Reading Assignment Chapter 11: Solution Thermodynamics: Theory (11.5 - 11.7) 1.

How is the Gibbs energy for an ideal gas mixture written? What is i(T)? How do we determine it?

G ig = xi i (T ) + RT xi ln xi P The i(T) is the constant of integration,

i i

which is a function of temperature only, is never really determined directly because the Gibbs energy is always expressed as a difference and not an absolute value. 2. What is the chemical potential? Does chemical potential have any meaning for a pure species? Does chemical potential have meaning when there is only one phase present? Why is it significant in thermodynamics? By definition, the chemical potential is the partial molar Gibbs energy of a component in a solution. Chemical potential has no meaning for a pure species, it only comes into play when there are 2 or more species present. Chemical potential does have meaning in a single phase with 2 or more components present, for example, as changes in the chemical potential help us determine the entropy and enthalpy of the fluid. Chemical potential is essential to determining the conditions for phase equilibria, as well as in chemical reaction equilibria, which are useful in process calculations. All the calculations made in process thermo assume equilibrium. For example, when we calculate the exit conditions from a turbine, we assume the fluid stream, which may have two phases present, is at thermodynamic equilibrium, or in stage separations we may assume that the fluid at each stage has reached equilibrium. We can determine if this is true based on the chemical potential of the phases of the stream. 3. Explain the difference between eqns. 11.27, 11.28 and 11.29 11.27 is the Gibbs energy of a pure species, i. 11.28 is the partial molar Gibbs energy, or chemical potential of component i in a solution. 11.29 is the Gibbs energy of an ideal gas mixture, obtained by applying the summability relation to the partial molar Gibbs energy values (eqn. 11.11). 4. Why is the fugacity introduced? What is it? Why is it useful? Fugacity is an "effective pressure" of real gases or species in solution that enables us to calculate the chemical potential.

5. Write the expression of the chemical potential of a species in an ideal gas mixture. Compare it with equation 11.42. iig = i(T) + RTln(xiP) i = Gi(T) + RTln eqn 11.28

fi

eqn. 11.42

Notice that this is different from the expression for the Gibbs energy of the pure component i: i = Gi(T) + RTlnfi eqn. 11.30

The only difference between these equations is that the fugacity is of the mixture component in eqn. 11.42, while it is for the pure component in eqn. 11.30.Notice the fugacity in 11.42 has a circumflex (a hat) since it is for a component of a mixture.
6. Under what conditions is i = 1? For an ideal gas mixture, i = 1. Likewise, for a pure ideal gas,

fi = 1.

7. Explain the significance of equation 11.51 as the fundamental residual-property relation. We know that Gibbs energy has the canonical variables, Pressure and Temperature, and for a solution, also the composition. Hence, the fundamental residual-property relation shows the solution Gibbs energy as a function of these three variables. From this equation, we are able to obtain all of the thermodynamic properties for a solution.