. . .

P. Somasundaran
Henry Krumb School of Mines
Columbia University
New YorkI New York 10027

VOL. 71, No. 150 t 975 PACES 1-15

 flotltion, I technique widely u.d for the concentretion or purifica- P. Somasundaran
tion of plrticulltes, is dictated mlinly by the interfacial properties of
the solid/liquid/gas system and chlnges in those properties due to Id-
sorption of various inorganic Ind organic reagents. Basic principles
governing the Idsorption process(1s) Ind the resulting flotation Ire reo
viewed in this introductory paper. Examples are discuaed to show the
effects of relevlnt controilible verilbles such IS solution pH; collector
structure and concentretion; ionic strength; concentrltions of floc-
cullnts, depreGlnu, and Ictivltors; Ind conditioning tempereture.

}. large variety of chemical speciesranging from molecules
and ions to micro-organisms and minerals can be separated
from one another or concentrated from solutions using flota.
tion processes. Even though the mechanismsinvolved in the
flotation or the nonflotation of each specieswith various reo
agents are not fuUy established, the flotation pro~sses can be
considered to be primarily the result of the tendency of cer.
tain surfa~ active speciesto concentrate at the liquid/gas
interfa~ and the tendency of some other speciesor particles
to associatewith or adsorb these surface active species. The
large number of flotation processestested have been classified
(Table I) according to the size (molecular, microscopic, or
macroscopic) of the flotated speciesand the mechanism (con-
sistent with natural or acquired surface activity) of flotation.
Thus, there is foam fractionation for the separation of surface
active speciessuch as.detergentsin aqueous solutions, and
foam flotation for that of naturally surface active organisms
and proteins. Techniques based on the tendency of various
speciesto associatewith surfactants are: ion flotation for the
separation of ions, micro flotation and ultraflotation for very
fme particulates, and froth flotation for the separation of min-
erals that possessmostly polar surfaces. In addition to these
techniques, there are also certain nonfoaming flotation
methods such as oil.flotation (2), bubble fractionation (3) and
solvent sublation (4), for which adsorption at the interface is
Henry Krumb School of Mines, Columbia University, New York,
New York 10027.
again the basis for separation, but the adsorbed material is col.
lected selectively with a liquid (instead of air) that is immisci-
ble with the bulk aqueous solution. At present, froth flotation
is the only technique that has significant industrial application,
and is therefore emphasized in this paper. Precipitate flota.
tion, which appears to hold promise for future applications, is
also discussed.
METHODS
For froth flotation. a pulp of the particulates is first con.
ditioned with the appropriate reagents. It is then agitated us-
ing impellers in a cell such as the one shown in Figure I. Air
is sucked in or sometimes fed into the cell near the impeDer
lone. The air bubbles. now dispersed by the impeller. collide
with particles and are attached to those that are hydrophobic
or have acquired hydrophobicity and rise to the cell top where
they are removed by skimming. Figure 1 is a schematic repre-
sentation of a typical industrial flotation cell.
As opposed to froth flotation which usesturbulent condi-
tions. foam separation techniques generally consist of aeration
at a low flow rate. and the separation of the foam containing
the collected material is followed by its breaking using various
chemical, thermal or mechanical methods (5). A stripping
mode in which the descending feed is introduced into the
foam and an enriching mode in which part of the foamate is
recycled to the top of the flotation column are recommended
for increasing the recovery and grade. respectively. of the
product (see Figure 2).
2 AIChE SYMPOSIUM SERIES

TABLE 1. FLOTATION TECHNIQUES CLASSIFIED ON THE BASIS OF MECHANISM OF SEPARATION

AND SIZE OF MATERIAL SEPARATED It I

Size Range
Mechanism Molecular MiuOtCOt)ic Mecroscopic
Natllrat surfec8 activity Fo.m fractionation F08m flOClcion Froth flot.tion of nonoo~
IX: IX: miner."
dltlrgents from aqueous micrOOfpni."s. prOteins ex:
solutions sulfur
In essoc~tion with surf8C8 Ion flot8tiOn. molecul.r Microfloutlon. colloid IIo~tion. Froth flotation
Ktiw agentl floutlOn, Idsorbing ultra flotation ex:
colloid flotation ex: miner.'s such .s silic.
,.: P8rticuletes in _ste weter. clay. Precipitate flotation
5rl+, Pbl+, Hgl +, cyanide micrOOf't8nisms {1st.nd 2nd kind}
.x:
f.ric hydroxide
ReprInted from CtNn SurfKft 1970. Courtesy of Marcel ~ker Inc

Cq, tite, and oxidized sulfides;and long chainaminesror quartz,

potash,reldspars,mica,etc.
Two recentreviewson xanthate-galena systemsby Gutier.
rez (7) and Granvilleet al. (8) dealwith the different mech-
anismsand the problemsinvolvedin the study or the flotation
chemistryor sulfide minerals. Xanthatesare consideredto
adsorbon sulfidessuchasgalenadue to chemicalrorcesbe-
tweenthe polar headand the surraceresultingin metal xan.
thates. Mechanisms involving the rormation and adsorptionor
dixanthogen,xanthic acid, etc. havealsobeenproposed. The
effect or the oxidation of sulfide mineralsurfaceson flotation
hasreceivedconsiderableattention. Gutierrez(7) noted in

BASIC PRINCIPLES
SELECTIVE HYDROPHOBICITY
As mentioned earlier. froth flotation of minerals or precipi-
tates is possible if they can be preferentially wetted by gas
rathe. than by water. Only a very smaUfraction of the min-
erals such as sulfur is naturaUy hydrophobic. Precipitates of
the second kind (6). formed by reaction between ions and cer-
tain organic reagents. are also hydrophobic. Hydrophobicity
has to be imparted to most other minerals and precipitates in
order to float them. Towards this purpose. a surfactant that
will selectively adsorb on the material to be floated is added to
the suspension in water and conditioned by agitation. This
surfactant. called a collector. possessesat least one nonpolar
and one polar portion. Owing to chemical. electrical. or phys-
ical attraction between the polar portions and the surface sites.
the collectors adsorb on the particles ~'ith their nonpolar ends
oriented towards the bulk solution. thereby imparting hydro-
phobicity to the particles. Collectors that are commonly used
include short chain alkylxanthates for base metal sulfides; long
chain fatly acids and their alkali soapsfor phosphates. berna-
No. ISO, Vol. 11 SOMASUNDARAN

