Quiz # 2 (Equalization/Neutralization) ------- Dec.

12, 2017
Quiz #3 (Coagulation) ---------------------------- Dec. 14, 2017
 ChE 507E
Industrial Waste
Management & Control

04-COAGULATION and FLOCCULATION

Day # 10
Dec. 07, 2017

references: * Water & Wastewater Engineering,

ML Davies, 2011
* Principles of Environmental Engineering,
Davies and Masten, 2004
 04 - Coagulation and Flocculation
Coagulation & flocculation are essential component in conventional water treatment
designed to:
 Remove infectious agents
 Remove. toxic compounds
 Remove precursors to the formation of disinfection products
 Makes water more palatable

The object of coagulation (and subsequently flocculation) is to turn small particles into
larger particles called flocs either as precipitates or suspended solids

For discussion purposes, coagulation means addition one or more chemicals to

condition the small particles for subsequent processing by flocculation, and
flocculation is the process of aggregation of the destabilized particles and precipitation
products.
COAGULATION (an electro-chemical process):
 The suspended/colloidal particles in untreated water carry the same charges,
and repulsion prevents them from combining into larger particulates to settle.
Thus, some chemical and physical techniques are applied to help them settle.
This process is known as coagulation.
 A well known method is the addition of electrolyte. Charged particulates
combine with ions neutralizing the charges. The neutral particulates combine
to form larger particles, and finally settle down.
 Coagulant is a chemical that is added to water to cause particles to coagulate. A
coagulant has 3 important properties:
 Trivalent cation – naturally occuring colloids are most commonly negatively-
charged, hence cations are required to achieve charge neutralization. Trivalent
cations are much mor effective than monovalent or divalent cations as Na+
and Ca++
 Have high charge density
 Non-toxic – for production of potable water, coagulant must be nontoxic.
 Insoluble in a neutral pH range. High concentration of coagulant in treated
water are undesireable, therefore coagulant must be insoluble at pH values
desired.
Particle characteristics:
 Electrical properties – the most important electrical property of colloidal &
suspended particles is their surface charge (which for most particles in water is
negatively (-) charge. This causes particles to remain in suspension without
aggregating for long periods of time, hence cannot be removed by sedimentation.
This charge arises in 4 different ways:
 Ionization – depending on the pH, can accept or donate protons. Example:
pH<<2 pH = 2 pH >>2
-Si – OH2+ <----------> -Si – OH <---------> -Si – O-
 Adsorption – the solute becomes bound to the solid surface.
 Amorphous replacement - Example: in an array of solid SiO2, the Si is placed by
Al (Al+3 has less 1 electron than Si4+), which makes the array negatively charged.
 Structural imperfection – in the formation of mineral crystals, bonds are broken
on the crystal edge leading to the development of a negative charge.
 Electrical double layer – because the particle is negatively charged, it tends to
accumulate positively-charged counter-ions on or near its surface forming a double
layer. The adsorbed layers of cations (Helmholtz or Stern layer) about 0.5 nm thick
is bound to the particle surface by statics forces and adsorption. A loose diffuse
layer forms above and beyond the Helmholtz layer. This double layer has a net (-)
charge over the bulk solution
 Zeta potential – when the charged particle is placed in an electric field, it will
migrate to pole of opposite charge. This movement is called “electrophoresis”, and
as it moves a portion of water near the surface moves with it. The electrical
potential between the shear plane and the bulk solution is called the “zeta
potential”. When the absolute value of the zeta potential is reduced to about 20
mM, rapid flocculation occurs.
 Particle stability:
Particles in water remain stable when there is a balance between the
electrostatics of the charged particles, and Van der Waals (attractive) force.
