide
(K' = 10- 16 '79) is formed instead of zinc ethyl xanthate
(Ks = 10- 8 • 31 ) on the sphalerite surface. This view would concur
wi!h that of Woods [71], who suggested that the sphalerite
surface oxidises at lower potentials than that required for the
elctrochemical adsorption of xanthate. Another possibility is
that, since ZnS is a semiconductor with a large band gap, unlike
most other sulphides the electrochemical reactions are limited by
the low number of carriers.

The driving force for the activation of sphalerite with copper


ions, is the difference in free energy of formation of copper and
zinc sulphides. The overall reaction can be summarised as
275

Modification by pH

Control of solution pH is one of the most widely used methods for


achieving flotation selectively between sulphide minerals. For
each sulphide and thio-collector, there is a critical pH,
dependent on the thio concentration, above which flotation is not
obtained. Typical curves of critical pH values against
diethyldithiophosphate concentration are show in Fig 13 for
pyrite, galena and chalcopyrite. Flotation of these minerals is
obtained at pH values to the left of the appropriate curve, so
the significance of these curves to the selective flotation of
pyrite, galena and chalacopyrite, is obvious. Similar curves are
obtained with ethyl xanthate, but they are closer together at
alkaline pH values. Critical pH values in the presence of 25
mg 1-1 potassium ethyl xanthate are summarised in Table 7.

Along a critical pH curve the ratio of the concentration of the


collector anion and hydroxyl ion is empirically constant. This is
known as the Barsky relationship [66], and its meaning has been
the sub ject of much protracted controversy. Recently, however,
Woods [35] has demonstrated using electrochemical techniques,
that at pH values below the critical value for pyrite in ethyl
xanthate solutions, the xanthate oxidises in preference to
pyrite, so that a hydrophobic dixanthogen layer is obtained. This
contrasts with the behaviour above the critical pH, where the
pyrite oxidises and not the xanthante, so producing a hydrophilic
oxide layer. Woods also gave the Barsky relationship some
theoretical validity by showing that the pyrite oxidation curve
shifts cathodically 70 mV for each increase in pH unit, which
corresponds to the shift obtained when the xanthate concentration
was increased by an order of magnitude. Thus the effect, on
flotation, of increasing the pH by one unit, can be circumvented
by a ten-fold increase in the xanthate concentration.

Although electrochemical investigations have only been conducted


with pyrite, it is reasonable to assume that a similar mechanism
is involved with the other sulphides, and that above the critical
pH value, oxidation of the sulphide surface occurs in preference
to the formation of a metal-collector compound or oxidised
collector layer.

Modification by sodium cyanide

Cyanide depresses the flotation of those sulphide minerals which


contain a metal ion capable of forming cyanide complexes. Thus
pyrite, chalcopyrite and covellite are depressed, whereas galena
is not. This behaviour is reflected in Fig.14 where the critical
pH - NaCN concentration curves are shown for different sulphides
in 25 mg 1- 1 potassium ethyl xanthate. Of the copper minerals,
276

chalcopyrite is depressed much more strongly than chalcocite and


covellite. No comprehensive theory explaining these curves has
yet been developed.

In the case of pyrite, it would appear that depression is


obtained at pH values above about 7, because of the formation of
ferric ferrocyanide on the pyrite surface, which inhibits
oxidation of the xanthate to dixanthogen [67]. The depression of
chalcopyrite would, however. appear to be similar to the effect
of pH on pyrite flotation, with oxidation of the surface
occurring in preference to that of the collector [35]. The lower
potential required to oxidise the surface, presumably results
from the dissolution of surface layers to form complex copper
cyanides. Detailed studies have not been made with other
sulphides.

120
"j"
-100
C'I
E Marcasite
c:
0
:.= 80 14
0 hal copyrite
.-
L..
c:
cu
u
c:
0
60
u
cu
:E
c:
.0
40
>.
u

E
::l
'0 20
0
Vl

7 8 9 14
pH

Figure 14 Critical pH curves in the presence of sodium cyanide.


(K-ethyl xanthate concentration = 25 mg 1- 1)[66].

Modification with sodium sulphide and other anions

Sodium sulphide is a strong depressant of the flotation of


sulphide minerals with thio-type collectors. In the ~resence of
25 mg 1- 1 K-ethyl xanthate the addition of 40 mg C Na 2 S.9H20
shifts the critical pH values from above 10 to acidic values.
277

ZnS + Cu 2+ + CuS + Zn 2+
surf (58)

which should go far to the right. The reaction would appear to


take place in two stages, an initial rapid stage followed by a
very much slower, continuing stage after the build up of several
layers. In the second stage, lattice rearrangement occurs because
of the conversion of Cu 2+S 2- to the more stable Cu 2+(S)2 2-[70].

The flotation characteristics of copper-activated spalerite are


very similar to those of copper sulphide minerals. Thus in
practice, sulphides such a galena or chalcopyrite can be floated
first from mixed s~lphides with xanthate. The sphalerite is then
activated with Cu 2 , collector added, and the sphalerite floated
from the non-sulphide minerals. Copper activated sphalerite can
be depressed with the sodium cyanide.

In some cases sphalerite becomes accidentally activated because


of the presence of heavy metal ions in the pulp. Depression can
be obtained in these cases by the addition of soluble zinc salts
which produce hydrophilic zinc complex species on the surface of
the sphalerite. These species are similar to Zn(OH)2' and ZnC0 3 ,
and relatively thick layers are required for effective
depression.

FIOATION OF NATURALLY FLOATABLE MINERALS

Naturally floatable minerals such as talc, pyrophyllite and


graphite and to some extent coal can be floated from other
minerals by the addition of frothing agents only. Improved
flotation is, however, often obtained if non-polar oils such as
kerosene are added to the pulp as an emulsion. The oil drops
collect on the non-polar surfaces and increase their
hydrophobicity.

Naturally flotable minerals can be depressed by starches and


gums.

EXAMPLES OF MINERAL SEPARATIONS

Recovery of beryl, feldspar, mica and quartz from pegmatites

The mineral beryl (Be3AI2[Si6018]) occurs in granite pegmatites


in association with mca, quartz and feldspars. Minor minerals
also present may include spodumene, garnets, tourmaline, topaz
and iron oxides. A possible flowsheet to treat such a material is
shown in Fig.15. An understanding of the conditions used in each
stage can be obtained by assuming the following i.e.p. values for
the major components present; beryl pH 3.5, quartz pH 2.5,
feldspar pH 2.5, mica pH 1 and iron oxides pH 6.
278

feldspar +
beryl float

ca\ciwn hypochlorite

thicken
and
repulp

iron oxides float

feldspar

Figure 15. Treatment of a pegmatite by flotation

In the first stage, mica is floated with amine collectors at pH


values between pH 2 and 2.5. Under these conditions, the mica is
negatively charged, but all the other minerals have zero or
positive charges. Next, the iron oxides are floated with anionic
collectors, such as petroleum sulphoni te at pH 3 to 3.5. The
third stage consists of conditioning the pulp with HF or sodium
fluorosilicate and adding more amine collector, at pH 3 to 3.5.
The HF activities both the beryl and feldspar so that both
minerals float, leaving quartz as the tailing.

Separation of the beryl and feldspar can only be achieved after


the amine present on the surface of the minerals is removed. This
can be achieved by oxidative washing with calcium hypochlorite
solution and then adding a petroleum sulphonate collector at pH
2.5 - 3.0, whereupon the beryl is floated away from the feldspar.

There are many possible variations to the flowsheet depending on


the major and minor components of the pegmatite. The process
described is based on that suggested to produce saleable
concentrates of quartz, mica, feldspar and beryl from a pegmatite
279

deposit. There are, however, existing operations which use a


similar flowsheet to recover mica, feldspar and quartz from non-
beryl containing pegmatites.

Treatment of an ore containing galena, cerussite, fluorite and


barite

Fluorite and barite are often found together in economic


quantities, associated with calcite,. Silicates, sulphieJes and
oxidised sulphides. A typical ore might contain 25 - 30% CaF2 , 10
- 15% BaS0 4 , 0.5% Pb as PbS, 0.2% Pb as PbOO 3 , 25% Cac0 3 , ana the
rest quartz and silicates. Fig.16 shows a possible flowsheet of a
process to treat such an ore. The process can be divided into
lead, fluorite and barite recovery stages.

In the lead recovery stage galena is floated with potassium amyl


xanthate at pH 9.0. Sodium carbonate is added to control the pH,
and sodium silicate is used to ensure that the pulp is dispersed.
Cerussite (PbOO 3) will not float with thio-type collectors unless
sodium sulphide is added to convert the surface layers to PbS.
Lead recovery therefore consists of two stages, with cerussite
being recovered in the second stage. Sodium sulphide cannot be
added prior to galena flotation because of its depressant action
on sulphide minerals.

After PbS and PbOO flotation, the pulp is conditioned with


sodium silicate to lepress the silicates, quebracho to depress
the calcite and dextrin/starch to depress the barite. Oleic acid
is added, the pH maintained at 9.0 and the fluorite floated. The
fluorite concentrate is often refloated several times before i t
attains the grade (98% CaF2 ) required for hydrofluoric acid
production.

Before the flotation of barite from the calcite and silicates, it


is often necessary to thicken the pulp and decant the water which
contains residual collector, depressants and soluble salts. The
thickened pulp is diluted with fresh water, quebracho added to
depress the calcite and the barite floated with sodium hexadecyl
sulphate at pH 9.

There are a number of possible variations to the flowsheets


shown, and in some cases barite is floated before the fluorite.
Why selectivity is obtained in the treatment of these types of
ore is still not fully understood.

Recovery of copper, lead and zinc from a complex sulphide deposit

Complex sulphide mineral deposits are an important source of


copper, lead and zinc; often concentrates of these metals are
obtained from the treatment of the same ore. The economic
280

frother pH 8.S - 9.0

CaF, float

frother
thicken
and
PbS float repulp

quebracho
alkyl sulppate
Na2C03

PbC0 3 float BaS04 float

oleic acid CaC03 I silicates

Figure 16. Treatment of a lead/barite/fluorite ore.

sulphide minerals in these deposits are usually galena,


sphalerite and chalcopyrite with waste minerals of pyrite,
carbonates and silicates. A typical analysis of the ore could be
0.9% Cu, 6% Pb, 10% Zn and 4% Fe. Fig.17 shows a possible
flowsheet for the treatment of this type of ore.

In the first stage of flotation, the copper and lead sulphides


are floated together at pH 6-7 with a xanthate collector. Pyrite
would float under these conditions, but addition of a small
amount of cyanide effectively reduces the critical pH (Fig.14) to
about pH 6. Zinc sulphate is added to depress any sphalerite
which might have been activated by heavy metal ions.

The tailings from copper-lead flotation are treated with CuSO to


activate the sphalerite, and sodium cyanide and lime are addea to
complete the depression of pyrite at pH 10.5. Sphalerite is then
floated with the addition of more xanthate collector. If required
the pyrite can be recovered from the tailings.

Separate copper and lead concentrates are obtained from the


combined concentrate by depressing the galena with S02 and/or
sodium dichromate at weakly acid pH values. Alternatively, the
copper sulphides are depressed with sodium cyanide at pH 8-9 and
the galena floated.
281

galena
sphalerite
chalcopyrite
pyrite I silicates

Pb andCu
sulphides float

S02
sodium dichromate
xanthate

pyrite I silicates

C'lI sulphide float

PbS

Figure 17. Treatment of a lead, copper,zinc ore.

Much more complicated flowsheets than this are possible depending


on the mineralogical composition and liberation characteristics
of the ore.

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282
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cassiterite with salicylaldehyde as a collector. In
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Vol.l, 549-560, A.I.M.E., N.Y., 1976.

