Solubility Product (Ksp) & Solubility

AzBy (s) <=> zAy+ + yBz-

Solubility product is an equilibrium constant:

Ksp = [A]z[B]y

Solubility: the amount of a substance in moles/liter

or mg/liter that can dissolve in a solution under a
given set of conditions

Solubility does not equal the solubility product, but

the two quantities are interrelated
Factors Affecting Solubility
Temperature
 In general, solubility increases with increasing temperature except
CaCO3, Ca3(PO4)2, CaSO4 and FePO4

Common ion effect

 When a solution contains an ion that is the same as one of the ions
which result from the dissolution of the solid, the solubility of the
solid will be less than that when the solid dissolves in pure water
 Ex: solubility of AgCl (s) in NaCl < solubility of AgCl (s) in water

Complexation
 Complexation will increase solubility
 Ex: Complexation of Cd with OH- (or Cl-) will increase the
solubility of Cd(OH)2 (s)
Removal of Heavy Metals by Chemical Precipitation
Chemical precipitation is one of the most common
methods of heavy metal removal from wastewater.

• Precipitating anions include S=, OH- and CO-3

• These anions are pH dependent therefore

solubility of ppt is also pH dependent

•Complexing anions such NH3, CN and organics

can hinder ppt.
To simplify the computation of precipitation of
the metals , we will be using Caustic Soda
(NaOH) as the source of OH- and pH on the pH
vs. Solubility graph OH- balance will be used for
the computation of the dosage of certain
concentration of NaOH .

See the graph on the next slide.

Explanation :

The optimum pH for the precipitation of

heavy metals using NaOH is the one which
has the lowest solubility. Example for Zn the
optimum pH is 9.5 , for Cd the optimum pH
is 11.0 .
 Example :
Given :

(X ml/min) (Y ml/min)
2% NaOH 15% NaOH

pH = 1.5 A B C D c = mg/L Zn
+ mg/L Cd
Zn = 50 mg/L
Cd = 30 mg/L pH = 9.5 pH = 11.0

200 GPM
a = mg/l b = mg/L
Zn(OH)2 Cd(OH)2
A = Mixer for Zn Precipitation
B = Settling Tank for Zn(OH)2
C = Mixer for Cd Precipitation
D = Settling for Cd(OH)2

Required : X , Y , a , b , c
By OH- balance :
OH- = ( 1 x 10-14 ) / 10-pH gmol/L

Input for Mixer A :

(1 x 10-14 /10-1.5 gmol/L)(200 gal/min)(3.785 L/gal)(17 g/gmol) = 12,869(1 x 10 -12.5) g/min

Output of Mixer A :
(1 x 10-14 /10-9.5 gmol/L)(200 gal/min)(3.785 L/gal)(17 g/gmol) = 12,869(1 x 10 -4.5) g/min

OH- from 2% NaOH :

(X)(0.02)(17/40) = 0.0085X 17 is the MW of OH- and 40 is the MW of NaOH

The resulting equation is :

12,869(1 x 10-12.5) + 0.0085X = 12,869(1 x 10-4.5)
0.0085X = 12,869[(1 x 10-4.5) – (1 x 10-12.5)]
X = 48 ml/min

Note : 1 g = 1 ml for water solution

Input for Mixer B :
(1 x 10-14 /10-9.5 gmol/L)(200 gal/min)(3.785 L/gal)(17 g/gmol) = 12,869(1 x 10 -4.5) g/min

Output of Mixer B :
(1 x 10-14 /10-11 gmol/L)(200 gal/min)(3.785 L/gal)(17 g/gmol) = 12,869(1 x 10 -3) g/min

OH- from 15% NaOH :

(Y)(0.15)(17/40) = 0.06375Y

The resulting equation is :

12,869(1 x 10-4.5) + 0.06375Y = 12,869(1 x 10-3)
0.06375Y = 12,869[(1 x 10-3) – (1 x 10-4.5)]
Y = 202 ml/min
Answers :
X = 48 ml/min
Y = 202 ml/min
a = 75.8 mg/L

from a = (50 – 0.1)(99.4/65.4) 99.4 is the MW of Zn(OH)2 and 65.4 is the At. Wt. of Zn
0.1 mg/L is the solubility of Zn at pH = 9.5 from the graph

b = 39.1 mg/L

from b = (30 – 0.003)(146.4/112.4) 146.4 is the MW of Cd(OH) 2 and 112.4 is the At.Wt. of Cd
0.003 mg/L is the solubility of Cd at pH = 11 from the graph

c : Zn = 0.1 mg/L the solubility of Zn at pH = 9.5 from the graph

Cd = 0.003 mg/L the solubility of Cd at pH = 11 from the graph