CHE 1316

Laboratory Measurements & Techniques

LECTURE 6
Gravimetric Methods
Precipitation Reactions
Theory of Precipitation

www.baylor.edu/chemistry
 Gravimetric Methods

1. Volatilization:
Reaction evolves a gas
Collect and weigh gas OR
Weigh sample before and after rxn

2. Precipitation:
Reaction forms sparingly soluble salt
Filter, dry, and weigh
 Precipitation Reactions
Brown, Lemay, and Bursten: Sections 17.4-17.5

• Barium Iodate in Water:

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)

saturated solution contains excess solid

• At Equilibrium:
Ksp = [Ba2+][IO3−]2

• Solubility Product (in general):

for salt MxAy: Ksp = [M]x[A]y
 Precipitation Reactions
How many grams of Ba(IO3)2 dissolve in 500 mL of water
At 25 C if Ksp = 1.57 × 10−9

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)

S S 2S

Ksp = [Ba2+][IO3−]2 = [S][2S]2 = 1.57 × 10−9

4S3 = 1.57 × 10−9

S (molar solubility of Ba(IO3)2) = 7.32 x 10−4 mol L−1

You must learn how to use your calculator!

 Precipitation Reactions
How many grams of Ba(IO3)2 dissolve in 500 mL of water
At 25 C if Ksp = 1.57 × 10−9

S = 7.32 × 10−4

mmol Ba(IO3)2 = S × Vml = (7.32 × 10−4)(500 mL) = 0.366 mmol

Wt. Ba(IO3)2 = 0.366 mmol × 487 mg mmol−1 = 178 mg  0.178 g

This could cause a significant error in a gravimetric analysis

 Common Ion Effect
The presence in solution of an excess of one ion from a slightly
soluble ionic substance depresses its solubility (more complete
precipitation).
How many grams of Ba(IO3)2 dissolve in 500 mL of 0.0200 M
Ba(NO3)2 at 25 C if Ksp = 1.57 × 10−9

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)

S S + 0.0200 2S

[Ba2+][IO3−]2 = (S + 0.0200)(2S)2 = 1.57 × 10−9

Assumption: S << 0.0200 M

(0.0200)(2S)2 = 1.57 × 10−9  S = 1.40 × 10−4 M

Wt. Ba(IO3)2 = 1.40 × 10−4 M × 500 mL × 487 mg mmol−1 = 34.0 mg

 Theory of Precipitation

• Precipitation occurs when the ion

product exceeds the solubility product
For MxAy: CMx × CAy > Ksp

• Two Steps in Precipitation

1. Nucleation: small groups of ions form

stable solid masses (nuclei)
2. Particle Growth: ions from solution add
on to nuclei to form particles
 Theory of Precipitation

The amount by which the ion product exceeds the

solubility product is expressed qualitatively as
supersaturation.

Supersaturation = Q − S

Q: instantaneous concentration

S: equilibrium concentration (molar solubility)

• Large supersaturation favors nucleation

• Small supersaturation favors particle growth

 Minimizing Supersaturation

Supersaturation = Q − S

1. Elevated Temperature (increase S)

2. Dilute Solution (decrease Q)

3. Slow Addition, good stirring

(decrease Q)
 Colloidal Particle in Solution
Positively charged primary adsorption
layer on colloidal particle

NO3−
NO3− H+
H+ NO3−
NO3−
Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+
NO3−
Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+

NO3− Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+

NO3−
Cl− Ag+ Cl− Ag+ Cl− Ag+
NO3−
H+ Ag+ Ag+
NO3−
H+
− Counter-ion
NO3
layer of solution
with excess anions Ag+

Colloidal solid
Homogeneous solution
(charges balanced)

Coagulation: aggregation of colloidal particles into larger filterable masses

 Impurities in Precipitates

• Adsorption: Excess precipitant ions and

counterions adsorbed on the crystal
surface (favored by small particles)

• Mixed Crystal Formation: A normally

soluble compound precipitates in the
presence of an insoluble compound.

• Occlusion and Mechanical Entrapment:

Ions from the counter-ion layer or pockets
of liquid trapped inside the crystal.
 Precipitate Purification

1. Digestion: allow precipitate to remain in

contact with the solution from which it
was formed at elevated temperature.
• Small particles dissolve faster
• Ions reprecipitate on larger particles
• Increase purity

2. Wash: soluble impurities removed by

washing.

All compounds have some solubility!

 Suggested Problems

• Problem Set 1 (lab manual):

8, 13, 14, 18, 22, 24, 29

• Problem Set 3 (lab manual):

20-24
• Problem Set 6 (lab manual):
6-9, 12