27. Granville,A.,Kinelstein,N.P. and Allison,S.A., Review of


reactions in the flotation system galena-xanthate-oxygen.
Trans.IMM 81, Cl-30, 1972.

28. Gutierrez,C., The mechanism of flotation of galena by


xanthates, Min.Sci.Engng. 5, 108-118, 1973.

29. Leja,J.,Little,L.H. and Poling,G.W., Xanathate adsorption


studies using infrared spectroscopy. Part II, Evaporated
lead sulphide, galena and metallic lead substrates. Trans.
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284

30. Greenler,R.G., An infrared investigation of xanthate


adsorption by lead sulphide. J.Phys.Chem 66, 879-883, 1962.

31. Mellgren,O., Heats of adsorption and surface reactions of


potassium ethyl xanthate on galena. Trans.A. I.M. E. 235, 46-
60, 1966.

32. Plaksin,I.N.,Shefeev,R.Sh. and Chanturia,V.A., Relationship


between energy structure of mineral crystals and their
flotation properties. 8th lnt.Mineral Proc.Congr., Leningrad
USSR, 1968.

33. Salamy,S.G. and Nixon,J.C., The application of


electrochemical methods to flotation research. Recent
devlopments in mineral dressing. IMM, London, 1953.

34. Woods, R., The oxidation of ethyl xanthate on platinum, gold


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35. Woods,R. ,Electrochemistry of sulphide flotation, In


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Vol.l, 298-333, A.I.M.E., N.Y. 1976.

36. Allison,S.A., Goold,L.A. ,Nicol,M.J. and Granville,A.,


determination of the products of reaction between various
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37. Chandler, S. and Fuerstenau, D.W.,The effect of potassium


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fotation of feldspar: adsorption of quartz. corundum and
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289

ENGINEERING ASPECTS OF FLOTATION IN THE MINERALS INDUSTRY:


FLOTATION MACHINES, CIRCUITS AND THEIR SIMULATION

G.Barbery

Formerly: Head, Mineral Technology Department


Bureau de Recherches Geologiques et Minieres, France.
Currently:Professor. Department of Mines and Metallurgy,
University Laval, Quebec, GIK 7P4. CANADA
INTRODUCTION

To try and cover in a single review paper all the engineering


aspects of flotation in the Minerals Industry is obviously a
formidable task. in front of which the present author is over
awed by the breadth and scope of materials to cover. and by the
existence of excellent review books or papers on the same
subject. It has been felt however that a unified presentation of
the state of knowledge in this field would be useful in the
context of the present NATO Advanced Study Institute on the
Scientific Basis of Flotation.

Although flotation as a unit process is used in many industries


it is only in minerals production that it has reached a status
which makes it an absolute requirement. \lithout flotation. the
availablity and thus price - of many non ferrous metals, would
be totally different of what it is now - e.g. copper. lead. zinc.
molybdenum. Very large units (some of them processing over
100,000 tons per day of run of mine ore) have been installed
demonstrating the reliability of the process- from the decision
maker point of view, and the success of equipment manufacturers
in designing large units.

Set against this favourable position, it must be recognised that


flotation as a separation process in the minerals industry, is
still an operation for which the scientific basis lacks solid
ground in its engineering aspects. Other authors in this book
have dealt with the surface chemistry of flotation, and its
importance in outlining conditions of selectivity.

Applied flotation research is also a very active field world


290

wide, but tends to concentrate on process testing and process


development on specific ores rather than on increasing knowledge
of the fundamental aspects of flotation as a unit process
operation, in the conventional meaning of Chemical Engineering.

STATEMENT OF THE PROBLEM

Flotation in the minerals industry has one basic function, which


is the separation of mineral phases which are present in an ore.
At least one of these phases contains a valuable element (e.g.
Cu, P,F ••• ) or can be in itself a valuable product (e.g. Na
feldspar, graphite ••• ), and the objective of any separation
process in Mineral Technology is to recover the valuable
constituent (element or mineral) in a concentrate, the
specifications of which, in terms of quality (purity, grade,
presence of desirable or undesirable associated elements or
minerals), are usually laid down by the purchaser, according to
fairly strict quantitative terms. Thus flotation, a unit process
based on differences in surface chemical properties of the
interfaces between minerals and aqueous solutions containing
reagents, one of them at least being a surfactant, can be placed
in the wider context of minerals separation.

The constraints that are inherently existent when dealing with


mineral particle systems, are the difficulties that are
encountered when trying to quantitatively describe populations of
such particulate systems. The feed to any solid/solid separation
system in Mineral Technology is the product of unit operations
involving comminution (by crushing and grinding), sizing (by
screening and clasiications), and consists. as far as the solid
phases are concerned. of particles. the make-up of which. in
terms of size, shape and mineralogical composition. is rather
difficult. if not completely impossible. to measure.

Since it is obvious that the engineering aspects of flotation


must be based to a large extent, on such a quantitative
description. it is felt that the state of the art in this field
should be reviewed briefly.

PARTICLE SIZE [1,2)

Particle size of interest in flotation range from 0 to a few


millimeters. Overall particle size compostion is the easiest
quantitative information than can be obtained. Methods in common
use in the laboratory consist of wet/dry sieving down to 40 lim
(with conventional woven screens) or sometimes 101lm (with
electroformed screens), and sedimentation in static centrifugal
fields for finer particle sizes. Particle counters and,
especially laser light diffusion patterns are becoming
increasingly common due to their simplicity of use in the 2-200
291

vm size range. Continuous monitoring of particle size


distributions in flotation plants is not yet common practice,
although various systems are available, based either on
attenuation of ultrasounds to give an 'average' particle size
information, or light diffusion pattern to provide complete
information on particle size composition.

The information obtained can be presented quantitatively in a


variety of ways, the simplest being a vector representation
relating the class, i, in which a measurement was made of the
equivalent or convenient particle size, between di and di+l' to
the mass (or volume) fraction in that class, D(i}; another
presentation is a fit to a continuous equation, usually the
integral form of vector D(i} is used - called the cumulative
fraction passing, or retained.

PARTICLE SHAPE [3,4]

At present no information is available on the influence of


particle shape on flotation. An excellent review has been made of
new developments in shape measurement for particulate systems.[4]

PARTICLE OOMPOSTION [5,6,7]

As already stated, flotation is a process based on differences in


surface properties of minerals, and to be properly used as a
separation process in the minerals industry, in theory each
particle in the feed to a flotation process should consist of
only one mineral. Moreover this constancy of volumetric
composition should extend to the very limited volume at the
interface between the particle and the water solution in which it
is suspended; or, additionally, each mineral should have the same
surface composition at that interface, in terms of hydration
layers, oxidation products etc ••• This theoretical composition of
particulate is called liberation, and is obviously never met in
Mineral Technology. Particulate systems fed to flotation cells
are produced by breakage of ores, and fractures in rocks do not
take place systematically at grain boundaries between minerals.
Particles are produced which consist of more than one mineral -
'composite particles' - , and methods to carry out measurements
which could be used to describe each D(i} class in terms of a
repartition into the various minerals present and also in terms
of their associations in composite particles, are not readily
available. Observation of a D(i) class or of a polished section
of D(i) class mounted in a matrix to reveal the intimate texture
of each particle tends to be a method progressing steadily with
the development of image analyzers, electron probe microanalyzers
and scanning electron microscopes. thus, in a not too long term
future, a description of each D(i} class into subclasses
consisting of mineralogical volumetric composition can be
292

Feed Characterisitics + Reagent Addition + Machine parameters

- Particle size dist- - surfactant at the - volume


ribution for each mineral/aqueous
mineral phase. solution interface. - area.

- mineralogical com- - selectivity of - size.


position distribution of - turbulence
surfactant between intensity in
- particle morphology each mineral phase various parts.
(shape). - aeration rate
- liberation/composite - value of a resulting - impeller charac
particle quantitative contact angle. teristics.
description. - frother addition - baffling
- mass flowrate. - resulting dynamic
surface tension at - mixing charac-
- specific gravity of air/water interface teristics
each mineral phase. (residence time
distribution) •
- water qual! ty
- solid water/ratio
- surface chemical Objective function Circuit Layout
properties
- state of flocculation/ -product quality cri- - type of flow
dispersion. teria. between cells
(open flow or
cell to cell).
- slurry rheological - recovery of valuable - arrangement of
property elements banks of cells
(number of cell
- temperature Economic factors per bank).
- capital cost - interconnection
between banks.
- operating cost
(labour, energy,
maintenance) reagents.

Figure 1. - Variables in flotation


293

envisaged. However, even that information, difficult and costly


to get, will not be sufficient since it should be complemented by
information on surface composition, since this is the driving
force behind selectivity in flotation. Some work is in progress
in this field [8).

Other parameters that have a large influence on flotation are


temperature (which is unfortunately very rarely recorded, even
during process testing and development) and relative proportion
of solids and water in the feed to flotation. this can be
expressed as a volumetric or mass fraction. Yater composition in
terms of equilibrium concentration (thermodynamic or kinetic) of
reagents added is not studied in the present paper since it is
widely covered in other presentations in this book. It is assumed
that conditions of selectivity have been found, that is, again
theoretically, the interface of one particular mineral/water
solution will have been made hydrophobic enough (as measured by
e.g. contact angle ••• ) to make the water film in contact with it
to thin and collapse in an extremely short time (e.g.10- 3s) when
an air bubble is approaching it.

FLOTATION MACHINES

To review flotation machine design after the papers written by


Harris in 1976 [44] and, very recently by Young [9] is either an
exercise in pliagiarism or in pretentiousness. It will be
attempted here to stress the main factors in cell design and
relate them to micro and macro-mechanisms in flotation, and to
mixing theory more generally.

Flotation cell deSign, if based on anything else that total


pragmatism, should rely on an optimisation, for any particular
problem, of the various parameters that are available. Figure 1,
based on similar ones drawn by Lynch et al [123] and Harris [44)
attempts to point out the mian parameters in a flotation cell.

The overall objective in flotation cell design should be a


minimization of overall production cost (operating + maintenance
+ part of amortized capi.tal costs) for separation of concentrate
from the ore pulp. In fact, when one wants to look into the
technical consequences of such a simple statement on cell type
and design, it becomes more important to look at some other
aspects of things:

1. Mechanism of transfer of hydrophobic particles from slurry to


froth launder, involving submechanisms of

1.1 - particle collection(often called the flotation microevent


i.e. the one resulting in a gas bubble - hydrophobic
particle attachment)
294

transfer of the elementary agglomerate into the froth


layer.

1.2 - detatchment of hydrophobic particle - bubble back to


slurry. either in the transfer stage or from the froth
layer.

1.3 non selective transfer of hydrophobic or hydrophilic


particles from slurry to froth layer - often called
mechanical entrainment.

1.4 removal of hydrophilic particles from the froth layer.

2. Transfer of hydrophilic particles and water away from the


cell

Quantitative information on any of these points is rather


limited. especially when one looks at fundamental aspects.
certainly for point 1.1., which is the most important. The basic
question of particle collection. as reviewed by Flint [10].
Harris [44] and Laskowski [11] still remains an open question,
leaving supporters of collison theory and precipitation theory at
basically the same level of understanding as the one reached when
Taggart wrote his Handbook of Mineral Processing [12] and in
which he expressed a rather strong point of view on collision:
"This idea, conceived in ignorance and born in litigation, was
fostered by selfish interest and, unfortunately, was copied in
some text books". this might be looked upon as a quarrel of
experts or theoreticians which has no consequence whatever on
practical results. In fact this is not at all the case, since
depending on the real limiting stage in flotation. various
flotation cell designs should give different results.

