CHEMICAL PRESIPITATION

Presipitation could happen if multiplication of molar

concentration the ions more than solubility-product
constant (Ksp)
Presipitation stages :
- nucleation
- particle growth
Example
CaCO3
Ca2+ + CO32-

[Ca 2 ][CO32 ]
K
[CaCO3 ]
If concentration of solid is considered as a constant Ks,
so ;

[Ca2+][CO32-] = K.Ks = Ksp = 5 x 10 -9 (25 C)

Ksp : solubility-product constant
- if multiplication of concentration molar ion < Ksp
solution is not saturated, no precipitate formed
- if multiplication of concentration molar ion > Ksp
solution is super saturated, precipitate is formed

 Ksp is not enough, need to know factors that affect

chemical precipitation ;
1. Common ion effect ;
repression of the solubility of a substance due to an
excess of one ion result in a decrease in a solubility
Exp: solubility of CaCO3 in pure water is 13 mg/l; in
water containing 100 mg/l alkalinity of CO32- the
solubility only 0,5 mg/l
2. Indifferent electrolyte effect ;
Formation or dissolution of a precipitate always occur
in the presence of indifferent electrolyte. Although the
ions do not participate directly in the solubility
equilibrium reaction, they do affect the behaviour of
the precipitate.

CA (s) C (aq) A (aq)

(K a ) eq (C)(A)
or (K a ) eq m [C] m [A]
can be written as (K c ) eq

( K a ) eq
( m ) 2

concentration of indifferent electrolyte ionic strength

of solution value of activity coefficient value of
(Kc)eq solubility of the solution

3. Other solutes effect ;

a. Competing acid-base equilibria
If anion could form weak acid (CO3-, S2-, PO43-), exp ;
CaCO3(s)

Ca

2+

+ CO3
+
H+

HCO3+
H+
H2CO3
+

If acid added (H ) increase in a solubility

b. Effect of complex ion formation
Complex formation increase in a solubility
c. Effect of hydrolysis;
- metal ion exist in aqueous solution as hydrated ions
(water-bound, exp Al(H2O)63+)
- in aqueous solution complex-forming reactions between
hydrated metal ion with hydroxyl ion occurs lead to the
formation of hydroxocomplexes which contain one or more
metal ions (mono or polynuclear complexes)

EXAMPLE :
Complex formation :
ZnCO3

Zn2+ + CO32+
+
NH3
Zn(NH3)2+
+
NH3

Zn(NH3)22+
+
NH3
Zn(NH3)32+ etc. until Zn(NH3)42+ formed
Hydrolysis :
Following generalized equations is used to to describe hydroxocomplexes
formation for trivalent metals ion (when only mononuclear complexes formed):
1.
2.
3.
4.

Me3+ + OHMe3+ + 2OHMe3+ + 3OHMe3+ + 4OH-

MeOH2+
Me(OH)22+
Me(OH)32+
Me(OH)42+

Since hydrated metal cations are weak acid called cation acids (asam-2
logam), the formation of metal hydroxocomplexes also considered as the
ionization of these cation acids. For trivalent metals ion that forms only
mononuclear complexes :

1.

Me(H2O)63+

Me(H2O)5(OH)2+ + H+

Me3+

Me(OH)2+ + H+

Me3+
Me3+
Me3+

Me(OH)22+ + 2H+
Me(OH)32+ + 3H+
Me(OH)42+ + 4H+

or

2.
3.
4.

These type of ionization occur whenever salts containing metal ions dissolved
in water, since H+ ions are produced resulting solution will be acidic.
increase the solubility & should be considered in solubility calculations
Hydroxocomplexes formation constants for Al and Fe table
A log [spesies] vs pH diagram can be used to describe the effect of metal
hydroxocomplex formation on the solubility. Diagrams will be constructed by
using the plotting equations ;
1. Al(OH)3(s)

Al3+ + 3OHKsp = [Al3+][OH-]3

Log Ksp = log [Al3+] + 3 log [OH-]

Log Ksp = -32,34

dari ionisasi air, diketahui log [OH-] =pH 14
substitusi dua hal tsb di atas didapat :
-32,34 = log [Al3+] + 3pH 42
atau
log [Al3+] = 9,66 3pH

.1)

2. Al3+

Al(OH)2+ + H+
) H
K Al ( OH
Al
2

-5,02 = log [Al(OH)2+] + log [H+] - log [Al3+]

log [Al(OH)2+] = 4,44 2pH

.2)

Dengan cara yang sama didapatkan :

