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Colloidal chemistry
General size classification of solids in water
Dissolved ( <1 nm)
Colloidal (>1 nm and < 1000 nm)
Impurities in water vary in size by about
-Nano ( 1- 100 nm)
a six orders of magnitude
Suspended (> 1m and < 100 m)
Classification of particles:
OH
OH O O O
Si Si Si Si
O OH
OH O O
Isomorphic substitution
OH
OH O O O
Si Al Si Si
O OH
OH O O
1 3
2. Adsorption of ions onto the particle surface
-preferential adsorption of either positive or negative ion
the adsorbed ions are called peptizing ions
- e.g. oil droplets
3. Ionization of surface sites:
- Ionization of surface functional group
-e.g. Proteins ( ionization of amino or carboxyl
group)
- pH dependent
Plane of shear
Zp
Distribution of potential in
Distribution of charges in the the electrical double layer
vicinity of a colloidal particle
1 5
Zp = zeta potential
4q q = charge on the particle
Zp = = thickness of the zone of influence of the
charge on the particle
D D = dielectric constant of the liquid
Energy barrier
Particle separation
1 6
Coagulation theory
Coagulation: The process of destabilizing forces and
causing the aggregation of the particles
To induce aggregation of colloidal particles
Step1: the repulsion force must be reduced (i.e., the
particle must be destabilized)
Step2: particle transport must be achieved to
provide contacts between the destabilized particles
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How to achieve particle destabilization?
mechanisms involved:
1. double layer compression
2. adsorption and charge neutralization
3. enmeshment in precipitate
4. adsorption and interparticle bridging
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1. double layer compression
Addition of ions having charge apposite to that of the
colloid
Coagulation power varies with valency of the ion Shuzlze
Hardy rule - valid only for indifferent electrolite
coagulation power of cation increased in the ration 1:10:100 as the
valence of the ions increased from 1 to 2 to 3.
A
A Counter ions
Ion conc., n
Energy barrier
Particle separation
rapid agglomeration
Particle separation
Derjaguin and Landau and Verwey and Overbeek (1948) has developed a model to
calculate the conc. of an indifferent electrolyte required to cease coagulation:
According to the model, conc. of the counter ion with charge numbers 1, 2 and 3 should
be
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Adsorption and charge neutralization:
1 13
Destabilization of colloids by enmeshment in a precipitate
Certain metal salts can form precipitate in water. The colloids may serve as
precipitate settle
here, a inverse relationship exist between the coagulant dosage and the
colloidal conc.
1 14
Destabilization by adsorption and inter particle
bridging
Many polymers are capable of destablizing
negatively charged particles
Neither the double layer compression model nor the
charge neutralization model can be used to explain
the phenomenon
Chemical bridging theory (LaMer and Healy (1963))
is useful in explaining the phenomenon
Natural polymers
15
Initial adsorption at
Colloidal optimum polymer dose
particle
Floc formation
Secondary adsorption of
polymer
1 16
Stable floc (no vacant
site)
Excess polymer
Rupture of floc
Floc fragments
Floc
Secondary adsorption of
polymer
1 18
Coagulation in Water Treatment
1 19
Characteristics of most conventional coagulants
Al2(SO4)3.14 H2O
FeCl3
Fe2 (SO4)3
water
Al2(SO4)3.14 H2O Al3+ Al(H2O)63+
Increasing pH
14 H2O
1 23
Understanding the relation between colloidal conc. and coagulant
dosage
Zone 4
Coagulation
region
Coagulant dosage, C
Zone 3 Zone 2
C1
Zone 1
S1 S2 S3 S4
Colloidal conc., S
Colloidal conc.
Zone 1 Zone 4 S4 (>S3)
Residual turbidity
2
Zone 1 Zone 2 Zone 4 Colloidal conc.
S2 (>S1)
Colloidal conc.
Zone 1 Zone 4
S1
Coagulant dosage, C
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Assignments
1 26
Questions for class-room discussion
1 27
Coagulant Aids
Flocs produced during
coagulation should ideally settle Zone 4
rapidly and be resistant to Coagulation
destruction by shearing forces. region
Coagulant dosage, C
Unfortunately, this is not the Zone 3 Zone 2
case with many coagulation
process, especially in the case of
waters low in turbidity or low C1
mineralized waters that are high Zone 1
in color. In such cases, certain
C3
materials referred to as
coagulant aids can be added to
the water to improve floc S1 S2 S3 S4
properties and hence
coagulation.
Colloidal conc., S
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Problem 2: What concentration of alkalinity is
theoretically required to react with an alum feed of
200 kg/ML
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Problem 5: A water with alkalinity of 12 mg/L as
CaCO3 will be treated with alum-lime
coagulation. Alum dosage is 55 mg/L.
Determine the lime dosage needed to react with
alum.
Problem 6: what is the amount of natural
alkalinity required for coagulation of raw water
with dosage of 15.0 mg/L of ferric chloride.
1 31
Determination of Coagulant Dosage
Difficult to calculate the
coagulant dosage
theoretically- normally
determined by simple
JAR TEST procedure.
The optimum dose
determined by the Jar Test
is frequently not same as
that of actual plant.
1 32
Derive a mathematical expression to estimate the effluent concentration (C3) for the reactor configuration given in the Figure 1. Assuming that the reaction rate is firs
Figure 1.
