Mandatory Experiment 2.

Qualitative tests for the anions CO32-, HCO3-, SO42-, SO32-, Cl-, NO3- and PO43- in aqueous solution
Teacher Material
The following solutions should be freshly prepared for use in this experiment: sodium sulfite solution and iron(II) sulfate solution. These solutions are relatively unstable. Ensure that all glassware is thoroughly cleaned after each test has been carried out. In the tests for the nitrate and phosphate ions, it is important to use the exact quantities specified. The equations for the reactions in the nitrate test are as follows: 2NO3- + 4H2SO4 + 6Fe2+ 6Fe3+ + 2NO + 4SO42- + 4H2O followed by Fe2+ + NO [Fe(NO)]2+ The yellow precipitate formed in the test for the phosphate ion is ammonium phosphomolybdate, (NH4)3[PO4(Mo12O36)]. There is an alternative test for the phosphate ion involving the use of barium chloride solution. Addition of this solution to a solution containing phosphate ions results in a white precipitate of barium hydrogen phosphate. This precipitate is soluble in dilute hydrochloric acid. The problem about using this test at school level is that solutions containing sulfite ions give a similar result an acidsoluble white precipitate of barium sulfite in this case. To distinguish between the sulfite and phosphate ions, the precipitate of barium sulfite must be allowed to be oxidised to acid-insoluble barium sulfate, either slowly on standing, or rapidly by warming with hydrogen peroxide solution or a little concentrated nitric acid. A variation on the above test involves addition of barium chloride solution in the presence of dilute ammonia solution to a solution containing phosphate ions this results in a white precipitate of the less soluble barium phosphate being formed. If this method is being used, it is necessary to be able to distinguish between the sulfate and phosphate ions. This is done by addition of barium chloride solution in the presence of dilute hydrochloric acid solution to a solution containing sulfate ions a white precipitate of barium sulfate results. No precipitate is obtained under these conditions with either phosphate or sulfite ions. In the tests for unknown anions, solutions of some or all of the following can be provided in beakers, each labelled with a particular number: sodium carbonate, sodium hydrogencarbonate, sodium sulfate, sodium sulfite, sodium chloride, potassium nitrate and disodium hydrogen phosphate. To avoid any

confusion between phosphate and sulfite (or sulfate), it is advisable to carry out the phosphate test prior to the sulfite and sulfate tests.

Preparation of Reagents
1. Solutions to be tested Sodium carbonate solution: One litre of approximately 0.5 M solution of sodium carbonate can be prepared by dissolving 143 g of Na2CO310H2O in deionised water to make 1 l of solution. Sodium hydrogencarbonate solution: One litre of approximately 0.5 M solution of sodium hydrogencarbonate can be prepared by dissolving 42 g of NaHCO3 in deionised water to make 1 l of solution. Sodium sulfate solution: One litre of approximately 0.1 M solution of sodium sulphate can be prepared by dissolving 32.2 g of Na2SO4 .10H2O in deionised water to make 1 l of solution. Sodium sulfite solution: One litre of approximately 0.5 M solution of sodium sulphite is prepared by dissolving 126 g of Na2SO3.7H2O in deionised water to make 1 l of solution. Sodium chloride solution: One litre of approximately 0.1 M solution of sodium chloride can be prepared by dissolving 5.85 g of NaCl in deionised water to make 1 l of solution. Potassium nitrate solution: One litre of approximately 0.1 M solution of potassium nitrate can be prepared by dissolving 10.1 g of KNO3 in deionised water to make 1 l of solution. Disodium hydrogenphosphate(V) solution: One litre of approximately 0.033 M solution of disodium hydrogenphosphate(V) is prepared by dissolving 11.81 g of Na2HPO4.12H2O in deionised water to make 1 l of solution. Since the above solutions are to be used for qualitative analysis in this experiment their exact concentrations are not critical. Spurious results can be avoided by using high quality reagents with low levels of impurities. 2. Other reagents Dilute hydrochloric acid, approximately 3 M, may be prepared in the fume hood by diluting 640 cm3 of concentrated HCl to 2.5 l by adding it to deionised water. It is stable.

