Chapter 13. Chemical Equilibrium

Chapter 13 Chemical Equilibrium

Section 13.1 The Equilibrium Condition

Section 13.5 Applications of the Equilibrium Constant

Section 13.5 Applications of the Equilibrium Constant c

Section 13.1 The Equilibrium Condition Chemical Equilibrium The state where the concentrations of all reactants and products remain constant with time. On the molecular level, there is frantic activity. Equilibrium is not static, but is a highly dynamic situation. Copyright Cengage Learning. All rights reserved 9

Section 12.1 Reaction Rates Average Kinetic Energy

Section 13.1 The Equilibrium Condition Chemical Equilibrium Concentrations reach levels where the rate of the forward reaction equals the rate of the reverse reaction. Copyright Cengage Learning. All rights reserved 12

Section 13.1 The Equilibrium Condition

Section 13.5 Applications of the Equilibrium Constant Law of mass action Q = K Law of mass action (Q=K) Chemical equilibrium systems obey the law of mass action. This law states that the reaction quotient, Q, will be equal to a constant when a system reaches chemical equilibrium.

Section 13.1 The Equilibrium Condition CONCEPT CHECK! Consider an equilibrium mixture in a closed vessel reacting according to the equation: H 2 O(g) + CO(g) H 2 (g) + CO 2 (g) You add more H 2 O(g) to the flask. How does the concentration of each chemical compare to its original concentration after equilibrium is reestablished? Justify your answer. Copyright Cengage Learning. All rights reserved 22

Section 13.1 The Equilibrium Condition CONCEPT CHECK! Consider an equilibrium mixture in a closed vessel reacting according to the equation: The concentrations H 2 O(g) + of CO(g) each product H 2 (g) will + CO increase, 2 (g) the concentration of CO will decrease, and the concentration of You water add will more be higher H 2 O(g) than to the the flask. original How equilibrium does the concentration, but of lower each chemical than the initial compare total to amount. its original concentration after equilibrium is reestablished? Justify your answer. Copyright Cengage Learning. All rights reserved 23

Section 13.1 The Equilibrium Condition CONCEPT CHECK! Consider an equilibrium mixture in a closed vessel reacting according to the equation: H 2 O(g) + CO(g) H 2 (g) + CO 2 (g) You add more H 2 to the flask. How does the concentration of each chemical compare to its original concentration after equilibrium is reestablished? Justify your answer. Copyright Cengage Learning. All rights reserved 24

Section 13.1 The Equilibrium Condition This is the opposite scenario of the previous slide. The concentrations of water and CO will increase. The concentration of carbon dioxide decreases and the concentration of hydrogen will be higher than the original equilibrium concentration, but lower than the initial total amount.

Section 13.5 Applications of the Equilibrium Constant Reaction Quotient, Q Used when all of the initial concentrations are nonzero. Apply the law of mass action using initial concentrations instead of equilibrium concentrations. Law of mass action (Q=K) Chemical equilibrium systems obey the law of mass action. This law states that the reaction quotient, Q, will be equal to a constant when a system reaches chemical equilibrium. Copyright Cengage Learning. All rights reserved 26

Section 13.2 The Equilibrium Constant Consider the following reaction at equilibrium: ja + kb lc + md K = c [C] l [A] j [D] [B] m k A, B, C, and D = chemical species. Square brackets = concentrations of species at equilibrium. j, k, l, and m = coefficients in the balanced equation. K = equilibrium constant (given without units). Copyright Cengage Learning. All rights reserved 27

Section 13.2 The Equilibrium Constant Conclusions About the Equilibrium Expression Equilibrium expression for a reaction is the reciprocal of that for the reaction written in reverse. When the balanced equation for a reaction is multiplied by a factor of n, the equilibrium expression for the new reaction is the original expression raised to the nth power; thus K new = (K original ) n. K values are usually written with no units. Copyright Cengage Learning. All rights reserved 28

