CHEMICAL EQUILIBRIUM Dr. Samina Nazir Chemical Equilibrium– Reversible reaction k1 k-1 Slide 2 of 55 Homogenous vs. Heterogeneous Reactions Kc = [CH3OH] [CO][H2 ]2 Kc = [NH3]2 [N2][H2]3 Slide 3 of 55 Equilibrium Constant of Pressure • Prentice-Hall © 2002 General Chemistry: Chapter 15 Slide 4 of 55 Reaction Quotient (Qc) • Prentice-Hall © 2002 General Chemistry: Chapter 15 Slide 5 of 55 Altering Equilibrium Conditions: Le Châtellier’s Principle • Reversible reaction proceed in both directions • A reaction is at equilibrium if the reaction quotient ( Q ) is equal to the equilibrium constant ( K ). • If a system at equilibrium is subjected to a perturbance or stress (temperature, pressure, or concentration) the position of equilibrium changes. • Since this stress affects the concentrations of the reactants and the products, the value of Q will no longer equal the value of K . • To re-establish equilibrium, the system will either shift toward the products (if (Q≤K) or the reactants (if (Q≥K) until Q returns to the same value as K . This process is described by Le Chatelier's principle. Prentice-Hall © 2002 General Chemistry: Chapter 15 Slide 6 of 55 Effect of Change in Concentration on Equilibrium • + ve Slide 7 of 55 Effect of Change in concentration and temperature on Equilibrium constant Add conc. HCl Add water Cold water bath Hot water bath Slide 8 of 55 Effect of Change in Pressure on Equilibrium • Adding CaCl2 or NaCl or conc. HCl results in concentration of reactant (Cl-) to increase, (Qc < Kc), the reactions shifts to the right to consume increased amount of Cl-, more [CoCl4]2-(aq) (blue) is produced. • Adding water, (Qc > Kc), the reactions shifts to the left as more water is consumed in making [Co(H2O)6]2+ • Placing [Co(H2O)6]2+ in boiling water, reaction shifts towards forward direction as this reaction is endothermic. • Placing [CoCl4]2-(aq) (blue) in ice bath shifts reaction towards to backward direction. • Adding or releasing pressure on gaseous reactions also has the same effect as concentration. Adding Catalyst has no effect on equilibrium. Learning Check Write the equilibrium constant expression for each reaction. • 2SO2(g)+O2(g)⇌2SO3(g) • N2O(g)+1/2O2(g)⇌2NO(g) • Cu(s)+2Ag+(aq)⇌Cu+2(aq)+2Ag(s) • CaCO3(g)⇌CaCO(s)+CO2(g) • 2NaHCO3(s)⇌Na2CO3(s)+CO2(g)+H2O(g) • H+(aq)+OH–(aq)→H2O(l) • Write the Partial Pressure Equilibrium: C(s)+O2(g)→CO2(g) • What is the Kc of the following reaction? 2SO2(g)+O2(g)⇌2SO3(g) SO2(g)=0.2M, O2(g)=0.5M, SO3(g)=0.7M Also, What is the Kp of this reaction? At room temperature? Answers • • • • • • Kc=[SO3]2/[O2][SO2]2 Kc=[NO]2/[O2]0.5[N2O] Kc=[Cu+2]/[Ag+]2 Kc=[CO2]/[CaCO3] Kc=[H2O][CO2] Kc=1/[H+][OH−] • Kp=PCO2/PO2 • Kc: 24.5, Kp: 1 atm Kc = [SO3]2 /[SO2] 2 [O2] = (0.7)2 /(0.2) 2 (0.5) = 0.49/0.02 = 24.5 Kp = Kc (RT)∆n = 24.5 (0.0820575 atm/mol.K × 298K)-1 = 24.5 (24.60) -1 = 24.5 × 0.04065 = 1 Prentice-Hall © 2002 General Chemistry: Chapter 15 Slide 11 of 55