Mandatory Experiment 8.1 Simple experiments to illustrate Le Chatelier's Principle Student Material (a) The equilibrium between CoCl42- and Co(H2O)62+ Theory Le Chatelier’s Principle states that when a disturbance is imposed on a system at equilibrium, the equilibrium shifts in such a way as to minimise the effect of the disturbance. Some reactions involving cobalt compounds are suitable for illustrating Le Chatelier’s Principle because they involve clear colour changes. Co(H2O)62+ is pink in aqueous solution and CoCl42- is blue. The equilibrium between the two species is CoCl42- + 6H2O Blue Co(H2O)62+ + 4ClPink The forward reaction is exothermic. The equilibrium between the two species can be disturbed by (i) adding Cl- ions or water or (ii) changing the temperature. In both cases the changes that occur are as predicted by Le Chatelier’s Principle. Chemicals and Apparatus Cobalt(II) chloride (or cobalt(II) nitrate) Deionised water Concentrated hydrochloric acid Ethanol Crushed ice Sodium chloride Boiling tubes and racks Dropping pipettes 250 cm3 Pyrex beakers 100 cm3 measuring cylinders Electronic balance Safety glasses 1 . Procedure NB: Wear your safety glasses. 1. Dissolve 4 g of cobalt chloride-6-water in 40 cm3 of deionised water. The following equilibrium is set up when the crystals are added to water: CoCl42- + 6H2O Blue Co(H2O)62+ + 4ClPink Since the pink colour is predominant, we may conclude that the equilibrium lies on the right hand side. 2. Using a fume cupboard, add concentrated hydrochloric acid, with stirring, until a violet solution is formed. 3. Adding more concentrated hydrochloric acid produces a blue colour, while adding water will restore the pink colour. By trial and error produce an “in between” violet (or lilac) colour which will contain the two cobalt ions. Place this solution in each of six boiling tubes to a depth of about 2 cm (Fig. 1). Fig. 1 4. To study the effects of concentration changes on equilibrium, keep one tube as a control. Add water to a second tube using a dropping pipette. The colour of the solution should change to pink. The equilibrium has now shifted to the right hand side as the forward reaction absorbs the stress of the increased concentration of water. 2 5. Using a fume cupboard add concentrated hydrochloric acid to a third tube using a dropping pipette. The colour of the solution should change to blue. The equilibrium has now shifted to the left hand side since adding the concentrated HCl increases the concentration of Cl- ions and, in keeping with Le Chatelier’s Principle, the concentration of these ions is decreased by the backward reaction taking place. . 6. To study the effects of temperature changes on equilibrium, keep one tube as a control. Place another tube in a beaker of hot water (over 90 0C). Note that the colour changes to blue. This is in keeping with Le Chatelier's Principle, i.e. the endothermic reaction (reverse reaction) predominates in order to absorb the added heat. 7. Place another tube in a beaker of crushed ice and water. Note that the colour changes to pink. This is in keeping with Le Chatelier's Principle, i.e. the exothermic reaction (forward reaction) predominates in order to replace the lost heat. Questions relating to the experiment 1. Why is a control used in this experiment? 2. Explain why there is a colour change in the mixture when a boiling tube containing it is placed in ice. 3. Explain why there is a colour change in the mixture when a boiling tube containing it is placed in hot water. 4. Explain why there is a colour change in the mixture when water is added. 5. Explain why there is a colour change in the mixture when concentrated hydrochloric acid is added. 6. How can it be shown that it is the chloride ions in the hydrochloric acid that cause this colour change? 