Unit 6.1 Chemical Equilibrium Sections: 14, 17.6, 18.4, 18.5 Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display.

Equilibrium is a state in which there are no observable changes as time goes by. Chemical equilibrium is achieved when: the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products remain constant Physical equilibrium NO2 H2O (l) H2O (g) Chemical equilibrium N2O4 (g) 2NO2 (g)

N2O4 (g) 2NO2 (g) equilibrium equilibrium equilibrium Start with NO2 Start with NO2 & N2O4

constant

N2O4 (g) 2NO2 (g) K = [NO2]2 [N2O4] = 4.63 x 10-3 aA + bB cC + dD K = [C]c[D]d [A]a[B]b Law of Mass Action

Equilibrium Will K = [C]c[D]d [A]a[B]b aA + bB cC + dD K >> 1 Lie to the right Favor products K << 1 Lie to the left Favor reactants

Homogenous equilibrium applies to reactions in which all reacting species are in the same phase. N2O4 (g) 2NO2 (g) Kp = NO2 P 2 N2O4 P Kc = [NO2]2 [N2O4] In most cases Kc  Kp aA (g) + bB (g) cC (g) + dD (g) Kp = Kc(RT)Dn Dn = moles of gaseous products – moles of gaseous reactants = (c + d) – (a + b)

Homogeneous Equilibrium CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq) [CH3COO-][H3O+] [CH3COOH][H2O] Kc = ′ [H2O] = constant [CH3COO-][H3O+] [CH3COOH] Kc = General practice not to include units for the equilibrium constant.

14.1 Write expressions for Kc, and KP if applicable, for the following reversible reactions at equilibrium: HF(aq) + H2O(l) H3O+(aq) + F-(aq) (b) 2NO(g) + O2(g) 2NO2(g) (c) CH3COOH(aq) + C2H5OH(aq ) CH3COOC2H5(aq) + H2O(l)

14.2 The following equilibrium process has been studied at 230°C: 2NO(g) + O2(g) 2NO2(g) In one experiment, the concentrations of the reacting species at equilibrium are found to be [NO] = 0.0542 M, [O2] = 0.127 M, and [NO2] = 15.5 M. Calculate the equilibrium constant (Kc) of the reaction at this temperature.

14.3 The equilibrium constant KP for the decomposition of phosphorus pentachloride to phosphorus trichloride and molecular chlorine PCl5(g) PCl3(g) + Cl2(g) is found to be 1.05 at 250°C. If the equilibrium partial pressures of PCl5 and PCl3 are 0.875 atm and 0.463 atm, respectively, what is the equilibrium partial pressure of Cl2 at 250°C?

14.4 Methanol (CH3OH) is manufactured industrially by the reaction CO(g) + 2H2(g) CH3OH(g) The equilibrium constant (Kc) for the reaction is 10.5 at 220°C. What is the value of KP at this temperature?

Heterogenous equilibrium applies to reactions in which reactants and products are in different phases. CaCO3 (s) CaO (s) + CO2 (g) [CaO][CO2] [CaCO3] Kc = ′ [CaCO3] = constant [CaO] = constant Kc = [CO2] Kp = PCO 2 The concentration of solids and pure liquids are not included in the expression for the equilibrium constant.

does not depend on the amount of CaCO3 or CaO CaCO3 (s) CaO (s) + CO2 (g) PCO 2 = Kp PCO 2 does not depend on the amount of CaCO3 or CaO

14.5 Write the equilibrium constant expression Kc, and KP if applicable, for each of the following heterogeneous systems: (NH4)2Se(s) 2NH3(g) + H2Se(g) (b) AgCl(s) Ag+(aq) + Cl-(aq) (c) P4(s) + 6Cl2(g) 4PCl3(l)

14.6 Consider the following heterogeneous equilibrium: CaCO3(s) CaO(s) + CO2(g) At 800°C, the pressure of CO2 is 0.236 atm. Calculate (a) KP and (b) Kc for the reaction at this temperature.

For which of the following reactions is Kc equal to Kp? Review of Concepts For which of the following reactions is Kc equal to Kp? 4 NH3(g) + 5 O2(g) ⇌ 4 NO(g) + 6 H2O(g) 2 H2O2(aq) ⇌ 2 H2O(l) + O2(g) PCl3(g) + 3 NH3(g) ⇌ 3 HCl(g) P(NH3)3(g)

Multiple Equilibria ′ ′ ′ ′ ′′ Kc = [C][D] [A][B] Kc = [E][F] [C][D] A + B C + D Kc ′ Kc ′′ C + D E + F [E][F] [A][B] Kc = A + B E + F Kc Kc = Kc ′′ ′ x If a reaction can be expressed as the sum of two or more reactions, the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions.

