Chemical Equilibrium

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1 1 Chemical Equilibrium Introduction: In many chemical reactions the reactants are not totally converted to products because of a reverse reaction. In reverse reactions, the products react to form the original reactants. These types of reactions are said to be reversible and use a double arrow in the equation. The reaction proceeding from left to right is normally called the forward reaction; the reaction from right to left is called the reverse reaction. Every chemical reaction proceeds at a certain rate or speed. The rate of a reaction depends on many things including the concentrations of the reactants and the conditions under which the reaction is conducted. When the rate of the forward reaction is equal to the rate of the reverse reaction, a state of chemical equilibrium exists. The concentrations of substances in equilibrium do not change, but both reactions, forward and reverse, are still occurring. The principle of Le Chatelier relates to systems in equilibrium and states that when the concentrations of a system in equilibrium are changed the system reacts to counteract the change and re-establish the equilibrium. This laboratory will allow you to observe the effect of changing the concentration of one or more substances in a chemical equilibrium. Suppose the following represents a system in equilibrium: A + B C + D When the concentration of any one of the substances in this equilibrium is changed, the equilibrium is disturbed (stressed). Changes in the concentrations of all the other substances will occur to establish a new position of equilibrium. For example, when the concentration of B is increased, the rate of forward reaction increases, the concentration of A decreases, and the concentrations of C and D increase. After a period of time, the two rates will become equal and the system will again be in equilibrium. Evidence of a shift in equilibrium by a change in concentration can easily be observed of one of the substances involved in the equilibrium is colored. The appearance of a precipitate or the change in color of an indicator can sometimes be used to detect a shift in equilibrium.

2 2 Procedure: Saturated Sodium Chloride Solution. Add a few drops of concentrated HCl to 2 to 3 ml of saturated sodium chloride solution in a test tube. Note the results on your report form. The net ionic equation for this equilibrium system is: NaCl(s) Na + (aq) + Cl (aq) Saturated Ammonium Chloride Solution. Add a few drops of concentrated HCl to 2 to 3 ml of saturated ammonium chloride solution in a test tube. Note the results on your report form. The net ionic equation for this equilibrium system is: NH4Cl(s) NH4 + (aq) + Cl (aq) Iron(III) Chloride plus Potassium Thiocyanate. Mix 1 ml of 0.1 M iron(iii) chloride and 1 ml of 0.1 M potassium thiocyanate and 50 ml of distilled water. Pour about 5 ml of this stock solution into each of three test tubes: (1) use the first test tube as a comparison control; (2) add about 1 ml of 0.1 M iron(iii) chloride to the second test tube and observe the color change record on report form; (3) add about 1 ml of 0.1 M potassium thiocyanate to the third test tube and observe the color change record on report form. The net ionic equation for this equilibrium system is: Fe +3 (aq) + SCN (aq) Fe(SCN) +2 (aq) pale yellow colorless red Potassium Chromate with Nitric and Sulfuric Acids. Pour 2 to 3 ml of 0.1 M potassium chromate solution into two separate test tubes. Add 2 drops of 6 M HNO3 to one test tube, add 2 drops of 3 M H2SO4 to the other. Note any color changes. Add 10% NaOH solution drop-wise to each test tube until the original color of potassium is restored. The net ionic equation for this equilibrium system is: 2 CrO4 2 (aq) + 2 H + (aq) Cr2O7 2 (aq) + H2O yellow orange

