FORMAL REPORT

Quantitative Determination of Sulfate

by Gravimetric Analysis
He Yinmei
P1445211
DBS/FT/1A/03

[A] Synopsis (20%)

The experiment conducted is to determine the amount of sulfate by the
gravimetric method. The steps included for this experiment are adding BaCl
to unknown sulfate solution, acidified slightly with concentrated HCL.
Following, a white precipitate will form. It is filtered and washed with
deionized water. Proceeding, it is brought to the oven to be dried and later
weighed for barium sulphate. By chemical calculations, the concentration of
sulphate is 3.62g/L while the weight of the precipitate is 0.2196g. However,
results were affected by a few factors such as coprecipitation (inclusion,
occulation and surface adsorbates), post precipitation, washing, filtering and
drying of the precipitate. Measures against such factors can be taken to
reduce inaccuracy of result.
[B] Objective (10%)
The experiment was conducted to determine the amount of sulfate by the
gravimetric method.
[C] Theory (5%)
Gravimetric analysis is a method based upon the measurement of mass and
can be classified generally to two methods- precipitation and volatilization. In
the experiment, the amount of barium sulfate is determined quantitatively.
The precipitation method of gravimetric analysis isolates a sulfate ion in a
dilute solution of barium chloride in excess by precipitation reaction, filtering,
washing the barium sulphate free of contaminants, conversion of the barium
sulphate to a product of known composition and finally weighing the barium
sulphate and determining the mass by the difference in the crucible. From
the mass and known composition of the precipitate, the amount of sulfate is
determined.
For the gravimetric analysis determination by precipitation to be accurate,
there are conditions to be fulfilled. Firstly, the desired substance must be
completely precipitated. For most determinations, losses from dissolution are
insignificant as long as the precipitate is of low solubility. The common ion
effect also further reduce the precipitates solubility. It pushes the chemical
equilibrium to the right.
Ba2+ +SO42- BaSO4 (precipitate)

Initial induction period is the period after adding the precipitating agent to
the solution of ion under analysis and before nucleation occurs. In this case,
the precipitating agent is the barium chloride solution. Period of initial
induction variates in time. It could happen instantly or after several minutes.
Nucleation comes after induction. For nucleation, nuclei of atoms form. The
nuclei of atoms are responsible for the crystals that forms the growth of
filtrate. These nuclei may be composed of just a few atoms so there may be
up to 1010 of the nuclei/mole of precipitating product. As these nuclei form
ions from the excess solution congregate around the product.
In this case, barium chloride was added very slowly to a solution of sulfate,
barium sulfate nuclei would form and chloride ions would congregate around
them. In addition to the primary absorbed barium ion, there are some
chloride ions aggregating further from the BaSO4 nucleus. These are counter
ions and tend to aggregate around the center because these centers have a
net positive charge because of the excess barium ions. This in turn, results in
the requirement of additional negative charge to maintain electrical
neutrality. The chloride ions are less tightly held than the barium ions and
the counter layer is somewhat diffused and contain ions other than those of
the counter ions which are the chloride ions. These layers of charges are

known as the electric double layer.

[The above picture is an example of an electrical double

layer. However, in this case, the primary absorbed ions are silver.
The counter ions are nitrate ions.]
After the nuclei have grown at the expense of the smaller nuclei
which dissolved, the filtering of crystal of process is simplified as
larger nuclei produces larger crystals. The process of growth of the
nuclei is amplified by digestion which is a process that involves the
heating of solid and a mother liquor for a certain period of time.
During this process, smaller particles dissolve and the larger one
grows. This is an essential practical process important to gravimetric
analysis.
[D] Procedures (15%)

Part (A): Precipitation of BaSO4

1. 25ml of given sulfate solution was pipetted into a 250-mL beaker.
2. 50ml of water and 5 drops of concentrated HCL was added
3. 10ml of 10% barium chloride solution was added dropwise from a
measuring cylinder after heating to boiling and stirring vigorously.
4. The beaker was covered with a watch glass and digested for 20
minutes.
5. Precipitation reaction was completed when a clear supernatant
liquid was observed after adding a few drops of BaCl2.
Part (B): Washing and filtration of BaSO4 precipitate
1. The supernatant liquid was decanted by filtration at the vacuum
pump into a pre-weighed crucible with filter paper that covers the
base of the crucible completely.
2. The beaker was dislodged of any particles and rinsed with warm
deionized water. The contents were emptied into the crucible while
the vacuum pump was at work. All the solids were ensured to have
been transferred to the crucible.
3. The precipitate was washed further with warm deionized water at
the vacuum pump. This procedure was repeated twice.
4. The filtrate was discarded.
Part (C): Drying and weighing of BaSO4 precipitate
1. The crucible with BaSO4 precipitate was dried in the oven at 150oC
for about 1/2 hour.
2. The crucible was cooled in a desiccator for 10 minutes.
3. The crucible was weighed once it had cooled down
4. The weight of BaSO4 was calculated from the difference between
the weight in step 3 and the weight of the empty crucible with filter
paper. Procedure (1) (4) was repeated until a constant weight of
precipitate was obtained.
[E] Results and Calculations (20%)
Weight of crucible with BaSO4 precipitate = 31.9422g
Weight of crucible (with a piece of filter paper) = 31.7226g
Weight of BaSO4 = 0.2196g
Ba2+ + SO42- BaSO4 (precipitate)

