Le Châtelier`s Principle
Transcription
Le Châtelier`s Principle
Le Châtelier's Principle “If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or total pressure, then the equilibrium shifts to partially counteract the imposed change change.” 60 Changes in Concentration PCl5 PCl3 + Cl2 Kc = 0.030 At equilibrium: Adding reactants shifts the reaction toward products Adding products shifts the reaction toward reactants Removing g reactants … shifts the reaction toward reactants Removing products … shifts the reaction toward products 61 Le Châtelier Sample Problem 65 Changes in Pressure and Volume 66 Pre-solved Example N2 (g) + 3 H2 (g) 2 NH3 (g) A system with 2.5 atm of N2 and 7.5 atm of H2 is allowed to equilibrate at 500°C, then the overall pressure is increased by a factor of 10. What happens? 2.0% of total pressure Before compression After compression PNH3 = 0.2 atm PNH3 = 8.4 atm PN2 = 2.4 atm PN2 = 21 atm PH2 = 7.2 atm PH2 = 62 atm 9.2% of total pressure The reaction shifts toward products because this minimizes the total number of molecules in the system 67 Further Examples 68 Changes in Temperature 69 Sample Question 70 Adding a Catalyst A catalyst is a substance that increases the rate of a reaction without itself being consumed in the reaction 71 Question Which of the following equilibria would not be affected by changes in overall pressure? (a) 2 NO(g) + O2(g) 2 NO2(g) (b) N2O4(g) 2 NO2(g) (c) 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) (d) CaCO3(s) CaO(s) + CO2(g) (e) CO(g) + H2O(g) CO2(g) + H2(g) 72 New Question What would happen if O2 were removed from the following system at equilibrium at 25°C? 2 NO2(g) 2 NO(g) + O2(g) Kc = 7.4 x 10–1 (a) The NO2 and NO concentrations would increase. (b) The NO2 and NO concentrations would decrease. (c) The NO2 concentration would increase and the NO concentration would decrease. (d) The NO2 concentration would decrease and the (d) The NO concentration would decrease and the NO concentration would increase. (e) none of the above 73 Yet Another Question The following chemical reaction has reached equilibrium. Which of the changes listed below would cause the equilibrium to shift back toward the reactants? N N2(g) + 3 H ( ) 3 H2(g) ( ) 2 NH 2 NH3(g) H = 92.2 ( ) H 92 2 kJ/mol kJ/ lrxn (a) increasing the pressure (b) increasing the concentration of N2 (b) increasing the concentration of N (c) increasing the temperature (d) decreasing the concentration of NH3 (e) none of these (e) none of these 74 Le Châtelier’s Principle Summary 75 The Haber-Bosch Process Artificial nitrogen fixation process to produce ammonia N2 2 (g) (g) + 3 H 3 H2 2 (g) (g) 2 NH3 3 (g) ΔH 2 NH (g) ΔH° = ‐92.2 92.2 kJ/mol kJ/mol ‐ Fertilizer for 1/3 of world population, chemicals, explosives Fritz Haber, 1918 Yield and rate °C C Keq 300 4.34 x 10–3 400 1.64 x 10–4 But increasing the temperature lowers Kc (yield) 450 4.51 x 10–5 What should we do to achieve the b t best compromise of K i f Kc and rate? d t ? 500 1.45 x 10–5 550 5.38 x 10 5 38 x 10–6 600 2.25 x 10–6 Low temperature results in a very slow reaction Low temperature results in a very slow reaction (low rate) 76 The Haber-Bosch Process Le Châtelier says: 1) Use high pressure to increase Kc (typically 150‐250 atmospheres) N2 (g) + 3 H2 (g) → 2 NH3 (g) 2) Use a moderate temperature (300‐550°C) to get a good reaction rate g c too much without lowering K 77 The Haber-Bosch Process 3) Use a catalyst to speed up the reaction ‐ Catalysts do not change K Catalysts do not change Kc ‐ Catalysts lower the activation energy of a reaction, increasing its rate Most Haber reactors use a porous iron catalyst made from Fe b l d f 3O4 4) Periodically remove NH3 from the reactor N2 + 3 H2 → 2 NH3 ‐ forces the reaction toward products 78 Adding a Catalyst 79 A Haber-Bosch Plant An American ammonia plant, c. 1970 80 Equilibrium Thermodynamics ∆G° measures the difference between the free energies of the reactants and products when all species are present at 1 atm (gases) and 1 M (solutes) Reactants Products ∆G° < 0 → spontaneous → products favored → K > 1 ∆G° > 0 → not spontaneous p → reactants favored → K < 1 ∆G° and K are related: exponential ti l relationship l ti hi 81 Standard Free Energy and Equilibrium ∆G° ∆G signifies standard conditions: 1 atm for gases 1 M for solutes at the standard state, Qc = Qp = 1 ∆G° tells us how far the standard state is from equilibrium and which direction the reaction must shift to reach equilibrium 82 ∆G° K large + small + 0 small ll large - << 1 <1 =1 >1 >> 1 Free Energy at Non-standard Conditions What is the value of the free energy change when we are not at standard conditions? (i.e., ≠ 1 atm for all gases and 1 M for all solutes) ∆G at any Q: For a rxn with ∆G° = -100 kJ/mol: ∆Gdelta (kJ J/mol) aG when Q = 1, ∆G = ∆G° when Q = K, K ∆G = 0 100 50 0 -50 50 equilibrium -100 -150 -200 -40 83 spontaneous not spontaneous ∆G = ∆G° -20 0 ln Q 20 40 60 Temperature Dependence of Keq Equilibrium constants change with temperature - Predictable based on ∆H° of the reaction We know: and So: ∆H° ∆H + (endo) - (exo) 84 K exp. increases with T exp. decreases with T Temperature Dependence of Keq • ∆H° and ∆S° are essentially constant for moderate changes in temperature Exothermic ln K Endothermic 1/T higher temp 85 Temperature Take-Homes The value of the equilibrium constant changes with temperature for a given reaction. Master Equations: Kc will increase with temperature if the reaction is endothermic (takes up heat). A + B + heat A + B + heat C+D C + D Kc will decrease with temperature if the reaction is exothermic (releases heat) heat). 86 A + B C + D + heat Temperature Dependence Example The dimerization of NO2 is exothermic (b/c of bond making): 2 NO2 ∆H° - (exo) Temperature °C N2O4 ∆H° = -57.2 ∆H 57 2 kJ/mol K decreases with T Kc Kp ‐78 400,000,000 25,000,000 0 1400 62.5 25 170 6.95 100 2.1 0.069 The dimer Th di i f is favored at low temperatures d tl t t 87 Sample Problem 88