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Chapter 14

Chapter 14. Chemical Equilibrium. 14.1: Equilibrium Constant, K eq. Objective: To write the equilibrium constant expression for a chemical reaction. Reversible Reactions and Equilibrium. Reversible Reaction: A chemical reactions in which products re-form the original reactants.

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Chapter 14

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  1. Chapter 14 Chemical Equilibrium

  2. 14.1: Equilibrium Constant, Keq • Objective: • To write the equilibrium constant expression for a chemical reaction.

  3. Reversible Reactions and Equilibrium • Reversible Reaction: A chemical reactions in which products re-form the original reactants. • Arrows that point in opposite directions are used to indicate a reaction is reversible. • Example: H2(g) + I2(g) 2HI(g) • Chemical Equilibrium: A state of balance in which the rate of a forward reaction equals the rate of the reverse reactions and the concentrations of products and reactants remain unchanged.

  4. Equilibrium Constant, Keq • Equilibrium Constant, Keq: a number that relates that concentrations of starting materials and products of a reversible chemical reaction to one another at a given temperature. aA + bB  cC + dD coefficient concentration

  5. Writing an Equilibrium Constant Expression • Step 1: Balance the chemical equation. • Step 2: Set up your Keq expression with the products on the top of a fraction and the reactants on the bottom of a fraction. • Step 3: Raise each substance's concentration to the power equal to the substance’s coefficient in the balanced equation. • Note: Solids (s) and pure liquids (l) are not used in the expression because their concentrations do not change.

  6. Example • Write the equilibrium constant expression for the following reaction: CaCO3(s) + CO2(aq)+ H2O(l) Ca2+(aq) + 2HCO3-(aq)

  7. Practice • Write the equilibrium constant expression for the following chemical reactions at equilibrium (don’t forget to balance the equation): 1.) H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+ (aq) 2.) COCl2 (g) CO(g) + Cl2 (g) 3.) CO(g) C(s) + CO2 (g)

  8. Answers 1.) H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+ (aq) 2.) COCl2 (g) CO(g) + Cl2 (g) 3.) 2CO(g) C(s) + CO2 (g)

  9. 14.1: Equilibrium Constant, Keq • Objective: • To calculate the equilibrium constant.

  10. What does the Keq tell us? • Keq < 1 Favors Reactants • Keq = 1 Same amount of Reactants and Products • Keq > 1 Favors Products • Practice: Determine if the following Keq values favor the reactants, products, or neither. 1.) Keq = 0.02 2.) Keq = 1 3.) Keq = 50

  11. Calculating Keq • Step 1: Write the balanced chemical equation. • Step 2: Set up your Keq expression. • Step 3: Substitute concentrations. • Step 4: Calculate!

  12. Example • An aqueous solution of carbonic acid reacts to reach equilibrium as described below: H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+ (aq) The solution contains the following solute concentrations: H2CO3 = 3.3 x 10-2 M; HCO3- = 1.19 x 10-4 M; H3O+ = 1.19 x 10-4 M. Determine the Keq. Note: Keq does not have units!

  13. Practice 1.a. Calculate the equilibrium constant for the following reaction: COCl2(g) CO(g) + Cl2(g) [CO] = 0.0178 M [Cl2] = 0.0178 M [COCl2] = 0.00740 M b. Are the reactants for products favored?

  14. Practice 2.a. For the system involving dinitrogen tetraoxide and nitrogen dioxide at equilibrium at a temperature of 100⁰C, the product concentration of N2O4 is 4.0 x 10-2 M and the reactant concentration of NO2 is 1.4x 10-1 M. What is the Keq value for this reaction? NO2(g) N2O4(g) b. Are the reactants or products favored?

  15. Practice 3.a. An equilibrium mixture at 852 K is found to contain 3.61 x 10-3 M of SO2, 6.11 x 10-4 M of O2, and 1.01 x 10-2 M of SO3. Calculate the equilibrium constant for the reaction. SO2 (g) + O2 (g) SO3 (g) b. Are the reactants or products favored?

