Chapter 6

Thermodynamic Properties of Fluids

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CONTENT

THERMODYNAMIC PROPERTIES OF FLUIDS

6.1 Property Relations for Homogeneous Phase
6.2 Residual Properties
6.3 Residual Properties by Equations of State
6.7 Generalized Property Correlations for Gases
6.4 Two-Phase Systems
6.5 Thermodynamic Diagrams
6.6 Tables of Thermodynamic Properties

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6.2 Residual Properties:
Comments on the Physics of Residual Energies:
The ideal gas contribution to the energy comes from the mechanisms by
which molecules can possess energy without interacting with other molecules.

The usual mechanism for interacting with other molecules & atoms are:

Translational movement
Rotational movement
Vibrational movement

The contribution described by the residual functions is directly related to the difference
between a real material & an ideal gas. These differences arise from the interactions
(attractive & repulsive) that occur between the molecules.

Separation of the calculation into these parts that depend upon different aspects of
physics allows information about individual materials to be stored in a very compact
form that includes ideal gas heat capacities, critical properties and etc…

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6.2 Residual Properties
Definition:
Residual Property = Real Property - Ideal Gas Property
The generic residual property

Example:
For example, to calculate ∆H or H the hypothetical path.

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 Hypothetical path
Sometimes, due to lack of information, we use residual property concept
to calculate the property change from state 1 to state 2:

Calculate the property deviation between real & ideal gas (i.e.,
“change residual property value”) for both states,

Take ideal gas change from state 1 to state 2 into consideration for
final result

Make correction of ideal gas change to real gas change (using

residual property change

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Rearrange

is mean heat capacity

Now how to determine HR

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To determine HR, let’s start with the Gibbs Free Energy

Divide by RT & differentiate,

Substitute for G & dG:

(6.37)

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Now let’s do for residual Gibbs energy, GR,

Divide by RT & differentiate,

Apply eqn. 6.37,

(6.42)

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Apply criterion of exactness:

(6.43) (6.44)

Rearrange eqn. (6.43) & integrate from ideal gas state (P=0) to
arbitrary P (actual P),

(6.45)

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Differentiate the above equation with respect to T at constant P,

Substitute into eqn. (6.44) for HR

(6.46)

Similarly from:
(6.47)

(6.48)

Hence, as in eqns (6.46) & (6.48), we need either PVT data or

correlations for Z to solve for HR & SR.

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Enthalpy For Real Gas

(6.50)

NOTE: The reference state is ideal gas at To & Po

is calculated as follows:

(6.53)

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Similarly, entropy for real gas:

(6.51)

where:

(5.17)

𝑇
𝜏= s = mean value specific to entropy calculations
𝑇𝑜
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 Summary:
(6.45) (6.46)

(6.47)

(6.48)

Enthalpy
for real gas
Entropy
for real gas
𝑇
𝜏= (5.17)
𝑇𝑜
s = mean value specific to entropy calculations
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How to Evaluate Integrals involving “Z”
Needed Integrals:
𝑃 𝑍−1
◦ ‫׬‬0 𝑑𝑃
𝑃

𝑃 1 𝜕𝑍
◦ ‫׬‬0 𝑃 𝜕𝑇 𝑑𝑃
𝑃

Evaluation Methods:
By Experimental Data (involving Numerical Integration).
[See Example 6.3]
By Equations of State (e.g., cubic EOS or Virial Equation).
By Generalized Method or Lee-Kessler Tables.

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 0.98 − 0.92
= 0.00600
313 − 3013

0.93 − 0.88
= 0.0100
308 − 303

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Problem 1: The solution is in BB/Chapter 1
An ideal gas with constant heat capacity undergoes a change of state
from T1 = 330 K, P1 = 1.2 bar to conditions T2 = 450 K, P2 = 6 bar. Given
that Cp/R = 7/2. Determine ∆𝐻 (J/mol) and ∆𝑆 (J/mol K).

Problem 2:
Calculate Z and V for ethane at 50 °C and 15 bar by the following equations:
(a) The truncated virial equation [Eq. (3.40)] with the following
experimental values of virial coefficients:
B = −156.7 cm3.mol−1
C = 9,650 cm6.mol−2
(b) The truncated virial equation [Eq. (3.38)], with a value of B
from the generalized Pitzer correlation [Eqs. (3.63)].
(c) The Redlich/Kwong equation.

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Example 6.3:

0.99753−0.99719
= = 1.7x10-5
370−350

1.7x10−5
= = 1.7x10-4
0.10

[− ( 0.99737−1)]
= = 2.63x102
0.10

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Solution 6.3:

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Solution 6.3:

Note that the

integral must start
from (P = 0), so
extrapolations were
needed
Exercise: Exercise:
try to try to
calculate calculate
these these
values values

Exercise:
try to calculate these
integrals from data above

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Solution 6.3:

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Solution 6.3:

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 Reference

Smith J.M., Van Ness H.C., & Abbott M. M., Introduction to Chemical
Engineering Thermodynamics, 7th Edition, McGraw Hill, New York, 2001.

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