′ N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g) = 4.63 x 10-3 K = [NO2]2 [N2O4] = 216 When the equation for a reversible reaction is written in the opposite direction, the equilibrium constant becomes the reciprocal of the original equilibrium constant.

14.7 The reaction for the production of ammonia can be written in a number of ways: N2(g) + 3H2(g) 2NH3(g) (b) N2(g) + H2(g) NH3(g) (c) N2(g) + H2(g) NH3(g) Write the equilibrium constant expression for each formulation. (Express the concentrations of the reacting species in mol/L.) (d) How are the equilibrium constants related to one another?

Review of Concepts From the following equilibrium constant expression, write a balanced chemical equation for the gas-phase reaction. Kc = [NH3]2[H2O]4 [NO2]2[H2]7

Writing Equilibrium Constant Expressions The concentrations of the reacting species in the condensed phase are expressed in M. In the gaseous phase, the concentrations can be expressed in M or in atm. The concentrations of pure solids, pure liquids and solvents do not appear in the equilibrium constant expressions. The equilibrium constant is a dimensionless quantity. In quoting a value for the equilibrium constant, you must specify the balanced equation and the temperature. If a reaction can be expressed as a sum of two or more reactions, the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions.

The reaction quotient (Qc) is calculated by substituting the initial concentrations of the reactants and products into the equilibrium constant (Kc) expression. IF Qc < Kc system proceeds from left to right to reach equilibrium Qc = Kc the system is at equilibrium Qc > Kc system proceeds from right to left to reach equilibrium

14.8 At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2 mol H2, and 6.42 x 10-4 mol NH3 in a 3.50-L reaction vessel at 375°C. If the equilibrium constant (Kc) for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.2 at this temperature, decide whether the system is at equilibrium. If it is not, predict which way the net reaction will proceed.

Calculating Equilibrium Concentrations Express the equilibrium concentrations of all species in terms of the initial concentrations and a single unknown x, which represents the change in concentration. Write the equilibrium constant expression in terms of the equilibrium concentrations. Knowing the value of the equilibrium constant, solve for x. Having solved for x, calculate the equilibrium concentrations of all species.

14.9 A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a 1.00-L stainless-steel flask at 430°C. The equilibrium constant Kc for the reaction H2(g) + I2(g) 2HI(g) is 54.3 at this temperature. Calculate the concentrations of H2, I2, and HI at equilibrium.

14.10 For the same reaction and temperature as in Example 14.9, suppose that the initial concentrations of H2, I2, and HI are 0.00623 M, 0.00414 M, and 0.0224 M, respectively. Calculate the concentrations of these species at equilibrium. H2(g) + I2(g) 2HI(g),

Le Châtelier’s Principle If an external stress is applied to a system at equilibrium, the system adjusts in such a way that the stress is partially offset as the system reaches a new equilibrium position. Changes in Concentration N2 (g) + 3H2 (g) 2NH3 (g) Add NH3 Equilibrium shifts left to offset stress

Le Châtelier’s Principle Changes in Concentration continued Remove Add Add Remove aA + bB cC + dD Change Shifts the Equilibrium Increase concentration of product(s) left Decrease concentration of product(s) right Increase concentration of reactant(s) right Decrease concentration of reactant(s) left

14.11 At 720°C, the equilibrium constant Kc for the reaction N2(g) + 3H2(g) 2NH3(g) is 2.37 x 10-3. In a certain experiment, the equilibrium concentrations are [N2] = 0.683 M, [H2] = 8.80 M, and [NH3] = 1.05 M. Suppose some NH3 is added to the mixture so that its concentration is increased to 3.65 M. (a) Use Le Châtelier’s principle to predict the shift in direction of the net reaction to reach a new equilibrium. (b) Confirm your prediction by calculating the reaction quotient Qc and comparing its value with Kc.

Le Châtelier’s Principle Changes in Volume and Pressure A (g) + B (g) C (g) Change Shifts the Equilibrium Increase pressure Side with fewest moles of gas Decrease pressure Side with most moles of gas Increase volume Side with most moles of gas Decrease volume Side with fewest moles of gas

14.12 Consider the following equilibrium systems: 2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g) (b) PCl5(g) PCl3(g) + Cl2(g) (c) H2(g) + CO2(g) H2O(g) + CO(g) Predict the direction of the net reaction in each case as a result of increasing the pressure (decreasing the volume) on the system at constant temperature.

