CHE 301: Chemical

Engineering Thermodynamics
Dr. O. J. ODEJOBI
Department of Chemical engineering
Obafemi Awolowo University
Ile-Ife, Nigeria
2.3-2 The Van de Walls Equation of State
•  The Van de Walls equation of state is:
(51)
• The equation of state to illustrate the evaluation of thermodynamic
properties.
• In this equation, the constant b accounts for the finite volume
occupied by the molecules and the term accounts for the attractive
forces between molecules.
• The Van der Waals parameters a and b can be determined from the
critical properties since there is an inflection point at the critical
isotherm as shown in Figure 2.3-1.
The Van de Walls Equation of State

Figure 2.3-1: Isotherms from the Van der Waals equation.

The Van de Walls Equation of State
•  At the critical point we have
(51)
• The isotherm passing through the critical point is given by

• The first and second derivatives of P with respect to v are given by

(51a)

(51b)
The Van de Walls Equation of State
•  We can solve the two equations (2.3-6a) and (2.3-6b) for the two
unknowns a and b.
• Multiplying equation (52a) by 2 and equation (52b) by and add them
together we get

(52)

(53)
The Van de Walls Equation of State
•  Substituting into equation (51a) and solving for a gives

• At the critical point we have

(54)
• We can use equation (54) to solve for in terms of critical temperature
and critical pressure.
• Substituting and into equation (54) we obtain
(55)
The Van de Walls Equation of State
•  Soling for in terms of and we have

• Hence

• Using and for propane, , we have

Example 6
• One
  mole of propane gas is to be expanded from 0.001 m3 to 0.040 m3 while in
contact with a heating bath at 100oC. The expansion is not reversible. The heat
extract from the bath is 600 J. Determine the work for the expansion using the
Van der Waals equation of state.

• From the first law we have . Since the amount of heat transfer q is given (600
J/mol), we only need to evaluate to find .
• We write as a function of the independent variables and since the values of
these two variables are given in the problem.
⇒
• Since the process occurs at constant , we have
Solution 6
•  We need to express in terms of measurable properties.
• From the property relations diagram

From Maxwell relation we have

Solution 6
•  The change in internal energy can now be expressed solely in terms of
measurable properties:

• In terms of molar quantities

• From the Van der Waals equation:

(a)

From (a)
(b)
Solution 6
• 

Recall: From Maxwell relation

So:

But
Solution 6
• 
Therefore:

Using and for propane, , we have

Solution 6
•Therefore
 

The required work for the expansion is

2.3-3 Soave-Redlick-Kwong (SRK) Equation
•• The
  Soave-Redlick-Kwong (SRK) equation belongs to a class of cubic equations of
state because, when expanded, they yield third-degree equations for the specific
volume.
• The SRK equation of state is
(56)
• The parameter a, b, and α are empirical functions of the critical temperature and
pressure, the Pitzer acentric factor, and the system temperature.
• The following correlations can be used to estimate these parameters:
Example 7
•  A gas cylinder with a volume of 2.50 m3 contains 1.00 kmol of carbon
dioxide at T = 300 K. Use the SRK equation of state to estimate the gas
pressure in atm. Data for carbon dioxide: Tc = 304.2 K, pc = 72.9 atm,
and ω = 0.225.
Solution
Solution 7
• 
Example 7
•A  stream of propane at temperature T = 423 K and pressure p(atm) flows at a rate
of 100.0 kmol/hr. Use the SRK equation of state to estimate the volumetric flow
rate flow of the stream for p = 0.7 atm, 7 atm, and 70 atm. In each case, calculate
the percentage differences between the predictions of the SRK equation and the
ideal gas equation of state. Data for propane: Tc = 369.9 K, pc = 42.0 atm, and ω =
0.152.
Solution
We first calculate a, b, and α from the following expressions:

The SRK equation is written in the form

Solution to Example 7
•is  then calculated using Newton’s method:
,
where

• The initial value for is obtained from ideal gas law: .

• The iteration process stops when is less than 0.0001.
• The percentage difference between and is
.
Solution to Example 7
• Once
  is known for a given , the volumetric flow rate corresponding to a molar flow
rate of 100.0 kmol/hr is obtained as

• The SRK equation of state (and every other equation of state) is itself an
approximation.

• At 423 K and 70 atm, the actual value for is 0.2579 L/mol.

• The percentage error in the SRK estimate ( = 0.289 L/mol) is 12%.

• In the ideal gas estimate = 0.50 L/mol and the percentage error is 92%.
2.4 Properties Evaluations
• This
  section will show the use of equation of state and property relations to
evaluate thermodynamic properties in several examples.
Example 8
Propane at 350oC and 600 cm3/mol is expanded in an isentropic turbine. The
exhaust pressure is atmospheric. What is the exhaust temperature? behavior has
been fit to the Van der Waals equation with a = 92×105 [(atm⋅cm6)/mol2] and b = 91
[cm3/mol]. Solve this using T as v as the independent variables, that is . The Van der
Waals equation is given as

The ideal gas heat capacity for propane is

Solution to Example 8
• Since
  propane is expanded in an isentropic turbine, we can construct a path such
that the sum of Δs is zero.

• Choosing T and v as the independent variables the change in entropy is given by

⇒
Solution to Example 8
•  Since

• Using Maxwell relation as shown on the following diagram, we have

From the van de Waals equation:

Solution to Example 8
•  For an isentropic process, we have