Moles of Sulfate
1
=
Moles of Barium Sulfate 1

Molarity of Sulfate Volume of Sulfate

1
Weight of Barium Sulfate
= 1
Molar Mass of Barium Sulfate
Molarity of sulfate 0.025
0.2196 g
233.33

1
1

Therefore, Molarity of SO42- = 0.037646 M

Therefore, Concentration of SO42- = Molarity of SO42 Molar Mass of SO42
=

0.0316 M 96.1

=3.62 g/L

[F]Discussion (15%)
The answer presented above is not within the range of answers. During an
experiment, there are many causes of inaccuracies. The following are some
that affects the results of the experiment.
Coprecipitation
This affects the results of the experiment as coprecipitation is anything
unwanted which precipitates with the desired product. It occurs to a certain
degree in every gravimetric analysis especially the barium sulfate and those
involving hydrous oxides. It cannot be avoided by can be minimized.
Examples of coprecipitation are inclusion, occlusions and surface adsorbates.

(A)Inclusion

Inclusion refers to a potential interference of an ion whose size and charge is

similar to a lattice ion which may substitute into the lattice structure,
provided that the interferer precipitates with the same crystal structure. The
probability of forming an inclusion is greatest when the interfering ion is a lot
greater than the lattice ions concentration. An inclusion would always affect
the precipitate mass as a larger than expected mass is obtained. Inclusion
would not decrease the amount of analyte as long as the precipitant is
present with enough excess.
(B)Occlusion
Occlusion is a type of coprecipitation in which impurities are trapped within
the growing crystals. An occlusion is localized unlike inclusion which are
diffused throughout the precipitate. Occlusion is present along the flaws
within the precipitates lattice structure or within aggregates of individual
precipitate particles. Like inclusion, inaccuracies because of occlusion
increases the mass of the precipitate. Therefore this will affect the results of
the experiment.
(C)Surface adsorbates
Unwanted materials are absorbed to the surface of precipitate. The surface
will continue to attract ions from solution even after precipitation. Surface
adsorbates comprises 1/3 of impurity. Removing it can be done through
washing however it cannot be guaranteed that there might be loss of analyte.
Therefore, this will affect the accuracy of the weight of the barium sulphate.

Post Precipitation
There are times when a precipitate standing in contact with the mother
liquor becomes contaminated by the precipitation of an impurity on top of
the desired precipitate
Washing and Filtering
With many precipitates, peptization occurs during washing. It is here that
part of the precipitate reverts to the colloidal form [BaSO4 (colloidal) BaSO4
(s)]. This results in the loss of part of the precipitate because the colloidal
form may pass through on filtration
Washing
The supernatant is rich with dissolved inert ions, therefore it is essential to
removal residual traces of supernatant to avoid a positive determinate error
without incurring solubility losses. In many cases this simply involves the use
of cold solvents or rinse solutions containing organic solvents such as
ethanol. The pH of rinse solution is critical, if the precipitate contains an
acidic or basic ion. While coagulation plays an important role in determining
the size of particles, adding a volatile inert electrolyte to the rinse solution
prevents the precipitate from reverting to smaller particles that might be able

to pass through the filter. This process is called peptization. The volatile
electrolyte is removed when drying the precipitate
Filtering
Filter papers are hygroscopic. Therefore it is not easy to dry a constant
weight. When
accuracy is important, the filter paper is removed before
determining the precipitates
mass. After transferring the precipitate and a
filter paper to a covered crucible, the
crucible is heated to a temperature
that converts the paper to CO2 (g) and H2O (g)
through a process known
as ignition.

Drying the solid

The precipitate is dried to remove residual traces of volatile impurities and
traces of residual. The volatility determines the temperature required for
drying. Solids are usually dried at 120oC but conditions for drying vary
considerably from one to another. This would affect the results.

However, there are countermeasures that can be taken against factors of

inaccuracies.
Coprecipitation (occlusion and inclusion) can be minimized by careful
precipitation and thorough washing. Coprecipitation (surface adsorbates) is
minimized by digestion, which is a process that reduces the amount of
surface area and hence the area available for surface absorption is reduced.
In addition, washing with cold solvents can also help to remove surface
material.
For washing, loss of analyte can be minimized by using small portions of
rinse solutions at a time instead of a single large volume. In addition, rinse
solution can be tested to ensure that there is no presence of impurities. For
filtration, filter paper used are to be of higher quality as poor quality filter
paper affects the results as it leaves behind inorganic ash. Filter paper
absorb moisture and therefore should be removed before weighing the
precipitate.
When drying the precipitate, a thermogravimetric balance can be used to
determine the optimum temperature for the precipitate to be dried.

[G]Conclusion (10%)

The amount of sulfate, rounded off to 3 significant figures is 0.2196g. The

concentration of sulfate is 3.62g/L. However, there were experimental errors
made and the results were affected. In particular, coprecipitation cannot be
avoided and only be minimized, indicating that to a certain degree, results
will be affected, regardless of how meticulous steps and measures taken
were. Hence due to experimental errors, the results obtained were not within
range and unsatisfactory.
[H] References (5%)
Singapore Polytechnic School of Chemical and Life Sciences Analytical and
Physical Chemistry Page 13-14
https://www.chem.tamu.edu/class/majors/tutorialnotefiles/gravimetric.htm
https://en.wikipedia.org/wiki/Precipitation_(chemistry)
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical_Chemistry_2.0/0
8%3A_Gravimetric_Methods/8B%3A_Precipitation_Gravimetry