GRAVIMETRIC

ANALYSIS
Aguilar, Michael
Donasco, Ma. Jessica Chelsea
What is gravimetric analysis?
■ It is the measurement of the weight of a substance in a sample or calculation of the
weight of a substance in a sample from the weight of a chemically equivalent
amount of some other substance, which can be accomplished in various ways.
■ the quantitative isolation of a substance by precipitation and weighing of
the precipitate.
■ Gravimetric analysis is a technique through which the amount of an analyte (the ion
being analyzed) can be determined through the measurement of mass. Gravimetric
analyses depend on comparing the masses of two compounds containing the
analyte.
■ One advantage of gravimetric analysis compared to volumetric analysis (titrimetric
analysis) is that there is greater likelihood of any impurities being seen, and
therefore a correction can be applied.
■ One disadvantage of gravimetric analysis is that it is generally more time-
consuming.
General reaction:
A+B C+D
- The weight of either reactant, A or B, can be calculated from the weight of either product, C
or D.
Principle of Gravimetric

The principle behind gravimetric analysis is that the mass of an ion in a pure compound
can be determined and then used to find the mass percent of the same ion in a known
quantity of an impure compound. In order for the analysis to be accurate, certain
conditions must be met:
■ The ion being analyzed must be completely precipitated.
■ The precipitate must be a pure compound.
■ The precipitate must be easily filtered.
 Theory
The chemical reaction analysis in gravimetric analysis take place in accordance
with the established laws and theories of chemistry i. e., law of mass action and
reversible reactions, solubility product principle, and common – ion effect.

Law of Mass Action and Reversible Reactions

Most of the reactions involved in quantitative analysis are of the reversible type.

Three general conditions tend to prevent reversal and lead to completion of a reaction:
1) The formation of an insoluble gas
2) The formation of a sparingly soluble solid
3) The formation of very slightly ionized molecules

According to the law of mass action, the rate of a reaction is proportional to the product of the
molecular concentrations of the reacting substances. Since the reaction depends upon the
concentration of every substance taking part in the reaction, the point of equilibrium will depend upon
the concentration of each of the components of the two opposing reactions.
For example, KNO3 + H2SO4 KHSO4 + HNO3, the rate of the reaction of potassium nitrate w/
sulfuric acid is expressed by this equation
Rate = [KNO3] x [H2so4] x k
■ Where k is a constant which corrects for all factors that affect the rate other than
concentration. In the opposing reaction,

Rate = [KHSO4] x [HNO3] x k1

■ At equilibrium the rates of the reactions are equal.

[KNO3] x [H2so4] x k = [KHSO4] x [HNO3] x k1

and,

 Since K1 and K are constants, their quotient K is a constant termed the

equilibrium constant.
General procedure:
1. Weigh the sample to be analyzed
2. Dissolve the sample in a suitable solvent, eg, water
3. Add an excess of the precipitating reagent to precipitate the analyte
4. Filter the mixture to separate the precipitate from the solution3
5. Wash the precipitate to remove any impurities4
6. Dry the precipitate by heating to remove water
7. Cool the precipitate in a dessicator to prevent the precipitate absorbing moisture from
the air
8. Weigh the cooled precipitate
9. Repeat the drying and weighing process until a constant mass for the precipitate is
achieved
10. Calculate the percent by mass of analyte in the sample
Solubility Product Principle

■ The Solubility product principle is an application of the law of mass action in

equilibria that generalizes the behaviour of difficulty soluble salt in their saturated
solution.
■ The product of the concentration of the constituent ions in a saturated solution of a
different soluble salt for any given temperature is practically constant
■ Each concentration being raised to a power equal to the relative number of ions
supplied by the molecule of the salt upon dissociating.
Common-ion effect

■ The equilibrium constant does not change, no matter what the concentration of the
reacting substances may be.
■ The relative concentration of the reacting substances may change, but there is no
change in the equilibrium constant.
ASSAY

■ Assay of sodium chloride

■ Assay of sodium lauryl sulphate for sodium sulphate content
■ Assay of mercaptomerin sodium
■ Assay of sodium phosphate solution
Problem
Ca = 40.08 C = 12.01 O = 16.00

A 2.00 g sample of limestone was dissolved in hydrochloric acid and all the calcium
present in the sample was converted to Ca2+(aq).
Excess ammonium oxalate solution, (NH4)2C2O4(aq), was added to the solution to
precipitate the calcium ions as calcium oxalate, CaC2O4(s).
The precipitate was filtered, dried and weighed to a constant mass of 2.43 g.
Determine the percentage by mass of calcium in the limestone sample.
Write the balanced chemical equation for the precipitation reaction:
Calculate the moles of calcium oxalate precipitated.
Find the moles of Ca2+(aq).
Calculate the mass of calcium in grams
Calculate the percentage by mass of calcium in the original sample:
ANSWER

■ Ca2+(aq) + C2O42-(aq) → CaC2O4(s)

■ moles (CaC2O4(s)) = mass ÷ molar mass
moles (CaC2O4(s)) = 2.43 ÷ (40.08 + 2 x 12.01 + 4 x 16.00)
moles (CaC2O4(s)) = 2.43 ÷ 128.10
moles (CaC2O4(s)) = 0.019 mol
■ From the balanced chemical equation, the mole ratio of Ca2+ : CaC2O4(s) is 1 : 1
So, moles (Ca2+(aq)) = moles(CaC2O4(s)) = 0.019 mol
■ mass (Ca) = moles × molar mass
mass (Ca) = 0.019 × 40.08 = 0.76 g
■ %Ca = (mass Ca ÷ mass sample) × 100
■ %Ca = (0.76 ÷ 2.00) x 100 = 38%
Reference/s

■ http://www.wiredchemist.com/chemistry/instructional/laboratory-
tutorials/gravimetric-analysis/
■ https://www.khanacademy.org/science/chemistry/chemical-reactions-
stoichiome/limiting-reagent-stoichiometry/a/gravimetric-analysis-and-precipitation-
gravimetry
■ https://www.ausetute.com.au/gravimetric.html