2.

2 Flotation Chemistry

The success of flotation depends greatly on the development of the correct

chemical conditions in the system in which a given flotation process is to be
carried out. An appropriate chemistry is built up by using different chemical
reagents. The reagents in use in flotation are broadly divided into two categories:
surfactants and regulating or modifying agents.

2.2.1 Surfactants

A great many of inorganic and organic reagents are used in flotation for the
purpose of controlling the characteristics of interfaces. As a result of a large
number of polar groupings and a still larger variety of nonpolar groups, there exists
a vast number of reagents which serve as surfactants. These can be classified either
according to the electrical charge associated with their polar group into anionic,
cationic, or nonionic, or according to the hydrocarbon structure (alkyl, aryl,
phenyl, cyclohexyl, alkylanyl, etc.), or according to the specific type of polar
group. The last one in the list is by far the most useful in differentiating the action
of surfactants and in specifying their characteristics. An overall subdivision of
surfactants into one group representing monopolar species and the other consisting
of multipolar ones is also helpful. Surfactants play a twofold role in flotation:
by adsorbing at the mineral (solid)–water (liquid) interface, they make the surface
of selected minerals hydrophobic in character (the reagents functioning in this way
are called collectors); they influence the kinetics of bubble–mineral attachment
The latter surfactants are customarily referred to as frothers, but their frothing
abilities are not the most important characteristic. Since flotation surfactants are, in
general, supplied to the interfaces through the aqueous solution phase, it is mainly
those reagents that are somewhat water-soluble are used in flotation. The
surfactants of particular importance to flotation may be conveniently grouped

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into:

(i) monopolar; and

(ii) multipolar.

Each group is subdivided into three classes in order to facilitate the discussion of
their characteristic behavior in aqueous solutions and during adsorption at
interfaces:

(i) thio compounds, which act mainly as collectors for metallic sulfides;
(ii) non-thio, ionizable compounds, which may act as both collectors and
frothers; and
(iii) nonionic compounds, some of which act mainly as frothers, while others
act as depressants, flocculating agents, and even as activators (collectors)

2.2.1.1 Frothers

An adequate froth is essential for flotation since it has to bear the mineral and
survive until the constituent bubbles pass out of the pulp. Following separation, the
froth should not be so persistent as to be resistant to destruction when sprayed. It
must possess elasticity for it must not break under the disturbance it controls
during its ascent to the surface, otherwise its mineral load would be lost. On
reaching the top of the pulp of the cell, a definite thickness of froth has to be
maintained to allow cleaning of the floated material to occur. Mechanically
entrained gangue particles will tend to escape with the draining liquid. With stiff,
rigid, and stable froths an additional spray of water over the top of the froth may
facilitate the cleaning action by drainage. Froth becomes stabilized by hydrophobic
solids when they adhere to the air–water interface so closely that the draining of
the liquid is restricted. If, in addition, extensive flocculation of particles takes
place, fairly thick layers of interlocked particles are formed at each of the two
air–water interfaces separating the bubbles. There are requirements for or
surfactant to serve as a good flotation frother. The primary purpose of a frother

2
addition is to change drastically the kinetics of particle–bubble attachment. It
achieves this feat by ensuring that the thinning of the liquid film between the two
colliding particulates, the particle and the bubble, and the rupture of the thinned
film (with the necessary establishment of the particle-bubble attachment area) can
occur within the collision time. Secondary requirements pertain to ensuring a
proper degree of stability of the aggregate particle–bubble aggregate and allowing
most (or preferably all) of the mechanically entrapped (and weakly adhering)
particles of unwanted minerals to escape with the draining liquid. It may be
pointed out that the stability of the particle–bubble aggregate and the stability of
the mineralized froth formed during the draining process atop the pulp in the cell
are not the same. The former is involved with adhesion and the latter with cohesion
behaviors within a mixed liquid–particle film. The mineralized froth should have a
restricted degree of stability; it should be stable enough to overflow in cell without
losing the attached solid particles, but should break down following entry into the
launder. The frother should not in itself be a strong collector, especially of minerals
meant for drowning. It should work in the presence of the other reagents necessary
for flotation. The frothers must be soluble in water to some extent; otherwise they
would be distributed very unevenly in an aqueous solution, with the result that
their surface activity would not be fully effective or exploited. There are three
main groups of reagents employed by the mineral industry as frothers (Figure 2.24)

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 2.2.1.2 Collectors

Once the stability of the bubbles has been assured by the use of frothers, it
becomes necessary to work on the mineral surfaces. These must be made
hydrophobic. Most minerals are ionically or covalently bonded, which explains the