The collision thoery expresses the view that hydrophobic particle


collection is obtained by direct contact between air bubbles and
particles in the pulp. Kitchener and Anfruns [13,14] have made a
very good demonstration by a simple experimental technique of the
theory that absolute rate of flotation in a simple system
consisting of injecting individual air bubbles into a settling
slurry of hydrophobic particles corresponds to the hydrodynamic
collison rate. every particle colliding with a bubble being
captured. Collision would be of course the main hydrophobic
particle collection mechanism in machines in which air bubbles
are formed independently of slurry agitation as in pneumatic
cells (flotation columns for example).

Proponents of the precipitation of air bubbles on hydrophobic


surfaces are able to give vacuum flotation - or dissolved air
flotation - as examples of systems in which separation takes
place although no air bubbles are dispersed into the suspension.
295

Dissolved air flotation, although conventional in waste water


processing systems is not yet used in the minera'ls industry, but
i t is clear that there are parts of flotation cells in which
cavitation takes place under conditions of dissolved air
saturation, and thus precipitation on hydrophobic surfaces can
occur.

Apart from these two theories, a third line of approach should be


considered, as suggested by Arbiter and Harris {33] Harris {44],
and the successful design of cells of the Davcra type {n] and
the froth separators as described by Young {9], which would
involve a study of interactions of streams of slurry and air in
which, locally, volumetric air flows are comparable in magnitude
to slurry flows, implying an intense and intimate contact between
solids (hydrophobic and hydrophillic) water solution and air -
not yet dispersed into bubbles at their equilibrium size.

Since flotation machines are reactors in which three-phase


(solid, liquid, gas) contacts are responsible for separation of
various solid phases, it is convenient to study their
characteristics in terms of mixing theory. Among the textbooks
and reviews available on this subject, Nagata's book [25] should
be pointed out as a particularly good presentation. Here again,
the pioneering work of Arbiter and Harris {32-44] in trying to
use the concepts of mixing in reactors to flotation cell analysis
should be mentioned.

FLOTATION CELLS AS MIXING REACTORS

Most of the analysis has been carried out for mechanically


agitated flotation machines. For obvious reasons of lack of
turbulence and bulk movement in the top part of the cell,
flotation machines are baffled mixers - fully or partially. This
type of mixers is usually analysed, in terms of its hydrodynamic
characteristics by a series of dimensionless numbers, which,
based on the Vaschy-Buckingham theorem, allow to reduce the
number of parameters to be correlated in such a complex system. A
brief presentation of this anlaysis is given below:

- it is assummed that a flotation cell is characterised by a set


of geometrical dimensions which describe its physical shape.
Parameters usually considered are the cell dimensions (length,
width,height) , its shape, the presence, number, dimension and
positioning of baffles, impeller geometry (diameter, geometry,
dimensions of vanes etc ••• ), presence of a stator and its
geometrical characteristics, method of air introduction.

- the speed at which the impeller is rotating (N), power consumed


(p), air flowrate (Qa) are then related by a set of
296

dimensionless numbers involving for a homogeneous liquid the


following conventional numbers:

Power number

Reynolds number

Froude number =---


N2 D
g

Air flow number N =_....Q,.;;;;a_


Qa U D3

Weber number NWe N2 D2


=---
oLG

Discharge flow number QL


NWL
N D3

where D is the impeller diameter, p is the liquid specific


gravity, ~ its viscosity and oLG is the gas-liquid surface
tension. QL is the volumetric flowrate of the discharge flow from
the impeller.

These numbers have the following physical meaning: Reynolds


number characterizes the ratio of inertia forces to viscous
forces, Froude number that of inertia to gravity, Weber number
that of inertia to surface forces; the power number quantifies
the use of power to set the liquid in motion, and the air flow
number describes the relative flow of air and liquid in the
impeller area. NOL relates the discharge flow from the impeller
to its maximum theoretically possible.

For fully baffed systems under high turbulence as those observed


in flotation cells of any size, for. which NR lies around 10 5-
106 , the power number in the absence of afr is a constant,
independent of Reynolds or Froude number, and only depends on the
geometrical characteristics of the internals of the reactors

Np = C1

Discharge efficiency of various impellers does not seem to have


been the object of many studies, due to the difficulties of
measurement. Nagata [25] provides data for 8 - flat - blade
297

paddle impellers, which are similar in geometry to some flotation


cell impellers; for fully baffled conditions in a cylindrical
tank with 8 baffles and an aspect ratio (impeller diameter/tank
diameter) of 0.3, he measured Np = 14.2 and N = 2.9 under fully
turbulent conditions. The following relationsHrp is claimed
D -2.5 b 0.7 (1)
NQL a ~L ~ • ~L ~ • Np

where D/L is the aspect ratio


and b/L is the blade height/tank diameter (0.1 in Nagata's
measurements)

Measurements of these types of flotation cell impellers are not


usually done. Two recent papers [50,65] provide some data on this
subject, based on measurements made on the Wemco 1+1 impeller
design for large cell developments and for the Minemet BCS
impeller design at laboratory scale. The result would indicate
NOL values of 0.505 and 0.558. respectively for the Wemco unit at
1it.1S and 28.3 m3 cell volumes, and N L = 1.-43 for the Minmet
laboratory unit. It should be howeve~, pointed out that the
measurements for Wemco unit were carried out in the presence of
air at its normal flowrate, and thus the various set of data are
not strictly comparable.

Nagata suggests the use of the ratio Np/NQL to compare the


discharge efficiency of various impellers. It would appear, from
the very limited information available, that some designs
retained for flotation machines are very efficienct on this
particular point (Minemet BCS).

A complete description of hydrodynamic behaviour of water in


flotation cells involve measurements of turbulence
characteristics. Very scarce data is available. Only Couderc and
coworkers [65] have attempted such an analysis with the use of
hot wire anemometry. Important parameters such as turbulence
intensity

I
v (2)

for fluid velocity in two directions, speed fluctuation spectra.


auto-correlation coefficients for time and position. turbulent
diffusion coefficient as well as E. power locally dissipated per
unit mass of fluid. have been measured for a Minemet BCS
laboratory flotation cell working with water only. Turbulence
microscale can be calculated from Kolmogoroff theory by
298

(3)

where v is p/p , the kinematic viscosity of the liquid. The


results show the rather high turbulence intensity (order of
magnitude 0.5 for both the radial and tangential directions), and
the large variations in £ as a function of the location in the
cell, as can well be expected. Local £ values, compared to p/pV,
show increases of 10 fold at a dis tance of 10mm from the tipof
the impeller, and give 1 values ranging 15-50 pm for usual
values of impeller speed. s

As well as a description of hydrodynamics, its consequence on


mixing dynamics should be quantified. A definition of mixing time
in a batch reactor has been given by Nagata [25]. A dimensionless
concentration variance

I
ac 2
==-- I [C(x) - On] dx
s
cm2 V
C2
m
(4)

where C is the average concentration in any specific species of


interesf in the agitated tank and C (x) the concentration at any
'point', the integral being taken along the volume V of the tank.
The time 6 required to reduce this value to 0 or to a specified
dectectabl~value 61 is the mixing time. This concept is related
to bulk transport du\ to turbulence. For mixing of low viscosity
liquids in fully turbulent range (case of flotation cells), the
mixing number N ==6 x N is constant for geometrically similar
vessels and the 1I):0flowing equation is proposed for fully baffled
conditions:

1 1 D 3 D NP D 2 (5)
Nm == 6 MxN
0.1 {(-) NQL + 0.21 - - } [l-exp-13(-) ]
L L 1NQL L

where L is the diameter of the agitated tank or its equivalent


for a flotation cell.

For the figures given for an impeller similar to the ones used in
some flotation cells the following value is obtained, for a cell
aspect ratio of 0.308 and the figures already given for Np and
NQL
N == 62
m

For impeller rotation speeds of the order of 3 s -1, common for


large flotation cells, 6 == 20.6 s. It must be pointed out that a
m
299
scale-up criterion based on constant mixing time cannot be
maintained constant for a series of geometrically similar units.

AGITATION IN AIR-WATER SYSTEMS

The introduction of a stream of air to be dispersed in bubbles


that will be responsible for flotation complicates matter already
considerably. The use of frothers, surfactants at the air-water
interface, makes flotation rather peculiar even in the study of
gas dispersions. The main points to be reviewed concern: effect
of agitator characteristics on gas hold-up, power consumption in
aerated pulps, flooding of the reactor by high flowrate of air,
bubble size distribution resulting from the dispersion of the air
stream.

When a gas stream is blown in a liquid under agitation, there is


a minimum rotation speed at which the impeller must be run to
disperse it. Correlations of the type:

N D = ~ oLGg ) (A + B l!.)
o p D (6)

with A and B depending on impeller geometry (e.g. A = 1.22 and B


= 1.25 for turbines, A = 2.25 and B = 0.68 for paddles) have been
put forwards by Westerterp et al [27]. Applications to flotation
cells show that impeller speeds actually used are much higher
than this minimum value.

Air hold up, ~, expressed as the ratio of volume occupied by air


to the overall volume in the cell, has also been correlated, for
example, by Van Dierendonck [28] for electrolyte solutions

3
... =
'I' 0.075 [ ll(NL- No)02 ] • [ -ea 4 ]1/4
a LG gll (7)

Power consumed by impellers under aeration condition has been the


subject of many studies. Strong positions on this point have been
expressed by Harris [44]. Nagata [25] has put forward a corre-
lation for turbine impellers

D 4.38 0.115
NFr 1.96 D/L U (8)
192 ~L~ NRe QA
where PAlp 0 is the ratio of power drawn in the presence and in
the absence of aeration. Extensive data for laboratory flotation
machines have been measured by Arbiter and Harris and their
coworkers at Columbia University (see Harris [42,44] as well as
elswhere. For industrial machines, valuable information' for self
300

aerating machines in the absence of solids has been provided by


the Wemco Company. Correlations for air water systems are the
following [48]

QA a D2 • 4 In N (9a)
P a D3 • 7 N1 • 8 (9b)

QL a (D rn O• 2 exp f (D) + 0 exp g (D) (9c)

where 0 represents clearance between impeller and tank bottom; f


(D) and g (D) represent unspecified functions of D. These were
later [50] presented as

In N - om (D) (lOa)

N1 • 8 [n 1 (D) + on 2 (D)] (lOb)

As coimpared to their equivalent relationships for homogeneous


liquids the results are obviously different, pointing out to the
marked influence of air in controlling hydrodynamics.

Bubble particle size resulting from its dispersion results from


equilibrium between stresses applied (especially shear stresses)
and surface forces (taking into account dynamic effects in dilute
surfactant solutions). It would thus appear that the Weber number
would be significant, as well as the power dissipated per unit
volume, which, according to Kolmogoroff theory, control the size
of smallest eddies in fully developed turbulent flow. Various
correlations have been put forward from that of calderbank [23]

(ll)

where ~G represents gas viscosity

and dSM the mean bubble diameter according to Sauter

En d 3
i i

(12)

Van Dierendonck [28] has put forwards the use of a new


dimensionless number, which is called Eotvos number
301

N-N
[1.2 + 260 ~ _ _ 0 D
(13)
°LG

for (N - N ) D
o
1.5 mls
Harris [44] has especially insisted on the importance of frother
addition on the control of bubble size in this sort of system.
Predicted bubble sizes according to these formulas are the
following for D/L = 0.25, D = 0.6m, oLG = 0.05H/m (to take into
account the effect of frother on lowering surface tension) N =93
tlmin for a turbine impeller and 74 tlmin for paddles). No~mal
flotation impellers of this size run at about 200 t/min. Thus $ =
13.55%, from Van Dierendonck's formula, a good average number for
a flotation cell and ds~ = 0.333 mm, also a reasonable predictive
figure. This example shows the value of multiple correlation
formulas based on dimensionless numbers.