Concentrated sulfuric acid should be used with great caution. Dilute ammonia solution, approximately 3 M, is prepared in the fume hood by adding 400 cm3 of 0.88 concentrated ammonia to deionised water to make 2.5 l of solution. Limewater is prepared by adding about 200 g of calcium hydroxide to 2.5 l of water. Calcium hydroxide has a low solubility in water. Shake vigorously at intervals over a period of time and finally allow to settle. Decant off the clear limewater solution from above the undissolved solids. Top up the vessel with deionised water and repeat the process. Magnesium sulfate solution: A solution of magnesium sulfate, MgSO4.7H2O of approximate concentration 0.25 M is prepared by dissolving 15.4 g of this hydrated salt in deionised water to make 250 cm3 of solution. Iron(II) sulfate solution: Dissolve 140 g in a solution containing 5 cm3 of concentrated sulfuric acid and making up to a volume of 500 cm3 with deionised water. Store in a refrigerator before use. This cold saturated solution of iron(II) sulfate, FeSO4.7H2O, is unstable as it suffers air oxidation to the iron(III) state and so should be freshly prepared. Barium chloride solution: A 1 M solution of barium chloride, BaCl2.2H2O, is prepared by dissolving 244 g in water and bringing the volume to 1 l. Silver nitrate solution: A 0.1 M solution of silver nitrate is prepared by dissolving 4.25 g of AgNO3 in 250 cm3 of deionised water. Ammonium molybdate solution: Ammonium molybdate reagent is prepared by dissolving 4.5 g of ammonium molybdate [(NH4)6Mo7O24.4H2O] crystals in a solution made from 4 cm3 0.88 ammonia solution and 6 cm3 deionised water. Add to this 12 g ammonium nitrate. Dilute with deionised water to 100 cm3 in a volumetric flask. Immediately before use, acidify with 1.5 cm3 of concentrated nitric acid per 10 cm3 ammonium molybdate solution. Ammonium molybdate reagent may also be prepared by dissolving 4 g of molybdenum(VI) oxide crystals in a solution made from 7 cm3 0.88 ammonia solution and 14 cm3 deionised water. Add to this a solution of 25 cm3 fuming nitric acid in 50 cm3 deionised water. Bring the volume to 100 cm3 in a volumetric flask. Transfer to a beaker, and allow to stand for 24 hours. Decant the clear solution. This solution is not as stable as that prepared by the other method, but has the advantage of not needing acidification.

Quantities needed per working group

25 cm3 of solution of sodium carbonate 25 cm3 of solution of sodium hydrogencarbonate 25 cm3 of solution of sodium sulfate

25 cm3 of solution of sodium sulfite 25 cm3 of solution of sodium chloride 25 cm3 of solution of sodium nitrate 25 cm3 of solution of disodium hydrogen phosphate 25 cm3 of each 'unknown' numbered sample 2 l deionised water 100 cm3 dilute hydrochloric acid solution 10 cm3 of concentrated sulfuric acid 10 cm3 dilute ammonia solution 10 cm3 limewater 10 cm3 of solution of magnesium sulfate 10 cm3 cold saturated solution of iron sulfate 10 cm3 of solution of barium chloride 10 cm3 of solution of silver nitrate 2 cm3 of acidified solution of sodium dichromate 10 cm3 of solution of ammonium molybdate reagent

Safety considerations
Caution must be exercised throughout the experiment when using glassware. When heating the contents of a test tube it should be held with a tongs at an angle in a Bunsen burner flame and the open mouth of the test tube should not be pointing at anyone. Safety glasses must be worn.

Chemical hazard notes

Potassium nitrate : A strong oxidising agent. Do not breathe dust; avoid contact with the skin and eyes. Sodium carbonate Wear eye protection.
i

is irritating to the eyes and skin, and its dust irritates the lungs.

All of sodium hydrogencarbonate, sodium sulfate, sodium sulfite and disodium hydrogen phosphate are eye irritants and contact with the skin should be avoided. Concentrated hydrochloric acid : Very corrosive to eyes and skin, and its vapour is very irritating to lungs. Add acid to water when diluting. Concentrated sulfuric acid : Corrosive and oxidising. Use with extreme caution. Add acid to water when diluting. Concentrated Nitric Acid : Vapour is dangerous to lungs and eyes. Severe burns from skin contact. Add acid to water when diluting. 4

Aqueous ammonia : Ammonia vapour is toxic and very irritating to the lungs. Use a fume cupboard when diluting. Calcium hydroxide Iron(II) sulfate Barium chloride
n i

: Avoid contact with the skin. Irritant to eyes, skin and lungs.

is harmful if swallowed. Irritant to eyes and skin.

n

is harmful by ingestion and inhalation.

Silver nitrate is corrosive and solutions of it less than 0.5 M are irritants. Solutions are very dangerous to the eyes and, if containing ammonia, can be explosive. Ammonium molybdate
n

is harmful by ingestion. Irritant to eyes and skin.

Disposal of wastes

(a) Carbonate and hydrogencarbonate tests: Dilute with water, and flush to foul water
drain.

(b) Sulfate and sulfite tests: Filter off barium sulfate and discard to refuse bin. Dilute
the filtrate with water, neutralise with anhydrous sodium carbonate and flush to foul water drain with excess water.

(c) Chloride test: Dilute with excess water, and flush to foul water drain. (d) Nitrate test: Dilute with water, neutralise with anhydrous sodium carbonate and
flush to foul water drain with excess water.

(e) Phosphate test: Dilute with excess water, and flush to foul water drain.