Because the particles have net (-) charged, repulsion mechanism is controlling.
Physics of Coagulation
There are 4 mechanism employed to destabiliz natutal water suspension:
 Compression of the electric double-layer
If the electric double layer is compressed, the repulsive force is reduced and the
particles will come together as a result of brownian motion and remain attached
due to van der Waals attraction.
 Adsorption and charge neutralization
Hydrolyzed metal salts, prehydrolyzed metal salts, and cationic polymers have
positive charge. They stabilize particles thru charge neutralization.
 Adsorption and interparticle bridging
Polymer chains adsorb od particle surfaces at one or more sites along the
polymer chain. Adsorption is a result of (1.) coulombic-charge interaction,
(2.) dipole interaction, (3.) hydrogen bonding, and (4.) van der Waals forces of
attraction. Other sites on the polymer extend into solution and adsorb on the
surfaces of other particles thus creating “bridges” between particles.
 Enmeshment in the precipitate
With doses exceeding saturation for metal hydroxides, aluminum and iron salts
form insoluble precipitates entrapping particulates. This is hypothesized to be
nucleation of precipitate on a particle surface followed by growth of an
amorphous that entraps other particles.
Alkalinity
 The sum of all titrable bases down to about pH 4.5
 It is found by experimentally determining how much acid it takes to lower the
pH of water to 4.5.
 In most waters, the only significant contribution to alkalinity are the carbonate
species of any free H+ or OH- .
 The total H+ that can be taken up by water containing primarily carbonate
species is:
 Alkalinity = [HCO3-] + 2[CO32-] + [OH-] – [H+]. The OH- and H+] are negligible in
most natural water situation, such that it can be approximated as:
Alkalinity = [HCO3-] + 2[CO32-]
 Below pH of 4.5, all carbonate species are present as H2CO3, and the alkalinity is
negative (due to H+).
 At pH of 8.3, most of the carbonate species are present as HCO3- , and the
alkalinity equals HCO3- .
 Above a pH of 12.3, essentially all of the carbonate species present are [CO32-]
and the alkalinity equals [CO32-] + [OH-]. The [OH-] may not be significant at this
pH.
 By convention, alkalinity is not expressed in molarity units, but in mg/li as CaCO3.
 To convert the species concentration in (mg/li ) to (mg/li as CaCO3):
o (mg/li as CaCO3) = mg/li as the species x [EWCaCO3/EWspecies]
Commonly used Coagulants:
1. Aluminum: Aluminum sulfate(Alum), available commercially as dry or liquid
alum [Al2(SO4)3.14H2O], has an average molecular weight of 594. When alum is
added to water with sufficient alkalinity, it reacts: accordingly as follows:
Al2(SO4)3.14H2O + 6HCO3- <----> 2Al(OH)3.3H2O(s) + 6CO2 + 8H2O + 3SO42-
such that 1 mole of alum added uses 6 moles of alkalinity and produces 6 moles of
CO2. The reaction shifts the carbonate equilibrium and decreases the pH.
However as long as sufficient alkalinity is present, and the CO2 is allowed to
evolved, pH will not drastically reduced. When sufficient alkalinity is not present to
neutralize the sulfuric acid produced, pH will be lowered significantly due to
formation of sulfuric acid.
Al2(SO4)3.14H2O <----> 2Al(OH)3.3H2O(s) + 3H2SO4 + 2H2O
If this 2’nd reaction occurs, lime or sodium carbonate maybe added to neutralize
the H2SO4 formed becuse the precipitate will dissolve.
If pH control is a problem, lime or sodium carbonate maybe added to
neutralize the acid, thereby stabilizing the acid. Two important factors in
coagulant addition are pH and dose. Optimum dose and pH are determined
from laboratory jar tests. The optimal pH range of alum is 5.5 – 6.5, with
adequate coagulation possible at pH between 5 and 8 under some
conditions.
2. Iron: ferric ion can be supplied either as ferric sulfate [(Fe2(SO4)3.7H2O], or ferric
chloride [FeCl3.7H2O]. The properties of iron with respect to coagulation
efficiency, dose and pH curves are similar to those of alum. An example of the
reaction of FeCl3 in the presence of alkalinity is:
FeCl3.7H2O + 3HCO3- <----> Fe(OH)3(s) + 3CO2 +3Cl- +7H2O
and without alkalinity
FeCl3 + 3H2O <----> Fe(OH)3(s) + 3H+ + Cl-