  16. Calculating Concentrations from Keq 4. Keq for the equilibrium below is 1.8 x 10-5 at a temperature of 25⁰C. Calculate [NH3] when [NH4+] and [OH-] are 3.5 x 10-4 M. NH3(aq) + H2O(l) NH4+ (aq) + OH-(aq) [NH3] = 6.8 x10-3 M

  17. Practice 5. a. If the equilibrium constant is 1.65 x 10-3 at 2027⁰C for the reaction below, what is the equilibrium concentration of NO when [N2] = 1.8 x 10-3 M and [O2] = 4.2 x 10-3 M. N2(g) + O2(g) NO(g) b. Are the reactants for products favored?

  18. Practice 6.a. At 600⁰C, the Keq for the reaction below is 4.32 when [SO3] = 0.260 M and [O2] = 0.045 M. Calculate the equilibrium concentration for sulfur dioxide. SO2(g) + O2(g) SO3(g) b. Are the reactants or products favored?

  19. 14.2 Solubility Product Constant, Ksp • Objective: (1) To calculate the solubility product constant, Ksp.

  20. Solubility • The maximum concentration of a salt in an aqueous solution is called the solubility of the salt in water.

  21. Solubility Product Constant, Ksp • Solubility Product Constant, Ksp: the equilibrium constant for a solid that is in equilibrium with the solid’s dissolved ions. • How much of a partially soluble salt will dissolve? AaBb (s) aA (aq) + bB (aq)

  22. Calculating Ksp • The lower the value of Ksp, the less soluble the substance. • Practice: Rank the following substances from least soluble to most soluble:

  23. Calculating Ksp • The lower the value of Ksp, the less soluble the substance. • Practice: Rank the following substances from least soluble to most soluble: CuS Least soluble Ca3(PO4)2 Ag2CO3 BaSO4 Most soluble

  24. Calculating Ksp • Step 1: Write and Balance the equation. • Step 2: Determine the concentration of the ions. • Step 3: Write the solubility product expression. • Step 4: Substitute values and calculate.

  25. Example • Most parts of oceans are nearly saturated with calcium fluoride. A saturated solution of CaF2 at 25⁰C has a solubility of 3.4 x 10-4 M. Calculate the solubility product constant for CaF2. CaF2(s) Ca2+(aq) + F-(aq)

  26. Solution • Balance equation: CaF2(s) Ca2+(aq) + 2F-(aq) • Determine Concentrations: CaF2(s) Ca2+(aq) + 2F-(aq) 3.4 x 10-4 3.4 x 10-4 6.8 x 10-4 3. Write solubility product expression: 4. Substitute values and calculate: Note: Ksp does not have units!

  27. Practice 1. Copper(I) bromide is dissolved in water to saturation at 25⁰C. The concentration of Cu+ and Br- ions in solution is 7.9 x 10-5 M. Calculate the Ksp for copper(I) bromide at this temperature.

  28. Practice 2. What is the Ksp value for calcium phosphate at 298 K if the concentrations in a solution at equilibrium with excess solid are 3.42 x 10-7 M for Ca2+ and 2.28 x 10-7 M for PO43- ions?

  29. Practice 3. If a saturated solution of silver chloride contains an AgCl concentration of 1.34 x 10-5 M, what is the solubility product constant?

  30. Practice 4. A saturated solution of magnesium fluoride contains a MgCl2 concentration of 1.19x10-3 M. What is the Ksp for magnesium fluoride?

  31. Calculating Concentration from Ksp 5. What is the concentration of Ca2+ in a saturated solution of CaF2 if the concentration of F- is 2.20 x 10-3M and Ksp = 5.30 x 10-9.

  32. Practice 6. What is the concentration of Al3+ in a saturated solution of Al(OH)3 if the OH- concentration is 7.90 x 10-9 M. Ksp = 1.30 x 10-33.

  33. Practice: Chem 331 7. The Ksp for lead(II) iodide is 7.08 x 10-9 at 25⁰C. What is the molar concentration of PbI2 in a saturated solution?

