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Chapter 6

Physical Chemistry. Chapter 6. Chapter 6. Reaction Equilibrium in Ideal Gas Mixtures. one-phase pure substance. (4.86)*. Physical Chemistry. Chapter 6. Chemical Potentials in an Ideal Gas Mixture. Chemical Potential of a Pure Ideal Gas. (4.36). isothermal, pure ideal gas.

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Chapter 6

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  1. Physical Chemistry Chapter 6 Chapter 6 Reaction Equilibrium in Ideal Gas Mixtures

  2. one-phase pure substance (4.86)* Physical Chemistry Chapter 6 Chemical Potentials in an Ideal Gas Mixture Chemical Potential of a Pure Ideal Gas (4.36) isothermal, pure ideal gas isothermal, pure ideal gas (6.1) pure ideal gas, Po1 bar (6.2)

  3.  - o RT 0 1 2 3 P/Po -RT -2RT Physical Chemistry Chapter 6 Chemical Potentials in an Ideal Gas Mixture For a pure ideal gas Fig. 6.1 T is fixed

  4. Ideal gas mixture at T and P membrane Pure gas mixture at and T Physical Chemistry Chapter 6 Chemical Potentials in an Ideal Gas Mixture An ideal gas mixture (1) (2) The mixture is separated by thermally conducting rigid membrane permeable to gas i only, and ideal gas mixture Fig. 6.2 (6.3)

  5. Ideal gas mixture at T and P No intermolecular interaction, no effect on from other gases in the mixture. membrane Pure gas mixture at and T ideal gas mixture (6.4)* Physical Chemistry Chapter 6 Chemical Potentials in an Ideal Gas Mixture ideal gas mixture (6.3) Fig. 6.2 The fundamental thermodynamic equation

  6. i - io RT 0 1 2 3 Pi/Po -RT -2RT Physical Chemistry Chapter 6 Chemical Potentials in an Ideal Gas Mixture For an ideal gas mixture Fig. 6.1 (modified)

  7. (6.4)* Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium For the ideal-gas reaction (4.36) the equilibrium condition

  8. Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.5) the equilibrium condition

  9. Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.6) (6.7)

  10. (6.7) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium the equilibrium condition (6.8)

  11. Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.9) (6.10) (6.11)*

  12. (6.11)* (6.10) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.12) (6.13)* (6.14)* (6.15)

  13. (6.9) Since depends only on T, for a given ideal-gas reaction is a function of T only. At a given temperature, is constant for a given reaction. (6.15) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium the standard equilibrium constant the standard pressure equilibrium constant

  14. (6.13)* Since is dimensionless, the standard equilibrium constant is dimensionless. (6.19) has dimensions of pressure raised to the change in mole numbers for the reaction as written. Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium the equilibrium constant the pressure equilibrium constant

  15. (6.13)* the molar concentration (6.21)* ideal gas mixture (6.22) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.23)

  16. (6.13)* (6.23) (6.24) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium n/mol same dimension as Po

  17. (6.13)* the standard equilibrium constant the standard pressure equilibrium constant (6.24) the standard equilibrium constant the concentration equilibrium constant Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium

  18. (6.23) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium (6.25) (6.26) (6.27)

  19. (6.31) (6.9) (6.32) Physical Chemistry Chapter 6 van’t Hoff Equation From (6.14)

  20. (6.31) (6.33) (6.34) (6.32) Physical Chemistry Chapter 6 van’t Hoff Equation From

  21. (6.36)* (6.34) (6.32) Physical Chemistry Chapter 6 van’t Hoff Equation

  22. Physical Chemistry Chapter 6 Gibbs-Helmholtz Equation

  23. Physical Chemistry Chapter 6 Gibbs-Helmholtz Equation When it is applied to changes

  24. Physical Chemistry Chapter 6 van’t Hoff Equation From (6.14) Differentiation of lnKPowith respect to temperature gives The differentials are complete because K and G depend only on temperature, not on pressure. Using Gibbs-Helmholtz equation (6.36)*

  25. (6.36)* (6.37) (6.38) (6.39) Physical Chemistry Chapter 6 van’t Hoff Equation

  26. (6.36)* (6.40) Physical Chemistry Chapter 6 van’t Hoff Equation The van’t Hoff equation is an expression for the slope of a graph of the equilibrium constant (specially, lnK) plotted against the temperature. It may be expressed in either of two ways:

  27. the reaction quotient (6.41) the equilibrium constant (6.19) Physical Chemistry Chapter 6 Ideal Gas Reaction Equilibrium The equilibrium extent of reaction The extent of reaction The reaction goes to right The reaction reaches equilibrium The reaction goes to left

  28. Physical Chemistry Chapter 6 Simultaneous Equilibria A system with several simultaneous reactions that have species in common. (6.47) (6.48)

  29. Physical Chemistry Chapter 6 Simultaneous Equilibria At 600 K, CH3Cl(g) and H2O(g) react to form CH3OH, and then form (CH3)2O with a simultaneous equilibrium shown: (1) (2) Starting with equal amount of CH3Cl and H2O, find the equilibrium amounts of all species.

  30. Physical Chemistry Chapter 6 Simultaneous Equilibria Suppose that a system initially contains 1 mole of CH3Cl(g) and H2O(g), x moles of HCl and y moles of (CH3)2O are formed at equilibrium. (1) 1-x 1-x+y x-2y x (2) x-2y y 1-x+y

  31. Physical Chemistry Chapter 6 Simultaneous Equilibria Suppose that a system initially contains 1 mole of CH3Cl(g) and H2O(g), x moles of HCl and y moles of (CH3)2O are formed at equilibrium.

  32. Physical Chemistry Chapter 6 Simultaneous Equilibria The equilibrium amounts of all species are (1) 0.952 0.961 0.03 0.048 (2) 0.03 0.009 0.961

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