this connection that due to the porosity of natural plena even
freshly ground galena will possessoxidized layers, and hence,
results reported for such systems do not necessarily determine
the effects of oxidation of the galenasurface on flotation.
The reaction of xanthate with the oxidation products of
galenaon the surface through an ion-exchange process is con-
sidered to be the major adsorption mechanism responsible for
the xanthate flotation of galena. Previous identification of
dixanthogen on plena is attributed by GranviUe et al. to its
formation during the evaporation of lead xanthate in ether or
CSz onto a surface. Their tests, however, do not conclusively
identify the speciesresponsible for flotation, becausethe
amount of dixanthogen observed on the mineral could have
been sufficient to causeflotation. Adsorption mechanisms for
sulfide flotation systems have been discussedelsewhere by
Finkelstein et al. (9) and hence are not covered in this paper.
Unlike xanthates on galena,alkyl amines, sulfonates, and
sulfates are considered to adsorb on minerals primarily due to
electrostatic attraction between the polar head of the coUector
and the charged surface sites on the mineral. These electro-
static forces, which are not u strong as the chemical forces in-
volved in xanthate adsorption, are assistedby the associative
interaction among the long alkyl chains that normally contain
8 to 20 carbon atoms (10-12). Becauseelectrostatic forces are
the basic cause for the selective adsorption in these cases,it is
important to understand the electrical nature of the mineral/
solution interface and the mechanismsgoverning its origin.
The electrical nature of the particle/solution interfal% is the
result of either a preferential dissolution of lattice ions u in
the caseof silver iodide, or of the hydrolysis of the surface
speciesfollowed by pH-dependent dissociation of the surface
hydroxyls as in the caseof silica (I I) and alumina (13):
under conditions of zero surface charge on the mineral. As-
suming that potential differences due to dipoles remain con-
stant, the total double layer potential is considered zero when
the surface charge is zero; such a condition is called the point
of zero CM'Ke (pzc). For oxides, the activities a. and a~ will
be that of hydrogen ions in the solution under consideration
and that at the point of zero charge, respectively. Similarly,
Q- and a~ will be the activities of hydroxyl ions under corre-
sponding conditions. Thus the oxides will carry a positive
charge in solutions that are more acidic than that a pzc and a
negative charge in solutions that are more alkaline. Sin~ the
system IS a whole must be electric:a1lyneutral, the medium
surrounding the particles must contain an equivalent amount
of ions, called counter ions, of charge opposite to that on the
surfa~ of the particle. Owing to the attraction by the charged
swface sites, these counter ions will not be uniformly distrib-
uted in the solution phase, but will be adsorbed at the oxide-
solution interfa~. This gives rise to an electrical double layer
consisting of one layer of surface charge and another layer of
counter ions. However, becauseof thermal agiution, this sec-
ond layer extends as a diffuse layer over a finite distan~ from
the particle surface. A schematic represenution of this elec-
trical double layer is given in Figure 3.
Point of zero charge of a mineral is an important dwacter-
istic becausethe adsorption of various organic and inorganic
ions will be governed by the location of the solution properties
(as pH) with respect to the pzc. Typical pzc values are given
in Table 2. It is important to note that these values are af-
SURFACE
CH4Rj STERN
PLANE

- M(HzO)Surtace
--
--
- MOHSwf8c:8 ~OH- .-

H. ~:
- M°Sutt.~ + H2O 0
e 0 e
The lattice ions are considered as (surface) p>tential determin-
ing ions for AgI type solids, whereas H+ and OH- are the cor-
0 0 0
resp>ndinl ions for oxide minerals. For minerals sudt as ::; 0
0
calcite (J 4) and apatite (J 5, J 6), both of the above mecl1a. 0
nisms can be operative since the lattice ions can undergo pt'Cf.
erential dissolution as wen as reaction with H+ and OH-. In
the caseof these mmerab, the lattice ions H+ and OH- and cn~ SHEAR e POTENTIAL-
certain complexes of the lattice ions with H+ or OH- can be PLANE \!) DETERMINING IONS
.
p>tential determining. Silicate minerals with layered structure '110 HYDRATED
such as that of clays, on the other hand, are negatively charled ..J 0 COUNTER IONS
~
under most natural conditions due to the substituion, for ex.
t='
"'a 0 NEGATIVE CO-IONS
ample, of AlJ+ for Si4+ in the silica tetrahedra.
The surface p>tential '" a in these systems is given by
z
w ~
...
0
-RTF Inoa. or -RT
~o. Z z F ino
a- a..

. a. - a-

where a. anda_are the activitiesof the positi~ and negative 8 01STANCE-

potential determinina ions in the solution with valenciesZ. Fia. 3. Schemaucrepresentationor the double layer accordiRIto
-
and Z (inclusiveof sign),anda: anda! are their activites Stem'smodel.
 4 ADVANCESIN INTERFACIAL PHENOMENA AIChE SYMPOSIUMSERIES

TABLE 2. POINT OF ZERO CHARGE OR ISOELECTRIC

POINT OF VARIOUS TYPICAL MINERALS

Min..-als pzc or i~ Ref.

OU8rtl, 5i02 pH 2-3.7 11-19
Rutile, Ti02 pH 6.0 20
Corundum, A120) pH 9.0 13
M~n..i8, MgO pH 12.0 21
Fluor8patite Inetur811 pH6 15
CasIPO.I) IF, CHI
Fluor8P8tite Isyntheticl pc. 4.4. pF 4.6. 22
pHPO. 5.22
HydroxY8P8tite. Cas (P041] pH 7-7.15. 22
10HI. Synthetic
Calcite CaCO]
Barite B8S04
pHPO. 4.19-4.48
pH9.5
PBa 6.7
,.
23
Silver iodide AgI PAt 5.6 2.
Silver sulfide At1S PAt 10.2 25
fectedby the presenceof impurities (26.27), previoushistory
including pretreatments(28), methodof storing and aging,
the extent of aging(17,29, 30) that it undergoesin an aqueous
solution. and the pH (17). Table 3 givesvaluesreportedfor
the point of zerochargeor isoelectricpoint- of alumina. It
canbe seenthat the pH rangesof plC and iep arewide, namely
3 to 10. indicatingthe magnitudeof the problem. Variations
in the sourceor method of preparationincluding mechanical
treatmentsand washingand drying. and the presenceof sur.
facedefectsand of adsorbedand structural impuritiesproduce
considerablechangesin the plC. Commoncleaningprocedures

.Isoelectric point (iep) refers to die conditions under which the elec.
trokinetic potentia!, commonly termed zeta potential (the potentia!
that manifests in die region of shear between die liquid and the solid
when one is moving relative to die other), as determined by electro- such as leaching in acidic (35) and hot solutions (36) have also
kinetic experiments is zero. The surface potentia! tJI0 need not be zero been found to alter the interfacial properties drastically. Fig-
when the zeta potential is zero, particularly in the presenceof $pecif- ure 4, for example, gives values reported for the zeta potential
icaUy adsorbing ions. Therefore pzc and iep need not be the same. of quartz leached with different acids; the variations when us-

