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Reading Assignment Chapter 11: Solution Thermodynamics: Theory (11.1-11.

4)

1. What is a solution?

A homogeneous system (may be solid, liquid, vapor or gas) that has more
than one component and the components are miscible.

2. Which two special "properties" will be explored in this chapter? What are they used
for in thermodynamics?

partial properties are used to determine properties of components in a


mixture.

excess properties are analogous to residuals in that they represent a


"difference from ideal" which in the case of excess properties, the
difference is from the ideal solution. Hence, they enable us to quantify
non-idealities of homogeneous mixtures.

3. What is the subscript n used for?

n represents the number of moles of a species. As a subscript it defines


that the "number of moles of all chemical species in the solution remain
constant."

4. Explain in words what the partial derivative in equation 11.1 describes.

∂(nG)
µi ≡  
 ∂ni  P,T ,n j

The chemical potential of component i in a solution is the change in the


gibbs energy with the change in the number of moles of i while keeping the
pressure, temperature and the number of moles of all other species
constant. Note that P and T are the canonical variables (independent
variables) of the Gibbs energy of a homogeneous fluid. P and T are the two
thermodynamic variables kept constant in all partial properties, and
hence, the chemical potential is a partial property of particular
importance in thermodynamics. For a solution, the nj are also a canonical
varible of the Gibbs energy.

5. What must be equal in all phases that are in equilibrium?

T, P and µi

6. Specifically, what is a partial molar property? How is it defined? What does it tell
us?
 ∂ (nM ) 
Mi =   A partial molar property tells us the
 ∂ n i  P ,T , n j
dependence on composition of thermodynamic properties. We have seen
how properties depend on other properties, but how the properties
specifically depend on the number of moles of the species of interest in a
homogeneous mixture is described here by partial molar properties.

7. What does equation 11.11 tell us?

How to find the value of a thermodynamic property of a mixture if we are


given the partial molar properties. These summability relations are a
specific characteristic of partial molar property relationships.

8. Explain the notational convention of the three kinds of properties used in solution
thermodynamics.

The solution property (the value that the solution has) has no special
notation such as H, U, S, G.

The partial property M i refers to the property of only one component in


the solution.

The pure species property Mi is the value of the species alone at the
pressure and temperature of the solution.

9. Draw and explain Figs. 11.1 (a) and (b). What do they tell us?

From the summability relation, M = ∑x M


i
i i we can obtain the solution

property from the partial properties. For a binary solution, M = xi M 1 +


x2 M 2 . If we want to know how to obtain the partial properties
graphically, we can solve for each of the partial properties from this
equation. Refer to page 375 for the details of the derivation. Whence we
optain:

dM dM
M 1 = M + x2 and M 2 = M - x1
dx1 dx1

graphically, this is shown on Fig. 10.1. The heavy line is a plot of the
solution property, M, as a function of x1 on the x axis. Note that x2 = 1 - x1
and where x1 is 0 on the axis, the solution is pure component 2, and the
intercept of the plot is the value of M for the pure species at the
temperature and pressure of the solution. (T & P are obviously constant
on this plot). The left hand y-axis intercept is the pure species value for
species 2, M2, and the right hand
y-axis intercept is the
pure species value for species 1, or M1. M1
The tangent to the curve at x = x1, M1
dM M(x1)
is and the intercepts of the
dx1
tangent show the partial
properties of component 1, M 1
(right y-axis, where we have pure M2
component 1) and of component 2
M 2 (left y-axis, where we have pure M2
component 2).
0 x1 1

M1∞
Figure 10.2 shows how we can obtain
the infinite dilution values of the partial
properties from our plot of M vs. x1.
M1
This time two tangents are drawn at

x1 = 0,showing us the value of M 1∞ M2
where it intersects the right y-axis,
and at x1 = 1, showing us the value
of M 2∞ where it intersects the left y-axis.
M2
These infinite dilution parameters
are particularly helpful in separation
problems, where we need to obtain
the removal of a particular component.
As the concentration gets lower and 0 x1 1
lower, we need to know how the component behaves in the solution where
it is "infinitely dilute."

10. What is the significance of equations 11.18 and 11.19?

The relationships are between the partial molar Gibbs energy change with
temperature at constant pressure and mole fractions of the other
components, which is the partial molar entropy, and the partial molar
Gibbs energy changy with pressure at constant temperature and other
mole fractions, which is the partial molar volume.