3 Teacher Material It is advisable to have supplies of boiling water and ice available in advance of the experiment. Sheets of white paper provide a useful background when the colours of the solutions are being observed. The “in between” violet solution described in step 3 of the procedure is crucial to the success of the experiment. It may therefore be advisable for the teacher to prepare this solution in sufficient quantity for the class in advance, to ensure that it has the correct colour. This would also save time; students could be given the “in between” solution, and asked to continue from there. This approach would also avoid potential problems caused by each group of students using 60 cm3 of concentrated hydrochloric acid. To avoid using too much concentrated hydrochloric acid for this experiment, the following variation may be found useful. Dissolve the cobalt salt in a small quantity of water and dilute this solution with ethanol, without precipitating the salt. Since the solution contains less water, it will be found that less hydrochloric acid is required. Extension work To show that it is the chloride ions in the hydrochloric acid that shift the equilibrium, add a spatula of sodium chloride to the pink solution. This produces a bluer colour eventually, although because the salt is slow to dissolve, it will take some time for the colour change to occur. Preparation of Reagents Dilute sodium hydroxide solution (1 M): Carefully add, in stages, 40 g of sodium hydroxide with constant stirring to about 800 cm3 of water. Continue stirring until all of the solid has dissolved. Transfer the solution to a volumetric flask. Rinse the beaker and add rinsings to the volumetric flask. Make the solution up to 1 litre with water. Stopper, and mix thoroughly. Dilute ethanoic acid solution (1 M): In a fume cupboard, add 57 cm3 to about 600 cm3 of water in a beaker. Stir, and pour the solution into a 1000 cm3 volumetric flask. Add rinsings to the volumetric flask. Make the solution up to 1 litre with water. Stopper, and mix thoroughly. 4 Quantities needed per working group 4 g cobalt chloride-6-water 100 cm3 concentrated hydrochloric acid Safety considerations Safety glasses must be worn. The use of gloves is recommended. Operations involving the use of concentrated hydrochloric acid should be carried out in the fume cupboard. Chemical hazard notes Concentrated hydrochloric acid is very corrosive to eyes and skin, and its vapour is very irritating to lungs. Solid cobalt chloride is harmful, and should not be allowed to be ingested or to come into contact with the skin. Solid sodium hydroxide is corrosive, and can cause severe burns to eyes and skin. Always wear eye protection. Concentrated ethanoic acid can cause severe burns. The vapour is very irritating to lungs. Ethanol - highly flammable; keep away from sources of ignition. Disposal of wastes Add 1 M sodium hydroxide solution to the waste. Filter off slurry and bag for landfill waste. Neutralise the filtrate with 1 M ethanoic acid solution and flush to foul water drain. Suggested Solutions to Student Questions 1. Why is a control used in this experiment? In order to be able to compare colours formed with the original colour. 5 2. Explain why there is a colour change in the mixture when a boiling tube containing it is placed in ice. In the equilibrium CoCl42- + 6H2O Co(H2O)62+ + 4ClBlue Pink the forward reaction is exothermic. Lowering the temperature favours the exothermic reaction, according to Le Chatelier’s Principle, and so the colour changes to pink. 3. Explain why there is a colour change in the mixture when a boiling tube containing it is placed in hot water. In the equilibrium CoCl42- + 6H2O Co(H2O)62+ + 4ClBlue Pink the reverse reaction is endothermic. Raising the temperature favours the endothermic reaction, according to Le Chatelier’s Principle, and so the colour changes to blue. 4. Explain why there is a colour change in the mixture when water is added. Adding water shifts the equilibrium to the right, according to Le Chatelier’s Principle, and so the colour changes to pink. 5. Explain why there is a colour change in the mixture when concentrated hydrochloric acid is added. Adding hydrochloric acid shifts the equilibrium to the left, according to Le Chatelier’s Principle, and so the colour changes to blue. 6. How can it be shown that it is the chloride ions in the hydrochloric acid that cause this colour change? Add solid sodium chloride to the “in-between” solution – a colour change to blue occurs. Since chloride ions are the only type of ion found in both hydrochloric acid and sodium chloride, the effect must be due to the chloride ions. 6 Student Material (b) The