GRAVIMETRIC METHODS OF ANALYSIS

S.O. 3.1, 3.2, 3.3, 3.4, 3.5.

3.1 Explain the principles upon which gravimetric analyses are based
3.2 Describe the functions of various pieces of basic equipment used in gravimetric analysis
3.3 Carry out experiments based on gravimetric determinations
3.4 Perform calculations based on data obtained from gravimetric analyses
3.5 Cite examples based on the use of gravimetric analysis in quality control

GRAVIMETRIC ANALYSIS
Gravimetric analysis is a macroscopic, quantitative method involving the accurate weighing of a compound.
This technique is used to determine the mass of an analyte or some compound chemically related to it and
usually involves large samples. The compound or element that is weighed should be in as pure form as possible
after some form of chemical treatment has been carried out. The compound or element is usually precipitated
from solution, volatilized or adsorbed onto a surface.
Mass measurements are made with an analytical balance ( 0.001g), an instrument that yields highly accurate
and precise data. Traditional gravimetric analysis techniques are essentially manual in characteristic and labor
intensive. However, recent technology now allows gravimetric analysis to be performed automatically.
A typical experimental procedure to determine an unknown concentration of an analyte in solution is as
follows:
quantitatively (and completely) precipitate the analyte from solution. [Ideally, the precipitate is of such
low solubility that losses from dissolution are negligible. An additional factor is the common ion effect,
this further reduces the solubility of the precipitate.]
collect the precipitate by filtering and wash it to remove impurities
dry the solid in an oven to remove solvent, allow to cool
weigh the solid on an analytical balance The weighed form of the product should be of known
composition. The product should be "pure" and easily filtered
calculate the analyte concentration in the original solution based on the weight of the precipitate

ADVANTAGES OF GRAVIMETRIC ANALYSIS

Accurate and precise when using modern analytical balances.
During precipitation reactions, possible sources of errors are reliably checked, since filtrates can be
tested for completeness of precipitation. Also, precipitates can be examined for the presence of
impurities.
Determinations can be carried out with relatively inexpensive equipment.
Possible to obtain repeatability of results.
It is an absolute method, i.e. it involves direct measurement without any form of calibration or
standardization being required and results are determined from experimental data.
DISADVANTAGES OF GRAVIMETRIC ANALYSIS

Time consuming.
Laborious.
Relatively large quantity of sample is required.
Not suitable for samples that undergo thermal decomposition.
The time consuming nature of gravimetry limits applications to a small number of determinations.

USES OF GRAVIMETRIC ANALYSIS

Analysis of standards to be used for the testing and/or calibration of other instrumental techniques.
Analyses requiring high accuracy.
Used in quality control.
Measurement of the essential elements in plant foods (phosphorus, for example, is converted into
the insoluble salt, magnesium ammonium phosphate).
Estimation of pollutants in the air, such as sulphur dioxide (by conversion to insoluble barium
sulphate).
Estimation of sulphur dioxide (used to prevent microbial spoilage) in soft drinks, such as orange
juice.
Estimation of chloride ions in water supplies (by conversion to insoluble silver chloride).
Determining the moisture content of soils, cereals, grains etc
Determining the percentage NaHCO3 in antacids
Determining the percentage sulphates/sulphites present in a sample

GRAVIMETRIC PRECIPITATION REACTIONS

Gravimetric analysis is suitable for precipitation reactions when the precipitate is:

Highly insoluble such that no appreciable loss occurs when filtered

Readily separated from the mixture by filtration
Able to be washed and impurities must be soluble
Unreactive with components of the atmosphere
Of known chemical composition after it is dried

To Obtain Larger Particles:

1.
2.
3.
4.
5.
6.
7.
8.

Use elevated temperatures

Use dilute solutions
Slow addition of precipitating reagent with constant stirring
pH control for precipitates whose solubility are pH dependant
Slow cooling
Digestion
Stirring
Adding an electrolyte to the solution
EXAMPLES OF GRAVIMETRIC ANALYSIS REACTIONS

Precipitation reactions- Determination of the concentration of sulphate ions by the precipitation of barim
sulphate
Volatility- Determination of the percentage of water of crystallization present in copper (II) sulphate
Adsorption- Calcium oxide adsorbing water in the laboratory preparation of ammonia, silca gel or anhydrous
calcium chloride in the laboratory preparation of carbon dioxide and oxygen.

EQUIPMENT USED IN GRAVIMETRIC ANALYSIS

1. Buchner funnel (suction flask)
2. Filter paper
3. Vacuum pump
4. Filtration flask (suction flask)
5. Crucible-sintered-glass, silica
6. Crucible holder
7. Heat proof mat
8. Bunsen burner, oven, furnace
9. Desiccator
10. Analytical balance
3

HOME WORK
1. Define the following terms: Analyte, Matrix, Adsorption, Absorption, Digestion, Precipitate,
Reprecipitation, Mother Liquor, Supersaturated, Heating to constant mass, Co-precipitation,
Occlusion

2. A certain barium halide exists as the hydrated salt BaX 2.2H2O, where X is the halogen. The
barium content of the salt can be determined by gravimetric methods. A sample of the halide
(0.2650 g) was dissolved in water (200 cm 3) and excess sulfuric acid added. The mixture was
then heated and held at boiling for 45 minutes. The precipitate (barium sulfate) was filtered off,
washed and dried. Mass of precipitate obtained = 0.2533 g. Determine the identity of X.
3. When a sample of impure potassium chloride (0.4500g) was dissolved in water and treated
with an excess of silver nitrate, 0.8402 g of silver chloride was precipitated. Calculate the
percentage KCl in the original sample.
4. Describe the use of the following pieces of apparatus in gravimetric analysis:
i.
Buchner funnel(suction flask)
vii.
Crucible holder
ii.
Filter paper
viii.
Heat proof mat
iii.
Vacuum pump
ix.
Bunsen burner, oven, furnace
iv. Filtration flask (suction flask
x.
Desiccator
v. Crucible-sintered-glass
xi.
Analytical balance
vi.
Crucible- silica

5. Gravimetric methods of analysis depend on the isolation of a product of a completed reaction

and the careful measurement of its mass. Therefore, for a gravimetric method to be both accurate
and precise, the precipitated form of the material isolated must meet certain criteria.
a) Explain how each of the following characteristics of the precipitate meets the criteria for
gravimetric analysis:
i.
Solubility
ii.
Size of crystals
iii.
Purity of crystals
iv. Molecular Mass
v. Composition of the precipitate
b) A 300 mg solid sample containing chloride ions is dissolved in water. The chloride is then
precipitated by addition of silver nitrate to the solution of the sample. The precipitate is
then collected, washed, dried and found to have a mass of 500 mg.
i.
Write a balanced equation for the reaction between silver nitrate and the chloridecontaining sample.
ii.
Calculate the mass of chloride present in the sample.
iii.
Calculate the percentage chloride present in the sample.
iv. State TWO assumptions made in the calculation.
c) State TWO advantages and TWO disadvantages of gravimetric analysis.