AGITATION IN SOLID-WATER SYSTEMS

Since a basic function of flotation cells is to allow transfer of


particles from the feed point to either froth discharge launder
or tailings transfer to the next cell or outside of the flotation
circuit, it is obvious that their design must include provisions
for maintaining the solid-water suspension, at any point in the
cell, as a handleable slurry. This is achieved in mechanically
agitated flotation cells by the action of an impeller. A review
of impeller characteristics for solid-liquid systems is available
in Nagata's textbook. [25] The most salient points are summarized
in the following paragraphs.

For suspension of solid particles in agitated liquids, there is a


optimum impeller diameter with respect to tank diameter, for a
relatively homogeneous fluidization of particles. Depending on
the bottom shape of the tank, impeller aspect ratios range from
0.35 to 0.5, the lower value being for spherical bottoms, and
the high value for flat bottoms. Baffling is especially important
in keeping solids fluidized, in order to transform circum-
ferential flows into vertical flows. Some flotation cells
designers have apparently paid a considerable attention to this
problem (e.g. Wemco with their draft tube below the impeller).

Dimensionless number correlations for determining critical


impeller speed for fluidization of solid particles have been
attempted; the main difficulty in obtaining reliable
relationships is the dramatic influence of baffle geometry
(localization in the tank, number, size).
Nagata proposes the following correlation:
302

_2/3
N = K D d 1/3
c P (14)

where r is a dimensionless number of the shape of particles, it


can be measured as the ratio of the bulk volume of a population
of particles to its true volume. Nagata obtained values of r=1.89
for sand and ground pyrite. This formula was obtained for solid
concentration of 0.105 kg/liter of water, and corrections must be
applied for other values. Nagata points out rightly to the
diffculty in obtaining simple correction factor for various types
of impellers and baffles. Typical values for K3 (for Nc in
r.p.m., D in m, dp in mm, Ps' PL in g/cm3 , ~L in cP) are 150-230
for flat bottom cylindrical fully baffled tanks.

Oyama and Endo [30] have put forwards the following correlation
for vaned disk turbines under fully baffled conditions:

2/3 1 3

£
gi .(p s - Pi)
C
16Pi (15)

when Pi is pulp density mass of liquid + mass of solid


total volume of liquid and solid
£c represents the power per unit mass of slurry required for
fluidization.

The power consumption of impellers for suspension of solid


particles, especially for the settling slurry case, has been
studied. For side wall baffles, the correlation is relatively
simple:

P P
s
Pw = Pw (16)

where Pw and Pw are the -power consumed with solids present and
absent respectively, and P is the average specific gravity of the
slurry, and Pw is water specific gravity.

For other types of baffles, especially bottom baffles, the


relationship becomes different, related to the presence around
the impeller, of a higher solid concentration:

p P*
s
Pw = Pw (17)
where p* is the average slurry specific gravity around
303

impeller,and can be obtained by

p* k (p - p )
w
+ pw (18)

k> 1, depends on size, shape and specific gravity of the solids


concerned. Nagata [25] provides curves for some minerals and
particle size (up to 415 ~m quartz).
1.0

p
a
p

NQ
~--------------------~----~ a
Figure 2 - Typical relationship between Pa/p power consumed in
the presence of air flow number Nq and without air,
in the presence of solid particles, as given by
Arbiter et al [38,43] NQ Earticles; common values in
laboratory cells are 2-4a~0 2.

For non Newtonian slurries, especially those of the Bingham


plastic type, other correlations can be applied, but it is felt
that they are never necessary in flotation, since dilution is
always adjusted to move away from these rheological conditions.

Other papers have been written on this subject. The work of


304

Harris [44] and his various coworkers is especially relevant


here. Nagata's correlation given above, when applied to flotation
cell data, tends to give much too low values for d at Np cell
design values. This result would indicate that flotdtion machine
impellers and tank internals are especially well designed to give
low K values (around or below ·100 for some designs [48,501). the
importance of Froude number in this context has been stressed by
the manufacturers of the Outokumpu cell [56,571, where a
constancy of the parameter N D2/L for a series of cells is
claimed

MIXING IN SOLID - AIR - WATER SYSTEMS

Flotation is a three-phase system, which is quite specific in its


mixing requirement, as far as particle size and air dispersion is
concerned. Similar types of operations are encountered in
leaching in the presence of dissolved gases, and fermentation; in
these systems, mixing requirements are quite different, and more
related to optimizing mass transfer for chemical reactions. It is
thus not too surpising that the only data available for mixing
solid - air - water systems, useful for flotation systems, has
been gathered weither by equipment manufacturers or by the few
research teams interested in the subject (especially at Columbia
University [32-441).

The complexity of the system is much greater than the ones


described above for solid - water or air-water. Assuming that one
starts, for example, from a solid water system, the
introduction of air complicates matter in that the efficiency of
solids dispersion is affected by the presence of air - water
mixtures around the impeller. The system can be described
graphically in the E, Nq plane, as put forwards by Schubert and
Bischofberger [15,161 orain the pIp - NQ plane as described by
Arbiter et al [38,431. In this latler ca~e, as can be shown in
Figure 2, there is an overall trend for decrease in power
consumption with an increase in air flow number, up to a point
where solids start to settle out of suspension. Koch [18]
recommends to characterize cells and impellers by the critical
air flow number at which this phenomenon takes place, Nc Qa •

For a 6.6 1 flotation cell fitted with a 59 IJII1 diameter double


finger impeller, N Q variations with E have been given for a tin
ore ground to 9sf ~elow 315 )Jm, as well as for a potash ore
ground finer than 1.5 mm [15]. Relationship of the type

EC a Nc Qab (19)
are presented with b=0.235 for the tin ore and b=0.05 for the
potash ore.
305

Most commercial cells, apart from special design for coarse


particles are working at specific power consumption and air flow
numbers very distant from these to prevent sanding up.

The effect of solid concentration on aeration does not seem to be


too important; it has been studied especially in the case of self
aerating machines

FLOTATION MACHINES DESCRIPTION

Complete presentation and comprehensive quantitative tables for


most sets of commercially available flotation cells have been
given by Harris [44] and Young [9], and it is not intended to
provide in this chapter the same information.

A classification of types of machines is given on Table 1 which


allows to schematically review design alternatives.
Characteristic features of impeller geometry and cell tank
profiles for mechanically agitated openflow machines are given in
Figures 3 and 4, as presented in Young's paper. A complete review
of developments in agitator less flotation cells up to 1964 has
been written by Iohn. [17] These cells, which were almost
completely abandoned in the Western World, show a revival for
difficult separations (coarse phosphate ores, selective flotation
of molybdenite from chalcopyrite) as well as for coal proceSSing,
especially in the Federal Republic of Germany. The papers listed
in the references and bibliography review recent papers on most
flotation machine designs, together with manufacturer addresses
for additional technical information.

ANALYSIS OF MECHANICAL FLOTATION MACHINE OPERATION

Since mechanical flotation machines are by far the most 'widely


used in the Minerals Industry, extensive technical research has
been spent on characterizing their operation. A very significant
contribution has been made by research workers at Columbia
University, New York, around Arbiter and Harris - see references
for list of publications. The basic problem was to try and
analyze flotation cells as far as their scale-up is concerned.

Flotation cells from any given manufacturer come in a series of


sizes, which have some geometrical similarity. They can be
characterized by:

- a geometric structure (e.g. parallelipiped,cylinder)


which defines the overall shape of the cell, in which
are included the following internal parts:

- an impeller (often surrounded by a stator and a


diffuser)
w
Booth o
0'
Self Aerating Humboldt wedag [58]
fKrupp
Wemco [45-52]

flow -+- Aeration \


I Aker
Denver
[55]
[53,54]
[ Agitair [59,60]
Supercharged Minemet [64,65]
Outokumpu [56,57]
Mechanical -+- Slurry transfer Sal a [61-63]
r (Denver [53,54]
i .,self Aerating 1Unifloc
Unit cell -+- Aeration",
Solids Supercharged -+- Maxwell [78-80]
/
Suspension
In froth layer ..JMachinoexport
frroth Separator
[72-76]
1 (Machinoexport [72]
Pneumatic -+- Pulp feed inlet Open Flow - {"Apatite"
\ +
In Cell -+- Slurry /
transfer \ Flotation column
[66-70]
Unit Cell ~ [ Davcra [77]
Flotaire [71]
(Slurry removal by
settling)
Table 1 - Classification of flotation machines
Rotation -.JIf Siandpipe Ib. 4-111.

/
Shan

--. Denver
Aker Prooeller Booth D-R

Shan 11/11 Siand


p;p.,

Wedag

Air port

Shan
-Slandploe
()f~ser
1~"Y- hood

_ v v - Oi~se.
Rotatlon/, .00. ~
~... . . . Sala
:=''::ay)~~-=
OK Wemco

Figure 3 - Description of impeller geometry in typical mechanically


agitated flotation cells.
w
o
From Young. '-J
w
,- o
1/ 00
1/
II f1 I .; i
,: ,f t--_ ...... ----7
\
!, JI' II \ ,
\
,.
f' ,'-r---' Jum!!!,, .,
:I : ~",'fl'::II:·"
I.J.,.o.;,s: .IJU !J \ ",
'/ \
!I "..
".. "" ..... ,.
\ ,,
\
nT:I~~1.1 •_,_,'-r-__t.,._,..., .
• ,-l:._~'" , Lj_lJ__tjJJ
Aker Booth Denver D-R

I'
,I
,/
"
"
I !I • !I,I
, II '
J
~.l ,I
I :
l.

--·1~!;-~·l.L1t-1-~;'1.--­ 11:,
u.. _:li;M~~J ._U
Agilalr Weda9 BCS

I/
/
/
I ! :
•I
I
I
• I
":~~;~~~~;;i->'>
PTJ-h"rrp
•..t._ .LLu.. J ,.. ... __ .. ______ ..L. __ .,
r---· I
OK Type U Sala Wem.::o

Figure 4 - Cell tank geometry ( section perpendicular to main flow


direction ) in typical open flow mechanically agitator
flotation machines.
From Young.
309

- means of introducing air in the cell (diaphragm,


diffuser, hollow impeller shaft, pipe located beneath
the impeller etc ••• )

Some cells can operate by self aeration, as shown in Table 1


making use of depression induced by cavitation in the impeller
area. However, especially since large flotation machines (say
around 40 m3 nominal volume) are being manufactured, this
approach tends to be replaced by compressed air addition.

Slurry transfer is either lateral (open cell design) or through


to the impeller of the next cell (cell to cell type).

The basic function of a mechanically agitated flotation cell are


the following:

- to maintain particles in suspension

- to disperse air flow into bubbles in the slurry.

- to create relevant conditions for contact between air


bubbles and hydrophobic particles.

Moreover, the design of the cells must be able to fulfill the


following criteria :

- to transfer cell particles in the feed slurry from the


feed inlet to the two discharge points (concentrate
launder through froth layer for hydrophobic particles,
next cell for hydrophilic particles and the part of
hydrophilic particles which have not floated) j i t is
important to ensure that any particle entering the cell
is removed relatively rapidly without having to be
ground to fine sizes by attrition in the impeller area.

- to ensure a low turbulence in the top part of the cell


so that the froth layer is not disturbed or that
particles which have already floated are not
reentrained in the slurry.

- to start up easily after stoppage (due to a power


failure for example) and solids sedimentation.

For all these points, the various manufacturers provide in their


commercial pamphlets details of the reasons behind their
selections.