TABLE 3. POINT OF ZERO CHARGE OR ISOELECTRIC POINT VALUES REPORTED BY VARIOUS WORKERS FOR ALUMINA 1281

Author. Material Tr.tment Method IEP R.narkl

Modi Ind Synthetic upphire L~hed in HCI, 9.4
Str~ing Hydroxylat8d
Fu8rlteneu 13'1 _ltIed, nor~ potentia' surf-
in -ter
Dobi8. It II. 1321 Synthetic S8pC)hir. L~h~ in 6% HCI, EI8Ctr~sis 8.7 Dehydr.ted wriece
_ltIed, dried .t
120.C. nored dry
Johansen.~ N8w,.1 COf'Undum ~hed in HCI, MicroelectrOOlmOsis 8.4 Dehydrated surf-
Buchanan 1331 _ltIed in _ter
.nd dri~.t 120.C
Schulyenborg end Natu,.' coNndum ~h~ in HCI, Microelectro- 3.0 Polym8fiation 8nd
Senger1341 _hed, di8lytit, phorlli. pl'0b8bly par-
nor~ dry tially d.,ydl'ated
surface
H..-czynlka end Chromatograpttlc As r8C8iYtd Titration 10.0
Proazynaka alumina
[cited in 1261)
Holm.. Fllm.fuled Ground. not c..ned. Microelectro- 7.5-8.2
[cited in 126)) synthetic stored in _t.. for
phor..i.
IIpphirt Ibout a day
Reprinted from C"'n Surl-, 1970. Courtesy of Marce' Oe~ker Inc-
No. 150. Vol. 71
ing different leaching media are evident here. It has been
found recently that the pzc of quartz can be raised from below
2 to as high as 6 by leaching it in hydrofluoric acid solution
(35). Upon aging the HF-leaclted quartz in water, the pzc can
be brought to its original value but only over a period of sev.
eral days. Washing minerals with hot solutions produces sim-
ilar long-term effects (36). For example, the zeta potential of
alumina contacted with a 2 X 10-1 N KNO1 solution changed
from about - 35 mv at pH 9.4 to about - 52 mv at pH 9.35,
after the suspensionpassedthrough a cycle of heating to 90°C
and cooling to room temperature. The original value of zeta
potential was not attained for days. The implication of this
should be noted on the usual procedure of cleaning minerals
by leaching in hot acid solutions.
In flotation clternistry research, the adsorption of organic
and inorganic ions at the mineral/solution interface is of con-
cern. The adsorption density r 6 in the plane 6, which is at a
distance of closest approach of counter ions to the surface, is
given by the Stem-Graharne equation
r, = 2rCexp.t~.!.
RT
where' is the effective radius of the adsorbed ion, C is the
bulk concentration in mole/crn3, ~ is the standard free
energyof adsorpti~ is the gasconstant,and T the abso-
lute temperature.~G~I is the driving force for adsorption
and canbe consideredto be madeup of a numberof terths.
eachterm for a giventype of interaction that is responsiblefor
the adsorption(40,41).
~ =dG:'ec + dG~ + dG:-c + dG:-s
+4Gft+4Gfl.o
~ is the electrostaticinteraction term equal to zFIlI6
wherez is the valencyof the adsorbate,F the Faradaycon-
stant and 1t16 the potentialat the S plane;~G~em is the chem-
ical term due to any covalentbond formation betweenadsor-
bateand adsorbent;~G~-c is due to the cohesivechain-chain
interactionthat could occurbetweenthe surfactantspecies
upon adsoprtion;~G~-I is similar to ~G:-c and is the vander
Waalsinteractionbetweenthe hydrophobicchain and the hy-
drophobicsiteson the mineralsurfa~; ~Gf. is due to hydro-
genbonding;~Gl\o is due to hydration or dehydrationof the
adsorbates or adsorbentsupon adsorption. Oneor more of the
abovetermscanpredominatefor eachsystem. l'hus, the
chemicalterm is consideredto be the predominantterm for
the adsorptionof xanthateson galena,and the electricaland
the chain-chaininteractiontermsareimportant for the adsorp-
tion of alkylsulfonatesor aikylsulfateson oxidessuchas
alumina.
The adsorptionof surfactantson aluminahasbeenrecently
studiedin detail (12,41). At low concentrationsof surfactant
and low surfa~ potentials,the surfactantions areindividually
adsorbedand the for~ of attraction, responsiblefor adsorp-
tion, betweentheseions and the mineralsurfa~ is mainly elec-
SOM AS UN DA RAN s
SOL
SURFACEPOTEN-
TIAL DETERMINING0 CO-IONS
IONS
SPECIFICALLY 0
COUNTERIONS
<:> ADSORBING
DEHYDRATED
r. c"""
\.~,..
COLLECTOR
CATIONS
COUNTERIONS
Fig. S. Schematic representation of adsorption of a Ionl chain anionic
surfactant (a) individuaUy at low concentrations and lb) with
lateral association between chains at higher co.ncentrations.
trostatic (see Figure 5). When the concentration of the re-
agent is increased, the adsorbed ions begin to associateto form
two-dimensional aggregatescalled hem;m;ce/les. Unde{ this
condition, the adsorption is due, in addition to the electro-
static forces, to favorable energetics of removal of alkyl chains
from aqueous solutions (42). The above adsorption mecha-
nism is formulated on the basis of the experimental observa-
tion that interfacial properties such as adsorption density, zeta
potential, flotation recovery, contact angle, sedimentation
rate, etc. undergo a marked change at a given surfactant con-
centration that is dependent upon pH and hence upon the sur-
face ootential of the oxide particles (12), solution temperature
(43), chain length (10,11,44,45), and chemical composition
of the surfactant (45) and the solution (46 to 48). Adsorption
data for the alumina/dodecylsulfonate system is given in Fig-
ure 6. Sharp increase in the slope of the adsorption isotherm
along with those of other parameters at an adsorption density
of 10-11 mole/cm1 can be clearly seen L"l this figure.
The mode of adsorption of the previously-mentioned sur-
factants on soluble salts such as sylvite is not established.
Fuerstenauand Fuerstenau(50) haveproposedthat adsorption
in these casesis governed by matching the size of the polar
head of the collector with the constituent ion of the solid
which carries the same charge as the polar head of the coUec-
tor. Thus amine adsorbs on sylvite (KCl) and not on halite
(NaCl), due to comparable sizesof the aminium ion and K.
ion. This theory, however, fails to explain. for example, why
the anionic aikylsulfate as a collector should distinguish be.
tween KCl and NaCl; it floats the former but not the latter.
According to an alternative theory proposed by Rogers and
Schulman (51), adsorption is governed by the hydration prop-
erties of the solid; the one with the larger negative heat of
solution is the most amenable to flotation. This theory cannot
explain why a particular mineral such as KCl will be floated by
certain collectorslike alkylsulfatebut not by carboxylatesor
6 ADVANCESIN INTERFACIAL PHENOMENA AIChE SYMPOSIUMSERIES