Le Châtelier’s Principle Changes in Temperature Change Exothermic Rx Endothermic Rx Increase temperature K decreases K increases Decrease temperature K increases K decreases N2O4 (g) 2NO2 (g) colder hotter

Le Châtelier’s Principle Adding a Catalyst does not change K does not shift the position of an equilibrium system system will reach equilibrium sooner Catalyst lowers Ea for both forward and reverse reactions. Catalyst does not change equilibrium constant or shift equilibrium.

Le Châtelier’s Principle - Summary Change Shift Equilibrium Change Equilibrium Constant Concentration yes no Pressure yes* no Volume yes* no Temperature yes yes Catalyst no no *Dependent on relative moles of gaseous reactants and products

N2F4(g) 2NF2(g) ΔH° = 38.5 kJ/mol 14.13 Consider the following equilibrium process between dinitrogen tetrafluoride (N2F4) and nitrogen difluoride (NF2): N2F4(g) 2NF2(g) ΔH° = 38.5 kJ/mol Predict the changes in the equilibrium if the reacting mixture is heated at constant volume; (b) some N2F4 gas is removed from the reacting mixture at constant temperature and volume; (c) the pressure on the reacting mixture is decreased at constant temperature; and (d) a catalyst is added to the reacting mixture.

Chemical Kinetics and Chemical Equilibrium ratef = kf [A][B]2 A + 2B AB2 kf kr rater = kr [AB2] Equilibrium ratef = rater kf [A][B]2 = kr [AB2] kf kr [AB2] [A][B]2 = Kc =

Gibbs Free Energy and Chemical Equilibrium DG = DG0 + RT lnQ R is the gas constant (8.314 J/K•mol) T is the absolute temperature (K) Q is the reaction quotient At Equilibrium DG = 0 Q = K 0 = DG0 + RT lnK DG0 = - RT lnK

Free Energy Versus Extent of Reaction DG0 > 0 DG0 < 0

DG0 = - RT lnK

17.6 Using data listed in Appendix 3, calculate the equilibrium constant (KP) for the following reaction at 25°C: 2H2O(l) 2H2(g) + O2(g)

AgCl(s) Ag+(aq) + Cl-(aq) 17.7 In Chapter 16 we discussed the solubility product of slightly soluble substances. Using the solubility product of silver chloride at 25°C (1.6 x 10-10), calculate ΔG° for the process AgCl(s) Ag+(aq) + Cl-(aq)

17.8 The equilibrium constant (KP) for the reaction N2O4(g) 2NO2(g) is 0.113 at 298 K, which corresponds to a standard free-energy change of 5.40 kJ/mol. In a certain experiment, the initial pressures are PNO2 = 0.122 atm and PN2O4 = 0.453 atm. Calculate ΔG for the reaction at these pressures and predict the direction of the net reaction toward equilibrium.

Spontaneity of Redox Reactions DG = -nFEcell n = number of moles of electrons in reaction F = 96,500 J V • mol DG0 = -nFEcell = 96,500 C/mol DG0 = -RT ln K = -nFEcell Ecell = RT nF ln K (8.314 J/K•mol)(298 K) n (96,500 J/V•mol) ln K = = 0.0257 V n ln K Ecell = 0.0592 V n log K Ecell

Spontaneity of Redox Reactions DG0 = -RT ln K = -nFEcell

Sn(s) + 2Cu2+(aq) Sn2+(aq) + 2Cu+(aq) 18.4 Calculate the equilibrium constant for the following reaction at 25°C: Sn(s) + 2Cu2+(aq) Sn2+(aq) + 2Cu+(aq)

2Au(s) + 3Ca2+(1.0 M) 2Au3+(1.0 M) + 3Ca(s) 18.5 Calculate the standard free-energy change for the following reaction at 25°C: 2Au(s) + 3Ca2+(1.0 M) 2Au3+(1.0 M) + 3Ca(s)

The Effect of Concentration on Cell Emf DG = DG0 + RT ln Q DG = -nFE DG0 = -nFE -nFE = -nFE0 + RT ln Q Nernst equation E = E0 - ln Q RT nF At 298 K - 0.0257 V n ln Q E E = - 0.0592 V n log Q E E =

Co(s) + Fe2+(aq) Co2+(aq) + Fe(s) 18.6 Predict whether the following reaction would proceed spontaneously as written at 298 K: Co(s) + Fe2+(aq) Co2+(aq) + Fe(s) given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M.

18.7 Consider the galvanic cell shown in Figure 18.4(a). In a certain experiment, the emf (E) of the cell is found to be 0.54 V at 25°C. Suppose that [Zn2+] = 1.0 M and PH2 = 1.0 atm. Calculate the molar concentration of H+.

Concentration Cells Galvanic cell from two half-cells composed of the same material but differing in ion concentrations.