Geometrical characteristics of cells are usually rectangular


parallelipepoid for obvious reasons of arrangements in banks of
cells (see paragraphs on flotation circuits), modified to allow
310

for preventation of sanding up (sedimentation in bottom corners),


enlargement in the froth area (known as spitzkasten) etc •••

Basic geometrical features:

h height
1 width
L length
D impeller diameter
C clearance of impeller above cell bottom

allow to compute usual reactor parameters

Volume .. V = hlL
Froth area = A - lL
D
Impeller aspect ratio R =-
L
Impeller clearance ratio C =~
D
Geometrically similar machines would lead to relationships of the
type

nand r values have been quantified by Harris and Lepetic [36]


for 22 families of flotation cell designs. n lies between 2 and
3, the most frequent value observed being between 2.5 and 2.7; r
is usually low and lies between - 0.25 and -0.5.

The hydrodynamics of mechanical flotation cells, as can be well


gathered from the preceding paragraphs on agitation in solid -
air-water systems are extemely important parameters. Usual
numbers considered are: Pow,er number, Reynolds number, Froude
number, Weber number and air flow number; impeller peripheral
speed is also an important parameter:

Vp .. 1f N DaDa a between 0 and 0.5

Np a (N n2)-c c between 0 and 0.33

NQa a Df f - a
a 1
Under these conditions, Froude number varies as D2 - whic~+is
nil for a = 0.5. Reynolds number is then proportional to D •
However, for a 100 fold increase in cell volume, Reynolds number
would increase 4-9 fold, in a range around 5 x 10 5 , which
characterizes high turbulence; variations in this range are not
too significant.
311

A useful number for quantification of turbulent phenomena, as


will be seen below, is the power consumed per unit volume (or
rather per unit mass of liquid):

E = ~ ; P a N3D5(N D2)-C

V a Dn (1 - r)

P n3- c D5- 2c- n (l-r) a D( 3-c)(a-l )+5-2c-n(l-r)( 20)


Va
depending on the value of a, c, nand r, some cases of constant E
can be observed. Figure 5, still taken from Young's paper [9]
shows that the overall for E as a function of V is a slow
decrease.

The same Figure provides manufacturer recomended nominal air flow


rate as a function of volume.

Air flow number should be constant, according to Harris [44]


Typical values for dimensionless numbers are the following
[41,44]
Power number 0.5 5

Reynolds' number

Froude number 0.1 5

Air flow number 0.01 - 0.1

Recently Schubert and Bischofberger [15,16] and Fallenius [57]


have attempted to relate turbulence theory, microevents in
flotation theory and dimensionless number relationships. It has
already been indicated that the Kolmogoroff length scale of
micro turbulence is given by

(21)
1
s

Dissipation of energy takes place mainly in the small eddies,


having a size up to a few tens of 1 • In this range, the relative
velocity between two points at a 'aistance II r in terms of its
root mean square expression, is given by

E
V (22)

Local isotropy in turbulence is usually observed for pure liquids


\.,0.)

~I
......
~Irl-------------------------------- N
'

5~~

CD
...... Ci(.~.~~..~:.•
............................
0·5]

0-21 02' "-~


i~aI31' bI(IYIe'
0,1 1 1 I I 011-1_ _--L_ _ _-..J11 _ _ _L -_ _.L-_ _ _-L_
1 2 5 _
~ 20 50 rol ., ~ 10 20 50 100
Cell size,m3

Figure 5 _ Relatio nship betwee n e. ,


power consum ed per unit 'Volume ( left )
or airflow (right ) and cell volume for typical cell design s:
( 1 ) Aker, (2) Booth, (3) Denve r, (4) Agitair ,
(5) Minem et -
two tank depths ,-, (6) Outokumpu, (7) Sala - two tank depths
-,
( 8 ) Wemc o, (9) Maxwe ll.
From Young.
313

submitted to E values typical of flotation cells. The effect of


solid particles and air bubbles is not known precisely although
Schubert and Bischofberger [16) have carried out some
measurements.

It has already been pointed out that typical 1 values would be


10-501lm for pure water, putting the range of e~ergy dissipation
in the particle size range fed to flotation cells, and thus in
the size of contacts between air bubbles and particles. In terms
of similitude, a constancy of E would result in equal magnitudes
of forces due to turbulence (tensile, shear stresses for example)
applied to air bubble/solid particles.

In terms of bubble size, the Calderbank relationship given above


can be rewritten as
d E-O.4 ",0.4
(23)
SM a 'I'

and N n2 0.4 (24)


<p a (-r--)

by assuming that N a No for similitude

then dSM a N n2 0.4 (25)


(7L-)

For constant E and D/L a Dr around -0.33 constant bubble mean


size is obtained for N D a D-r: N DaD 1/3, which was determined
by Arbiter and Harris [39) as an appropriate value for variation
of peripherial velocity as a function of impeller diameter.

Attempts to relate actual flotation to flotation cell design or


hydrodynamics have been rather limited up to now. Noteworthy in
this respect is the work of Arbiter, Harris and Yap [3~,43) who
tried to relate scale-up parameters and flotation of a lead -
zinc sulphide ore, tested in a laboratory size, pilot plant size
and industrial size Wemco cell. Their main conclusion was that
air flow number is the main parameter to maintain constant for
scale - up to achieve similar overall flotation results. More
recently Schubert and Bischofberger [15,16) have studied the
optimum hydrodynamics in batch flotation of a tin ore and a
potash ore, and have pointed out to the combination of E - power
consumed per unit volume and air flow number; depending on
theparticle size range to be flotated, different combinations of
E, NQa are obtained to give optimum ranges.

For coarse particle size the trend is towards lower E at which.


at a given N one observes settling in the cell. Casalis (64)
has analyzed ~~e behaviour of the Minemet B C Scells under plant
conditions, by comparison with the results obtained for the
314

flotation of a lead suphide ore for another Minemet cell design.


Condi tion for improved recovery were analyzed in terms of power
consumed. air flow rate. impleller diameter and speed of
rotation.

The main conclusions that can be reached at the present state of


knowledge is that flotation cell performance is probably best
analyzed in terms of power consumed per uni t volume - air flow
number. that a constancy of these two numbers may provide
adequate scale - up. but that the optimum of the combination of
these two factors has to be determined in each specific
application. I t would appear that .for difficult cases (coarse
particle sizes, for example). average conditions of manufacturer
designs might be remote from optimal conditions.

MAXIMUM PARTICLE SIZE FLOATABLE

The upper size limit for flotation to take place has been the
object of many investigations. In the absence of turbulence. this
size can be defined for an indefinitely extended surface area -
i.e. for a particle attached to an air bubble of finite diameter,
in which case capillary pressure can become a significant factor
for bubble diameters below O.5mm, and for particle size at which
self buoyancy can be obtained by the air bubble/particle
aggregate at a given bubble diameter. Schulze [19] has recently
given a complete analysis of the forces acting at the three-phase
interface, and conditions for stability. depending. for spherical
particles and bubbles, on particle and bubble diameters, contact
angle value, surface tension at the air-water interface, and
solid specific gravity.

Under turbulent conditions, the same investigator has attempted


an analysis of stresses which are applied on the bubble/particle
aggregate, due to tensile and shear stresses in turbulence
vortices. Assuming homogeneous turbulence, it eas shown that the
main controlling parameter is £. power dissipated per unit mass
of water, through the induced root mean square turbulence
velocity ";;;'2.
t
Measurements of ~2 are not too common for flotation cells.
Schulze gives figures of 20-60cm/s for energy dissipations of 2-6
kU/m 3 • This is in agreement with the recent measurements of
Costes et al [65] for a Minemet Laboratory size impeller. Figure
[6] represents typical results obtained by Schulze. It can be
seen that depending on turbulence intensity, the maximum particle
size that can be floated might be as low as one tenth of the size
that can be recovered in the absence of turbulence. Active work
seems to be in progress in Eas t Germany on the application of
turbulence theory to flotation cell appraisal and design.
315
5000
= 2.500 kg m
-3
p 1
~ p -1
d
- tun VLc. = 71.5 mN m
p

1000
2

500

100

50

10L-____ ~ __ ~~ ______ ~ __ ~ __ ~~ ________ ~

10 50 100 contact
'"
Figure 6 - Maximum particle size flotable
1. Static condition, plane interface. angle 0

2. Static condition, maximum size for buoyancy of a


0.511DD bubble.
3. Turbulent condition ;;'2
= 0.2 m s=~
4. Turbulent condition ~'2 = 1 m s
From Schulze [19]
316

The conclusion to be drawn from this type of work is rather


obvious for application to industrial coarse particle flotation.
Turbulence intensity, either expressed as iv,2 or e: should be
reduced as much as possible. Compatibility tetween low e: and
suspension of coarse particle cannot be met, and special designs
must be considered. the application of froth separators in
U.S.S.R. [75] for coarse potash ore flotation is especially
noteworthy here, since coarse particles are fed directly in the
froth layer, under very low turbulence conditions. Flotation
columns, the application of which is starting in the U.S.A. for
coarse phosphate flotation [71] would also provide low
turbulence. Settled solids removal might be a problem in these
types of cells.

FLOTATION OF FINE PARTICLES

Flotation of fine particles has been the object of many papers,


since there appears to be a lower size unit for solids recovery
with this process [22-24]. Although not specifically the object
of the present review, it is important to consider some aspects
of this problem.

Recovery of fine particles in flotation cells is usually


considered to be the result of two mechanisms: entrainment in the
froth layer due to the water split, in rough proportionality to
the water yield in froth product, and by attachment to air
bubbles. This second mechanism will be analyzed here, entrainment
aspects will be discussed in flotation simulation below. Due to
their low volume, and low mass, small particles (below ~ lO~m to
give an order of magnitude) give problems of successful
encounters with air bubbles, which. under usual flotation cell
conditions. are much larger than them. Scheludko et al [22] have
put forwards an analysis of sequential probabilities:

- probability of contact between a particle and an air bubble


- probability of attachment
- prbability of non detatchment

and have stressed the importance of the last two probabilities in


controlling fine particle flotation. Minimum particle size
floatable would be, according to their theory:

(26)

where v is the relative velocity of particle with respect to


bubble, 1/1 is the three phase contact angle and A is the line
surface tension of the parameter of contact. Data available for A
317

is very_~imite<Lsand very larg~5 variation in estimates are giy:yn


from 10 to 10 • For A = 510 dyn, W= 40°, a LG = 50 dyn em
p = 3 g/cm3
d min = 0.811m

The effect of turbulence intensity on this lower limit does not


seem to have been studied at all, but it is readily seen that an
increase in e: will lower the average air bubble size and thus
would favour a reduction in v leading to a decrease in d m, as
well as an increase in the number of bubbles favouring faster
kinetics.

FLOTATION KINETICS

In order to assess properly flotation circuit lay - outs and


methods used for the simulation of flotation plants, it is
necessary to review the state of knowledge on flotation kinetics.
Flotation is a fairly complex process, and building up quantative
descriptions from applied surface chemistry to overall rate data
for industrial flotation is not poss;i.ble at present, although
some limited attempts have been presented, for example by Mika
and Fuerstenau [81] and Haynman [82].

Overall flotation kinetics. as can be observed, for example in a


laboratory experiment, has been studied sine the 1930's. A good
review of early work was made by Arbiter and Harris [83].
Extensive development in this field has taken place since 1960.

I t is common to separate in the analysis phenomena that take


place in the pulp from those taking place in the froth, leading
to what is known as a two-phase model. Pulp phase macromechanisms
tend to be described as a simple first order rate equation

(27)

where C is the concentration of floatable particles in the


flotation cell at time t - assumed initially to have all the same
rate constant k. Tomlison and Fleming [84] have tested this
hypothesis for controlled conditions and have demonstrated its
validity for "non crowded flotation", i.e. when there is enough
air bubble surface area, otherwise a zero order is observed.

