MECHANISM OF COAGULATION

 In water treatment plant, plain sedimentation is used to remove suspended settleable

particles of larger size (greater than 50µm).
 Very fine suspended particles and colloidal matter of size less than 50µm cannot settle
in plain sedimentation tank in ordinary detention period.
 They can, however, be settled by increasing their size by changing them into
flocculated particles.
 For this, certain chemical compounds called coagulants are added to water which on
thorough mixing form floc.
 The fine particles get attracted and absorbed in the floc, forming the bigger sized
flocculated particles that can settle easily.
 The colloidal suspension has very large specific area (surface to volume ratio), due
to their very small size. Hence the surface phenomenon predominent over the mass
phenomenon.
 The most important surface phenomenon is the accumulation of electric charge at
the particle surface.
 In most surface water, colloidal surfaces are negatively charged.
 Ions contained in the water near the colloid will be affected by the charged surface.

 The first layer of cations (+ve ions) attracted to the –vely charged surface is “bound”
to the colloid and will travell with it.

 Other ions in the vicinity of colloid arrange themselves with greater concentration of
+ve (or counter ions) being closer to the colloidal surface.

Fig. 1 Charge System in a Colloidal Suspension

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Mechanisms of Coagulation
  When two colloids come in close proximity, there are two forces acting on them
i. Electrostatic Force (FE): Act to repel particles, thus preventing contact
FE α 1
d2

ii. Van der Waals Force (FV): An intermolecular attrective force, support contact
FV α 1
d6
(Water molecules in liquid water are attracted to each other by Van der waals
force/bound)
 FV decreases more rapidly than FE with increase in distance.
 FV is stronger force at closer distance.

Fig. 2 Force Fields Between Colloids of Like Charge

The above figures shows the sum of two forces (FE & FV) as they relate to one colloid in
close proximity to other.
 The net force is repulsive at greater distances and becomes attractive only after
passing through a maximum net repulsive force, at some distance between the
colloids.
 The maximum net repulsive force is called the Energy Barrier.
 Once the force becomes attrective, contact between the particles take place.
 A means of overcoming the energy barrier must be available before agglomeration of
particles can occur.

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Mechanisms of Coagulation
  The Brownian movement (random movement of smaller colloids because of milecular
bombardment) may produce enough momentum for particles to overcome the energy
barrier.
 Mechanical agitation of the water may impart enough momentum to large particles to
move them across the energy barrier.
 However, these forces are too slow to be efficient in water purification and neither
results in collision of medium sized colloids.
 The other means of agglomeration is chemically coagulating the colloids into clusters
or flocks, which are large enough to removed by gravity settling.

 The mechanisms of coagulation include

1) Ionic layer compression,
2) Adsorption and charge neutralization,
3) Entrapment in a flocculent (Sweep coagulation) and
4) Interparticle bridging
Ionic layer compression

 The quantity of ions in the water surrounding a colloid has an effect on the decay
function of the electrostatic potential.
 A high ionic concentration compresses the layers composed predominantly of counter
ions toward the surface of the colloid.
 If this layer is sufficiently compressed, then the Van der Waals force will be
predominant across the entire area of influence, so that the net force will be attractive
and no energy barriers will exist.
 An example of ionic layer compression occurs in nature when a turbid stream flows
into the ocean. There the ion content of the water increases drastically and coagulation
and settling occur. Eventually, deposits (deltas) are formed from material which was
originally so small that it could not have settled without coagulation.
 Although coagulants such as aluminium and ferric salts used in water treatment
ionize, at the concentration commonly used, they would not increase the ionic
concentration sufficiently to effect ion layer compression.

Adsorption and charge neutralization

 The nature, rather than the quantity, of the ions is of prime importance in the theory
of adsorption and charge neutralization.

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Mechanisms of Coagulation
  Although aluminium sulphate (alum) is used, as in the example given below, ferric
chloride behaves similarly.
 The ionization of aluminium sulphate in water produces sulphate anions (SO42-) and
aluminium cations (Al3+).
 The sulphate ions may remain in this form or combine with other catoins.
 However, the Al3+ cations react immediately with water to form a variety of
aquametalllic ions and hydrogen.

Al3+ + H2O  AlOH2+ + H+ (1)

Al3+ + H2O  Al(OH)2 + + 2H+ (2)
3+
7Al + 17 H2O  Al7(OH)174+ + 17H+ (3)
- - - - - - - -
Al3+ + 3H2O  Al(OH)3 + 3H+ (4)

 The aqua metallic ions formed become a part of the ionic cloud surrounding the
colloid and, because they have a great affinity for surfaces, are adsorbed onto the
surface of the colloid where they neutralize the surface charge.
 Once the surface charge has been neutralized, the ionic cloud dissipates and the
electrostatic potential disappears so that contact occurs freely.

Sweep coagulation
 The last product formed in the hydrolysis of alum is aluminium hydroxide, Al(OH)3 .
 The Al(OH)3 forms amorphous, gelatinous flocs that are heavier than water and
settle by gravity.
 Colloids may become entrapped in a floc as it is form or they may become enmessed
by its stickey surface as the floc settle.
 The process by which colloid are swept from suspension in this manner is known as
sweep coagulation

Interparticle bridging
 Large molecule may be form when aluminium or ferric salts dissociated in water.
 Synthetic polymer may also be use in addition to metallic salts.
 This polymer may be linear or branched and are highly surface reactive.
 Thus several colloids may become attached to one polymer and several of the
polymer-colloids groups may become enmeshed, resulting in a settleable mass.

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Mechanisms of Coagulation