Particularly interesting in this ooMection is a recent sugges-

tion by Sorensen(55) that in the caseof the anionic flotation
of simple salts such as fluorite. hydrogen bonding between the
oxygen of the collector and fluoride speciesis active and that
it is wisted by the electron resonanceof the pow groups. the
structure of which must be compatible with the geometry of
the mineral crystal. Correlation that exists in several casesbe-
tween adsorption and insolubility of oompounds formed be-
tween the collector and the chemical oonstituents of the solid
suggestsyet another mechanism dependent essentially on what
could be considered as the precipiution of sud\ oompounds at
the mineral/solution interface.
While mud\ emphasis has been placed in flotation researdt
on collector adsorption on the mineral. the role of the ooUec-
tor speciesadsorbed on the bubble has been largely neglected.
Using a semi-empirical model. it has been shown for the
quartz.amine system at neutral pH that the collector adsorp-
tion density at the liquid/ps interface can be several times
higher than that at the solid/liquid interface (see Figure 7).
Furthermore. recent studies have shown that collector migra-
tion at the liquid/air interface is several times faster than that
from the bulk aqueous solution to an interface (57). During
the contact of an air bubble with a particle. it is therefore pos-
sible for the speciesadsorbed on the bubble to migrate to the
solid/gas interface and thus establish the desired adsorption for
the attachment of the bubble. It must be noted that such a
migration is dependent upon the presenceof a sufficient quan-
tity of coUector ions on the bubble surface at the time of cOn-
tact with a particle and therefore upon the kinetics of adsorp-
tion of the collector speciesat the liquid/air interface. The
phosphates. The authors have alternative explanations for cer- strong correlation that exists between flotation and the
tain exceptions.
Fatty acids are widely used collectors. Adsorption of
oleate on hematite, apatite, fluorite, calcite, varite, etc. has
been attributed in neutral and alkaline solutions to chemical
bonding between the oleate and the mineral surface species.
In addic solutions, oleic acid formed would indeed predpitate
due to its very low solubility in water. Infrared studies have
been considered to provide evidence for the formation of
chemical bonds between oleate and fluorite (52) and oleate
and hematite (53). It remains questionable as to whether the
chemical states identified by such spectroscopic tectU\iques
on sampleswhich have been subjected to various treatments
for the spectroscopic analysis itself can be considered to be
identical to the original chemical state of the oleate adsorbed
on the mineral in an aqueous solution. Recently, it was shown
that the oleate-oleic acid complex which forms in the neutral
pH ranse was hishlY surface active and therefore was pro-
posed to be responsible for the maximum hematite flotation
which was observed in that pH range. This mechanism is dis-
cussedelsewhere (54). -
10-6 10" -10-4 10'" - 1~'2
One mechanism of adsorption that probably governs the
adsorption in various rnineral-collector systems, including pos- CONCENTRATION, mole/liter
sibly some that had been attributed in the past to chemical Fit. 7. Adsorption density of dodccyllrnmonium acetate at different
and electrostatic mechanisms, is that based on the similarity interfaces lafter Somasundaran(56)!. Reproduced by permis-
in geometry between the mineral crystal and the coUector. sion of AmeriaR Inst. Min. Met. EftlJl. (AIME).
 SOMASUNDARAN
No. iSO,Vol. 71
kinetia of adsorption at the liquid/air interface for the
hematite-oleate system is discussedelsewhere(54). The mi-
gration of collector speciesfrom the bubble/liquid interface
to the solid/gas interface caMot be expected to be nonselec-
tive with respect to various minerals becausethe adsorption
density at the interface of the bubble and the mineral particle
(with possibly severallayers of water molecules strongly at-
tached) will be essentially detennined by the surface prop-
erties of the particle.
From Young's equation relating the three interfacial ten-
sions '11,.,'1"., and '1" to the contact angle 9, one obtains the
-
condition that '1", '1" must be smallerthan '11,.for a large
contact angle and thereby good flotation (56). The larger the
value of '11,.,the lower is the froth stability the above condi-
tion can be fulfilled only by keeping '1". small and '1" as large
as possible. Becausethe adsorption of surfactant at any inter-
face will only decreasethe interfacial tension there, it is clear
that the above condition can best be satisfied by allowing the
transfer of surfactant speciesfrom the bubble surface (or from
the gaseousphase) to the solid/gas interface. Perhaps for this
reason,Wada (58), on passingthe collector into the cell in the
fonn of an aerosol with the gasstream, obtained optimum
flotation at reagent concentrations as low as lis to I/aO of
those used in the conventional process.
FROTHING
Nonionic surfactants. generally slightly soluble, monohy-
droxylated compounds such as cresol, are added to induce the
desired froth stability during flotation. particularly when the
chain length of the collector is relatively small. Sulfide flota-
z adsorption of the collector species. Adsorption of the acti-
Q vators is attributed to electrostatic attraction between them
(/)
Z and the mineral surface in such casesas calcium adsorption on
LiJ
..-
LiJ
U
~ Stern potential and thereby cause the adsorption of collectors
~ that have a charge of the same sign as that of the mineral. In
(/)
CONCENTRATION OF SOLUTE
Fig. 8. Diagram illustratin& the correlation
between froth stability and surface
tension lowerin& due to the addition
of a surfacunt (after Cook (.59)).
Reproduced by permission of John
WUey-lnterscience.
7
tion using short-chained alkylxanthates invariably requires the
addition of a frother. The desired concentration of the frother
in the system is approximately that at which there is a signifi-
cant changein surface tension with concentration so that a
restoring force is available to prevent the rupture of bubbles
subsequentto any local extension of the surface (see Figure 8).
It is also necessarythat the diffusion of the surfactant species
from the subjacent surface to the locally extended surface
region is not fast enough to reduce the difference between the
surface pressurein the vicinity of the extended region and
within it becausethis difference is mainly responsible for the
restoring force.
In addition to providing froth stability, the frother can play
another role that must be taken into consideration in the
study of flotation mechanisms. Similarly to collector species
adsorbed on the bubble, frother speciesalso can migrate from
the bubble surface to the particle/solution/bubble contact line
and particle/bubble interfacial regions and co-adsorb on the
particle along with the collector species(60 to 62). Such
frother adsorption can be favorable for flotation, possibly be-
causethe neutral frother molecules adsorbing among the ionic
collector speciescan shield each adsorbed collector ion from
repulsion by others (63) and thereby enhance the overall ad-
sorption of surfactant.
ACTIVATION
Activators enhance the flotation of a mineral by collectors
that will not float it in their absence. Examples include cal-
cium activated flotation of quartz using oleate, and copper
sulfate activated flotation of sphalerite with xanthate at rel-
atively high pH values. Activators normally act by adsorbing
at the mineral-solution interface, thereby providing sites for
negatively charged quartz. Bivalent ions such as calcium, upon
adsorption on minerals, are capable of reversing the sign of the
some cases,activators have been effective becauseof their re-
actions with collectors to form compounds of low solubility
product. This aspect is discussedin a paper by Fuerstenau
(64).
DEPRESStON
Reagentsthat prevent the adsorption of collectors on min-
erals and thereby retard their flotation are known as depres-
sants. Uke an activator, a depressant often reversesthe Stern
potential of the mineral, but the resulting potential in this case
is of same sign as that of the charge of the collector ion so that
collector adsorption is reduced.
Polymers such as starch can also depressflotation, but as
discussedin detail later, in this casecollector adsorption is en-
hanced by the depressant (65). The decreasein flotation ob.
tained in spite of the increased collector adsorption can be
attributed to the peculiar structure of the coUector-stardt
clathrates formed with a hydrophilic exterior-
 8 ADVANCES IN INTERfACIAL PHENOMENA AIChE SYMPOSIUM SERIES

DEACTIVATION
Deactivators prevent activation, generally, by interacting
with the activators to form an inert speciesof a stable ionic
complex. Addition of cyanides for the deactivation of copper
in the xanthate flotation of sulfides is a well-known example
of this type of deactivation reaction.