Section 13.2 The Equilibrium Constant K always has the same value at a given temperature regardless of the amounts of reactants or products that are present initially. For a reaction, at a given temperature, there are many equilibrium positions but only one equilibrium constant, K. Equilibrium position is a set of equilibrium concentrations. Copyright Cengage Learning. All rights reserved 29

Section 13.3 Example Equilibrium Expressions Involving Pressures Write the equilibrium constant for this reaction: N 2 (g) + 3H 2 (g) 2NH 3 (g) K = 2 PNH P N PH p 3 3 2 2 K NH 3 = N 2 H 2 2 3 Copyright Cengage Learning. All rights reserved 31

Section 13.3 Example Equilibrium Expressions Involving Pressures Write the equilibrium constant involving gas pressures for this reaction. N 2 (g) + 3H 2 (g) 2NH 3 (g) K = 2 PNH P N PH p 3 3 2 2 K NH 3 = N 2 H 2 2 3 Copyright Cengage Learning. All rights reserved 33

Section 13.3 Example Equilibrium Expressions Involving Pressures Calculate the equilibrium constant for the following reaction: N 2 (g) + 3H 2 (g) 2NH 3 (g) Equilibrium pressures at a certain temperature: P P P NH N H 2 2 3 2 = 2.9 10 atm 1 = 8.9 10 atm 3 = 2.9 10 atm Copyright Cengage Learning. All rights reserved 35

Section 13.3 Equilibrium Expressions Involving Pressures K = N 2 (g) + 3H 2 (g) 2NH 3 (g) 2 PNH P N PH p 3 3 2 2 K 2 = 2.9 10 8.9 10 2.9 10 p 3 1 3 2 K p = 3.9 10 4 Copyright Cengage Learning. All rights reserved 36

Section 13.3 Equilibrium Expressions Involving Pressures

Section 13.3 Equilibrium Expressions Involving Pressures The Relationship Between K and K p K p = K(RT) Δn Δn = sum of the coefficients of the gaseous products minus the sum of the coefficients of the gaseous reactants. R = 0.08206 L atm/mol K T = temperature (in Kelvin) Copyright Cengage Learning. All rights reserved 41

Section 13.3 Equilibrium Expressions Involving Pressures Example N 2 (g) + 3H 2 (g) 2NH 3 (g) Using the value of K p (3.9 10 4 ) from the previous example, calculate the value of K at 35 C. K p = 2 4 4 3.9 10 = K 0.08206 L atm/mol K 308K K K RT = 2.5 10 n 7 Copyright Cengage Learning. All rights reserved 43

Section Homogeneous 13.3 Equilibria Equilibrium Expressions Involving Pressures Heterogeneous Equilibria

Section 13.4 Heterogeneous Equilibria Homogeneous Equilibria Homogeneous equilibria involve the same phase: N 2 (g) + 3H 2 (g) 2NH 3 (g) HCN(aq) H + (aq) + CN - (aq) Copyright Cengage Learning. All rights reserved 46

Section 13.4 Heterogeneous Equilibria Heterogeneous Equilibria Heterogeneous equilibria involve more than one phase: 2KClO 3 (s) 2KCl(s) + 3O 2 (g) 2H 2 O(l) 2H 2 (g) + O 2 (g) Copyright Cengage Learning. All rights reserved 50

Section 13.4 Heterogeneous Equilibria The position of a heterogeneous equilibrium does not depend on the amounts of pure solids or liquids present. The concentrations of pure liquids and solids are constant. 2KClO 3 (s) 2KCl(s) + 3O 2 (g) K = O 3 2 Copyright Cengage Learning. All rights reserved 51

Section 13.4 Heterogeneous Equilibria

Section 13.4 Heterogeneous Equilibria Additional Concepts

Section The Extent 13.4 of a Reaction Heterogeneous Equilibria

Section 13.5 Applications of the Equilibrium Constant The Extent of a Reaction A value of K much larger than 1 means that at equilibrium the reaction system will consist of mostly products the equilibrium lies to the right. Reaction goes essentially to completion. Copyright Cengage Learning. All rights reserved 65