equilibrium between CrO42- and Cr2O72Theory Some reactions involving chromium compounds are also suitable for illustrating Le Chatelier’s Principle because they involve clear colour changes. One such equilibrium is Cr2O72- + H2O orange 2CrO42- + 2H+ yellow This experiment will be used to demonstrate the effects of concentration changes on an equilibrium mixture. Adding an acid will increase the concentration of H+, and adding a base will reduce it. Chemicals and Apparatus Sodium dichromate solution Sodium hydroxide solution (2 M) Dilute hydrochloric acid (2 M) i Boiling tubes and racks Dropping pipettes Safety glasses Procedure NB: Wear your safety glasses. 1. Quarter fill a test tube with the solution of sodium dichromate provided. This should have an orange colour. The following equilibrium exists: Cr2O72- + H2O orange 2CrO42- + 2H+ yellow Since the orange colour predominates, the equilibrium must lie on the left hand side of the equation. 2. Keep a second sample of the sodium dichromate solution in a test tube as a control. 7 3. Carefully add some bench dilute sodium hydroxide solution until the orange colour changes to yellow. The sodium hydroxide removes the H+ ions giving rise to a stress and therefore, in keeping with Le Chatelier's Principle, the forward reaction predominates to produce more H+ ions. 4. Carefully add dilute hydrochloric acid until the yellow colour changes back to orange. The added hydrochloric acid creates an excess of H+ ions that causes the equilibrium reaction to be shifted to the left in order to absorb this excess of H+ ions. Questions relating to the experiment 1. When sodium hydroxide solution is added to a solution of potassium dichromate, a colour change occurs. Describe the colour change, and explain why it happens. 2. Why does adding hydrochloric acid reverse the colour change referred to in question 1? 3. Why is a control used in this experiment? 4. Describe and explain what happens when hydrochloric acid is added to a solution of potassium chromate. 8 Teacher material Sheets of white paper provide a useful background when the colours of the solutions are being observed. Extension work This experiment can also be carried out starting with a solution of sodium chromate, to which first hydrochloric acid solution and then sodium hydroxide solution are added. In this case a sample of the original sodium chromate solution should be kept as a control. Preparation of Reagents Sodium dichromate solution (0.17 M): Dissolve 20 g of sodium dichromate in deionised water and make up to 400 cm3. Stopper, and mix thoroughly. Dilute hydrochloric acid (2 M): Using a fume cupboard, dilute 170 cm3 of concentrated hydrochloric acid to 1 litre with deionised water. Stopper, and mix thoroughly. Dilute sodium hydroxide solution (2 M): Carefully add, in stages, 80 g of sodium hydroxide with constant stirring to about 800 cm3 of water. Continue stirring until all of the solid has dissolved. Make the solution up to 1 litre. Stopper, and mix thoroughly. Sodium chromate solution (0.21 M): Dissolve 20 g of sodium chromate in deionised water and make up to 400 cm3. Stopper, and mix thoroughly. The 1 M sulfuric acid solution for disposal of the waste from the reaction is prepared as follows: (Always dilute sulfuric acid by adding the acid to water and not the other way round.) 56 cm3 of the concentrated acid is added slowly to about 700 cm3 of deionised water containing about 20 ice cubes. The mixture is stirred and made up to 1 litre in a volumetric flask with deionised water. The flask is stoppered and inverted a number of times. Quantities needed per working group 20 cm3 sodium dichromate solution 30 cm3 dilute sodium hydroxide solution 30 cm3 dilute hydrochloric acid Safety considerations Safety glasses must be worn. 9 The use of gloves is strongly recommended, and they should definitely be worn when the solutions are being made up. The acid solution, dichromate solution and chromate solution should each be made up in a fume cupboard. Chemical hazard notes Concentrated hydrochloric acid is very corrosive to eyes and skin, and its vapour is very irritating to lungs. Solid sodium hydroxide is corrosive, and can cause severe burns to eyes and skin. Always wear eye protection. Solid sodium