The effect of particle parameters (size, shape, surface


composition, surface reactivity ••• ), of flotation cell parameter
(air flowrate, hydrodynamics), of solution composition (reagent
concentration) of slurry composition (solid concentration) on k
has been attempted by various workers.

Two major schools working in this field have been active in South
318

Africa, at the Durban Group of the National Institute for


Metallurgy (ex-NIM now Mintek), and in Australia at the Julius
Kruttschnidtt Mineral Research Center (JKMRC). (see References
105-122).

The NIM group around King has developed a kinetic model which
classifies particles in size fractions (D classes) and mineral
content fraction (G classes). As far as the particles are
concerned, each G class is assumed to have a characteristic
distribution of k values which must be determined from a
flotation experiment. Variations of this rate constant with size
has been taken as [108]

Ito
cP (d) = 2.33
a d 1.5
- (1-(-)
fj.
a
) exp - (-)
2
d
(28)

where Il is the largest particle floatable under the particular


conditions of flotation, and a is a parameter which is assumed to
be related to collision/attachment phenomena, and is estimated by

a = 0.5 d 2
max
where' d is the size at which one observed maximum relative
recover~~e model specifically takes into account variation of
the rate constant as a function of aeration by making it
proportional to the average bubble surface area:

A (29)

where T is the average bubble residence time in the cell. It also


takes into account the effect of bubble loading, by trying to
assess the fraction of the average bubble surface area which is
not covered by solids.

In this case, King and coworkers have expanded Pogorely's


pioneering work [85].

f3 (30)
S AV= 1
1= exp
f3

V
where f3=WKf; W is the mass of solids in the cell,
and K = H/d k cp (d) all particles

f is a shape factor relating particle silhouette area to its


volume; f is in fact calculated so that f/d is the surface
319

covered per unit mass of solid.

Lynch and coworkers at JKMRC [118,122] have analyzed carefully


particle departure from pulp by differentiating flotation sensu
stricto from entrainment in the froth. Flotation in the strTC't
sense is assumed to be valid for particles which contain a
mineral, the surface of which has been made hydrophobic by the
reagents added, and variations in k as a function of particle
characteristics are only considered for size. Each size fraction
is classified into two groups: a fast floating and a slow
floating, which induces three parameters: k f , ks and the relative
proportion of each. Entrainment is assessed as a function of
water flowrate into froth, and a classification vector, providing
for any particle size, and any solid specific gravity the ratio:

(mass of solid entrained per unit mass water) froth


CF
(mass of solid per unit mass water) slurry

If one assumes that water transfer rate

(31)

then solids transfer rate by entrainment is

dC
E-) .. - k CF C
(32)
dt e W

Lynch and his coworkers have analyzed some aspects of the


influence of flotation machine parameters on these rates,
including air flowrate. They have assumed a direct
proportionality between k and Q •
a
These two approaches belong to what is known as discrete
parameters modelling, in which one tries to simplify rate
constant analysis by lumping ranges of values to be estimated
into groups of values. King, at the limit, would allocate only
one rate constant to each of his G class, and then model all the
other effects based on the assumptions made for the effect of air
flowrate etc ••• Lynch would tend to use for simplification sake,
only two rate constants, independently of size. Other workers in
the field have included the concept of floatable solids with a
zero rate constant to cope with flotation results in which, at
infinite time, one never observes complete recovery.

Another mathematical analysis has been used, still for pulp


phenomena, in which, instead of a limited number of k classes, a
complete range is assumed (from 0 to CD). and a statistical
function is fitted, to provide possibilities of estimating a
limited number of parameters to experimental data. Among the most
320

Feed Tailings
from to
previous next cell
cell

a) Typical section through a cell to cell mechanical flotation


machine

Froth layer V Mf , Cf C oncentrate


f '
Qf' C f
k II kd
'"
I

Agitated V
siurry t ' Mt' Ct

F eed Tailings
....r "'"
r

Q0' C 0 Qt' C t

b) Harris and Rimmer two phase model of a flotation machine.


V=volume, M=mass, C=concentration, Q=volumetric flowrate

Figure 7 -, Two phase model of a flotation machine [97]


321

useful functions, the incomplete gamma function (86-93,106]

ba + 1 a (33)
y (k)
r (a+I)
k exp ( - b k)

has been used extensively, due to the wide variety of shapes it


can provide for distribution between 0 and + 00, with only two
parameters.

Simple modifications : truncation to prevent inclusion of very


large rate constant material, (90] inclusion of zero rate
material (non floatable) have also been considered.

Usually these functions are applied to characterize the complete


material submitted to flotation, independently of its composition
(particle size, shape, composition); Huber Panu (91] has been the
only researcher to apply incomplete gamma function to particle
size fractions (D classes). The effect of machine parameter (e.g.
aeration rate) is usually not considered, except in the work of
Huber Panu et al (91] and Mehrotra and Kapur (92,93].

Coming back to the rate equation

dC (34)
-= - k C
dt

integration of the differential equation from t .. 0 (C = co )to t:

c eo exp (- k t) (35)

If particles doe not have all the same k, but have a distribution
according to f (k), then
00

e co J exp (- kt) f (k) d k (36)


o

Kapur and Mehrotra (96] have noticed, after a few other workers
(notably Harris and Chakravarti (89] that obtaining f (k) from
ele corresponds to an inversion of a Laplace transform, which
canobe done numerically, and they have presented results on this
line. The experimental data is usually not good enough to
calculate f (k) with a high precision.

Phenomena taking place in the froth are much more difficult to


describe, and only limited work has been carried out on this
topic. Earliest, but still most significant contribution, was
that of Harris and Rimmer (97]. The model put forward is
schematized on Figure (7]; it separates phenomena taking place in
322

pulp, which are assumed to be under perfectly mixed reactor


conditions, having a rate constant of transfer from pulp to froth
of k , from those taking place in the froth layer, also assumed
to b~ a perfectly mixed volume, with a rate constant of material
in froth back to pulp of kd •

Mass balances for pulp volume and froth volume are respectively

(37)

(38)

At steady state

(39)

If the froth volume were not considered, the apparent overall


rate constant would have been k such as

dM t (40)
Qo C0 - k Mt - Qt Ct
dt

at steady state
Qf Mf (41)
k
Vf Mt
so that
k
k u (42)

l+k 1i.
d Qf

v /Q is the average residence time in the froth layer 6f ,


sKowIng that the apparent rate cons tant is, in fact, a function
of froth removal rate, at constant froth depth. This apparent
rate constant is the one which is measured in conventional
experiments.

The perfect mixing assumption, is rather difficult to accept for


the froth volume, and various papers, among which the recent work
of Mays [118] is worth mentioning, have tried to develop an
323
aDal1~i8 in which plug flow is assumed. The resulting models tend
to be cumbersome and parameters are difficult to quantify •

.Bisshop and White (121) have studied the effect of froth


.retention.time on entrainment as described by Lynch (123). It was
shown that

(43)

where k corresponds to froth water drainage rate. King, in


this mode1~ only assumes a proportionality constant between rate
of material reaching froth and removal rate from pulp.

RESIDENCE TIME DISTRIBUTION IN FLOTATION CELLS

Having described rates in pulp and froth phenomena, it remains to


describe residence time destributions in flotation cells.

A normal flotation laboratory experiment is called a semi-batch


experiment, involving continuous froth .product removal and water
addition to maintain cell content volume constant. Under these
conditions, the simplest rate equation integrates as:

C m C exp (- kt) (44)


o
For distributed values, it can be seen that the incomplete gamma
function provides a.simple closed form solution:
GO

C ... C
0 J exp - k t f (k) d k
0 (45)

a + 1 GO

C= C b J k2 exp (- bk) exp (-kt) dk (46)


o r
(a + 1) 0

(47)
C = C (---E-)a+l
0 b+t

which explains the use which has been made of this function.

For continuous flotation, in which slurry feed is added


continuously, tailings slurry is removed continuously and
concentrate is scraped off or overflows continuously, it is
necessary to describe residence time distribution:

E (t) dt which represents the probability for an element of


slurry introduced at time 0 to leave the cell at a time between t
324
and t + dt.

Two extreme ,cases of residence time distribution are observed in


reactors: plug flow and perfect mixers.

In plug flow reactors, all elements have the same residence time,
e. In perfect mixers, residence time distribution is:

E (t) dt = e1 exp (-tie) dt


(48)

where e is the average residence time, which can be calculated as


v/Q where Q is the feed (or product) flowrate.
Various models have been put forwards for continuously stirred
tank reactors, a class to which flotation cells can be compared.
Nagata [25] among others have reviewed these models. Measurements
which have been made for mechanically agitated flotation cells,
[79,100,101] as reviewed by Lynch et al [123] show that, at least
for water, perfect mixing in each cell is observed. For solids,
various authors have questioned the validity of perfect mixing,
and Harris and coworkers [102-104] have recently developed a
model in which the slurry part of a flotation cell is divided
into two perfectly mixed volumes with transfer between the two,
to represent the impeller zone and the upper part of the cell.
The application of such a model to real cases does not seem to
have been attempted yet but it should lead to interesting
developments.

In banks of flotation cells in which there is almost open flow


between each unit cell, interstage m1xing does take place and
should be assessed. Lynch et al [123] have stressed this point,
and the scarce data available that have been collected would
indicate that interstage flowrate is larger than the volumetric
feed flowrate.

Assuming perfect mixing in each cell, the rate of accumulation in


any cell is:

(49)

calling e = _V_
qt
at steady state:
qoc o - qtCt (1+ke)

and qfc f - qtCt ke


325

Recovery of k species .. --
qfc f
qoc o
ke
l+kB
(50)

For n cells in series n


qoc o qt nCt n (l+ke) (51)

1
then Recovery .. 1 - (l+ke)n

which can also be written as

1 (52)
R .. 1 - --"':k---:n
(l +-.ne)
n

where ne is the total average residence time in the series of n


cells. This recovery can be compared to the one obtained for a
semi-batch flotation experiment:

R - 1 - exp - (k n e) (53)

FLOTATION CIRCUITS

The two following equations enable to understand the basic


reasoning behind the conception of flotation circuits as banks of
flotation cells. It is is assumed that a time T is required under
semi-batch conditions, there is a choice of possibilities for n
and a to give the same overall recovery R, the equation is:

e [ (......L.)1/n]/ In ~) (54)
--=
T 1-R 1-R

As an example for T=15 min at R .. 0.95

then
n 1 2 5 10 15
e min 95.13 17.38 4.11 1.75 1.11
n a min 95.13 34.77 20.54 17.48 16.60

As n increases, it can be seen that ne diminishes and gets closer


to T; total flotation cell volume, which is Qo/ne diminishes as
well; at the limit, the minimum flotation volum will be obtained
for n+~. This situation is of course totally unrealistic, since,
as already mentioned, selection criteria for flotation circuits
must take into account economic parameters such as capital cost
and maintenance cost •. Economic data would give. variations in
capital cost on a function of flotation cell volume as
0.66
cost a V
326

,.
a) Simple one product circuit :
number of cleaner banks can be
large (e.g. 6 - 8 for some ores
presenting selectivity problems).

b) Typical three product


notation circuit,
involving in 1 bulk
notation of species 1 + 2
in . 2 selective separa-
tion of 1 from 2.
Tailings from this circuit
is concentrate 2.

Figure 8; Examples of flotation circuits. Each box represents a


bank of flotation cells. R: rougher, S: scavenger, C:
cleaner, C means an eventual grinding operation.
327

so that it would favour the installation of flotation cells as


large as possible i.e. in as small in number as possible.

