Synopsis This experiment was carried out to determine the amount of sulphate by a process called gravimetric analysis.

In the experiment, an unknown sulphate was reacted to form a white precipitate of barium sulphate. A dilute solution of barium chloride was slowly added to a hot unknown sulphate solution, which was slightly acidified with concentrated Hydrochloric acid. After digestion, the solution is being filtered using vacuum filtration. The remains on the filter paper are then dried in the oven, followed by cooling in the desiccator. Ba2+(aq) + SO42-(aq) BaSO4(s) (precipitate produced) Objective The main objective of this experiment is to determine the amount of sulphate by the gravimetric method. At the same time, skills in precipitation gravimetric method of qualitative analysis were acquired. Theory Gravimetric analysis is a technique through which the amount of an analyte (the ion being analyzed, which is sulphate in this experiment) can be determined through the measurement of mass. It involves changing one compound containing the constituent into another compound containing that constituent and measuring the percentage of sulphate in the new compound to determine the percentage of sulphate in the unknown sulphate. 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 the analysis for sulfate, the sample to be analyzed is brought into solution and reacted with a solution of BaCl2, a source of Ba2+, to yield BaSO4 as a white precipitate. In the procedure, the solution is first acidified with HCl (aq) to prevent the precipitation of BaCO3and Ba(OH)2 , as well as to aid in the formation of larger precipitate crystals because fewer crystallite nuclei are formed. To avoid contamination of the precipitate with other substances, the procedure requires slow precipitation, to form large purer particles of barium sulfate, and repeated washing to remove other substances that could be adsorbed in the precipitate. To acidify the solution, Hydrochloric acid was added. The solution is acidic to avoid producing barium hydroxide, or barium carbonate co-precipitate. Barium sulphate has a low solubility. Barium carbonate, BaCO3, will precipitate in basic solution and this has to be

avoided because it would cause an error in the analysis. Carbon dioxide dissolves easily in water and most water contains a fair amount of CO2 just by sitting around. When the solution is acidified, the carbonates are prevented from precipitating. This will shift the following equilibrium to the left and prevent the formation of carbonate:

H2O + CO2 H2CO3

H2CO3 2H+ + CO32-

Procedures Below are the procedures which were carried out during the experiment: Firstly, BaSO4 was precipitated. 1) 25 mL of the given sulphate solution was pipetted into a 250-mL beaker. 2) 50 mL of water and 5 drops of concentrated HCl was added. 3) The solution was heated to boiling and, with vigorous stirring, 10 mL of 10% barium chloride solution was added dropwise from a measuring cylinder. 4) The beaker was covered with a watch glass and digested (heated to just below boiling) for 20 minutes. 5) A few drops of BaCl2 was added to the clear supernatant liquid to test for complete precipitation. Secondly, BaSO4 precipitate was washed and filtrated. 1) The clear supernatant liquid was decanted by filtration at the vacuum pump into a preweighed crucible with filter paper. Prior to that, the filter paper was positioned such that the base of the crucible was covered completely.

2) Using a rubber-policeman, the particles on the beaker were dislodged and the beaker was rinsed with warm deionized water. With the aid of the vacuum pump, the contents were emptied into the crucible. 3) The precipitate was further washed with warm deionized water at the vacuum pump two more times. 4) The filtrate was discarded. Finally, BaSO4 precipitate was dried, followed by weighing. 1) The crucible was dried with the BaSO4 precipitate in the oven at 150C for about hour. 2) The crucible was cooled in a desiccator for about 10 minutes. 3) After cooling, the crucible was weighed. 4) The weight of the BaSO4 precipitate is the difference between this weight and the empty crucible (plus filter paper).

Results and Calculations Weight of crucible with the precipitate Weight of crucible (with a piece of filter paper) Weight of BaSO4 precipitate moles of SO42moles of BaSO4 14.0822g 13.8794g 0.2028g

1 1

molarity of SO42- x volume of SO42weight of BaSO4 mol weight of BaSO4

=

1 1

molarity of SO42- x 0.2028 233.33

25 1000

1 1

molarity of SO42-

0.2028 233.33
=

25 1000 = 0.03476 M 0.0348 M (to 3 significant figures)

concentration of SO42- in g/L

= = =

molarity of SO42- x mol wt of SO420.03476 x 96.1 3.340 g/L 3.34 g/L (to 3 significant figures) 25 1000

mass of SO42-

= =

3.340 x 0.08352 g

0.0835 g (to 3 significant figures)

percentage of sulphate in BaSO4

0.08352 x 0.2028 = 41.186 %

100%

41.19 % (to 2 decimal places)

References

1. Professor Stephen Bialkowski, Utah State University (2004). Gravimetric Analysis. Available from: http://ion.chem.usu.edu/~sbialkow/Classes/3600/overheads/Gravimetry/gravimetric.ht ml. [Accessed on 5 June 2012] 2. The Shodor Education Foundation, Inc. (1998). Chemical Stoichiometry. Available from: http://www.shodor.org/appstchem/basic/stoic/index.html [Accessed on 5 June 2012] 3. Santa Monica Collage (2011). Gravimetric Analysis. Available from: http://www.smc.edu/projects/28/Chemistry_11_Experiments/Gravimetric_Analysis_P rocedure.pdf [Accessed on 2 June 2012] 4. Stoichiometry: Limiting Reactant. Available from: http://www.chem.tamu.edu/class/majors/tutorialnotefiles/limiting.htm [Accessed on 7 June 2012] 5. Claude Yoder (2012). Gravimetric Analysis. Available from: http://www.wiredchemist.com/chemistry/instructional/laboratorytutorials/gravimetric-analysis [Accessed on 3 June 2012]