Gravimetric Determination of Barium Sulfate

Keziah Villena

Gravimetric analysis is one of the most accurate and precise analytical methods of determining
the amount of analyte/s in a sample using mass measurements and knowledge of reaction
stoichiometry. There are different types of gravimetric analysis methods including, but not
limited to, precipitation, volatilization and electrodeposition methods. In precipitation gravimetry,
the analyte goes through a process of isolation through precipitation and is heated to be
converted to a compound of known composition that can be weighed.

The process of isolation through precipitation consists of a number of operations intended to

obtain a precipitate that is composed of sufficiently insoluble, large crystals such that it can
easily be filtered and is suitable for weighing. The smaller surface area of larger precipitate
particles also ensures less chance of contamination by adsorption of impurities in contrast to
larger surface area of smaller particles.

Several factors that determine the particle size of precipitates include the concentration of the
reactant, the presence of other constituents, its temperature, and pH level. The net effect of
these factors can be accounted for by assuming that the particle size is related to a single
property of the system called relative supersaturation, where
𝑄−𝑆
𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑠𝑢𝑝𝑒𝑟𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 = eq 2.1
𝑆

In the equation, Q stands for the concentration of the reactants and S stands for solubility at
equilibrium. When relative supersaturation is high, the precipitate is likely to be composed of
many small crystals. On the other hand, when the relative supersaturation is low, it is more likely
for the precipitate to have fewer, larger crystals. Several steps to be taken to improve the
particle size of the precipitate include minimizing the concentration of the reactants(Q), by
precipitating from dilute solutions and adding the precipitating agent slowly with efficient mixing,
and maximizing equilibrium solubility(S) by precipitating from a hot solution and adjusting the pH
level. It is important that when the precipitation is performed, a slight excess of precipitating
reagent is added to decrease solubility and assure complete precipitation. Generally, if the
approximate amount od analyte is known, a 10% reagent is added.

A practical treatment of precipitate with very fine particles is known as digestion. This process
improves both filterability or the precipitate and its purity. By allowing the precipitate to stand in
the presence of the the solution from which it was precipitated, the large crystals grow at the
expense of the small ones and weakly bound water appears to be lost. The result is a denser
mass that is easier to filter.

After filtration and washing of the precipitate, it is then heated to drive off moisture and any
volatile species carried down with the precipitate. Aside from heating, some precipitates are also
ignited to form a compound of known composition suitable for weighing.
From the weight of the precipitate and the weight relationship between the analyte and the
precipitate, the weight of the analyte can be calculated. This can be done by using a direct
proportion. The gravimetric factor (GF) represents the weight of the analyte per unit weight of
the precipitate as shown in the equation:

𝑓𝑤 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑎 𝑚𝑜𝑙 𝑎𝑛𝑎𝑙𝑦𝑡𝑒

𝐺𝐹 = × ( ) eq 2.2
𝑓𝑤 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑏 𝑚𝑜𝑙 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒

where a and b are integers that make the formula weights in the numerator and denominator
chemically equivalent. The weight of the substance sought is then obtained by multiplying the
weight of the precipitate by the gravimetric factor:

eq 2.3
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑠𝑜𝑢𝑔ℎ𝑡(𝑔)
𝑔
𝑓𝑤 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑠𝑜𝑢𝑔ℎ𝑡 ( )
= 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒(𝑔) × 𝑚𝑜𝑙
𝑔
𝑓𝑤 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑤𝑒𝑖𝑔ℎ𝑒𝑑 ( )
𝑚𝑜𝑙
𝑎 𝑚𝑜𝑙 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑠𝑜𝑢𝑔ℎ𝑡
× ( )
𝑏 𝑚𝑜𝑙 𝑤𝑒𝑖𝑔ℎ𝑒𝑑

The general formula for calculating the percentage composition of the substance sought is as
follows:

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 (𝑔)×𝐺𝐹(𝑔 𝑠𝑜𝑢𝑔ℎ𝑡/𝑔 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)

%𝑠𝑜𝑢𝑔ℎ𝑡 = × 100%
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒(𝑔)
eq 2.4

The procedures done in precipitation gravimetry are shown in the gravimetric determination of
sulfate. A solution containing sulfate ions is mixed with one containing barium ions to form
sparingly soluble barium sulfate precipitate. However, since barium sulfate precipitates as very
fine particles, digestion is done to make particles of larger size through recrystallization.
Because barium sulfate is stable in air and is non-hydroscopic, the weighing can be done in an
open crucible.

The precipitate is collected in an ashless filter paper. The precipitate and filter paper are then
dried in a crucible. However, the crucible to be used should be dried to constant weight
beforehand. This is done by heating the crucible for a specific amount of time, followed by
cooling and weighing and repeating the cycle until successive weighings agree within about 0.3
mg. After the drying process, the filter paper is charred and ashed to leave only the dried
sample in the crucible. The paper ashing operation should be followed carefully to reduce
errors. The lid should be in place so that escaping gases do not catch flame. When the volume
of smoke evolved suddenly increases, it means that the paper is about to burst into flame so the
burner must be immediately removed. When no more smoke is detected, the temperature is
gradually increased and air is allowed too get inside the crucible. Failure to follow this operation
carefully causes negative systematic error since carbon will reduce sulfate ion to sulphide ion,
carbon monoxide and leading to lower mass determinations.
The following experiment aims to define the principles and proper techniques involved in
precipitation and gravimetric analysis, perform properly the relevant technique in precipitation
and gravimetric analysis and calculate the percent composition of an analyte in the sample
using gravimetric data.

Table 1.1 Taring of crucible + lid

Condition Trial 1 Trial 2
Initial mass of crucible + lid , g 34.190
Mass of crucible + lid after 1st heating, g 34.190
Mass of crucible + lid after 2nd heating, g
Mass of crucible + lid after 3rd heating, g

Table 1.2 Constant weight of crucible + lid + BaSO4

Condition Trial 1 Trial 2
Mass of crucible + lid + BaSO4, g 37.003
Mass of crucible + lid + BaSO4, after 2nd
heating, g
Mass of crucible + lid + BaSO4,after 3rd
heating, g

Table 1.3 Determination of barium sulfate

Condition Trial 1 Trial 2
Volume of sample, mL 25 mL
Mass of crucible + lid, g 34.190 g
Mass of crucible + lid + BaSO4, g 37.003 g
Mass of BaSO4, g 2.813 g
% BaSO4
% SO42- 4.632 %
M Na2SO4 0.48 mol/L
% Na2SO4 6.849 %
% relative error