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CO(g) + H2O(g) CO2(g) + H2(g) CO(g) + H2O(g) CO2(g) + H2(g) CO(g) + H2O( g) CO2(g) + H2(g) K >>1 Forward rxn dominates (rxn lies to the right). Mostly products at equilibrium, [products] >> [reactants] Cl2(g) + 2 NO(g) 2 NOCl(g) K = 6.2 x 104 K <<1 Reverse rxn dominates (rxn lies to the left). Mostly reactants at equilibrium, [products] << [reactants] COCl2(g) CO(g) + Cl2(g) K = 2.0 x 10-10 K 1 Forward and reverse rxn occur to roughly the same extent, [products] [reactants] H2(g) + F2(g) 2 HF(g) K = 10 2.0 moles of NH3 gas are introduced into a previously evacuated 1.0 L container. At a certain temperature the NH3 partially dissociates by the following equation. 2 NH3(g) N2(g) + 3 H2(g) At equilibrium 1.0 mol of NH3 remains. Calculate the equilibrium constant for this reaction. Reaction Quotient (Q) Q = K: The rxn is at equilibrium. No shift. Q < K: The rxn shifts right to produce products to increase Q. Q > K: The rxn shifts left to produce reactants to decrease Q. Le Chatelier’s Principle If a change (stress) is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction that tends to reduce that change (stress). Le Chatelier’s Principle 2 SO2(g) + O2(g) 1. 2. 3. 4. 2 SO3(g) H = 198 kJ SO2(g) is removed. O2(g) is added. SO3(g) is added. The volume of the reaction container is halved. 5. An inert gas like Ar is added. 6. A catalyst is added. 7. Temperature is increased. Le Chatelier’s Principle CaCO3(s) 1. 2. 3. 4. CaO(s) + CO2(g) H = 556 kJ CO2(g) is added. CaCO3(s) is added. The volume is increased. The temperature is decreased. N2O4(g) 2 NO2(g) 1.0 mol of N2O4(g) is placed in a 10.0 L vessel and then reacts to reach equilibrium. Calculate the equilibrium concentrations of N2O4 and NO2. K = 4.0 x 10-7 Brønsted-Lowry Model Acids – are proton donors Bases – are proton acceptors HC2H3O2 is a stronger acid then HCN which Has the stronger conjugate base? Comments on the Conjugates of Acids and Bases. • The weaker the acid the stronger its conjugate base. • The weaker the base the stronger its conjugate acid. • The conjugate base of a weak acid is a WEAK base. • The conjugate base of a strong acid is worthless. • The conjugate acid of a weak base is a WEAK acid. Acid Ka HCl ~106 HF 7.2 x 10-4 HC2H3O2 1.8 x 10-5 HOCl 3.5 x 10-8 NH4+ 5.6 x 10-10 Realative acid strength Conjugate base Kb Relative base strength Acid Ka Realative acid strength Conjugate base Kb HCl ~106 Cl- ~10-20 HF 7.2 x 10-4 F- 1.4 x 10-11 HC2H3O2 1.8 x 10-5 C2H3O2- 5.6 x 10-10 HOCl 3.5 x 10-8 OCl- 2.9 x 10-7 NH4+ 5.6 x 10-10 NH3 1.8 x 10-5 Relative base strength Stuff you should now know. 1. 2. 3. 4. 5. 6. 7. 8. Ka value is directly related to acid strength. Weak acids vs. strong acids (Ka’s and % dissociation. Conjugate acid-base pairs. KaKb=Kw Kb value is directly related to base strength. How to write out Ka and Kb rxns and expressions. The weaker the acid the stronger the conjugate base (and vice versa). Conjugate bases of strong acids have no basic properties whatsoever! (Kb << Kw) Calculate the pH of a 0.10 M HBr solution. Calculate the pH of a 0.10 M HOCl solution. KaHOCl = 3.5 x 10-8 