Co C1 C2 C3
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Comparison of Various coagulants
Types of water Alum Ferric salt Polymer Magnesium
Hihg turbidity, Effective for pH 5-7 . Effective for pH 6-7 Cationic polymer very Effective due to
high alkalinity ( Coagulant aid no Coagulant aid no effective high precipitation of
Type 1) Alkalinity - no Alkalinity - no molecular wt best Mg(OH)2
Hihg turbidity, low Effective for pH 5-7. If Effective for pH 6-7. Cationic polymer very Effective and results
alkalinity (Type 2) pH drops-need to add If pH drops-need to effective high increased alkalinity-
alkalinity add alkalinity molecular wt best makes water easier to
stabilize
Low turbidity, high Effective in large dosage- Effective in large Coagulant aids such Effective due to
alkalinity (Type 3) dosage- as clay should be precipitation of
Coagulant aid : yes to added ahead of Mg(OH)2
weight floc and improve Coagulant aid : yes polymer
settling to weight floc and
improve settling
Low turbidity, low Effective in large dosage: Effective in large Coagulant aids such Results in increased
alkalinity (Type 4) sweep flocculation dosage: sweep as clay should be alkalinity, which
flocculation added ahead of makes water easier to
Must add alkalinity to polymer stablize
produce type 3 or clay to Must add alkalinity to
produce type 2 water produce type 3 or clay
to produce type 2
water 1 34
Mechanism of coagulation Field condition
High turbidity and High alkalinity (type 1)
Sweep floc coagulation
Less lowering of pH
Adsorption and charge neutralization less effective
High turbidity and Low alkalinity (Type 11)
Adsorption and charge neutralization
Care should be taken to prevent excessive lowering of pH
Low turbidity and high alkalinity (Type III)
Sweep floc coagulation
Addition of coagulant aid is preferred
Low turbidity and Low alkalinity (Type IV)
Very difficult to treat
Addition of coagulant aid or alkalinity or both required
1 35
Rapid Mixing and Flocculation
Rapid mixing and flocculation units to achieve chemical
mixing and particle transport
Coagulation and Particle transport is interdependent
process
Rapid Mixing
To provide complete mixing of the raw water and coagulants
Proper design of rapid mixing units can reduce coagulant demands
and improved aggregation in flocculation unit (Letterman et al.,
1973)
Devices for rapid mixing baffle chambers; hydraulic jumps and
mechanically mixed tanks.
Most common device is completely mixed tanks detention time
of 2 min and G value of 700/s to 1000/s
36
Non uniform mixing: Problems
37
Types of Rapid Mixers
impeller
Coagulant feed
Square tank with Back mix impellers ( most common configuration
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In-line mixers
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Important design parameter for rapid mixers
Velocity gradient, G (1/sec)
optimum design values G = 700 to 1000/sec
Mixing time, Sec
Typical mixing time 0.5 to 2 min
1 40
velocity gradient varies through the mixing basin Camp and
Stein (1943) proposed a mean velocity gradient G to describe the
average condition
P Qh
G= G=
V = V
G = mean velocity gradient, 1/sec
P = power input, W (N.m/s)
V = volume of mixing basin
= dynamic viscosity, N.s/m2
Q = flow rate of water ( m3/sec)
= weight of water ( kg/m3)
H = head loss ( m) ( head loss due to friction + head loss due to
baffles) 1 41
Flocculation
Particle contact : Mechanisms
Thermal motion (Brownian motion)
Bulk liquid motion (stirring)
Differential settling
Perikintic flocculation or microflocculation
Aggregation of the particle are brought about by random thermal
motion of the fluid molecules (Brownian motion)
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Flocculation contd.
Perikinetic Orthokinetic
t =0
t =t
Bulk Differential
liquid settling
Effective for particle size -0.001 to 1 m
motion
Effective for particle size 1 to 2 m
1 43
dN 2 G d T
0 3
J ok = = 0 2
(N ) 1
dt 3
dN 4kT
0
J pk = = 0 2
(N ) 2
dt 3
Where N0= total conc. of particles in suspension at time t
= collision efficiency factor
K = Boltzmanns constant (1.38 x 10-16 erg/degree)
T = absolute temperature in K
= fluid viscosity (g/cm-s)
G = velocity gradient
d = particle diameter (cm)
Jpk = rate of change of particle conc. by perikinetic flocculation
Jok = rate of change of particle conc. by orthokintic flocculation
1 44
Design parameter Flocculation unit
Gt = 104 to 105
t ranging from 10 to 30 min
Larger G value with short time produce small, dense floc
Low G value with long time produce, lighter and larger
flocs
Reduction in G value from the influent end to the effluent
end results better settling floc.
1 45
A rapid mixing tank is 1 m x 1 m x 1.2 m. The
power input is 746 W. Find the G value.
= 0.00102 Ns/m2 (at 20 0C).
1 46
Design of Paddle Mixers
vp =
p
Power, P = FD x vp =
p
2 2
1/ 2
C D Av 3
2rn
G=
p
vp =
2V 60
FD = drag force, N
CD = Coefficient of drag of paddle moving perpendicular to fluid, 1.8 for flat blades
Ap = cross-sectional area of paddles, m2
vp = relative velocity of paddles w.r.t . the fluid, m/s (0.75 times paddle tip speed, v)
n= no. of revolution per min, rpm
r = distance from shaft to centre line of the paddle,
1 m 47
Design tips
1 48
Problems for practice
1 50
A flocculator is 4.88 m deep, 12.2 m wide, and 24.4 m long. The
flow of the water to the plant is 0.566 m3/s. Rotating paddles are
supported parallel to four horizontal shafts. The rotating speed is 2.0
rpm. The center line of the paddles 1.68 m from the shaft ( mid depth
of the basin). Each shaft is equipped with 6 paddles . Each blade is
25 cm wide and 11.6 m long. Assume the mean velocity of the water
is 28% of the velocity of the paddles and their drag coefficient is 1.9
m. Estimate
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