  34. The Ksp for lead(II) iodide is 7.08 x 10-9 at 25⁰C. What is the molar concentration of PbI2 in a saturated solution? Step 1: Write and Balance Equation PbI2 (s) Pb2+ (aq) + 2I- (aq)

  35. The Ksp for lead(II) iodide is 7.08 x 10-9 at 25⁰C. What is the molar concentration of PbI2 in a saturated solution? Step 1: Write and Balance Equation PbI2 (s) Pb2+ (aq) + 2I- (aq) Step 2: Write the Ksp expression

  36. The Ksp for lead(II) iodide is 7.08 x 10-9 at 25⁰C. What is the molar concentration of PbI2 in a saturated solution? Step 1: Write and Balance Equation PbI2 (s) Pb2+ (aq) + 2I- (aq) Step 2: Write the Ksp expression Step 3: Assign x values to concentrations PbI2 (s) Pb2+ (aq) + 2I- (aq) x x 2x

  37. The Ksp for lead(II) iodide is 7.08 x 10-9 at 25⁰C. What is the molar concentration of PbI2 in a saturated solution? Step 1: Write and Balance Equation PbI2 (s) Pb2+ (aq) + 2I- (aq) Step 2: Write the Ksp expression Step 3: Assign x values to concentrations PbI2 (s) Pb2+ (aq) + 2I- (aq) x x 2x Step 4: Solve x = [PbI2] = 1.21 x 10-3 M

  38. Practice 8. The Ksp of calcium sulfate is 9.1 x 10-6. What is the molar concentration of calcium sulfate in a saturated solution?

  39. Practice 9. The Ksp of CdF2 is 6.4 x 10-3. What is the molar concentration of cadmium fluoride in a saturated solution?

  40. 14.3 LeChatelier’s Principle • Objective: (1) To use LeChatelier’s Principle to determine how a system at equilibrium will respond to an external stress.

  41. LeChatelier’s Principle • LeChatelier’s Principle: When a system at equilibrium is disturbed, the system adjusts in a way to reduce the change. • There are 3 possible disturbances: Change in (1) concentration, (2) temperature, or (3) pressure

  42. 1. Change in Concentration • Increase concentration of reactant  Equilibrium shifts toward products • Decrease concentration of reactant  Equilibrium shifts toward reactants • Increase concentration of product  Equilibrium shifts toward reactants • Decrease concentration of product  Equilibrium shifts toward products

  43. Use the following reaction to answer the questions below: H2 (g) + I2 (g) 2HI (g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase H2 2.) Decrease I2 3.) Increase HI 4.) Decrease HI

  44. Use the following reaction to answer the questions below: H2 (g) + I2 (g) 2HI (g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase H2RIGHT 2.) Decrease I2LEFT 3.) Increase HI LEFT 4.) Decrease HI RIGHT

  45. 2. Change in Temperature • Think of heat as a reactant or product • Exothermic: heat is a product • Endothermic: heat is a reactant • For an exothermic reaction: • Increasing temperature  equilibrium favors reactants • Decreasing temperature  equilibrium favors products • For an endothermic reaction • Increasing temperature  equilibrium favors products • Decreasing temperature  equilibrium favors reactants

  46. Use the following reaction to answer the questions below: 2SO3(g) + CO2 (g) + heat CS2 (g) + 4O2(g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase the temperature 2.) Decrease the temperature

  47. Use the following reaction to answer the questions below: 2SO3(g) + CO2 (g) + heat CS2 (g) + 4O2(g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase the temperature RIGHT 2.) Decrease the temperature LEFT

  48. 3. Change in Pressure • Only affects gases! • Increasing pressure  Equilibrium shifts toward the side with fewer moles of gas • Decreasing pressure  Equilibrium shifts toward the side with more moles of gas

  49. Use the following reaction to answer the questions below: 2SO3(g) + CO2 (g) + heat CS2 (g) + 4O2(g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase the pressure 2.) Decrease the pressure

  50. Use the following reaction to answer the questions below: 2SO3(g) + CO2 (g) + heat CS2 (g) + 4O2(g) In which direction (left or right) does the equilibrium shift in each of the following situations: 1.) Increase the pressure LEFT (3 moles gas) 2.) Decrease the pressure RIGHT (5 moles gas)

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