EFFECT OF VARIABLES
There is a large number of variables that affect flotation
processes. These variables originate from the physical and
chemical nature of the ore, its storage, its preparation includ-
ing grinding, the chemical constituents that may be present in
water, reagents added and the type of flotation cell used. It is
relevant to examine here only the physicochemical variables
that affect the interfacial processes. The nature of the min-
erals and other components in the ore wiU indeed govern the
interfacial processes,but there is very little control that one
can exercise on this. However, with the composition of the
ore known, a knowledge of the effect of controUable variables
can be helpful to obtain maximum processefficiency.
CHAIN LENGTHOf THE COLLECTOR
Increase in length of the nonpolar part of a surfactant in-
creasesits adsorption at interfaces, thus generaUyenhancing
the flotation of minerals. Results in Figure 9 for the flotation
of quartz at natural pH using aikylammonium acetates of vary-
ing chain length show an increase in flotation with an increase
in chain length (10). The chain length effect on flotation was
ascribed to the increased adsorption at the solid/liquid inter-
face owing to lateral interaction among the adsorbed species
to form two-dimensional aggregatesand at the liquid/gas inter-
face. The length of the chain is often limited by solubility
which decreaseswith increasing chain length. If very long
chain surfactants are to be introduced into the flotation ceU,
it can be done through an oil emulsion.
CHEMICALSTRUCTUREOf THE SURfACTANT
Substitution of hydrogen in CH1 or CH3 groups of the sur-
factant with fluorine increasessurface activity and flotation
Fig. 10. Flotation of alumina as a function of pH with CF )(CF1)6
COOK and CH)(CH1)6 COOK as collectors in 2 x 10-)
mole!1 KNO) solutions (after Somasundaranand Kulkalni
(45) J. Reproduced by permission of Institute of Mining and
Metallurgy (IMM) London.
considerably (45). In the caseof perfluoro-carboxylates, an
additional advantage is their better pH tolerance, compared
with any corresponding hydrocarbon homologue, attributed to
the reduced tendency of the former to hydrolyze in acidic
solutions (see Figure 10). However, their current cost is pro-
hibitive for any application in flotation processing. Uke per-
fluoro compounds, silyl reagents are also reported to be highly
surface active (66). While geometrical modifications in the
structure such as distribution of the methyl groups into var-
ious branches in general reduces the surface activity, addition
of active groups at appropriate points in the surfactant mole-
cule, so that the distance between the groups will correspond
to the distance between active sites on the mineral surface, can
be beneficial. The role of Zwitter ions in flotation is discussed
by Gupta and Smith (67). A better understanding of the role
of chemical constitution of the surfactant in flotation will in-
deed be highly beneficial for developing tailor-made flotation
reagents with desired selective adsorption properties.

COLLECTORCONCENTRATION
eo! 18C
16C~
It can be seen from Figure 9 that flotation recovery is also
~ i

strongly dependent upon the concentration of the coUector.

060'
101 This effect is not due to the dependence of the mechanical
t-
properties of the foam on collector concentration becausethe
~ 40
-'
16-
20
I particular casereported in Figure 9 is for Hallirnond tube tests
for which such effects are absent.
Rubin and co-workers (68), among others, have observed
the dependence of precipitate flotation on collector concentra-
10-8 10.7 10.6 10.' 10-4 10'S 10-2 10.1 1 tion. A collector to colligend (copper speciesin this case)
CONCENTRATION, mole/liter ratio of one was found necessary to get nearly complete re-
Fic. 9. The effect of alkyl chain length on the flotation of quaru in moval of copper. For foam separation techniques, the most
alkylammonium acetate solutions (after Fuerstenau, Healey, suitable surfactant concentration is the lowest one that pro-
aJKISom.sundaran (10)). Reproduced by permission of Amer- vides the desired foaming properties (69 to 71). Transiency of
ican (nst. Min. Met. Engrl. (A(ME). the foam found desirable for effective extraction (72) is higher
No. ISO,Vol. 71 SOMASUNDARAN 9

pH
Fig. 12. Flotation of calcite with dodecylammonium acetate (DDAA)
at lower coUector con~ntration. An ex~ss of coUector has and sodium dodecylsulfate (DDSO4) solutions (after
Somasunda.ranand Alar (14»). From Journal CoUoid and
been reported to reduce the flotation of minerals (45) and pre-
Interface Science 24, 439 (1967). Reproduced by permis$ion
cipitates (73). In particulate flotation this is sometimes due to of Academic PressInc.
a reduction in the size of the bubbles to such a level that they
are not capable of levitating the large number of particles that
caUect on them (45). Adsorption of a second layer of coUec-
tor (at high con~ntrations) with an orientation opposite to
that of the flfst layer, or adsorption as micelles can also de-
creaseflotation, but this is less likely since only a small frac.
tion of the surface need to be hydrophobic for flotation to
occur (see Figure 11).
SOLUTIONpH
pH is a major controlling factor in the separation of oxides,
silicates, etc. Proper choice of pH and the type of coUector is
in fact a requirement for selective flotation of one mineral
from another. The effect of pH iUustrated in Figure 12 is for
the flotation of calcite with an anionic and a cationic collector
as a function of pH at two concentrations (14). The isoelec-
tric point of calcite is in the pH range 8 to 9.5 (14). It is evi.
dent that significant flotation with an anionic collector is pos-
sible only below the isoelectric point when the particles are
positively charged, and with a cationic collector only above
the isoelectric point when the particles are negatively charged.
The pH will also influence flotation through its effect on
collector hydrolysis. A typical example of this is the amine
flotation of quartz in basic solutions. A critical pH-coUector
con~ntration curve for the incipient flotation of quartz with
dodecylammonium acetate is given in Figure 13. Quartz is
negatively charged above pH 2, and therefore it should be pos-
sible to float it with a cationic collector above this pH. It can
be seen from Figure 13 that flotation ceasesonce the pH ex-
ceeds 12. This observation was ascribed to the fact that at 12
2 4 6 8 ...0

this pH most of the collector was in the form of neutral mol- pH

ecules which do not absorb on quartz (see Figure 14). It must Fic. 13. Critical-pHconcentrationcurves for incipient vacuum flota-
be noted, however. that neutral molecules can act as excellent tion of quaru usina dodecylammonium acetate solutions (75).
 10 ADV ANCES IN INTERFACIAL PHENOMENA AIChE SYMPOSIUM SERIES

1)0

102 I I I I I I I

-
~
Q) 80 f ~
J
:: -~
~
0
E
Z
-
10

-4
ae60
Q
IAJ
~
g40.
..J '
II
I
"
, 1I
1
Q 10 MAXIMUM :"
~
~ RNH2
20
~
cr- If . .-:-~~~--:~~-Jin(OH I' n(OH)z(s)'. (. ) -

I- _£, . ,"
..'
0.2
Z
W
lO-
/
~ .
0 2 4 pH 6 8 10 12
u I
Z I AI FiC.15, Efrector pH on zinc notation usinasodiumlaurylsulfatcat
I coUectorratiosor 0.2. I, Z.and ) from I x 10-4 molc/bter
I zinc (II) solution. In the halchedreSion,nolalion or
.j
I
lAM Zn(OH)2precipitateoccurs(ICter RubinInd upp (78)1.
... I Reprintedrrom Se'pGrgrion SC;,ltce'6 )57 (1971). ColUtesy
~. I or Marcd DekkerInc.
0" -