dichromate is toxic, and should not be allowed to be inhaled, ingested or to come into contact with the skin. The solid salt may cause cancer by inhalation of dust. Avoid raising dust during preparation of the solution – prepare the solution in a fume cupboard. Solid sodium chromate is toxic, and should not be allowed to be inhaled, ingested or to come into contact with the skin or eyes. Ulceration may occur on damaged skin. n Sodium metabisulfite is harmful if swallowed. It produces the toxic gas sulphur dioxide on contact with acids. Using this material in the disposal of waste material from the experiment should therefore be carried out in a fume cupboard. Concentrated sulfuric acid is very corrosive to eyes and skin. Due to its very considerable heat of reaction with water, it is essential that the acid be added to water when it is being diluted. i Dilute sulfuric acid is harmful to eyes and an irritant to skin. Disposal of wastes Add some 1 M sulfuric acid to the waste. In a fume cupboard add sodium metabisulfite to produce a green solution of chromium(III). Dilute with excess water and flush to foul water drain. Suggested Solutions to Student Questions 1. When sodium hydroxide solution is added to a solution of potassium dichromate, a colour change occurs. Describe the colour change, and explain 10 why it happens. The colour changes from orange to yellow. In the equilibrium Cr2O72- + H2O 2CrO42- + 2H+ orange yellow adding sodium hydroxide solution removes H+, and so shifts the equilibrium to the right, according to Le Chatelier’s Principle. Therefore the colour changes to yellow. 2. Why does adding hydrochloric acid reverse the colour change referred to in question 1? The colour changes from yellow to orange. In the equilibrium Cr2O72- + H2O 2CrO42- + 2H+ orange yellow adding acid increases the concentration of H+ ions and therefore shifts the equilibrium to the left, according to Le Chatelier’s Principle. Therefore the colour changes to orange. 3. Why is a control used in this experiment? In order to be able to compare colours formed with the original colour. 4. Describe and explain what happens when hydrochloric acid is added to a solution of potassium chromate. The colour changes from yellow to orange. In the equilibrium Cr2O72- + H2O 2CrO42- + 2H+ orange yellow adding acid increases the concentration of H+ ions and therefore shifts the equilibrium to the left, according to Le Chatelier’s Principle. Therefore the colour changes to orange. 11 Student Material (c) The equilibrium between Fe3+ and Fe(CNS)2+ Theory Some reactions involving iron compounds are suitable for illustrating Le Chatelier’s Principle because they also involve clear colour changes. One such equilibrium is Fe3+ + CNSyellow Fe(CNS)2+ red This experiment will be used to demonstrate the effects of concentration changes on an equilibrium mixture. Adding hydrochloric acid reduces the concentration of Fe3+ by forming a complex ion containing iron and chlorine. This causes a shift of equilibrium to the left. The equilibrium can be shifted to the right hand side by adding some potassium thiocyanate solution. Chemicals and Apparatus Concentrated hydrochloric acid Iron(III) chloride solution (0.05 M) Potassium thiocyanate solution (0.05 M) Boiling tubes and racks Dropping pipettes Safety glasses Procedure: NB: Wear your safety glasses. 1. Mix together about 5 cm3 respectively of solutions of iron(III) chloride and potassium thiocyanate in a beaker. Note the formation of the red complex. Fe3+ + CNSyellow Fe(CNS)2+ red Since the red complex above is formed, the equilibrium must lie on the right hand side of the equation. 2. Divide the mixture into three portions in separate boiling tubes (Fig. 2). Keep one of these as a control. 12 Fig. 2 3. Using a fume cupboard, add some concentrated hydrochloric acid to the second tube until the red colour disappears. In keeping with Le Chatelier's Principle, the red colour disappears as the equilibrium is shifted to the left hand side to replace the Fe3+ ions removed. 4. Add an equivalent amount of water to the third tube, and compare. This comparison should indicate that the extent of lightening of the colour is not due to a diluting effect. 