There has been a tendency recenctly to develop large flotation


cells; it is not common to find installed in many plants cells
having a volume larger than 10 m3 • Manufacturers, as indicated in
Figure 5, have put on the market cells in the 35-40 m3 range,
which have been installed in various plants (for base metals
ores, phosphate ores etc ••• ). This trend, which is progressing
continuously since some manufacturers claim to have on their
design boards cells having a volume between 65 and 100 m3 , might
have reached a plateau as far as practical applications are
concerned, since there must be compatibility, in a minerals
processing plant between grinding circuit capacity and flotation
circuit layout; maximum grinding circuit capacity with
conventional equipment (rod mills - ball mills or autogeneous
grinding mills) is around 250 tonnes/hour. At solid
concentrations usually encountered in flotation, and for the
average ore specific gravity, this corresponds to - 10 m3/min of
slurry feed to flotation. A 35 m3 cell would give a unit
residence time of 3.5 minutes. Young [9) and Spada [124) have
reviewed average residence time in cells installed in industrial
plants and give a figure of 1-3 minutes as common practice in the
Western World. Young [9) has pointed out to an apparent different
practice in U.S.S.R. and Eastern Europe, where unit retention
times of around 30 seconds and less are used, meaning of course a
much larger number of unit cells per circuit. Apart from obviOUS
reflections on the on the way economics of scale are applied in
these two types of societies, there might be a technical point
worth studying.

In this general context, it can be seen that flotation machines


much larger than 50 m3 will only be used in cases where grinding
capacity is not a limiting factor. Arbiter et al [125) have
provided an analysis of the savings induced by using large
flotation cells in circuits.

Circuit arrangements have been described extensively [128-130).


Conventionally, flotation machines are grouped in banks
containing a number of cells in series, which, from the feed
point onwards are called rougher, scavenger; the rougher
concentrate is reprocessed in cleaner circuits. Figure 8 provides
some typical layouts of flotation circuits. Number of cells in
each bank is a compromise between residence time distribution and
economics; it is never smaller than 4, it tends to be on average
8 to 10, i t reaches 16 to 20 in the Western World, and up to 30
in Eastern Europe. Number of unit cells in cleaner circuits can
be much smaller since the criterion for successful operation is
concentrate final grade, and intermediate products (cleaner
tailings) are recirculated for recovery.
I-i
W
~ N
...... CO
Ii)

EI +F s:: Feed
&6f
Ii) Ol c Conce ntrate
...... Ol
.
.-.
...... 0-
~c or Tailing s
NP> (Jonce ntrate
W ...... Tailin gs
......... P> Flowra te Feed
::I oc= 'aQ f
>0 Q, 0 ... =11-flaO~
~fi) Volum etric Im3 /min'
P> flowra te (1 - f~'(1 - xIs '~(l-xls
'tl + Qf + Qf'-
I"t P> Pg
It)
"1 Pg
~O
~ xSO( nk. (1-alk
...,::1 XS( a- + - - 1-a) 0" Qf
J
"1 ~ +- - .
+ - - - + - -k, -
P. 1 + k,O 1+ D
o P. 1 + k.8 1 + /e,0
EI P>
fa QI'-
~..., Im3 /minl aQr- (1-"aQ "
"1 ......
Water
0- 0 fIJ11 - x, 5 Q" ®
it/minI (1 - xis Q~ 11- fj'J)(l-x 'sQ" G>
III I"t Gangue
"1 p>
'< I"t 1 k.D
Low rate CV - - x a sQ:F ®
it/minI xa 5 Qf --Oxa sQ." 1 + k,O
~O
.-.'"'" cOfi~tant 1 + k,
W::l SO S
o k,O
High rate 1 . (3)
ofi)
--xI1- a'sO. O' --x(1 -a'sO .(- ®
...... c03sta nt it/minI x(l-a's QF 1 + k,O
...... 1 + k,1I
soli 8
it/minI sQr- <!J+<?;>+@ @)+@1-@
~ Solids
Ol
t-'.
::I
(JQ

t""
'<
::I
o
::r
329

Complex circuits involve sequential flotation of various


minerals, bulk (i.e. global flotation of more than one mineral
species) flotation followed by selective depression in the
cleaner circuits, fine particle elmination (desliming) grinding
of intermediate products for further liberation etc.

SIMULATION OF FLOTATION CIRCUITS

Extensive development has taken recently on the implementation of


computer programmes to simulate flotation circuits. Two such
programmes are available today, which have been described in a
series of publications [106-122] and in a book [123], by the two
research teams that have already been mentioned for their
contribution to flotation kinetics. Recent reviews by Woodburn
[116], King et al [117] and Lynch et al [123] point out to
successes and limitations of their programes, as well as to
objectives of simulations of flotation circuits.

At present, steady state simulation is mostly developed. Dynamic


simulation would be required to assess and design strategies, but
does not seem to be available yet. The use of steady state
simulation is common practice in many fields of process
engineering, and general simulation programmes are available.
However, their value for simulation of flotation circuits is not
too great. Flotation, compared to many chemical engineering
processes is both simple and complex. It is simple in that the
number of unit operations or unit cells is rather limited, the
number of flowstreams is also limited; however it is complex
because materials properties cannot be estimated Simply, and
solid phase description, as was stated in the introduction of
this chapter is difficult to quantify.

Steady state simulation has three basic uses 1n engineering


practice as outlined by King (117).

it can demonstrate the feasibility of a flotation process,


by outlining grade - recovery performances to be expected
under industrial conditions, using data obtained at a small
scale (laboratory experiment).

i t allows to properly design plants, based, for example on


pilot plant data. Quantification of all streams is obtained
for equipment selection and Sizing, alternative flowsheets
can be studied for optimum layouts at lowest possible
capital cost, lowest maintenance cost.

i t enables to evaluate modifications to an operating plant


without having to risk affecting production by implementing
them in practice.It can predict changes in performance by
adding equipment, changing flows,reagent combinations etc.
330

In order to get an idea of the asumptions and calculations behind


a simulator for flotation example can be considered: let the
first cell in a bank of n identical flotation machines, each
having a useful volume V be fed with QF slurry volumetric
flowrate, containing a water fraction 'a', it will be assumed
that the solid particles in the feed (representing a solid
concentration of s kg/m 3 have a flotable fraction, of specific
gravity pv, at a concentra.tion x (fraction per unit mass of
solid), which has flotation properties characterized by two first
order rate constants k (slow) and k f , and that the slow floating
part represents a (friction by mass), frother addition is such
that a fraction f of feed flowrate is transferred with the
concentrate (froth product) stream, and hydrophilic solids
(specific gravity p ) are entrained with a classificator factor
a. The flotation cefi is assumed to be perfectly mixed and froth
phenomena are assumed to be negligible. The average residence
time distribution, which is 8 = V/Q , where Qt is the tailings
flowrate, is unknown; it will be taken, as a starting value as
v/Q F = 8 0 then the quantities given on table 2 can be calculated.
The calculations can be made for any numerical values, and,
having the first value of Q 1 from 8 , the calculations can be
repeated from 8 1 = V/Q 1 an~ the serie~ of calculations repeated
until convergence is ob~ained. This can of course be repeated for
the next cell in the bank with the feed corresponding to the
equilibrium value found for the first cell.

This example is fairly typical of usual assumptions in simulation


for flotation circuits:

- pulp chemical environment is constant enough in a bank of


cells for kinetic parameters to remain constant.

- cell parameters in a bank are constant ( volume,


hydrodynamic characteristics, aeration rate ••• ).

- perfect mixing in each cell is assumed.

As usual in any process simulation problems, a description of


flowsheet configuration is required. Woodburn [116] and King
[117] have reviewed this topic recently, and a complete
documentation on the NIH simulator is available [109,110].

A typical analysis can be given as follows:

For any class of particle, j, which corresponds implicitly to a


kinetic constant k., the following relationship which was derived
previously, holds: J
(55)
331

a) Typical flotation circuit for simulation :


cells 1 to 6 are rougher, 7 to 10 scavenger,
11 and 12 cleaner.

, . . . . - - - - - - - 0 -I
o

~ O~I
-I . . . . . . 0
01-------.....::0 1

b) B configuration c ) A configuration
matrix matrix

Figure 9 -Simulation of flotation circuits.


Example of a circuit in a)j
configuration matrices for tailings
flows B in b), and A for concentrate
flows A in c).
332

1 l+ks61,0,0,0,0,0,-ks67,-ks68' -k s 6 9 , -k s 610 ,0, -1


2 -1, l+k s 6 2 ,0,0,0,O,O,O,O,0,O,O
3 0,-1, l+k s 6 3 ,0,0,0,0,0,0,0,0,0
4 0,0 -1,I+k s 6 4 ,0,O,O,O,0,0,0,O
5 O,O,O,-I,I+k s 6 5 ,O,O,O,O,O,O,0
6 0,0,0,0,-I,I+k s 6 6 ,0,0,0,0,0,0
7 0,0,0,0,0,-I,I+k s 6 7 ,O,0,0,0,0
8 0,0,O,0,0,0,-I,I+k s 68 ,0,0,0,0
9 0,0,0,0,0,0,0,-I,I+k s 6 9 ,O,O,0
10 0,0,0,0,0,0,0,0,-I,I+k s 6 IO '0,0
11 -ks61,-ks62,-ks6,-ks64,-ks65,-ks66,0,0,0,0,I+ks611'0
12 0,0,0,0,O,0,0,0,0,0,-1,1+ks 6 l2

a) Elements of the D matrix for k


s

(l+k 6)m -k 6 m -k 6 -k 6 m -k
s 1 stl s 7 st7 s 8 s 9 st9 s6l0mstlO-mst12=fs

-mst 1 + (l+k s 6 2mst 2) = 0

-k 6 m -k 6 m -k 6 m -k 6 m -k
s 1 stl s 2 st2 s 3 st3 s 4 st4 s65mst5-ksu6mst6

+ (1+ks6l1)mstll = 0

b) Materials balance equations obtained from


E.~j=!j for species having a rate constant ks.

Table 3- Example of configuration matrix for species k and


s
resulting materials balance equation
The large amount of 0 elements (less than 3% of
elements are different from 0) is characteristic of
flotation circuits.
333

where mf j is the mass flowrate of class j in the froth product


and mtj loS the mass flowrate of the same class in the tailings,
and 6 loS the slurry residence time in the cell. mtj can be given
a vector representation by numbering all tailings streams in the
flotation circuit from 1 to N, total number of cells. The
description of flowsheet configuration will be given by
configurationmatrices having N x N dimensions: a tailings
configuration matrix, the elements of which will be bik such as
bik = - 1 when the tailings stream from cell k enters cell i; a
concentrate configuration matrix aik having the similar
definition i.e. aik = 1 when concentrate stream from cell k
enters cell i. All other elements in the matrices are zero,
except aii = bii = 1.

The overall transfer matrix will have elements such as in each


cell the steady state equation is satisfied; a matrix OJ can be
defined as

d ikj = b ik + a ik k j 8 i (56)

If the description of the feed to the circuit is described by a


vector Fj for class j, the elements of which would represent the
feed mass flowrate of class j into each cell (for a circuit
having one feed point there will be N-l elements having a 0
value), then the mass balance will be given as

O . • m.=F. (57)
=J =tJ =J
representing for each species N simultaneous linear equations.
The overall system is, of course, non linear since 6i is a
function of ~tj. An example of flotation circuit as well as the
derived configuration matrices is given in Figure 9. The
resulting mass balance equations are given in Table 3. As roughly
sketched above in the simple example given, an iterative
procedure is required to get the value of all flows at
convergence.

Interested readers are referred to the publications of King and


coworkers for relevant information on data preparation for use of
simulator.

