Gravimetry

Gravimetry
• Quantitative method based on
determining the mass of a pure
compound that is chemically
related to the ANALYTE

• One of the most accurate classes

of analytical methods available
Advantages
Provides for an exceedingly precise analysis

Provides very little room for instrumental error

Does not require a series of standards for the calculation of an

unknown

Does not require expensive equipment

Precipitation Gravimetry
• The formation of an insoluble
compound when a precipitating
agent is added to a solution of
the analyte

• Most precipitation gravimetric

methods developed in the 19th
century involved the analysis of
ores
Weighing of Sample
• Weigh about 0.50 g of unknown
sample in a 400-mL beaker
Dissolution of Sample
+ 25 mL dH2O To release analyte and
+ 5 mL 6 N HCl interfering substances

+ Conc. HNO3 dropwise (max 2 Fe, Fe2+ → Fe3+

mL) into gently boiling solution HNO3 must be added in excess:
until solution becomes clear o To convert all Fe2+ → Fe3+
yellow → DONE UNDER THE o To prevent backward reaction
HOOD

POISONOUS
Precipitation
• To recover analyte in a form in which it can be separated and weighed
• Precipitating agent: 6N NH3 (basic medium)

• Add NH3 slowly with stirring at HIGH TEMPERATURE (to avoid

formation of very small colloidal particles)
Use of filtered NH3: to prevent introduction of silica (POSITIVE ERROR)
Experimental Considerations
Characteristics of an ideal precipitating
agent:
Specific or selective with the
analyte
Use of NH3 as precipitating agent
• It is a weak base so [OH-] can be
controlled
• Other metal ions in the sample
may form hydroxides, oxides, or
basic salts in the presence of a
strong base
Experimental Considerations
Characteristics of an ideal precipitate Ferrous hydroxide vs Ferric hydroxide;
in gravimetric analysis:
Of low solubility Fe(OH)2•xH2O Ksp = 8 x 10-16
Of high purity Fe(OH)3•xH2O Ksp = 1 x 10-38
Of known composition
Easy to separate from the Fe(OH)3 is less soluble than Fe(OH)2
reaction mixture that precipitation is almost
quantitative.
Mechanism of Precipitate Formation
Nucleation Particle Growth

• Molecules in solution come • Involves the addition of more

together randomly and form molecules to a nucleus to form a
small aggregates crystal
• Leads to a large number of • Leads to a smaller number of
SMALL PARTICLES LARGE PARTICLES

Nucleation tends to proceed faster in a SUPERSATURATED solution.

Conditions that favor particle growth
Increasing the temperature to increase solubility which leads to a
decrease in supersaturation

Adding precipitating agent slowly with stirring, to prevent a local,

highly supersaturated condition where the stream of precipitant first
enters the analyte

Using a large volume of solution so the concentrations of analyte and

precipitant are low
Coagulation of Colloids
• As colloidal particles approach
one another, the electrical
double layer exerts a repulsive
force that prevents particles
from colliding and adhering
• Heating and stirring: decreases
the number of adsorbed ions
• Adding an electrolyte: shrinks
the counter-ion layer

Colloidal particle Primary adsorption Counter-ion layer

layer
Digestion
• Precipitate is heated in the solution from which it was formed
(mother liquor) and allowed to stand in contact with the solution
• Continue boiling solution for 5 minutes after precipitation is complete

• TO INCREASE PARTICLE SIZE OF CRYSTALS

• Small crystals redissolve and recrystallize back on the surfaces of
larger crystals
• Purity is also increased as impurities are expelled from the crystal as it
redissolves and recrystallizes
Effects of Prolonged Digestion
• Loss of precipitate due to its dissolution in the mother liquor

• Postprecipitation – precipitation of impurities on the desired product

• Contamination of precipitate with silica formed from the reaction of

the basic medium with the glass container
Filtration
• Filter while HOT: gelatinous precipitate
becomes viscous as it cools
• Promotes rapid flow during filtration
• Prevents impurities from hardening
with the gelatinous precipitate
 ASHLESS filter paper decomposes into H2O & CO2 upon ignition
 Avoid a positive error contributed by the weight of the ash (if ordinary filter paper
was used)
Washing the precipitate
• Washing solution: hot NH4NO3
• 1st washing: 25-30 mL
Retain most of the precipitate in
the beaker
• 2nd & 3rd washing: transfer the
precipitate in the filter paper
QUANTITATIVELY
• Use of NH4NO3
Remove impurities/interfering
ions
Prevent peptization – coagulated
colloid returns to its dispersed
state
Peptization might occur if pure
H2O is used for washing
Drying
• Allow filter paper to drain
thoroughly
• Transfer to tared crucible
• Fold filter paper so precipitate is
completely enclosed
• Precipitate is dried at 100°C for 3
hours to volatilize the solution
Ignition
• 650°C for 3 hours
• Converts Fe(OH)3•xH2O to Fe2O3 which is a form suitable for weighing
Gravimetric Factor
• Relates the mass of the product to the mass of the analyte
2 𝐹𝑀 𝐹𝑒
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐹𝑒 = 𝑚𝑎𝑠𝑠 𝐹𝑒2𝑂3
𝐹𝑀 𝐹𝑒2𝑂3
𝑚𝑎𝑠𝑠 𝐹𝑒2𝑂3
%𝐹𝑒2𝑂3 = × 100
𝑚𝑎𝑠𝑠 𝑠𝑎𝑚𝑝𝑙𝑒

2 𝐹𝑀 𝐹𝑒
𝑚𝑎𝑠𝑠 𝐹𝑒2𝑂3
𝐹𝑀 𝐹𝑒2𝑂3
%𝐹𝑒 = × 100
𝑚𝑎𝑠𝑠 𝑠𝑎𝑚𝑝𝑙𝑒
For next meeting
Bring one 500-mL plastic bottle & one 500-mL glass bottle with cap per
group