- (j.eo"0 8I J I
00"
I I I I
10 10 12
pH
Fil. 14. Concenuation of neutral molecules (M) and ions (I) in a 2
2 x 10-i mole!1 (A) and 2 x 10-4 mole!1 (8) dodecyiammo-
mum chloride solution as a function or pH. Solid lines indi-
cate the maximum solubility (after Gaudin l76»). From
110141;011,2nd Edit., by A. M. Gaudin (1957). Used with per-
mission or McGraw-Hill Book Co.
collectors when present along with ionic surfactant species.
This is supported by the observation that maximum flotation
of hematite with oleate was obtained in the PoHrange in which
half of the oleate was present in the neutral form (57). This
was attributed to the significantly higher surface activity of
the I : I acid-soap complex formed in this pH range and its ad.
sorption at various interfaces. Fuerstenau and Yamada (63)
obtained an increase in flotation of alumina with dodecylsul-
fate upon the addition of dodecylalcohol. They ascribed the
flotation increase to an increase in the total adsorption of the
surfactant speciesat the solid/liquid interface facilitated by
the screening of the repulsion among the ionic parts of the
adsorbed surfactant speciesby the neutral alcohol molecules
coadsorbed between. There is, however, no direct experi-
mental evidence available yet to support such a hypothesis.
There has been observed an increase in flotation of alumina,
but not hematite, owing to the dissolution of methane and
butane in sodium dodecylsulfonate solutions (76, 77). The
reason for this selective activation is not yet established.
The effect of pH on ion flotation and precipitate flotation
has been discussedin an earlier publication (1). The selected
pH of the solution may in fact determine whether the process
I will be ion fl~tation or precipitate flotation; thus zinc is re-
14
moved from solution by ion flotation below pH 8 and by pre-
cipitate flotation above pH 8 (see Figure I S). It can also be
seen from Figure 1S that ion flotation is influenced by collec.
tor concentration to a greater extent than precipitate flotation.
Grieves found precipitate flotation to be most efficient when
the sign of the charge of the precipitate was opposite to that
of the collector and when the amount of soluble specieswas at
a minimum (1). Microflotation of organisms is also reported
to be highly sensitive to pH (79. 80); thus. flotation of E. coli
using lauric acid and alcohol is maximum in the pH range of 4
to 8 (79).
IONIC STRENGTH
If the adsorption of the collector on the particles is pri.
marily due to electrostatic attraction of the coUector species
to the charged mineral surface. a significant increase in ionic
strength will decreaseits adsorption on solids becausethe ad-
sorption of the collector ions must take place in competition
with other ions that are similarly charged. This effect is
clearly shown by the results obtained recently for the cat-
ionic flotation ofquartl (46) (see Figure 16). In this case.
potassium nitrate, added to increase ionic strength. acu as a
depressant. An increase in ionic strength by the addition of
uni-univalent electrolytes has in general been found to be det-
rimental to froth flotation. An exception has been noted reo
cently for hematite flotation using oleate (81). In this case,
an increase in KNO) concentration from 8 X 10-5 to 2 X 10-1
mole/liter was found to increase flotation from about 28 to
9O'roat an oleate concentration of 1.5 X 10-5 mole/liter. Con-
ditioning was carried out at 2SoC and pH 8.0. When the con-
ditioning was carried out at 95°C. the effect of an increase in
ionic strength was. however. found to be detrimental. If the

~
No. 150.Vol. 71 SOMASUNDARAN ii

100

80

If
0601
w 1
too

940l
~
1
1.5 .
1O-4~.OOA
QUARTZ
20 pH- 5.8

0
K5 K5 K53 Kj"- K)-t
K~3 CONCENTRATION, mole/ liter

Fil. 16. Flotation of quartz as a function of KNO) concentration at

natural pH of S.B in I.S X 10-4 mole/l dodecylammonium
acetate solutions (46).

added salt contains multivalent ions of the same sign as that of

the collector ions, depression is more marked due to the ten-
dency of the multivalent ions for stronger specific adsorption
and resultant larger competition with the collector ions. This
effect is clearly illustrated by the results of Modi and Fuer-
stenau (82) reproduced in Figure 17. Evidently, the presence
of bivalent sulfate ions is more detrimental to the anionic flo-
tation of alumina than the monovalent chloride ions. If the
bivalent ions are of opposite charge to that of the particle and
the collector ions, then activation of flotation can occur due
to charge reversalof the particle causedby the adsorbed bi-
valent ions. Thus, as shown in Figure 18, Modi and Fuer.
stenau (82) obtained flotation of alumina, positively charged
in water at pH 6, using a cationic surfactant after the addition
of bivalent sulfate. Their electrokinetic results (31), repro-
duced in Figure 19, show that the sulfate ions can adsorb in
quantities sufficient to reversethe effective charge on the alu.
mina particles, thus promoting the cationic surfactant to ad.
sorb and to make the particles hydrophobic. Bivalent cations
such as calcium can similarly activate the anionic flotation of
originally negatively charged particle.. It has been reported
that alkaline earth ions such as calcium can function most ef-
fectively in the pH range where they are in the hydrolyzed sol.
uble form. Fuerstenau et al. (84, 85) studied the role of iron,
aluminum, lead, manganese,and calcium in the anionic flota-
tion of quartz as a function of pH and found that each cation
began to activate flotation when the solution pH corresponded
to the beginning of metal ion hydrolysis and ceasedthe activa.
tion at the precipitation pH of the metal hydroxide (see Fig-
ure 20).

100 .it..~!,!. ',' I. 0 NaCl

I

.eOr
6 NozSO.
80 > I
e +40 ~
- I
~ I
- 60 ~ :.
~
Q ~ ,
!AI Z '
~ IAI 0
«
... I -~~
0 40 ~ r
..J
I&. . I ALUa8IA

20 4
ALUMINA
-s
. 10 M RSO. ~
... -40
IAl
N
r-
.
.
0

0
NoC1.
NoZSO.
RSO.No
pH6 -80r pH 6.5
0
-7
I
-6
I
-S
I
-.
I
-3
I
-I -1
i
-1
'.
-&
.
-s
.
-.
."
-s
.1
-Z -I
10 10 10 10 10 10 10 10 K) K) K) K) K) K)
ELECTROLYTE CONCENTRATION. mole/ life'
CONCENTRATION OF ADDED SALT, mole/liter
Fic. 17. Thedepression of notation of aluminaby NaCIand NatSO. Fil. 19. Effect of addition of NaCl.Na1S0.. and Na dodecylsulfo-
with sodiumdodecybulfatcIS collectorIt pH 6 [after Modi nateon the ~etl.potentialof aluminaat pH 6.S (after Aplan
and Fuerstenau (82)). Reproducedby permissionor Amer- and Fuerstenau(81)J. Reproducedby permissionof Amer-
ican Inst. Min. Met. Engrl. (AIME). ican 1nst.Min. Met. En,q. (AlME).
 ADVANCESIN INTERFACIAL PHENOMENA AICbE SYMPOSIUM SERIES

80l
~ ~
- t~
60

~
-C 40
r
,
0 r-

~ ~
20l

0
2 4 6 8 10
pH
Fig. 21. Effect of additionof alumon the flotation of illite UDnIso-
dium laurylsulfateascollector. . -no alum;. -6.25 lng/I
alum;e-50 mg/l alum (after Rubinand Erickson(92}J. Re-
printed from Wale'Res.5437 (1911)by Rubinand Erickson.
Reproducedby permissionof Pergamon Pressinc.