5. To the second tube, add some potassium thiocyanate solution. The red complex reforms because the equilibrium is shifted to the right. Questions relating to the experiment 1. Why is a control used in this experiment? 2. When potassium thiocyanate solution is added to a solution of iron(III) chloride, a colour change occurs. Describe the colour change, and explain why it happens. 3. Why does adding hydrochloric acid reverse the colour change referred to in question 2? 4. How can it be shown that it is the chloride ions in the hydrochloric acid that cause this reversal? 5. Why is water added in step 4 of the procedure? 6. Name a substance other than hydrochloric acid that can reverse the colour change referred to in question 2. 13 Teacher material Saturated potassium chloride solution can be used instead of hydrochloric acid in this experiment, but because it contains much less chloride per unit volume than hydrochloric acid, it is not as effective. This solution should be shaken immediately before use. Sheets of white paper provide a useful background when the colours of the solutions are being observed. Preparation of Reagents Iron(III) chloride solution (0.05 M): Dissolve 13.5 g of iron(III) chloride in about 500 cm3 of deionised water containing about 20 cm3 of concentrated hydrochloric acid. Make the solution up to 1 litre. Stopper, and mix thoroughly. Potassium thiocyanate solution (0.05 M): Dissolve 5 g of potassium thiocyanate in deionised water. Make the solution up to 1 litre. Stopper, and mix thoroughly. Saturated potassium chloride solution: Add, with stirring, potassium chloride to 200 cm3 of deionised water until some remains undissolved, even after vigorous stirring. Stopper, and mix thoroughly. Quantities needed per working group 30 cm3 iron(III) chloride solution 30 cm3 potassium thiocyanate solution 10 cm3 saturated potassium chloride solution 10 cm3 concentrated hydrochloric acid Safety considerations Safety glasses must be worn. The use of gloves is recommended. Operations involving the use of concentrated hydrochloric acid should be carried out in the fume cupboard. Chemical hazard notes Concentrated hydrochloric acid is very corrosive to eyes and skin, and its vapour is very irritating to lungs. 14 i Iron(III) chloride is an eye and skin irritant, and severe eye burns may result if not attended to. n Potassium thiocyanate is harmful if swallowed. i Sodium carbonate (anhydrous) is an irritant to eyes and skin, and its dust irritates lungs. Disposal of wastes Neutralise wastes with anhydrous sodium carbonate. Dilute with excess water and flush to foul water drain. Suggested Solutions to Student Questions 1. Why is a control used in this experiment? In order to be able to compare colours formed with the original colour. 2. When potassium thiocyanate solution is added to a solution of iron(III) chloride, a colour change occurs. Describe the colour change, and explain why it happens. The colour changes from yellow to red. In the equilibrium Fe3+ + CNSFe(CNS)2+ yellow red some of the red complex Fe(CNS)2+ is formed, giving rise to the red colour. 3. Why does adding hydrochloric acid reverse the colour change referred to in question 2? In the equilibrium Fe3+ + CNSFe(CNS)2+ yellow red adding hydrochloric acid causes the removal of Fe3+, due to the formation of a complex ion containing iron and chlorine. This results in a shift of the equilibrium to the left, according to Le Chatelier’s Principle, and so the colour changes to yellow. 4. How can it be shown that it is the chloride ions in the hydrochloric acid that cause this reversal? Add saturated potassium chloride solution (or saturated sodium chloride 15 solution) to the red solution – a colour change to yellow occurs. Again, this is due to the removal of Fe3+ because of the formation of a complex ion containing iron and chlorine. Since chloride ions are the only type of ion found in both hydrochloric acid and sodium chloride, the effect must be due to the chloride ions. 5. Why is water added in step 4 of the procedure? To show by comparison that the extent of lightening of the colour is not due to a diluting effect. 6. Name a substance other than hydrochloric acid that can reverse the colour change referred to in question 2. Potassium chloride, or sodium chloride. 16