Chapter 8

Gravimetric Methods of Analysis

Gravimetric method is quantitative method

based on determining the mass of sample
precipitation of known composition

Dr. Hermin Sulistyarti

1. Preparation of sample solution
2. Precipitation: Gravimetric precipitating agent
should react specifically or selectively with the
analyte. rR + aA = RrAa (solid)
3. Digestion
4. Filtration and washing
5. Drying, ignition and weighing
6. Computation of results
 Examples of gravimetry
+ –
Ag + Cl = AgCl
Excess AgNO3 [Cl – ] = ?

Ag+ + Cl– = AgCl

1 mol 1 mol 1 mol = 143.321g
AgCl x x mol = 0.4368g
0.4368 g
x = 0.4368 g/143,321 g/mol
= 3.048 ×10–3mol
10.00 ml Cl–
[Cl– ] = 3.048 ×10–3 mol / 10.00ml
= 0.3048 M

T.W. Richards : Nobel Prize-winning research

 Requirements of the ideal product of a
gravimetry:
 1) very insoluble: Low Ksp
 2) easily filterable: large crystal particle
 3) very pure
 4) known and constant composition
 1) Solubility of precipitate
H<0
T   solubility 
Vant Hoff equation:
H>0
log Ksp = –(H / 2.3RT) + J

1/T

Polarity of solvent   solubility 

Hexane CCl4 Benzene Toluene CHCl3 Pyridine HAC Acetone EtOH MtOH CH3CN Water

Non-polar Polar
2) Filterability: large particle size 
Precipitation mechanism:
1. Induction period (few min): A precipitant (counter ion) is
added
2. Nucleation: form small aggregates: Nucleus has 4 molecules
3. Particle growth: to form larger crystal
4. Adsorption
5. Electrostatic attraction: to coalesce electric double layer
 Techniques to decrease supersaturation
(promote particle growth) 
1. T   S   Q   degree of relative supersaturation 
2. The precipitant is added slowly with vigorous mixing.
3. Low concentrations of analyte and precipitant
4. Low pH (acidic)

Relative supersaturation = (Q–S)/S

Crystal

Rate
Von Weimarn equation, where: growth
Q = actual concentration of solute Nucleation
supersaturation
S = concentration at equilibrium
(Q– S)/S
Increase particle size
Coagulation of colloids
Heating  particles’ kinetic energy
Silver chloride lattice
Increase the concentration of electrolyte(HNO3)

Primary adsorption layer

Counter ion layer

Electric double layer

The electrical double layer of a
colloid consists of a layer of charge
adsorbed on the surface of the
particle (the primary adsorption
layer) and a layer of opposite charge
(the counter-ion layer) in the
solution surrounding the particle.
Increasing the electrolyte
concentration has the effect of
decreasing the volume of the
counter-ion layer, thereby increasing
the chance for coagulation.
 3. Purification
Treatment after precipitation
Peptization: a process by which a coagulated colloid returns to its
dispersed state.
Self purification : Internal ripening
Ostwald ripening
Digestion : following precipitation, for a period of standing with
heating the precipitate in contact with its mother liquor accelerate
the ripening of crystalline particles.
Washing Mother
Reprecipitation liquor
Precipitation
 Impurities of ppt: co-precipitation
1. Surface adsorption
2. mixed-crystal
formation: inclusions:
impurity ions that A B
randomly occupy
crystal lattice
3. Occlusions: pockets of
impurities that are C D
literally trapped inside the Types of coprecipitation:
growing crystal
A: surface adsorption
4. Mechanical entrapment B: inclusion-isomorphic carrying
C: inclusion-mechanical entrapment in crystals
D: occlusion-mechanical entrapment in colloidal
aggregate.
Homogeneous ppt
Control the supersaturation by using slow generating of
precipitant by means of chemical reaction  enhance particle size
Ex. ppt of ferric formate by using urea and formic acid
NH2CONH2 + 3H2O  CO2 + 2NH4+ + 2OH–
OH– + HCOOH  HCOO– + H2O
3HCOO– + Fe3+  Fe(HCOO)3. nH2O

Aluminum hydroxide formed by

the direct addition of ammonia
(left), and the homogeneous
production of hydroxide (right).
 Drying and Ignition of precipitates
Precipitate form
Ignition (strong heating) is used to change the chemical
form of some precipitate.
Weighing form

Thermogravimetric curve for calcium salicylate.

Effect of temperature on precipitate mass.
 Calculations of gravimetry

Relating mass of product to mass of reactant:

piperazine + 2 CH3COOH  piperazine diacetate
MW 84.121 MW 60.053 MW 204.227 = 1 mol
x mol ppt 0.7121 g = x mol
 y = (84.121/204.227) x 0.7121 g
= 0.2933 g
Weight percent of piperazine in the commercial material (0.3126 g)
= (0.2933 g/ 0.3126 g)× 100 % = 93.83 %