The effect of ionic strength on precipitate flotation can also meric type reagentssuchasstarch. Figure22 illustratesthe ef.
be expected to be of a similar nature. Sheiham and Pinfold re- fect of starchon the flotation of calcite usingoleate(65). It
port a decreasewith increasing ionic strength in the precipitate canbe seenthat the addition of evena smallamountof starch
flotation of strontium using dodecylpyridinium chloride. hexa- decreases the flotation of calcite drastically. As mentioned
decyltrimethylammonium chloride, and a dialkylammonium earlier,starchdoesnot reduceflotation by inhibiting the ad.
chloride (87). As expected, they did not observe such an ef- sorption of the surfactanton calcite particles. In fact, the ad.
fect in the precipitate flotation of "the second kind" of nickel sorption of oleate on calcite was found to be higher in the
and palladium with nioxime (88,89) becausethe collector at- presenceof starchthan otherwise. Similarly, the adsorption
tachment to the colligend is a part of the precipitation process of starchwasalsoenhancedby oleate(seeFigures23 and 24).
and independent of electrostatic attraction between the col-
Thus even though the particlesadsorbedmore surfactant in
lector speciesand the precipitate. Ion flotation also should be
retarded by an increasein ionic strength becausethe colligend
ions will now have to compete with other inorganic ions for at-
tachment to collector ions. Rubin et al. (78, 90) and Grieves
(9 J) have observed the interference of ionic strength to the
ion flotation of zinc, copper, and orthosphosphate, respec-
tively. Indeed, in ion flotation and other foam separation
techniques, the effect of ionic strength on foam stability and
drainage can be a governing factor. The foam separation of
~
0
surfactants is assistedby an increase in ionic strength because
of the enhancement of their adsorption on the bubbles, at 0
~
least below the critical micelle concentration. ..-
<{
0
FLOCCULANTSAND DISPERSANTS .oJ
~
Complete flotation of a material can be achieved in several
casesby adding auxiliary" reagents. For example, Rubin et at.
found that the flotation of illite, titania, and B. cerew with
sodium laurylsulfate was increased to almost 100% by adding
alum (92-94). Figure 21 shows the typical effect of alum on
microflotation. It is not clear whether the increased flotation
is due to charge reversal of the coUigend particles or simply 0
0 4.5 9 13.5 18
due to their flocculation. In the froth flotation of minerals,
CONCENTRATION OF STARCH, ppm
flocculation is valuable only if it is selective. Such selective
flocculation followed by flotation has been found to be useful Fig. 22. The depression of calcite notation using sodium oleate by
for the large-scaleseparation of fine hematite from quartz (95). starch (after Sornasundaran(6.5»). From Journal Conoid and
Interface ScienceJ 1 (4). 19. Reproduced by permission of
Separation by flotation is affected by the addition of poly- Academic PressInc.
 No. ISO. Vol. 71 SOMASUNDARAN 13

10.4 with a hydrophilic exterior and a hydrophobic interior. Mu-

tual enhancement of adsorption is possible owing to the forma-
IAJ tion of a helical starch-oleate clathrate with the hydrophobic
... oleate held inside the hydrophobic starch interior. The hy-
U
-J drophilic nature of calcite in the presenceof starch and oleate
«
u results from the fact that the adsorbed oleate is obscured from
the bulk solution by such wrapping by starch helixes whose
~ exterior is hydrophilic and possibly also by simple overwhelm-
~
-~0 ing of it by massivestarch species.
-
E 10 CONDITIONINGTEMPERATURE
0 In the caseof flotation dependenton the physicaladsorp-
IAJ
m tion of the collector, adsorptionand henceflotation can be
~
0
expectedto decreasewith an increasein the temperatureof
(/)
0
conditioning (reagentizing)while for flotation dependenton
<t chemisorptionthe reverseis true. Therehasbeenactually very
IAJ tittle work doneon the temperatureeffects on froth flotation.
...
« Flotation of hematitewith oleate(96) and fluorspar(97) has
IAJ beenreportedto increaseon heatingthe pulp. Recentresults
-J
0 - for hematiteflotation usingoleate,however,Mve shown this
100 I ~ I ~ I ~ I ~ I l~ l~5 to be true only at low ionic strengths(81): Above an ionic
strengthof 2 X 10-3 N flotation wasfound to decreasemark-
CONCENTRA T ION OF STARCH, ppm
edly with increaseof reagentizingtemperature.
Fic. 23. Effect of Starchaddition on the adsorptionof oleateon cat. Effect of temperatureon flotation canaffect the perfor-
cite at naturalpH of 9.6 to 9.8; verticallinesindicatethe
manceof foam separationby its influenceon foam drainage,
standarddeviationdue to the variationin scintillationcount-
ing (after Sornasundaran (65»). From JournalCoUoidand transiency,andadsorptionat the liquid/gasinterface. Such
InterfaceScienceJ 1 (4). 19. Reproducedby permission multiple effectsmight be responsiblefor the absenceof any
of AcademicPressInc. definite trend in the effect of temperatureon foam separa-
tions. For example,while an improvementin flotation with
the presenceof starch. they remained hydrophilic. This effect
temperatureis reportedby Grievesfor the foam fractionation
was ascribed to the helical structure: that starch assumesin the
of ethylhexadecyldimethylammoniumbromide (98), and
presenceof hydrophobic speciesand under alkaline conditions.
Ma1meand Pinfold for the precipitat~flotation of the rust
kind of strontium with a cationic collector and of the second
1200
.~ -- kind of nickel with. nioxime (87,99), tittle or no effect is re-
ported by the latter authorsfor precipitateflotation of the
~ 1000 secondkind of palladiumwith nioxime (100), and by Rubin
~~ ~ ~~
~.-- and co-workersfor the ion flotation of copper(l) usingsodium
~
4 lalirylsulfate (90). Clearly, more work undera wide rangeof
U b ' controlled conditions is neededin this areato elucidatethe
~ 800
0 mechanisms involved.
~
"-
~
:t.. 600 I CONCLUSION
0
IAJ
Froth flotation phenomena are governed by the properties
CD
~
of the various interfaces formed between the solid, liquid, and
0 400
(/) gas phases. Attachment of a bubble to a particle for its levita-
c
~ tion takes place if the free energy change is favorable for dis-
:I: placing the solid/liquid interface with solid/gas interface. Sur-
~ 2001
factants are added to help to meet this criterion by adsorbing
~ :
at various interfaces. The role of adsorption at various inter-
(/)
fa~s is now well recognized. Mechanisms of adsorption of
n- -. - - -, surfactants on minerals are understood in many caseswith the
K) K) K> K)
SODIUM OLEATE CONCENTRATION,mole/liter help of experimental tools such as electrokinetic techniques,
adsorption isotherm determinations and spectroscopic tech-
Fig. 24. Effect of oleateadditionon the adsorptionof starchon cal- niques. However significant these techniques are in elucidating
cite at variouspH values(after Somasundaran (65»)- From
adsorption mech2nisms, they must almost always be used with
JOlUnalColloid and InterfaceScienceJ1 (4), 19. Repro-
ducedby pennissionof AcademicPressInc. some reservation, becausea direct application of some of the