If alkalinity is insufficient, the addition of ferric chloride results in the release

of 3 moles of protons for every mole of ferric chloride added. The release of
protons lowers the pH. Ferric salts have generally wider pH range for effective
coagulation than alum, that is pH ranges from 4 to 9.
Example Problems
Example 1: Water contains 100 mg/li CO32- and 75 mg/li HCO3- , at a pH of 10.
Determine (at 25oC): a.) the exact alkalinity, b.) the approximate alkalinity
Solution:
First convert the units of [CO32-], [HCO3-], [OH-], and [H+] to mg/li as CaCO3.
CO32- = (100 mg/li as CO32-)(EW CaCO3./EWCO32-) = (100)(50/60) = 167 mg/li as CaCO3.
HCO3- = (75 mg/li as HCO3-)(EW CaCO3./EWHCO3-) = (75))50/61) = 61 mg/li as CaCO3
at pH = 10, [H+] = (10-10 moles/li as H+)(1 g/mol)(1000 mg/g)(10-7 mg/li as H+)(50/1)
= 5 x 10-6 mg/li as CaCO3
Ionization of water (or ionic product of water), Kw = [H+][OH-] = 10-14
[OH-] = Kw /[H+] = 10-14/10-10 = (10-4 moles/li as OH-)(17g/mol)(1000mg/g)(50/17)
= 5mg/li as CaCO3
a.) the exact alkalinity
= [HCO3-] + 2[CO32-] + [OH-] – [H+] = 161 + 61 – 0.000005 +5 = 233 mg/li as CaCO3
b.) the approximate alkalinity
= [HCO3-] + 2[CO32-] = 161 + 61 = 228 mg/li as CaCO3 (an error 2.2%)
Example 2: a.) Estimate the amount of alkalinity (in mg/li) consumed from the addition
of 100 mg/li of alum.
Solution:
Al2(SO4)3.14H2O + 6HCO3- <----> 2Al(OH)3.3H20(s) + 6CO2 + 8H2O + 3SO42-
From the equation, 6 moles of HCO3- are consumed for every mole of alum added:
Alum added = (100 mg /li alum)/[(594 g/mole)(103 mg/g)] = 1.68 x10-4 moles/li
Alkalinity consumed = 6(1.68 x10-4 ) = 1.01 x 10-3 moles/li
= (1.01 x 10-3 moles/li)(61 g/mole)
= 6.16 x 10-2 g/li = 61.6 mg/li as HCO3-
Example 3: a.) Estimate the pH of that results from addition of of 100 mg/li of alum to
water with no alkalinity, b.) estimate the amount of NaOH (in mg/li) required to bring the
pH to 7.0.
Solution:
Al2(SO4)3.14H2O + 6HCO3- <----> 2Al(OH)3.3H20(s) + 6CO2 + 8H2O + 3SO42-
From example 2, alum added = 1.68 x10-4 moles/li
From the equation: 3 moles of H2SO4 are produced for each mole of alum added.
H2SO4 formed = 3(1.68 x10-4 moles/li) = 5.04 x 10-4 moles/li
H2SO4 dissociates : H2SO4 <-----> 2H+ + 3SO42-
H+ formed = 2(5.04 x 10-4 moles/li) = 1.01 x 10-3 moles/li
a.) estimated pH: pH = - log[H+] = -log[1.01 x 10-3] = 3.0
At pH 3.0, it is out of range for coagulation.
Using NaOH for neutralization, the reaction is: H2SO4 + 2NaOH ---> Na2SO4 + 2H2O
NaOH required = 2(1.01 x 10-3 moles/li)(40 g/mole)(103 mg/g) = 80.64 = 81 mg/li
Example 4:
A water treatment plant with an average flow = 0.044 m3/s treats its water with alum
[Al2(SO4)3.14H2O] at a dose of 25 mg/li. Alum coagulation is used to remove particulate
matter, reduce concentration of organic matte, and reduce alkalinity of water. If the
organic concentration is reduced from 8 mg/li to 3 mg/li, determine:
(a.) the total mass of alkalinity consumed, and
(b.) the total mass of dry solids removed per day.
Solution
a) Use equation 9-1 to determine the total amount of alkalinity consumed. For every
mole of alum added, 6 moles of alkalinity (bicarbonate form) are removed.
Al2(SO4)3.14H2O + 6HCO3- <----> 2Al(OH)3.3H20(s) + 6CO2 + 8H2O + 3SO42-
Convert the alum dose to molar units using its molecular weight of 594 g/mol.
(25 mg/li)( 0.001g/mg)/(594 g/mol) = 0.00004206 mole alum/li
amount of alum = (0.00004206 mole/li)(1000 li/m3)(0.044 m3/s) (86400s/day)
=159.895 moles/day
 The amount of alkalinity remove (bicarbonate form) = (6)(0.00004206) = 0.000252
mol/li of HCO3- or 2.52 x 10-4 eq/li of alkalinity.
* Total alkalinity removed per day:
(0.000252 eq/li)(0.044 m3/s)(1000 li/m3)(86400 s/day) = 959.4 eq/day
Convert to mass basis: (using the equivalent weight of bicarbonate =
= 1+12+3*16 = 61g/mole = 61 g/eq
(959.4 eq/day)(61 g/eq) = 58.526 g/day = 58.5 kg/day

b) For every mole of alum added 2 moles of solids precipitate is produced, so: the
amount of solids = (2 mols Al(OH)3.3H2O/mole alum)(0.00004206 mol/li alum
= (0.00004206 mole alum/li)(1000li/m3)(0.044 m3/sec)(86400 s/day)(1000li/m3
= 159.895 mol/day.
Converting to mass basis = 159.9 mol/day [2(77.98+54) g/mol] = 42196 g/day
= 42.2 kg/day
The total solids removed includes the organic matter. The total organics removed =
(8 – 3) mg/li = 5 mg/li
Total organic removed per day = (5 mg/li)(0.044 m3/s)(1000 li/m3)(86400 s/day) =
19 kg/day

Total solids removed = 42.2 + 19.0 = 61.2 kg/day

FLOCCULATION (a physico-chemical process):
 The removal of suspended/colloidal particles in water is done by addition of long-
chain organic polyelectrolytes which form flocs as it is added to water.
 The suspended/colloidal solids get entangled/adsorbed into the floc. The flocs
gets bigger as they collide with other flocs and are easier to settle compared to
coagulation.
 Examples of coagulants use: polyacryamines and polyamides whose molecular
weights ranges from 1 x 105 to 6 x 106.