Specimen Results
Carbonate Effervescence, colourless gas evolved Limewater becomes milky: CO2 evolved. Na2CO3 + 2HCl 2NaCl + H2O + CO2 White precipitate formed Na2CO3 + MgSO4 Na2SO4 + MgCO3 No change observed None Hydrogencarbonate Effervescence, colourless gas evolved Limewater becomes milky: CO2 evolved. NaHCO3 + HCl NaCl + H2O + CO2 No change observed 2 NaHCO3 + MgSO4 Na2SO4 + Mg(HCO3)2 White precipitate appears Mg(HCO3)2 MgCO3 + H2O + CO2

Observations upon addition of HCl solution Observations and conclusion from limewater test Equation for reaction between the salt and HCl Observation upon addition of MgSO4 solution Equation for reaction between the salt and MgSO4 Observation upon heating Equation for reaction upon heating

Observation upon addition of BaCl2 solution Equation for reaction between the salt and BaCl2 Observation upon addition of HCl solution Equation for reaction upon addition of HCl

Sulfate White precipitate formed Na2SO4 + BaCl2 2NaCl + BaSO4 No change observed None

Sulfite White precipitate formed Na2SO3 + BaCl2 2NaCl + BaSO3 White precipitate disappears BaSO3 + 2HCl BaCl2 + H2O + SO2

Observations upon addition of AgNO3 solution Equation for reaction between the salt and AgNO3 Observation upon addition of NH3 solution

Chloride White precipitate appears NaCl + AgNO3 NaNO3 + AgCl White precipitate dissolves

Observations upon addition of FeSO4 solution Observation upon addition of concentrated H2SO4

Nitrate Nothing observed A brown ring appears at the boundary between the liquid layers Phosphate Yellow precipitate appears Precipitate dissolves

Observations upon addition of ammonium molybdate reagent and heating Observations upon addition of ammonia solution

Unknown (e.g. carbonate) Observations upon addition of HCl solution Gas evolved Conclusion from limewater test on any gas CO2 evolved Result from addition of MgSO4 solution White precipitate formed Result from addition of BaCl2 solution nothing observed followed by addition of HCl solution Observation upon addition of AgNO3 nothing observed solution Observation upon addition of FeSO4 nothing observed solution followed by concentrated H2SO4 Observation upon addition of ammonium nothing observed molybdate reagent CONCLUSION Carbonate

Solutions to student questions

1. Describe the appearance of pure samples of each of the following salts: sodium carbonate, sodium hydrogencarbonate, sodium sulfate, sodium sulfite, sodium chloride, sodium nitrate, disodium hydrogen phosphate. They are all white crystalline solids. The samples used in the experiment are aqueous solutions of the salts. 2. Explain the steps you would take to identify which of these anions are present in a mixture of salts.

(i) Take a 2 cm3 sample of the mixture. Add dilute hydrochloric acid solution and collect any gas evolved and test with limewater. If carbon dioxide gas was evolved then either a carbonate or a hydrogencarbonate or both anions are present. Take another 2 cm3 sample of the mixture. Add MgSO4 solution. If a precipitate forms, carbonate anion is present. Filter off the precipitate and heat. If further precipitate appears after heating, hydrogencarbonate ion is also present. (ii) Take another 2 cm3 sample of the mixture. Test with AgNO3 solution. If chloride ion is present a white precipitate is formed. This precipitate dissolves in dilute ammonia solution. (iii) Take another 2 cm3 sample of the mixture. Test with FeSO4 solution and concentrated sulfuric acid. A brown ring is observed if nitrate ion is present. (iv) Take another 2 cm3 sample of the mixture. Test with ammonium molybdate reagent. If phosphate ion is present a yellow precipitate is formed. This precipitate dissolves in dilute ammonia solution. (v) Take another 2 cm3 sample of the mixture. If there is no phosphate ion present, add BaCl2 solution and a precipitate will appear if either sulfite or sulfate is present. Add dilute hydrochloric acid dropwise. If all the precipitate dissolves only the sulfite anion was present. If there is a mixture of sulfite and sulfate anions some of the precipitate will remain but some will dissolve producing sulfur dioxide gas, which has a distinctive smell. 3. Which of these anions might be expected to be found in treated tap water? Give a possible source of each anion you mention. Hydrogencarbonate anion from water hardness. Sulfate ion from flocculating agents or water hardness. Chloride ion from water hardness or sterilisation treatment. 4. How would you distinguish two unlabelled samples, one of which is a carbonate and the other which is a hydrogencarbonate, from each other? Take a 2 cm3 sample of each sample. Add MgSO4 solution. If a precipitate forms, it confirms the carbonate anion is present. Heat the other test tube and a precipitate appears upon heating a sample with the hydrogencarbonate ion. 5. How would you distinguish two unlabelled samples, one of which is a sulfate and the other which is a sulfite, from each other?

Take a 2 cm3 sample of each sample. Add BaCl2 solution and a precipitate will appear in each test tube. Add dilute hydrochloric acid dropwise. If all the precipitate dissolves the sulfite anion was present. In the case of the sulfate anion, the precipitate is insoluble.

Extension Work
1. Use of a home soil test kit to test for nitrogen and phosphorus in soil extract would provide an interesting comparison to this experiment. 2. The tests could be applied to examine a sample of seawater for these anions. 3. Polluted water could be tested for phosphate and nitrate ions.

Industrial, Environmental & Social Links

Industry, medicine, and environmental science are more concerned with quantitative measurement of these anions than with just identifying their presence. Simple home soil test kits are an application of these types of test to establish the presence of nitrogen, phosphorus and the cation potassium in soil extract and crudely estimate the quantity present.