3 3 Cobalt(II) Chloride Solution. Put about 2 ml of 0.1 M cobalt(ii) chloride solution into each of three separate test tubes. To the first test tube, add about 3 ml of concentrated HCl drop-wise and note the result. Now add water dropwise to the solution until the original color is evident. To the second test tube, add about 1.5 grams of solid ammonium chloride and shake to make a saturated salt solution. Compare the color with the solution in the third test tube (the control). Place the second and third test tubes (unstoppered!) in a beaker of boiling water, shake the test tubes occasionally, and note the results. Cool the test tubes under tap water until the original color is evident. The net ionic equation for this equilibrium system is: Co(H2O)6 +2 (aq) + 4 Cl (aq) CoCl4 2 (aq) + 6 H2O pink blue Ammonia Solution. Add 2 drops of concentrated ammonia and 3 drops of phenolphthalein indicator to 50 ml of tap water and mix. Pour 5 ml of this stock solution into two separate test tubes. To the first test tube, dissolve a small amount of solid ammonium chloride and note the results. To the second test tube, add a few drops of 6 M HCl, mix and note the results. The net ionic equation for this equilibrium system is: NH3(aq) + H2O NH4 + (aq) + OH (aq) Copper(II) Sulfate Solution. Place 20 drops of 0.1 M CuSO4 solution into a clean test tube. Add drop-wise 1 M NH3 solution, mixing the contents after each drop. Continue to add until the color changes. Note the new color and the number of drops of 1 M NH3 added and record on your report sheet. To this equilibrium mixture, add drop-wise 1 M HCl solution until the color changes back to pale blue. Record the number of drops of HCl added. The net ionic equation for this equilibrium system is: Cu(H2O)4 +2 (s) + 4 NH3(aq) Cu(NH3)4 +2 (aq) + 4 H2O pale blue colorless cool blue

4 4

5 5 Name Date Report for Chemical Equilibrium Experiment: Questions: Saturated Sodium Chloride: 1. What is the evidence for a shift in equilibrium? 2. Which ion caused the equilibrium to shift? 3. In which direction did the equilibrium shift? Saturated Ammonium Chloride: 4. What is the evidence for a shift in equilibrium? 5. Which ion caused the equilibrium to shift? 6. In which direction did the equilibrium shift? Iron(III) Chloride plus Potassium Thiocyanate: 7. What is the evidence for a shift in equilibrium when iron(iii) chloride is added to the stock solution?

6 6 8. What is the evidence for a shift in equilibrium when potassium thiocyanate is added to the stock solution? Potassium Chromate with Nitric and Sulfuric Acids: 9. What is the evidence for a shift in equilibrium when the nitric acid and the sulfuric acid were added to the potassium chromate solution? 10. Explain how sodium hydroxide caused the equilibrium to shift back again. Cobalt(II) Chloride Solution: 11. What is the evidence for a shift in equilibrium when concentrated hydrochloric acid was added to the cobalt chloride solution? 12. Tell whether the concentration of each of the following substances was increased, decreased, or unaffected when conc. hydrochloric acid was added to cobalt chloride solution: Co(H2O)6 +2 (aq) Cl (aq) CoCl4 2 (aq)

7 7 13. What did you observe when ammonium chloride was added to cobalt chloride solution? 14. What did you observe when this mixture was heated? 15. What did you observe when the mixture was cooled? Ammonia Solution: 16. What is the evidence for a shift in equilibrium when ammonium chloride was added to the stock solution? 17. Explain, in terms of the equilibrium, the results observed when hydrochloric acid was added to the stock solution. 18. Tell whether the concentration of each of the following substances was increased, decreased, or unaffected when hydrochloric acid was added to the ammonia stock solution: NH3(aq) NH4 + (aq) OH (aq) pink color

8 8 Copper(II) Sulfate Solution: 19. What is the color of the copper-ammonia complex? 20. How many drops of 1 M NH3 did you add to cause a change in color? 21. How many drops of 1 M HCl did you add to cause a change in color back to pale blue? Problems: 1. For the reaction PCl3(g) + Cl2(g) PCl5(g) at 25ºC, the equilibrium concentrations are : [PCl3] = 7.2 M, [PCl5] = M, and [Cl2] = 7.2 M. Find the equilibrium constant for the reaction. 2. The above reaction is exothermic. If the reaction was run at 15ºC, would the equilibrium concentration of [PCl5] be greater, smaller, or the same as M?

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