~
14 ADVANCESIN INTERFACIAL PHENOMENA
techniques can very weU be the causefor frequent misinterpre-
tation, particularly when one is dealing with heterogeneous,
natural minerals. Electrokinetic experiments provide only an
averagemeasurement for the whole solid particle. Further-
more, the measured property depends upon the type of pre-
treatment and storage that the mineral has received. Spectro-
scopic techniques can also causemisinterpretation if it is not
recognized that the surface speciescan undergo significant
changesduring the preparation of the sample for the analysis.
E~n today, flotation practice leans rather more on expe-
rience than on a meaningful scientific undentanding. It ap-
pean that the effects and interactions of a large number of
variables, including the chemical constituents present in a nat-
ural flotation system, need to be recognized. studied. and un-
derstood if the knowledge gained from researchon the physical
chemistry of the mineral-solution-gas system is to be of any
significant application in actual froth flotation practice.
LITERATURE CITED
1. Somasundaran,P., S~poralion ond Purifico/ion M~llrod.r. I, 117
(1972).
2. ui. R~. w.. ~nd D. w. Fucr~tenau. Trans. AI."E. 241. S49
(19681; See~I~o R~8h~van.S.. and D. W. Fuentenau,AIClrE
Symp. ~,. No.. 71 (197S).
3. Sh.h, G. N.. and R. Lcmlich,lnd En,.. Ch~m. FuIIdG~nlols, 9.
35011970).
4. Sheibm. I.. and T. A. Pmfold. ~pt1rvlion Sa., 7.43 (1972).
S. Goldber8. ~.. and E. Rubin. Ind. En,.. "'~m. houu D~sip
D~II~/op..6,195(1967).
6. Pinfold. T. A.. ~pGlV/ion Sri.. 5. 379 (1970).
7. Gutierrez. C..."in~rvISa. En,., 5,108 (19731.
S. GrAnville. A., N. P Finkelstein. ~nd S. A. Allison. r,ons. IMM. 81,
Cl (1972).
9. Finkelstein. N P..S A. Allison. and V. M. ~veU.AIClrESymp.
S~,. No. 150.71,165 (197S).
10. Fuenten~u. D. W., T. W. Healey, and P Somasunduan, rrvns.
AJ."£. 229. 321 (1964).
II. Somasundaran.P.. T. W. Healy. and D. W. Fuer~tenau.J. Pltys.
Ch~m..68,3562(1964).
12. Somasundaran.P..~nd D. W Fuerstenau.ibid.. 70.90 (1966).
13. Yopp~, J. A.. and D. W. Fucntenau,J. Colloid Sa.. 19.61 (1964).
14. Somasund~ran,P., ~nd G. E. Agar,J. Colloid In/~'foc~ Sci.. 24.
433 (1967).
IS. Somasundaran.P..ibid., 27.659 (1968).
16. Somasund~ran.P.,and G. E. Alar, ibid.. 252. 348 (1972).
17. KulkarnI, R. D..~nd P. Sornasundaran,in "Oxide- Electrolyte
Interfaces:' Am. Electrochem. Soc., 31-44 (1972).
18. Gaudin. A. M.. D. W. Fuentenau. r,ons. AIM£. 202. 66 (19S5).
19. Iwasaki. 1., R. R. B. Cooke,~nd H. D Choi.ibid..120. 394
(1961).
20. Berube. Y. G.. and P. L deBruyn.J. Colloid In/~'fo« Sri., 27.
305 (1968).
21. Robinson. M.. J. A. Pask..and D. W. Fuerstenau. 1. A~'. C~rvmic
Soc., 47, 516 (1964).
22. Saleeb. F. Z. and P L deBruyn. El~ctrocrnol Ch~m. fnl"foc.
E/~ctroclr~m., 37.99 (19721.
23. Buchanan. A. S..and E. Heym~nn.Proc. Ro}'oISoc.. A195.1S0
(1948).
24. Overb~ek. J. Th. G., in Colloid Sci~nc~. H. R. Kruyt. (ed.), Vol. 1.
ElseVIer.New York (19~2).
25. Freyberger. W. L. aad P. L deBruyn.J. PItyr. Chtm.. 63,1475
(19S71.
AIChE SYMroSIUM SERIES
26. Parks. G A.. Ch~1PI. R~p., 65.177 (1965).
27. D~ju, R. A., and R. B. Bhappu. "A Chcmiallnt~rprctation of
Surface Phenomena in Sitiate Minerals:' New M~~iQ) State
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DISCUSSION
Emesto Valdes-Krei&: How do collector ratios studied in a
batch ~ll reprodu~ in a continuous system? We have ob-
served that true concentration in a batch cell are often not re-
corded, but rather their initial values are given. The adsorp-
tion capacity of the mineral and the continuous aeration may
modify the conclusion derived.
P. Somasundann: PhysiQI chemistry of froth flotation has
been studied in the past using batch tests with no correspond-
ing continuous tests for comparison. The best comparison
that is possible is between laboratory batch tesU and large-
scale plant continuous tests. The ratio of collector to col-
ligend is in general found to be rugher under p~t conditions
than under the laboratory test conditions. For example, while
an oleate con~ntration of only S X Iv-4 mole!1 was needed
to obtain nearly complete flotation of hematite at pH 1 to 8 in
a laboratory batch test using Denver ~ll, a ooncentration of
S X 10-3 mole!1 is reportedly used in the plant during oondi-
tioning for the notation of the same ore. We found concentra-
tion for similar flotation. but of a different type of hematite,
in a HaIlimond ~ll to be S X 10-5 mole!l. The need for in-
creaseddosageunder a larger-scalecondition might be due to
the presenceof various additional colligends (that compete for
the co~ctor), particularly slimes that might often be present
in higher amounts in a large-scaleoperation.
Flotation results are usually reported in tenns of the initial
surfactant con~ntration rather than the equilibrium bulk
concentration. In an ordinary laboratory flotation test the
equilibrium bulk concentration will be lower than the initiai
concentration and such differences could indeed affect the in-
terpretation to some extent. Reported effects of such vari-
ables as solution pH and interpretations based on them, how-
ever, can be expected to be in seneral valid for a given flotation
system. Moreover, in the caseof HaUimond tube tests (that
have been widely used to study the physical chemistry of flo-
tation), surface area of the solid available for surfactant de-
pletion by adsorption is very small, and hence equilibriwn
surfactant concentration will be very close to that of the in-
itial concentration. It might be noted that results obtained for
adsorption tests during flotation research(which use rugh sur.
face area systems) are usually reported in tenns of equilibrium
bulk concentration. It will indeed be advisable to check the
equilibriwn concentration for all tests if available time per-
mits the required chemical analysis.