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Chapter 8 Gravimetric Methods of Analysis
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
1.
Preparation of sample solution
2.
Precipitation: Gravimetric precipitating agent
should react specifically or selectively with the
analyte. rR + aA = R r A a (solid)
3.
Digestion
4.
Filtration and washing
5.
Drying, ignition and weighing
6.
Computation of results
Examples of gravimetry Ag + + Cl – = AgCl [Cl – ] = ?
Examples of gravimetry
Ag + + Cl – = AgCl
[Cl – ] = ?
Excess AgNO 3
Ag + +
1 mol
Cl –
=
1 mol
AgCl
1 mol = 143.321g
AgCl
x
x mol = 0.4368g
0.4368 g
x
= 0.4368 g/143,321 g/mol
= 3.048 ×10 –3 mol
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 
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
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
CCl 4
Benzene
Toluene CHCl 3 Pyridine HAC Acetone EtOH MtOH CH 3 CN
Water
Polar
Non-polar
2) Filterability: large particle size  Precipitation mechanism: 1. Induction period (few min): A precipitant
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  
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
Von Weimarn equation, where:
growth
Q = actual concentration of solute
Nucleation
supersaturation
S = concentration at equilibrium
(Q– S)/S
Increase particle size
Rate
Coagulation of colloids Heating  particles’ kinetic energy Increase the concentration of electrolyte(HNO 3 )
Coagulation of colloids
Heating  particles’ kinetic energy
Increase the concentration of electrolyte(HNO 3 )
Silver chloride lattice
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 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
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 Precipitation
liquor
Impurities of ppt: co-precipitation 1. 2. Surface adsorption mixed-crystal formation: inclusions: impurity ions that
Impurities of ppt: co-precipitation
1.
2.
Surface adsorption
mixed-crystal
formation: inclusions:
impurity ions that
randomly occupy
crystal lattice
A
B
3. Occlusions: pockets of
impurities that are
literally trapped inside the
C
D
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
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
NH 2 CONH 2
+
3H 2 O
CO 2 + 2NH 4 + + 2OH –
OH – +
HCOOH
HCOO – + H 2 O
3HCOO – + Fe 3+ 
Fe(HCOO) 3 . nH 2 O
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
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.
Effect of temperature on precipitate mass.
Calculations of gravimetry Relating mass of product to mass of reactant: piperazine + 2 CH
Calculations of gravimetry
Relating mass of product to mass of reactant:
piperazine
+
2 CH 3 COOH  piperazine diacetate
MW
84.121
MW 60.053
x mol
MW 204.227 = 1 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 %