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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?

mixture.

"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.

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

constant."

∂(nG)

µi ≡

∂ni P,T ,n j

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.

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.

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 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?

i

i i we can obtain the solution

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."

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.

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