1. Chapter 14 Chemical Equilibruim

2. Objectives Describe chemical equilibrium Write an equilibrium constant expression Calculate the equilibrium constant for a reaction Relate the equilibrium constant to the position of a reaction

3. Chemical Equilibrium Point in a chemical reaction where the forward and reverse reactions happen at the same rate. There does not need to be equal amounts of reactants and products –There can be a large amount of product or a large amount of reactant at equilibrium The rates just need to be equal

4. Chemical Equilibrium Equilibrium is indicted by double arrows in reactions –Forward reaction points right Products –Reverse reaction points left Reactants The right is still products, the left is still reactants

5. Chemical Equilibrium Equilibrium is a dynamic process –Continually happening Reaction will continue even though it will appear to have stopped Similar to a person on a treadmill

6. Example Consider the reaction A + B  C Initially only A & B are present

7. Example Consider the reaction A + B  C A & B begin to disappear, C begins to appear

8. Example Consider the reaction A + B  C A & B begin to disappear, C begins to appear

9. Example Consider the reaction A + B  C A & B begin to disappear, C begins to appear

10. Example Consider the reaction A + B  C A & B begin to disappear, C begins to appear

11. Example Consider the reaction A + B  C Eventually equilibrium is reached

12. Equilibrium Constant Expressions A mathematical equation that relates the concentration of products to the concentration of reactants for a reaction at equilibrium The equilibrium constant is Keq K for Konstant, eq for equilibrium General form of the expression is concentration of products over concentration of reactants –Pressure can also be used

13. The Equilibrium Constant Expression For the reaction jA + kB  lC + mD Where j, k, l, & m are coefficients and A, B, C, and D are chemicals The equilibrium constant expression is

14. Equilibrium Constant Expressions A species in brackets indicates concentration Only solutions and gases are included in equilibrium expressions If you have a solid or liquid leave it out –Just think of it as a 1 in the expression

15. Example Write the equilibrium expression for the following reaction. HF (aq)  H + + F -

16. Example Write the equilibrium expression for the following reaction. 2NO (g)  N 2(g) + O 2(g)

17. Example Write the equilibrium expression for the following reaction. 2C (s) + O 2(g)  2CO (g)

18. The Equilibrium Constant A value that relates the position of a reaction at equilibrium Calculated by inserting values into the equilibrium constant expression Keq does NOT have units Keq > 1 –Product favored Keq <1 –Reactant favored

19. The Equilibrium Constant & Temp Equilibrium constants are constant for a given temperature –If the temp. changes so does the constant –Change depends on whether the reaction is exothermic or endothermic More on that later

20. Example Calculate the equilibrium constant for the following reaction and equilibrium concentrations [HF]= 0.12M [H + ]= 9.3x10 -3 M [F - ]= 9.3x10 -3 M HF (aq)  H + + F -

21. Example Calculate the equilibrium concentration of NO given the reaction, Keq, and equilibrium concentrations. [N 2 ] = 0.37M [O 2 ] = 0.45M Keq = 2.3x10 -9 2NO (g)  N 2(g) + O 2(g)

22. Homework p.573 #26,32,35,39,52,55,61

23. Objectives Explain LeChatliers Principle Predict equilibrium shifts Describe solubility equilibrium Write Ksp expressions Perform calculations with Ksp

24. My Equilibrium is Stressed A reaction at equilibrium can be stressed out by changing reaction conditions –There are three stresses for reactions Concentration Pressure Temperature Q) If you are stressed what do you do? A) Work to relieve the stress! –Same goes for reactions

25. LeChatlier’s Principle When a stress is applied to a reaction at equilibrium the reaction will shift to relieve the stress placed upon it.

