8

Ion removal
by chemical precipitation

8-1. Solubility Relationships

As was discussed in Section 7-1, the solubility relationship existing

in a saturated solution between the undissolved salt, BmAn, and its
ions can be represented as

Bm^n(8oiid) ^ mB+ + nA~ (7-12)

and the equilibrium expression as

[B+MA-]" = K. (7-13)

If the ionic activities in a solution are of a magnitude that the ion

product in Equation 7-13 (the term on the left-hand side of the equa
tion) is less than the activity solubility product K„ then the salt BmAn
dissolves either until the total quantity of the salt in the solid state
dissolves, or until the ionic activities reach a magnitude where the ion
product reaches K„ whichever occurs first. On the other hand, if the
ionic activities are such that the ion product is greater than K,, the
salt BmAn precipitates out of solution until the ion product and K,
become equal.
Consider a situation in which a solution initially is undersaturated
with respect to the salt BmAn, that in which all the salt dissolved
is,

is

and exists in an ionic state. to this solution added another solute

If

is

CpA, containing common ion A~, the ion product in Equation 7-13,
a

109
no UNIT PROCESSES OF SANITARY ENGINEERING

[B+]m[j4-]", would be increased proportionately. If CpAq is added in

quantities such that the activity of the common ion A~ increases the
ion product until it equals the solubility product K,, saturation occurs
with respect to BmAn. Further addition of CpAq increases the activity
of A~ and causes precipitation of BmAn with a corresponding decrease
in the activity of B+. This decrease in the solubility of an ionized salt
as the result of adding one of the ionic constituents of the salt to the
solution is called the common ion effect. The common ion effect is most
demonstrable on slightly soluble salts. This effect plays a key role in
the removal of ions from solution by the addition of chemicals.
The solubility concentrations of slightly soluble salts are increased
by a phenomenon commonly referred to as a secondary salt effect.
The activity of a solution is related to the concentration by Equa
tion 7-3,
a — yc

where 7 = activity coefficient (7-3)

In concentrated solutions of electrolytes, the ionic strength is high

and, hence, the activity coefficient is low. (See Figure 7-1). Conse
quently, if for such solutions the activity equilibrium expression for
the salt BmAn is to hold (Equation 7-13), then the solubility concentra
tion has to increase.

8-2. Water Softening

Chemical precipitation is widely used in softening municipal water

supplies. Hardness in water is caused by the ions of calcium, magne
sium, iron, manganese, strontium, and aluminum. These ions combine
with fatty acid radicals introduced by soap to produce undesirable
precipitates. Practically all of the hardness producing elements can be
found in natural waters in some concentration. However, in most
waters only the ions of calcium and magnesium are present in sizeable
concentration and, hence, are of major concern in the majority of
softening processes.
The anions generally present with calcium and magnesium are bicar
bonate and sulfate. Occasionally, significant quantities of nitrates and
chlorides are present also. The calcium ions are removed by intro
ducing, directly or indirectly, the normal carbonate ion. Since the
equilibrium constant for calcium carbonate is

[Ca++][C03-] = K, = 4.82 X 10-9 (8-1)

the solubility is quite low and calcium carbonate is precipitated from

solution.
ION REMOVAL BY CHEMICAL PRECIPITATION 111

The normal carbonate ion is produced by adding hydroxy] ions to

the solution.The latter react with the bicarbonate ions.

HC03- + OH- ^ COr + H20 (8-2)

If the concentration of bicarbonate in solution is insufficient to pro

duce the number of normal carbonate ions required to precipitate out
with the calcium ions present, then normal carbonate ions are introduced
directly to the solution through the addition of a soluble carbonate.
Since the solubility of Mg(OH)2 is quite low,

[Mg++][OH-]2 = K„ = 5.5 X 10-12 (8-3)

the magnesium ion too can be removed by adding hydroxyl ions to the
solution.
Mg++ + 20H- ^ Mg(OH)2 (8-4)

The removal of calcium and magnesium ions from solution must be

compensated for by the addition of other cations in order to maintain an
ionic balance in the system. This is generally performed by adding a
non-hardness producing cation, such as sodium. The change in the
ionic composition of a particular water brought about by softening
might be represented as follows:

Before Softening After Softening

Cations Anions Cations Anions

Ca++ HC03- 3Na+ S04-
Mg++ SO- Cl-
ci-

Softening reactions are not complete so there would still be some

bicarbonate, calcium, and magnesium ions remaining in solution after
softening.
Carbon dioxide in solution (H2C03) dissociates to form hydrogen and
bicarbonate ions. (See Figure 7-2). Both species of ions react with
hydroxyl ions. The overall reaction can be expressed as

H2COa + 20H- ^ CO3- + 2H20 (8-5)

When the hydroxyl ion is added to soften water, the demand exerted by
dissolved carbon dioxide must be taken into account when computing
quantities to be added.
The hydroxyl ion is conveniently and most economically provided by
adding hydra ted lime Ca(OH)2 to the water. The normal carbonate
ion is generally introduced by adding soda ash Na2C03. At normal
112 UNIT PROCESSES OF SANITARY ENGINEERING

temperatures the softening reactions are slow and incomplete. How

ever, reactions are considered to go to completion when computing
quantities of lime and soda ash required for the process.
Precipitation of calcium carbonate and magnesium hydroxide is facili
tated by contacting the water solution with slurries of previously precipi
tated calcium carbonate and magnesium hydroxide. In some softening
processes, alum or some other coagulating agent is used to hasten the
sedimentation of the precipitates resulting from the process.
The precipitation of magnesium hydroxide is aided by adding lime
in excess of the quantity computed for the process. The excess hydroxyl
radical exerts a common ion effect on the solubility of magnesium
hydroxide. The equilibrium concentration of both magnesium and cal
cium ions as a function of pH is illustrated in Figure 8-1. It is to be
noted that maximum insolubility of magnesium hydroxide is reached
at a pH value of about 10.4. As a rule, about 1 g me/liter of lime is
required to elevate the pH to this value.