Section 13.5 Applications of the Equilibrium Constant The Extent of a Reaction A very small value of K means that the system at equilibrium will consist of mostly reactants the equilibrium position is far to the left. Reaction does not occur to any significant extent. Copyright Cengage Learning. All rights reserved 66

Section 13.5 Applications of the Equilibrium Constant CONCEPT CHECK! If the equilibrium lies to the right, the value for K is. large (or >1) If the equilibrium lies to the left, the value for K is. small (or <1) Copyright Cengage Learning. All rights reserved 67

Section 13.5 Applications of the Equilibrium Constant 2014 AP Exam

ICE Section 13.5 Applications of the Equilibrium Constant

Section Le Chatelier's 13.5 principle Applications of the Equilibrium Constant Reaction Quotient Q In order to determine the direction of the equilibrium shift, the reaction quotient Q is compared to the equilibrium constant K.

Section 13.5 Applications of the Equilibrium Constant Reaction Quotient, Q Used when all of the initial concentrations are nonzero. Apply the law of mass action using initial concentrations instead of equilibrium concentrations. Copyright Cengage Learning. All rights reserved 90

Section 13.5 Applications of the Equilibrium Constant Reaction Quotient, Q Q = K; The system is at equilibrium. No shift will occur. Q > K; The system shifts to the left. Consuming products and forming reactants, until equilibrium is achieved. Q < K; The system shifts to the right. Consuming reactants and forming products, to attain equilibrium. Copyright Cengage Learning. All rights reserved 93

Section 13.5 Applications of the Equilibrium Constant EXERCISE! Consider the reaction represented by the equation: Fe 3+ (aq) + SCN - (aq) FeSCN 2+ (aq) Trial #1: 6.00 M Fe 3+ (aq) and 10.0 M SCN - (aq) are mixed at a certain temperature and at equilibrium the concentration of FeSCN 2+ (aq) is 4.00 M. What is the value for the equilibrium constant for this reaction? Copyright Cengage Learning. All rights reserved 100

Section 13.5 Applications of the Equilibrium Constant K = 0.333 Copyright Cengage Learning. All rights reserved 101 Set up ICE Table Fe 3+ (aq) + SCN (aq) FeSCN 2+ (aq) Initial 6.00 10.00 0.00 Change 4.00 4.00 +4.00 Equilibrium 2.00 6.00 4.00 2 FeSCN 4.00 = M K = Fe 3 SCN 2.00 M 6.00 M

Section 13.5 Applications of the Equilibrium Constant EXERCISE! Consider the reaction represented by the equation: Fe 3+ (aq) + SCN - (aq) FeSCN 2+ (aq) Trial #2: Initial: 10.0 M Fe 3+ (aq) and 8.00 M SCN (aq) (same temperature as Trial #1) Equilibrium:? M FeSCN 2+ (aq) 5.00 M FeSCN 2+ Copyright Cengage Learning. All rights reserved 102

Section 13.5 Applications of the Equilibrium Constant EXERCISE! Consider the reaction represented by the equation: Fe 3+ (aq) + SCN - (aq) FeSCN 2+ (aq) Trial #3: Initial: 6.00 M Fe 3+ (aq) and 6.00 M SCN (aq) Equilibrium:? M FeSCN 2+ (aq) 3.00 M FeSCN 2+ Copyright Cengage Learning. All rights reserved 103

Section 13.6 Solving Equilibrium Problems Solving Equilibrium Problems 1) Write the balanced equation for the reaction. 2) Write the equilibrium expression using the law of mass action. 3) List the initial concentrations. 4) Calculate Q, and determine the direction of the shift to equilibrium. Copyright Cengage Learning. All rights reserved 104