3. 2Al3+

Al2(OH)24+ + 2H+
log [Al2(OH)24+] = 13,05 4pH

4. 6Al3+

Al6(OH)153+ + 15H+
log [Al6(OH)153+] = 10,96 3pH

5. 8Al3+

.4)

Al8(OH)204+ + 20H+
log [Al8(OH)204+] = 8,58 4pH

6. 13Al3+

.3)

.5)

Al13(OH)345+ + 34H+
log [Al13(OH)345+] = 28,19 5pH .6)

7. Al3+

Al(OH)4- + 4H+
log [Al(OH)4- ] = pH 13,91

.7)

Log [spesies] vs pH diagram for the Al(OH)3(s)-H2O system

(equations 1 to 7) is presented bellow.

Fe(OH)3(s)-H2O system can be found in the same way

APPLICATION OF CHEMICAL PRECIPITATION IN

ENVIRONMENTAL ENGINEERING

A. Defluoridation
Defluoridation applicaions:

- water treatment
- wastewater treatment

In wastewater treatment, fluoride is precipitate by adding

lime
Ca(OH)2 + 2HF

CaF2(s) + 2H2O

pH 11 - 12

B. Metals removal
- Mostly metals can be precipitated as metal carbonate &
metal hydroxide, some in the form of metal sulfide
- Need to consider process condition, especially pH to
achieve minimum solubility
- Some metals is amphoter (amfoter), exp ; Cr & Zn

At pH < 7
H+
Cr(OH)3(s) + 3H2O

Cr(H2O)63+(aq)

At pH > 8
Cr(OH)3(s) + 3H2O

Cr(H2O)63+(aq)

For some metals, reduction/oxidation reaction must be

conduct before apply precipitation, exp:
- Fe & Mn removal; Fe2+ & Mn2+ are oxidized first &
then are precipitated as Fe(OH)3 dan MnO2
(oxidator : O3 > MnO4 > Cl2 > O2)
6+
3+
- Cr removal; Cr is reducted as Cr (using NaHSO3 or
Na2S2O5 at pH 2 s/d 3-4), then is precipitated as
Cr(OH)3 at pH 7,5

Attention if wastewater contains CN (cyanide) &

NH3(ammonia). complexes formation increase
solubility more difficult to be precipitated

C. Phosphor removal
- Phosphor can be precipitated using Ca, Fe or Al.
- precipitaion of phosphor as Ca salt is pH depending.
5Ca2++7OH-+ 3H2PO4

Ca5OH(PO4)3+6H20
hydroxyapatite

Solid of Calcium phosphate is slowly formed, by adding

seed, could enhance reaction. The presence of Mg(OH)2
will aid the precipitation of Calcium phosphate

Precipitation of phosphor using Al may produce Al(OH)3

& AlPO4. 1,5 3 mol Al is needed per mol phosphor to
conduct precipitation of P at pH 6 6,5. When water is
alkaly, pH need to be reduced before Al addition to
minimize Al(OH)3 precipitation.

When Fe is used, Fe can be added as FeSO4 or FeCl3.

The dose depends on DO, pH, biologic catalyst and
S & CO3 presence. To precipitate P, 1,5 3 mol Fe3+ per
mol phosphor is needed (at pH 5)

D. Water softening (removal of hardness)

- Precipitation reaction using lime soda ash

1. CO2

+ Ca(OH)2

Penurunan
2. C.
Ca(HCO
Ca(OH)2
3)2 +kesadahan

CaCO3(s) + H2O
2CaCO3(s) + 2H2O

Ca-C

Reaksi presipitasi dengan

kapur 3)soda
abu : 2
3. Mg(HCO
CaCO3(s) + MgCO3 + H2O Mg-C
2 + Ca(OH)

MgCO3

+ Ca(OH)2

Mg(OH)2(s) + CaCO3(s)

4. MgSO4

+ Ca(OH)2

Mg(OH)2(s) + CaSO4

Mg-NC

5. CaSO4

+ Na2CO3

CaCO3(s) + Na2SO4

Ca-NC

- Chemical needed:
(concentration of species in meq/l)

Discription

Lime

Soda Ash

CO2

1x

Ca carbonate

1x

1x

Mg carbonate

2x

Mg non carbonate

1x

1x

Ca non carbonate

 Lime soda process ;

a. Excess lime treatment
To establish optimum precipitation, especially
Mg presipitation, excess lime is added in amount of
35 mg/l CaO (1,25 meq/l)
b. Split treatment
A fraction of raw water is treated in excess-lime
process, and neutralized the excess lime using (part of)
untreated water