Separation of

Ions by
Fractional
Precipitation
NAVARRO, PRINCESS T.
MAED – GENERAL SCIENCE
 Learning
Objectives:
• At the end of the lesson, the students shall be
able to:
1. Describe Fractional Precipitation.
2. Calculate the selected ions
precipitated/remained on given
concentrations.
3. Use solubility constant to calculate precipitate
form on given the concentrations.
 Definition of Terms
• Ion - any atom or group of atoms that bears
one or more positive or negative electrical
charges.

• Precipitates - are insoluble ionic solid

products of a reaction, formed when certain cations
and anions combine in an aqueous solution.
 Symbol
Ksp - solubility
product constant
 Fractional
Precipitation
• Fractional precipitation is
a technique that
separates ions from
solution based on their
different solubilities.
 Fractional
Precipitation
• a method of separating a mixture of 
substances by means of their gradual
precipitation from a  solution. 
• The possibility of quantitative separation 
of a mixture depends on the ratio of  the 
original concentrations of compounds being 
precipitated and on the values of their 
solubility product.
 Sample Problem No.
1
1. A solution has 0.020 M both
Cd 2+ and Ni 2+. When you add
S2-, CdS and NiS will precipitate.
Question:
a. Which compound precipitates first?

b. When the 2nd compound begins precipitating,

what will be the concentration of the cation
precipitated first?
The equilibrium equations and the equilibrium
constant expressions of interest are:

1. CdS(s) Cd 2+
+ S 2-

Ksp = [Cd ] [S ] = 3.6 x 10

2+ 2- -29

2. NiS(s) Ni 2+
+ S 2-

Ksp = [Ni ] [S ] = 3.0 x 10

2+ 2- -21
Cd 2+ Ni 2+

I. What concentration of S2- is

needed for each cation to
precipitate?
I. Write the equilibrium equation
of CdS.
1.) Ksp = [Cd2+] [S2-]
II. Follow the equilibrium equation.
Let (s) be the missing value.

2.) 3.6 x 10-29 = (0.020) (s)

III. Substitute the given
values.
Given: Ksp CdS = 3.6 x 10-29
2+ = 0.020
[Cd ]
3.) 3.6 x 10 = (0.020) (s)
-29

s= _3.6X10 -29

0.020
3.) s = _3.6X10 -29

0.020

[S ] = 1.8 X 10 M
2- -27
Question:
a. Which compound precipitates
first?
Let’s find the Molar Concentration
of Cd
1.) Ksp = [Cd ] [S ]
2+ 2-

2. ) 3.6 x 10-29 = (s) (1.8 X 10-27 M)

3.) s = 3.6 x 10 -29

1.8 X 10-27 M
[Cd] = 2 X 10 M -2
Find the Molar Concentration of
Ni
1.) Ksp = [Ni2+] [S2-]
2.) 3.0 x 10-21 = (s) (1.8 X 10-27 M)
s = 3.0X10 -21

1.8 X 10 -27

[Ni] = 1.67 X 10 M 6
Question:
a. Which compound precipitates first?
A. 2 X 10 M Cd
-2

B. 1.67 X 10 M Ni6

Since a much lower [S2-] is needed to

begin precipitating the Cd2+, Cd be the
first to precipitate.
b. When the 2nd compound begins precipitating,
what will be the concentration of the cation
precipitated first?

Cd Ni
b. When the 2nd compound begins precipitating, what will
be the concentration of the cation precipitated first?

1. ) Ksp = [Cd ] [S ]
2+ 2-

2. ) 3.6 x 10-29 = (s) (1.8 X 10-27 M)

3. ) s = 3.6 x 10 -29

1.8 X 10-27 M
[Cd] = 2 X 10 M -2
Sample Problem No.
2  is added slowly
• A 1.0 M solution of BaCl2
to a solution that is 1.0 x 10¯4 M in sodium
sulfate, Na2SO4 and 1.0 x 10¯4 M in
sodium selenate, Na2SeO4.
The Ksp for
• BaSO4 is 1.1 x 10¯10 
• BaSeO4 is 2.8 x 10¯11
Sample Problem No.
2
• What is the approximate
percentage of one anion has
precipitated at the point which the
second anion just begins to
precipitate? The Ksp for
• BaSO4 is 1.1 x 10¯10 
• BaSeO4 is 2.8 x 10¯11
a) What is [Ba2+] when BaSO4 begins to precipitate?

1.) Ksp = [Ba2+] [SO4]

2.) 1.1 x 10¯10 = (s) (1.0 x 10¯4)

3.) s= 1.1 x 10¯10 

1.0 x 10¯4

[Ba2+] = 1.1 x 10¯6 M

2) At the above [Ba2+], what is the [SeO42¯]?

Ksp = [Ba2+] [SeO4]

2.8 x 10¯11 = (1.1 x 10¯6) (s)

S = 2.8 x 10¯11
[1.1 x 10¯6]

[SeO42¯] = 2.54 x 10¯5 M

3) What percentage of the SeO42¯ has
precipitated?