Testing of the simulator has been made for pilot plant runs at
the University of Natal, as well as simulation of industrial
flotation circuits. The value of such a programm for testing
modifications in circuit modifications has been presented by King
[110]. Figures 10 and 11 give an idea of the quality of
saimulation and of the interest in using the simulator for
outlining optimal configurations. Problems lie in data
acquisition, in a limited capacity to model froth behaviour and
to take into account predicted water flowrates.
VJ
VJ

""'"

60

~ -----0 Plont dolo 50


Ot
... Model predlcllo"s
tai
ti
It
I- 40
ffi
~
0
u 30
~
c 0.1
:J
~ 20
IL
0
.I.
-.---~-I'-- ---f_, -",t-_ I'10
~
It --,
~
IL

2 6 10 II 12
CELL NUMBER
Figure 10 - N.i.m. simulator. Demonstration of its validity in
modelling industrial flotation circuit.

From King.
~Toillno.

This conflgurollon produces


Ihls vrode recovery curve

10ko/a 1 .~"".'
~-:==-=--:--==-:-=~- 6lccj/s ~ Thl. configurollon produces
60. I ~ Ihls grade recovery curve
15kO/s 10110 • "
I\,
1I.
6 kO/s ,
~:.. 211 /s
o:!!. \ 0 Plont feed rates normally
ThiS confiIJurolion produces , ronlJl! from 1.5 10 4 kO/s
0:
w this grade recovery curve \ (510 13.5 lon/h)
Q.
Concentrate J \
&
u \
\
...J 'OI'~-p-'!I11'" , \
g
f- Feed 0.5k9/5

40'~------------~------------~------------~-
84 89 94 99
RECOVERY. %

Figure 11 - Simulation. Application to plant modification assessment.

From King.
w
W
IJ1
336

Lynch and copworkers in their review book [123] have presented


the main elements of their simulator. It is not certain if a
comprehensive programme, comparable to NIM's, is available at
JKMRC at the present time.

Woodburn et al [116] have stressed the value, as well as the


limitations in the development and use of mathematical models and
simulators of flotation cells and circuits. One of its major
values is to make it comp1,llsory to have a detailed knowledge of
flotation as a unit process of solids separation, and i t is felt
that it would be only though an improvement in all the aspects of
flotation which complement the simple application of surface
chemistry at the minerals - aqueous solution interface, that
applications of flotation will develop.

CONCLUSION

At the end of a chapter in which a large quantity of subjects was


covered, very varied in their scope, it is hoped that the review
which has been presented will have provided an understanding of
problems encountered in the engineering aspects of flotation,
which must be tackled and solved in a less pragmatic manner than
the one which is common practice today, i f progress is to be
achieved.

Three phase systems,in which one-the solid particles phase - is


difficult to describe quantitatively,are cumbersome to analyze;
the presence,in flotation cells, of two such systems of markedly
differing behaviour-the slurry and the froth-makes i t even more
complex to study. Excellent pioneering work has been accomplished
by dedicated researchers and engineers. The contribution of this
chapter would have met it objective i f enough interest has been
raised by this presentation, so that new efforts in the
development of knowledge of flotation systems are implemented, by
the contributions of workers in many different disiplines:
hydrodynamics , process engineering,applied mathematics,mineral
technology •••
337

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35. Arbiter N. and Steininger J., Hydrodynamics of Flotation


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38. Arbiter N., Harris C.C. and Yap R., Hydrodynamics of


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39. Arbiter N. and Harris C.C. Impeller speed and air rate in the
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40. Harris C.C. and Raja A., Flotation machine impeller 5peed and
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340

41. Harris C. C., How much flotation research really pays off,
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Wemco

45. Reck W.H. and Kind P., Developements recents de la cellule de


flottation Wemco-Fagergren, Revue Ind.Minerale, 1970. also
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46. Reck W.H. and Kind P., New concepts in a large scale
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47. Cus tred U. K., Degner V. R. and Long E. W., Recent advances in
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48. Degner V.R. and Treveek H.B., Large flotation cell design and
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49. Kind P., Design criteria and recent decelopment on large


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1976.

50. Degner V.R. Engineering and Design consideration scale-up to


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11.01.1977.

51. Kind.P., Les cellules de flottation Wemco a grand volume et


leur utilisation, Revue Ind. Minerale, 2, 1979.

52. Olson S.l. and Miller H.H., Improved recovery of Florida


phosphate Rock by modifying standard 14 m3 Wemco cells with
28m3 cell mechanisms, Presented at the S.M.E. -AIME Fall
Meeting, Denver, Preprint 81-

Address: Wemco Division, Envirotech Corporation, P.O. Box


15619, Sacramento, California 95813, USA.
341

Denver

53. Anonymous, Les cellules de flot.tation Denver - tendances


nouvelles - cellules DR - cellules de grande dimension, ~
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54. Plouf T.M., Design and development considerations for Denver


single mechanism 36m3 DR flotation machine, Mineral
Processing, Proceedings 13th Int. Miner. Proc. Congr.,
Laskowski J., ed., Elsevier, p. 1288, 1981.

Address: Joy Manufacturing Company, Denver Equaipment


Division, P.O.Box. 340, Colorado Springs, Colorado 80 901,
USA.

Aker

55. Sidery D., Sydvaranger's New Mill, Min.Mag., 146 (1), 1982.

Address: Aker Trondelag A/s, Trondhjems Mek. Verksted A/S.


Innherredsveien 18, Postboks 896, 7001 Trondheim, Norway.

Outokumpu Oy

56. Fallenius K., Outokumpu Flotation Machines, ~'lotation.


Fuerstenau M.C. ed. AlME, New York, vol.2, p.838, 1976.

57. Fallenius K., A new set of equation for the scale-up of


flotation cells in Mineral Processing, Proceedings 13th
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Address: Outokumpu Engineering Division, P.O.Box 27, SF -


02201, Espoo 20, Finland.

Humbold - Wedag

58. Cerdes H., Isenhardt F., Saljmann G., Untersuchungen an


Flotationszellen, Aufbereirtungstechnik, 17, p.487, 1964.

Address : KHD Humboldt - Wedag, Postf. 91 04 04, D 5000, Koln


91, F.R.G.

Agitair

59. Spada M., Flotation Cell Agitair No.120, Revue Ind. Minerale,
52, p.179, 1970.
342

60. Bateman E. L., Agitair: Developments of Flotation machines,


South African Institute of Mining and Metallurgy Colloquim,
Recent Advances in the Design and performance of Flotation
Equipment, March 1975.

Address: The GaUgher Company, P.O.Box 209, Salt Lake City,


UT 84110, USA.

Sala

61. Fahlstrom P.H. Fagremo O. and Marklund 0., Boliden FR


Flotation machine, why and how it developed, World Mining,
23, p.66, 1970

62. Lindgren E., Broman P.G., Aspects of Flotation circuits


Design, Concentrates (published by Sala International), I,
p.6, 1976.

63. Broman P.G., Process and equipment scale-up in Flotation,


Sala document, may 1979.

Address: Sala International AB., S 73300 Sala, Sweden.

Minemet

64. Casalis J.A., Determination des conditions optimales de


fonctionnement d'une machine de flottation industrielle,
~ Prague, p. 102, 1970.

65. Costes J., Ahan C., Bertrand J., Courderc J.P.,


Caracteristiques des ·ecoulements d'eau dans un systeme
mecaniquement agite, utilisable pour des operations de
flottation, Entropie, 93, p.48, 1980.

Address : Minemet Industrie, I, Avenue Albert Einstein, B.P.


106, 78191 Trappes Cedex, France.

Flotation Column

66. Anonymous, The flotation column, Canad.Min.J., 84, p.55,


1963.

67. Anonymous, Flotation column due for mill scale tests in


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68. Wheeler D.A., Big flotation column mill tested, Engng.


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69. Boutin P. and Wheeler D.A., Column flotation, World Min. ,


120, p.47, 1967.
343

70. Mathieu G.I., Comparison of Flotation column with


conventional flotation for concentration of a molybdenum ore,
Canad.I.M Bulletin, 5, p.41, 1972.

Address : The Column Flotation Company of Canada Ltd., 327


Parkwood Circle, Dorval H9S 3A4, Quebec, Canada.

Flotaire

71. Hollingsworth C.A., The Flotaire phosphate beneficiation


system, Paper presented at the American Chemical Society
Meeting, Las Vegas, August 24-29, 1980.

Address : The Deister Concentrator Company, P.O.Box 1, 901


Glasgow Avenue, Fort Wayne, Indiana 46 801, USA.

Russian Machines of innovative design

72. Golovanov G.A., Zhehnin V.S., Kotilevski V.I. and Makarov


A.M. Processing of apatite ores at the ore-dressing plants of
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73. Uljanov N.S. and Meshcheriakov N.• F., Development of flow


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1968.

74. Malinovsky V.A., Marveyenko N.B., Knaus O.M., Uvarov U.P.,


Teterina N.N. and Boiko N.N. Technology of froth separation
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75. Zikov V.A., Zhehnin V.S., Uvarov U.P., Gurevitch


R.I.,Teterina N.N., Serviskij L.J. and Arsentjev V.A., New
technology and equipment for flotation of potassium ore, 11th
International Congress of Mineral Processing, Cagliari,
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Sardinia, 1975.

76. Malinovsky V.A., Matveyenko N.B., Orlov B.D., Denegina N.N.


Miklim B.M. and Uvarov U.P., Development and Application of
Froth separation Flotation machines, 12th International
Mineral Processing Congress, Sao Paulo, Paper 2, Meeting 5,
1977 •

Address Machinoexport, 35 Mosfilmovkaya ul, 117330, Moscow,


USSR.
344

Davcra

77. Cusak B. L., The development of the Davcra Flotation cell,


Austral.I.M.M. Mongraph series No.3, Melbourne, p.481, 1968.

Address Foster Wheeler Energy Ltd., P.D.Box 31775


Braamfontein, 2017 S.Africa.. Con~inc Rio Tinto Australia,
55,Collins street, Melbourne, Victoria 3001, Australia.

Maxwell

78. Maxwell J.R., Large flotation cells at Opemiska Concentrates,


Trans AIME , 252, p.95, 1972.

79. Dinsdale J.D. and Berube Y., A characterization of


hydrodynamics in a 700 cu. ft. Maxwell flotation cell,
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80. Chalmers H.J., Hughes G.M.,Maxwell J.R., and Boutin


E.A.Flotation machines the Bigger, the Better,
Canad.Min.J. 6,p.59, 1974.

Address : Technequip Ltd., 297 Garyway Drove. Weston M 9L


1P2, Ontario, Canada.

Others

Address Booth Company P.O.Box 1747, Salt Lake City UT 84110,


USA.

- Krupp Polysius A.G., Box 2340, 4720 Beckum, West


Germany.

- Mitsubishi Metal Corp. 23 F World Trade Center Bldg,


Hamamatsuch, Minato - ku, Tokyo, Japan.

- Nikex H-I016 Budapest I, Meszaros utca 48-59,


Hungary.

- Unifloc Ltd., 11-16 Adelaide Stresst, Swansea SAl


IQS, UK.
- Norton Harty Colliery Engineering Ltd., Central
Works, Market Place, Great Bridge, Typton West
Midlands, DY4 7AT, UK.

Flotation Kinetics-general

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345

82. Haynman V.J. Fundamental model of flotation kinetics, in 11th


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50th Anniversary Volume, Fuerstenau D.W. ed. AlME New York,
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84. Tomlinson H.S. and Fleming M.G. Flotation rate studies, in


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85. Pogorely A.D. Limits of the use of the kinetic equation


proposed by K.F. Beloglazov, Izv. Vuz Tsvetnaya Met., 5, 33,
1