Section 13.6 Solving Equilibrium Problems Solving Equilibrium Problems 5) Define the change needed to reach equilibrium, and define the equilibrium concentrations by applying the change to the initial concentrations. 6) Substitute the equilibrium concentrations into the equilibrium expression, and solve for the unknown. 7) Check your calculated equilibrium concentrations by making sure they give the correct value of K. Copyright Cengage Learning. All rights reserved 105

Section 13.6 Solving Equilibrium Problems EXERCISE! Consider the reaction represented by the equation: Fe 3+ (aq) + SCN - (aq) FeSCN 2+ (aq) Fe 3+ SCN - FeSCN 2+ Trial #1 9.00 M 5.00 M 1.00 M Trial #2 3.00 M 2.00 M 5.00 M Trial #3 2.00 M 9.00 M 6.00 M Find the equilibrium concentrations for all species. Copyright Cengage Learning. All rights reserved 106

Section 13.6 Solving Equilibrium Problems EXERCISE! Answer Trial #1: [Fe 3+ ] = 6.00 M; [SCN - ] = 2.00 M; [FeSCN 2+ ] = 4.00 M Trial #2: [Fe 3+ ] = 4.00 M; [SCN - ] = 3.00 M; [FeSCN 2+ ] = 4.00 M Trial #3: [Fe 3+ ] = 2.00 M; [SCN - ] = 9.00 M; [FeSCN 2+ ] = 6.00 M Copyright Cengage Learning. All rights reserved 107

Section 13.6 Solving Equilibrium Problems CONCEPT CHECK! A 2.0 mol sample of ammonia is introduced into a 1.00 L container. At a certain temperature, the ammonia partially dissociates according to the equation: NH 3 (g) N 2 (g) + H 2 (g) At equilibrium 1.00 mol of ammonia remains. Calculate the value for K. K = 1.69 Copyright Cengage Learning. All rights reserved 108

Section 13.6 Solving Equilibrium Problems CONCEPT CHECK! A 1.00 mol sample of N 2 O 4 (g) is placed in a 10.0 L vessel and allowed to reach equilibrium according to the equation: N 2 O 4 (g) 2NO 2 (g) K = 4.00 10-4 Calculate the equilibrium concentrations of: N 2 O 4 (g) and NO 2 (g). Concentration of N 2 O 4 = 0.097 M Concentration of NO 2 = 6.32 10-3 M Copyright Cengage Learning. All rights reserved 109

Section 13.7 Le Châtelier s Principle If a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction that tends to reduce that change. Copyright Cengage Learning. All rights reserved 110

Section 13.7 Le Châtelier s Principle Effects of Changes on the System 1. Concentration: The system will shift away from the added component. If a component is removed, the opposite effect occurs. 2. Temperature: K will change depending upon the temperature (endothermic energy is a reactant; exothermic energy is a product). Copyright Cengage Learning. All rights reserved 111

Section 13.7 Le Châtelier s Principle Effects of Changes on the System 3. Pressure: a) The system will shift away from the added gaseous component. If a component is removed, the opposite effect occurs. b) Addition of inert gas does not affect the equilibrium position. c) Decreasing the volume shifts the equilibrium toward the side with fewer moles of gas. Copyright Cengage Learning. All rights reserved 112

Section 13.7 Le Châtelier s Principle

Section 13.7 Le Châtelier s Principle To play movie you must be in Slide Show Mode PC Users: Please wait for content to load, then click to play Mac Users: CLICK HERE Copyright Cengage Learning. All rights reserved 114

Section 13.7 Le Châtelier s Principle Equilibrium Decomposition of N 2 O 4 To play movie you must be in Slide Show Mode PC Users: Please wait for content to load, then click to play Mac Users: CLICK HERE Copyright Cengage Learning. All rights reserved 115

Section 13.7 Le Châtelier s Principle

Section 13.7 Le Châtelier s Principle 2014 AP Exam