CHY 46.

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Experiment 3
GRAVIMETRIC DETERMINATION OF SULFUR AND SULFATE

OBJECTIVES
1. To learn the techniques associated with gravimetric analysis.
2. To use stoichiometry to calculate the percentage by mass of sulfur and sulfate in an unknown sample.
BACKGROUND

Gravimetric analysis is a quantitative method for accurately determining the amount of a substance by selective
precipitation of the substance from an aqueous solution. The precipitate is separated from the remaining aqueous solution by
filtration and is then weighed. Assuming that the chemical formula for the precipitate is known and that the precipitation
reaction is stoichiometric (goes to completion) the mass of the substance in the original sample can be determined.

In this experiment you will determine the percentage (by mass) of sulfur and sulfate in an unknown mixture of sulfate
salt by gravimetric analysis. First you will dissolve a measured mass of the unknown salt in water. Next you will add an
excess of aqueous barium chloride to the aqueous solution of the unknown salt. This will result in the precipitation of the
sulfate as barium sulfate.

BaCl2 (aq) + M2SO4 (aq)  BaSO4 (s) + 2MCl (aq) (M=metal cation, assuming +1 charged cation)

BaCl2 (aq) + M2SO4 (aq)  BaSO4 (s) + MCl2 (aq) (M=metal cation, assuming +2 charged cation)

The barium sulfate precipitate is collected by filtration, dried and weighed. The number of moles of sulfate can be
determined from the mass of the barium sulfate. Since barium chloride is added in excess, and since the precipitation
reaction is assumed to go to completion, the number of moles of sulfate recovered in the precipitate can be assumed to be
equal to the number of moles of sulfate in the original sample allowing for the calculation of the percentage by mass of sulfate
in the original sample.

In order to obtain the best results, the BaSO4 crystals should be as large as possible. This facilitates filtration and
washing of the crystals and the decreased surface area minimizes the number of impurities adsorbed onto the crystals.
Generally, the largest crystals are obtained when the rate of precipitation is as low as possible. The rate of precipitation is
minimized by slowly adding the BaCl2 solution to the aqueous mixture containing the unknown salt while continuously
stirring the mixture. The rate of precipitation can be decreased farther by slightly increasing the solubility of the BaSO4
(remember that a substance that is said to be insoluble is in fact very slightly soluble). The increase in solubility is achieved
by lowering the pH with 6M HCl and by increasing the temperature. The resulting decrease in the yield of the BaSO4 is
insignificant.

B. Safety
 Be careful while handling 6M HCl. If any HCl comes in contact with your skin or eyes you should immediately wash
with water for several minutes.
 Make sure to allow ample time for the crucible to cool after it has been heated.

C. Procedure

Preparation of Crucibles

1. Borrow crucibles with lid. The crucible should be cleaned, rinsed thoroughly with distilled water, and marked properly
with a pencil so they can be distinguished from one another.
2. For drying, place the cleaned crucibles in the oven for 30 minutes at 110oC. Remove the crucibles with tongs (never
touch crucibles with your hands or with paper for the duration of the experiment) and allow them to cool for 1 minute
before placing them in a desiccator for cooling to room temperature for about 10 minutes.
3. Weigh the crucibles to the nearest 0.0001 g. Return them to the oven for 30 minutes. Repeat the heating and weighing
process until two consecutive masses agree to within ±0.0003 g. Note: Only the crucible will be weighed, do not include
the lid!

Note: You need to use the same balance throughout the course of this experiment. Use of different balances, when
weighing the crucibles, will introduce an error into your calculations.

Preparation and Precipitation of Sample

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1. Measure and record the mass of a clean, dry 250 mL beaker using the analytical balance to the nearest 0.0001 g. Add
between 0.30 g and 0.35 g of the unknown sample to the 250 mL beaker and record the mass of the beaker plus sample
to

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 the nearest 0.0001 g.

2. Add 50 mL of distilled water to the sample in the beaker. Next add 20 drops of 6M HCl to the beaker. Stir the contents
of the beaker until the sample has entirely dissolved. Leave the stirring rod in the beaker.

3. Measure 25 mL of 0.1M BaCl2 solution in a graduated cylinder. The graduated cylinder should be clean and rinsed with
distilled water but does not need to be dry.

4. Heat the solution containing the sample in the 250 mL beaker until it is near boiling. Turn the hotplate off. Remove the
beaker from the hot plate. Slowly pour small portions of the BaCl2 solution into the 250 mL beaker containing the
sample. Note: This addition of BaCl2 should take at least 3 minutes otherwise the BaCl2 is being added too rapidly. Stir
the contents
of the beaker as you add the BaCl2 solution. You should observe the formation of the white BaSO4 precipitate in the
beaker. Rinse any precipitate that remains on the stirring rod into the solution with a small amount of distilled water
and allow the precipitate to settle in the beaker for about 20 minutes.