Calculate the pH of a 0.10 M NaF. KaHF = 7.2 x 10-4 Calculate the pH of a 0.10 M Ca(OH)2 solution. Calculate the pH of a solution containing 0.10 M HOCl and 0.02 M NaOCl. KaHOCl = 3.5 x 10-8 Calculate the pOH of 0.05 M Ba(OH)2. Calculate the pOH of 0.50 M KOCl. KaHOCl = 3.5 x 10-8 Calculate the pOH of 1.00 M HI. Calculate the pOH of 0.25 M NH4Cl. Ka NH4+ = 5.6 x 10-10 Calculate the pOH of a solution containing 0.25 M NH4Cl and 0.10 M NH3. Ka NH4+ = 5.6 x 10-10 Calculate the pH of 1.6 x 10-13 M HNO3. A solution of 8.00 M HCOOH is 0.47% Ionized. What is the Ka for the acid? pH? Acid HF C6H5NH3+ HC2H3O2 HCN NH4+ Ka 7.2 x 10-4 2.6 x 10-5 1.8 x 10-5 6.2 x 10-10 Acidic, Basic, or Neutral? 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. NaCN NH4NO3 KI LiC2H3O2 C6H5NH3Cl KF NaNO3 HClO4 Ca(OH)2 NH4CN NH4C2H3O CaO SO3 Acidic, Basic, or Neutral? 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. NaCN NH4NO3 KI LiC2H3O2 C6H5NH3Cl KF NaNO3 HClO4 Ca(OH)2 NH4CN NH4C2H3O CaO SO3 Na+ - worthless, CN- - weak base, basic NO3- - worthless, NH4+ - weak acid, acidic K+ - worthless, I- - worthless, neutral Li+ - worthless, C2H3O2- - weak base, basic Cl- - worthless, C6H5NH3+ - weak acid, acidic K+ - worthless, F- - weak base, basic Na+ - worthless, NO3- - worthless, neutral HClO4 – strong acid, acidic Ca(OH)2 – strong base, basic KaNH < KbCN - basic KaNH = KbC H O - neutral metal oxide - basic nonmetal oxide - acidic - 4 4 2 3 - Buffers Buffer – A solution where a weak acid and its conjugate base are both present in solution. • Buffers resist changes in pH Good Buffers • Good buffers will have the following: – EQUAL concentrations of the weak acid and its conjugate base. – LARGE concentrations of the weak acid and its conjugate base. – pKa = pH of desired pH. Examples of Buffers • HCN/CN• NH4+/NH3 • H2PO4-/HPO42- - intracellular fluid buffer • H2CO3/HCO3- - blood buffer Calculate the pH of a solution that is 1.00 M HNO2 and 1.00 M NaNO2. KaHNO = 4.0 x 10-4 2 Calculate the pH when 0.10 mol of HCl is Added to a 1.00 L solution containing 1.00 M HNO2 and 1.00 M NaNO2. KaHNO = 4.0 x 10-4 2 Calculate the pH when 0.10 mol of NaOH are added to a 1.0 L solution containing 1.00 M HNO2 and 1.00 M NaNO2. KaHNO = 4.0 x 10-4 2 Calculate the pH of a solution formed by Mixing 500.0 mL of 0.100 M NH3 and 500.0 mL of 0.0500 M HCl. KbNH = 1.8 x 10-5 3 You want to prepare a HOCl buffer of pH 8.00. You want to make a 500. mL solution and use all of the 0.75 mol of HOCl you have on hand. How many mol of KOCl must you add? KaHOCl = 3.5 x 10-8 Calculate the pH of a solution formed by mixing 500. mL of 1.50 M HCN with 250. mL of 1.00 M NaOH. KaHCN = 6.2 x 10-10 • Total Points in course: 800 • Points to be decided next week: ~415 Proposed Study Plan • • • • • • • • Thursday: HE III Material (finish Lon Capa) Friday: HE I Material Saturday: HE II Material Sunday: HE III Material Monday: HE III Material Tuesday: He III Material Wednesday: HE I, II Material Thursday: HE I, II, III Material A 100. mL solution of 0.10 M HF is titrated by 0.10 M NaOH. Calculate the pH when 0.0, 25.0, 50.0, 100.0, and 125.0 mL of NaOH have been added. KaHF = 7.4 x 10-4