26. Concentration A reaction is stressed when the concentration of a reactant or product is increased OR decreased –Add a chemical to increase –Remove a chemical to decrease Reactions shift away from increased concentrations Reactions shift toward decreased concentrations

27. Example Consider the reaction 2SO 2(g) + O 2(g)  2SO 3(g) How will the reaction shift with the following –Increase the amount of SO 2 Right –Increase the amount of SO 3 Left –Decrease the amount of O 2 Left

28. Pressure Pressure can increased By decreasing volume Pressure can be decreased By increasing volume Increased pressure shifts reactions away from side with more gas molecules Decreased pressure shifts reactions toward side with more gas molecules

29. Example Consider the reaction 2SO 2(g) + O 2(g)  2SO 3(g) How will the reaction shift with the following –Increase the pressure in the container Right –Decrease the pressure in the container Left

30. Temperature Direction of shift depends of whether the reaction is exothermic or endothermic –How do you know Exothermic reactions release heat –It is a product Endothermic reactions absorb heat –It is a reactant

31. What Type of Thermic Is It? Exothermic A + B  C + 49kJ A + B  C ΔH = -49kJ ΔH means enthalpy (energy change) Endothermic A + B + 49kJ  C A + B  C ΔH = 49kJ

32. Temperature Change Think of the temp as a concentration of heat –Increasing the temp. will shift the reaction away from the heat –Decreasing the temp. will shift the reaction toward the heat. Same as concentration shift Change in temp. is the only stress that changes the equilibrium constant.

33. Example Consider the reaction 2SO 2(g) + O 2(g)  2SO 3(g) + 197kJ How will the reaction shift with the following –Increase the temperature Left –Decrease the temperature Right

34. Common Ion Effect The addition of an ion that is present in the equilibrium HF  H + + F - Adding a H + or F - shifts the reaction left How do you add them? –H + can come from any acid –F - could be from NaF, KF, CaF 2

35. Addition of Other Stuff Adding species not related to the equilibrium reaction have no effect on the reaction –NO SHIFT For Example –Catalysts –Inert Gases

36. Solubility Equilibrium Dissolving is an equilibrium process Chemicals that we say are insoluble are actually very slightly soluble –Meaning only a small amount of the solute dissolves –Concentrations are very small 10 -5 M to 10 -20 M are common

37. Solubility Equilibrium Iron (II) Sulfide is “insoluble” by solubility rules However, it still dissolved to a small extent Consider the reaction FeS (s)  Fe +2 + S -2 Since dissolving is an equilibrium process we can write an equilibrium expression Keq = [Fe +2 ] [S -2 ] FeS is omitted because it is a solid

38. Solubility Product Constant The previous equilibriums expression is a “special” type of equilibrium expression Ksp – solubility product constant Ksp = [Fe +2 ] [S -2 ] –Only used for slightly soluble salts –Never includes the reactants –Ksp’s are very small –Check out the table 14.1 page 568

39. Ksp Values Lead (II) Chloride 2.4X10 -4 Strontium Carbonate 3.8X10 -9 Nickel (II) Hydroxide 5.5X10 -16 Copper (II) Hydroxide 2.2X10 -20 Cadmium Sulfide 8.0X10 -28 Silver Sulfide 6.0X10 -51 And my personal favorite Bismuth Sulfide 1.6x10 -72

40. Ksp Values Q) What does a small Ksp value mean? A) Low concentration of ions Small solubility Q) Is the compound with the smallest Ksp the least soluble? A) Not necessarily –There are different numbers of ions that changes the expression

41. Solubility of Salts We can easily compare solubility for salts that have the same # of ions When there are the same # of ions the salt with the smallest Ksp is least soluble Which salt is least soluble, most soluble AgCl, FeS, – FeS 6.0x10 -19 Least soluble –AgCl 1.6x10 -10 Most soluble –BaSO 4 1.1x10 -10 Middle

42. Calculating Solubility We can calculate solubility of salts and the concentration of the ions in solutions from Ksp Deal with saturated solutions –The salt has dissolved as much as it can Ksp has been reached In saturated solutions the concentrations of the ions are related to the mole ratio

43. Example Calculate the solubility of silver chloride

44. Example Calculate the solubility of mercury (II) sulfide

45. Example Calculate the solubility of calcium phosphate

46. Example A saturated solution of Iron (III) Hydroxide has a concentration of Fe +3 of 1.8x10 -8. What is the Ksp of Iron (III) Hydroxide?

47. Common Ion Revisited Anyone ever have a barium shake for a scan? Contains barium sulfate. –Barium ions are very toxic to the body –Treated as calcium How can you have fewer barium ions in solution? Add Sodium Sulfate

48. Homework p.574 #71,77,89,95,97,102