= [SeO42¯] x 100 %
Original [SeO42¯]
= 2.54 x 10¯5 M x 100 %
1.0 x 10¯4 M

= 25.4 % the amount remaining in solution;

74.6% of the Selenate has precipitated
Sample Problem No.
3
A solution of 0.10 M (each) Ni  and Cu  are
2+ 2+

separated using selective precipitation by the

addition of solid Na2CO3. Assuming no volume
change upon this addition, how much of the
first precipitated ion (in %) remains at the point
where the second ion begins to precipitate?
Sample Problem No.
3
How much of the first precipitated ion (in %)
remains at the point where the second ion
begins to precipitate?
The Ksp for
NiCO3 ⇒ 1.4 x 10¯7
CuCO3 ⇒ 2.5 x 10¯10
1. We begin with the more soluble substance (the larger
Ksp). The less soluble substance will have already
precipitated when the NiCO3 begins to precipitate:

Ksp = [Ni2+] [CO32¯]

1.4 x 10¯7 = (0.10) (s)

s= 1.4 x 10¯7 M
0.10
[CO3] = 1.4 x 10¯6 M when NiCO3 is ready to precipitate.
2. Let us solve for the copper(II) ion still in solution at the
above carbonate concentration:

Ksp = [Cu2+] [CO32¯]

2.5 x 10¯10 = (s) (1.4 x 10¯6)

s= 2.5 x 10¯10
1.4 x 10¯6 M
[Cu] = 1.786 x 10¯4 M in solution at carbonate
concentration
3. What percent of the copper(II) ion is still in
solution when NiCO3 begins to precipitate?

[(Cu] / Orig [Cu] ) X 100 % = 0.1786%

(1.786 x 10¯4 / 0.10) X 100 % = 0.1786%

0.18% of Cu2+ in solution when NiCO3 begins to

precipitate
 Sample Problem No.
4 M NaCl mixture
A 0.207 M NaBr and 0.0870
is going to be treated with AgNO3. Calculate
the % of bromide ion present when the
choride starts to precipitate.

The Ksp for
AgCl is 1.77 x 10¯10
AgBr it is 5.35 x 10¯13
 Sample Problem No.
4
1. Calculate the silver ion concentration when
AgCl (the more soluble) just starts to
precipitate:
Ksp = [Ag+]  [Cl¯]

1.77 x 10¯10 = (s) (0.0870)

s= 1.77 x 10¯10 Ag = 2.0345 x 10¯9 M
0.0870
 Sample Problem No.
4
2. Calculate the bromide concentration at the
above silver ion concentration
Ksp = [Ag+]  [Br¯]

5.35 x 10¯13 = (2.0345 x 10¯9) (s)

s= 5.35 x 10¯13 Br = 2.63 x 10¯4 M
2.0345 x 10¯9
 Sample Problem No.
4
3. Calculate the percent bromide remaining in
solution
[Br] / Orig [Br] X 100 % = 0.127%

(2.63 x 10¯4 / 0.207) X 100 = 0.127%

0.127% Br remaining in the solution.

ACTIVITY
TIME!
 ACTIVITY NO. 1
•  A dilute solution of AgNO3 is added slowly and
continuously to a second solution containing
both Cl¯ and CrO42¯. If the CrO42¯
concentration is 0.010 M when the first trace of
Ag2CrO4 precipitate appears, what is the
concentration of the Cl¯ at that point? (Ksp of
AgCl is 1.77 x 10¯10; Ksp of Ag2CrO4 is 1.12 x
10¯12)
 ACTIVITY NO. 1
The Ksp of
AgCl is 1.77 x 10¯10
Ag2CrO4 is 1.12 x 10¯12)
 ACTIVITY NO. 1
1. Calculate the silver ion concentration
required to just precipitate silver chromate

Ksp = [Ag+]2 [CrO42¯]
 ACTIVITY NO. 1
2. Calculate the silver ion concentration
required to just precipitate silver chromate

Ksp = [Ag+]  [Cl¯]

 ACTIVITY NO. 2
The solubility products of PbSO4 and
SrSO4 are 6.3 x 10¯7 and 3.2 x 10¯7,
respectively. What are the values of
[SO42¯], [Pb2+], and [Sr2+] in a solution
at equilibrium with both substances?
 ACTIVITY NO. 2
1. Which is the more soluble?
What is value of [Pb2+]?
 ACTIVITY NO. 2
2. What is the [Sr2+] when [SO42¯] = 7.937
x 10¯4 M?
 ACTIVITY NO. 2
3. What is the value of [SO42¯]?
 APPLICATIONS AND SUMMARY

• Precipitation reactions are applied to many

sample preparation processes. As mentioned
before, they can be used to remove salts or
specific ions depending on their solubility
equilibria. They can also be used to remove
proteins and other biomolecules from
mixtures.
 REFERENCES
• Kotz, J., Treichel, P., Townsend, J. Chemistry
and Chemical Reactivity. 8th ed. Brooks/Cole,
Belmont, CA (2012).
• Arakawa, T., Timasheff, S.N.  Mechanism of
Protein Salting In and Salting Out by Divalent
Cation Salts: Balance between Hydration and
Salt Binding. Biochemistry. 23, 5912-5923
(1984).
 REFERENCES
• https://chem.libretexts.org/Bookshelves/Gene
ral_Chemistry/Map%3A_General_Chemistry_(
Petrucci_et_al.)/18%3A_Solubility_and_Compl
ex-Ion_Equilibria/18.6%3A_Fractional_Precipit
ation
• https://web.nmsu.edu/~snsm/classes/chem11
6/notes/solubility.html
REFERENCE
• Kolthoff, I. M., and E. B. Sandell. Kolichestvenn
yi analiz, 3rd ed. Moscow-
Leningrad, 1948. (Translated from English.)
• The Great Soviet Encyclopedia, 3rd Edition
(1970-1979). © 2010 The Gale Group, Inc. All
rights reserved.