4
fact that they are hydrophilic. Surfactants capable of adsorbing in such a manner
that the solid surface is converted from hydrophilic to hydrophobic in character are
referred to in flotation systems as “collectors”. They are the most critical of the
flotation reagents. It may be recalled that if the mineral is to be nonwetted by
water, θ must be greater than 90°. Then γAM < γMW. To lower γAM, an
extraneous addition adsorbs at the mineral–air interface must be added. This must
not lower γWM and must, therefore, present a surface which has a repelling action
on water. Such a substance is the “celebrated collector”, this is chemically best
described as a heterogeneous (heteropolar) compound that contain a functional
inorganic (polar) group coupled with a hydrocarbon chain (nonpolar end). In
general, the polar group is the portion of the collector molecule that adsorbs on the
mineral surface, while the nonpolar end, being nonionic in nature, provides
hydrophobicity to the mineral surface as a result of collector adsorption. In effect,
the nonpolar ends of collectors are oriented towards water, and this is responsible
for imparting hydrophobicity to the particles. Collectors and frothers bear the
similarity that both are heteropolar in nature. The difference between them lies in
the fact that the polar groups of collectors have an affinity for the particular
mineral of interest, whereas the polar groups of frothers have an affinity for water
only. These characteristics have been depicted in Figure 2.25. The collectors are
seen to have two functional “ends”, one ionic, which is adsorbed at the mineral
surface by chemisorption (chemical reaction with the ions of the mineral surface)
or by physical adsorption (electrostatic attraction to the mineral surface), and the
other an organic chain or group, nonionic in nature, which has provided the
hydrophobic surface to the mineral. In a situation where different minerals are
present, if the collector can be made to adsorb specifically on one mineral rather
than on the others present, this mineral can be rendered nonwettable and can be
floated selectively from the other minerals. This represents a selective flotation
5
process. It is important to add that collectors are generally added in small amounts
just to provide a monomolecular layer on the substances concerned. Addition of
increased amounts, apart from cost, may lead to co-float other substances, a
welcoming situation especially when selectivity is desired. It is the experience of
practioners of flotation that it is always more difficult to remove a collector that is
already adsorbed than to forestall its adsorption

Collectors classification :

1- cationic- if the part which impart water repellency to the mineral surface
carries a negative charge
2- anionic - if the part which impart water repellency to the mineral surface
carries a positive charge Collectors are heteropolar that means one portion is
polar and other is non polar.
Examples of collectors : Anionic collectors : potassium or sodium ethyl
xanthate, dithio phosphate, fatty acids
Cationic collectors: fatty amines aceates

6
 Figure 3. Adsorption of anionic collector onto a solid surface. The anionic
portion is responsible for the attachment of the collector molecule to the
surface, while the hydrophobic part alters the surface hydrophobicity.

Collectors

Non- Ionizing Ionizing

Anionic Cationic

Sulfhydr
Oxyhydryl
l

Carboxylic Sulfates Sulfonates Xanthates Dithiophosphates

Figure 4. Basic collector types, after Glembotskii et al. (1972). In the

structures, “R” represents a hydrocarbon chain, different collectors will use
different hydrocarbons for “R”

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  Non-Ionizing
o Non-polar hydrocarbons that do not dissociate in water.

 Cationic
o Based on pentavalent nitrogen cation.

 Carboxylic
o Sodium oleate and fatty acids with this polar group occur in
vegetable oils. Collector for hematite and other metal oxide
minerals. Strong collector, low selectivity.

 Sulfates and Sulfonates

o Less-used than fatty acids. Less collecting power, higher
selectivity.

 n is tetravalenXanthates and Dithiophosphates

Carbot, has four bonds; phosphorus is pentavalent with five bonds. Sulfur atoms
chemically bond to sulfide mineral surface.

Modifiers or Regulator :

They modifies the action of collector either by enhancing or by reducing its water
repellent effect on the mineral surface . They make collector action more selective
towards certain mineral

1- activator – it help in reactivate or increase the susceptibility to flotation of

some mineral that has been depressed ex- cuso4 is a standard activator for
sphalerite
2- pH regulator: optimum result only in a particular ran ph value of the pulp
.for this reason proper ph control of the pulp is of greater importance. ex-
,soda ash, and h2so4
3- - dispersant :sometimes the gangue may be of such nature that it flocculates
to such an extent which may interfere with efficient flotation of the desired
mineral .

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 A dispersant or a dispersing agent or a plasticizer or a superplasticizer is
either a non-surface-active substance added to a suspension, usually a
colloid, to improve the separation of particles an settling or clumping.

figure 2.27 Classification of flotation reagents–regulators.