140 1 1 1
—i
1 1 1

FIGURE 8-1. Equilibrium concentrations of calcium and magnesium ions as a

function of pH. After Fig. 6, p. 94, S. T. Powell, Water Conditioning for Industry,
McGraw-Hill, New York, 1954.
ION REMOVAL BY CHEMICAL PRECIPITATION 113

The softening reactions are accelerated and driven further to com

pletion by increasing the temperature of the water to approximately
212 °F. The latter practice, called the hot process, is used in the soften
ing of industrial water supplies.
Plants used for the lime-soda ash softening of municipal water supplies
are of two types. One type consists of a sludge contact unit in which
a sludge blanket is utilized to facilitate the precipitation reaction.
Water flowing into the unit is mixed with a slurry of previously precipi
tated solids, lime, soda ash, and coagulent. Softened water separates
from the sludge blanket, rises, and is collected at the surface. Units
are designed on the basis of surface loadings which generally range
from 1 to 3 gal per square foot per minute. Equipment for such units
are almost all proprietary.
The other type of plant consists of a flash mix unit, a flocculation
basin, and a sedimentation basin. Softening chemicals and coagulent
dosage are added to the water in the flash mix unit. Following a short
period (1 to 3 minutes) of violent agitation, the water is subjected from
30 to 60 minutes to gentle stirring to promote the growth of precipitate
and coagulent flocs. From the flocculation basin, the water flows to
a sedimentation basin having a retention time of from 2 to 6 hours.
The settled water is then filtered through a rapid sand filter.

EXAMPLE 8-1
An analysis of a water yielded the following information:

Carbon dioxide 0.4 g me/liter

Total alkalinity 2.0 g me/liter
Total hardness 4.0 g me/liter
Magnesium hardness 1.0 g
me/liter

Calculate the necessary quantities of hydrated lime and soda ash

required to soften the water.

Solution
1. Assuming that the bicarbonate alkalinity is equal to the total
alkalinity (an assumption that is approximately true for most natural
waters that are hard), the quantity of lime required is

C02 0.4 g me/liter

HCOr 2.0 g me/liter
Mg++ 1.0 g me/liter
Excess to elevate pH 1.0 g me/liter

4.4 g me/liter

For each million gallons of water, 4.4(74.1/2) 8.34 = 1,360 lb.

114 UNIT PROCESSES OF SANITARY ENGINEERING

2. The soda ash required to furnish the additional normal carbonate

ion required to precipitate out all original and applied calcium ions in
solution is

Initial Ca++ in water 3.0 g me/liter

Ca++ added to provide OH~ for Mg++ 1.0 g me/liter
Ca-i"i- added to provide OH~ for elevat
ing pH l.Ogme/liter
5.0 g me/liter

Normal carbonate formed from HC03~ 2.0 g me/liter

Normal carbonate formed from C02 0.4 g me/liter
2.4 g me/liter

2.6 g me/liter

For each million gallons of water, 2.6(106/2) 8.34 = 1150 lb.

8-3. Iron and Manganese Removal

Iron and manganese impart the same characteristics to water, have

approximately the same chemical behavior, and are removed from water
by the same processes. For this reason, the discussion which follows
deals primarily with iron, the most commonly occurring of the two
elements.
At normal pH values, iron in the ferrous state is quite soluble. When
oxygen is added to a system containing the ferrous ion, the latter is
oxidized to the ferric state.

2Fe++ + l£02 + 3H20 -> 2Fe(OH)3 (8-6)

Since

[Fe+++][OH-]3 = K, = 4 X lO"38 (8-7)

iron precipitates out as ferric hydroxide.

However, even with an abundant supply of oxygen, the precipitation
of ferric hydroxide is impeded when the pH of the water is less than 7.8.
The pH effect on the solubility of iron and manganese is illustrated in
Figure 8-2.
Iron removal generally results from softening water with lime or soda
ash. Removal is also accomplished by aeration. Aeration provides
oxygen for the oxidation of the ferrous to the ferric ion. Furthermore,
when water contains carbon dioxide in excess of the amount required
for carbonate equilibrium, aeration removes some of the excess, thereby
elevating the pH of the water. If aeration fails to elevate the pH
ION REMOVAL BY CHEMICAL PRECIPITATION 115

above 7.8, lime or soda ash must be added to induce maximum precipita
tion of ferric hydroxide.
Aeration for the purpose of iron removal is performed with dispersed
aerators, sprays, cascading devices, and coke trays. The latter con
sists of a series of trays, one over the other, filled with coke. Water
applied to the top tray trickles over the coke from the top tray to the
bottom. The coke besides providing a maximum of contact surface
between the air and water also serves to catalyze the oxidation process.
Following aeration, provision must be made for the separation of the
iron precipitate from the water.

_ 0.75
a;

"Ei
E

o 0.50

rtanganic ion
■o
i 0.25

Ferric io n
■
1
0.00
7.5 8.0 8.5 9.0 9.5
PH
FIGURE 8-2. Removal of manganic and ferric ion in treated water at various pH
values. Based on data presented in R. S. Weston, "Manganese in Water, Its Occur
rence and Removal," J. AWWA, 24 (1932), 1272.