Review for Second Hour Exam

Chapters 4 & 5

Chapter 4. Fundamental Equations of Thermodynamics

closed systems:

   dU = TdS - PdV

   dH = TdS + VdP

   dA = -SdT - PdV

   dG = -SdT + VdP

• Combined 1st and 2nd laws expressed in exact differentials for the 4 thermodynamic energy potentials U, H, A, and G.

• Significance of the fundamental differentials, e.g., (dU/dS)_V = T, (dU/dV)_S = -P

• Maxwell relations and how they are related to mixed partial 2nd derivatives, e.g., (dT/dP)_S = (dV/dS)_P

• Criteria for spontaneity, e.g., dG < 0 for a system at constant T and P or dA < 0 for a system at constant T and V

  • Equilibrium at constant T and P, dG=0

• The coefficient of thermal expansion, alpha, and the isothermal compressibility coefficient, kappa.

• Open systems and the chemical potential; molar Gibbs energy

• Partial molar quantities

• Temperature dependence of Delta_G: the Gibbs-Helmholtz equation (and its application in Chapter 5 for the temperature dependence of K)

• Pressure dependence of Delta_G

  • ideal gases

  • real gases: fugacity, fugacity coefficients, activities

• Chemical potential and spontaneity: high -> low chemical potential

• Partial molar quantities, e.g., G = n₁ mu₁ + n₂ mu₂ + ...

Chapter 5. Chemical Equilibria for Gas Reactions

• Extent of reaction, x:    n_i = n_i,0 + nu_i * x

• Reaction Gibbs energy, Delta_G_r, and its change with x

  • relation of the chemical potential to Delta_G_r

  • Delta_G_r = Delta_G_r^o + RTln(Q)

• Standard reaction Gibbs energy, Delta_G_r^o and K (i.e., K_p). Delta_G_r^o = -RTln(K)

• Temperature and pressure dependence of K