5. W h i l e w a i t i n g , o btain a piece of ashless filter paper and fold it into quarters. Open the folded paper into a
cone, place it into a funnel and wet the filter paper with distilled water so that it adheres to the funnel. Place a 250 mL
Erlenmeyer flask under the funnel to collect the filtrate. Note: Height of folded filter paper should not exceed the height
of the funnel cone. Cut the excess filter paper with scissors.

6. After 20 minutes has passed, slowly pour the mixture containing the BaSO4 precipitate down your stirring rod into the
funnel. Be careful that the level of liquid in the funnel is never more than three-fourths of the way to the top of the filter
paper. When the transfer is complete use your wash bottle (filled with distilled water) to rinse the residual precipitate
from the beaker and the stirring rod into the funnel.

7. After all the liquid has drained from the funnel, carefully press the top edges of the filter paper together and fold the
filter paper into a compact package that will fit into the crucible. To avoid tearing the filter paper it is important that you
do not use too much force. Place the folded filter paper into the previously weighed (to constant mass) crucible, and heat
in the oven at 110-120 °C until the filter paper becomes dry.

8. After several minutes when you are sure the paper is dry, transfer the crucible to a furnace. Set furnace to 500 C°. Allow
the sample to be heated at 500 °C for 1 hour to burn away deposited carbon particles. When the filter paper is entirely
combusted, only the white BaSO4 should remain in the crucible.

Note: Start the timer only when the furnace temperature reaches 500 °C.

9. After 1 hour, turn off the furnace. With a heat-resistant glove, slightly open the furnace by carefully pulling the furnace cover towards
you. Allow the temperature to drop down to 200 °C before fully opening the furnace.

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10. Allow the crucible to cool and then place it in a desiccator for 15 minutes and weigh. Repeat the heating, cooling, and
weighing process until successive weighing agree to within ±0.0003 g as you did in step 3.

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 11. Finally, when constant mass is attained, complete the information required in your data notebook

Calculation
The percentage of sulfate the sample in terms of barium sulfate is calculated using the following equation:

% 𝐵𝑎𝑆𝑂4
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑆𝑂4
= 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100 Eq 1

𝑚𝑎𝑠𝑠 𝑠𝑢𝑙𝑓𝑎𝑡𝑒 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓𝑠𝑢𝑙𝑓𝑎𝑡𝑒

%𝑠𝑢𝑙𝑓𝑎𝑡𝑒 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑆𝑂4×
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑆𝑂4
𝑥100 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝐵𝑎𝑆𝑂4 x 100 Eq 2

𝑚𝑎𝑠𝑠 𝑠𝑢𝑙𝑓𝑢𝑟 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓𝑠𝑢𝑙𝑓𝑢𝑟

%𝑠𝑢𝑙𝑓𝑢𝑟 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑆𝑂4×
𝑠𝑎𝑚𝑝𝑙𝑒 𝑥100 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑎𝑆𝑂4
x 100 Eq 3
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝐵𝑎𝑆𝑂4

CHY 46.1
Experiment 3
GRAVIMETRIC DETERMINATION OF SULFUR AND SULFATE

Table 3-A. Raw Data for the heating to constant mass of the crucible (without lid)

Trial 1 Trial 2 Trial 3

Mass of crucible without Cycle 1

the cover, g
Cycle 2

Cycle 3

Cycle 4

Cycle 5

Cycle 6

Constant mass of crucible, g

Table 3-B. Raw Data for the heating to constant mass of the crucible (without lid) and precipitate

Trial 1 Trial 2 Trial 3

Mass of crucible + dried Cycle 1

precipitate heating, g

Cycle 2

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 Cycle 3
Cycle 4
Cycle 5
Cycle 6
Constant mass of crucible + dried
precipitate after heating, g

Table 3-C. Data for the determination of BaSO4, sulfate, and sulfur in an unknown sample using
gravimetry.

Trial 1 Trial 2 Trial 3

Mass of 250 ml Beaker

Mass of 250 ml Beaker + unknown sample
Mass of unknown sample, g
Constant mass of crucible, g

Volume of 0.1 M Barium chloride solution Revised by: Opog,

used Armenia C.
Constant mass of crucible + dried
precipitate after heating, g
Mass of dried precipitate (BaSO4), g

% BaSO4
Amount of sulfate in the sample, g

% of sulfate in the sample

Amount of sulfur in the sample, g

% of sulfur in the sample
Mean of % sulfur
Standard deviation of % sulfur
Relative standard deviation of % sulfur
95% confidence limit for the % sulfur
99% confidence limit for the % sulfur