CDB2033 Chemical Engineering

Thermodynamics

THERMODYNAMIC
PROPERTIES OF FLUIDS

1
 Learning Outcome

By the end of this lecture, you are expected to:

Understand and be able to calculate the
thermodynamic properties for real gas using
Tables of thermodynamics Properties.
Understand and be able to calculate the
thermodynamic properties for real gas using
residual properties.
Understand and apply the Maxwell relations
for analysis
Note: For easy reference, numbers assigned to equations are equivalent to Smith et al. 2005

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 Introduction
Internal Energy, Enthalpy, Entropy for ideal gas system
can be determined using ideal gas capacity, Cvig & Cp ig
Yet, the calculated properties only valid under ideal gas
conditions (low pressure and high temperature).
There are 2 methods used to estimate the properties
for pure substances under real gas conditions as
follows:
Using Established database (e.g., steam table)
Using residue properties.

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Using Established database (e.g., steam table)

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Using Established database (e.g., steam table)

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 Problem
Determine the H, S, V for water for the following conditions:

(a) Saturated liquid 100C to saturated vapour 100C

(b) Superheated steam 400C & 50 kPa to 500C & 100 kPa

(c) Saturated vapour 100C to 400C & 20 bar.

(d) Saturated liquid 100C to 400C & 20 bar.

(e) Water at 250C and 1 bar to saturated liquid at 100C

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 Problem
Determine the final state, H, S, V for water at the following
conditions:

(a) Isochoric process from saturated vapour 200C to 300C.

(b) Isobaric process from saturated vapour 200C to 300C.
(c) Isentropic process from saturated vapour 200C to 300C
(d) Isenthalpic (constant enthalpy) from saturated vapour
200C to 300C

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 Two Phase system
Total Volume for two phase can be determined by:
nV = nlVl + nvVv
V =(nl/n)Vl + (nv/n)Vv
V = xlVl + xvVv
V = (1-xv)Vl + xvVv
H = (1-xv)Hl + xvHv
S = (1-xv)Sl + xvSv

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 Example 6.7
Superheated steam originally at P1 and T1 expands through
a nozzle to an exhaust pressure of P2. Assuming the
process is reversible and adiabatic, determine the down-
stream state of the steam and H for the following
conditions:

P1 = 1000 kPa, T1 = 250C and P2 = 200kPa

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 Using Residual Properties

= = +
= +
= +

= +
=

= ( 1)

=
0

= ( 1)
0
0

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 Using Residue Properties- Generalized
Properties Correlation

= 0 + 1 =
= +
= ( 1)

( )0 ( )1
= + = +

( )0 ( )1
= + = +

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 Example 6.4
Find the values for the residual enthalpy HR and the
residual entropy SR for n-butane gas at 500 K and 50 bar
using generalized Lee/Kesler correlation.

Ans: HR = - 4966 J/mol; SR = - 7.632 J/mol.K

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Generalized Properties Correlation for
Gas Mixture
Pseudocritical Parameters
=

Pseudoreduced Parameters

= =

( )0 ( )1
= +

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 Example 6.10
Estimate V, HR and SR for an equimolar mixture of carbon
dioxide (1) and propane (2) at 450 K and 140 bar using
Lee/Kesler correlation.

Ans: Z = 0.736, V = 196.7 cm3/mol, HR = - 4937 J/mol;

SR = - 1.762 J/mol.K

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 Introduction Properties of Fluids
The Gibbs phase rule allows the calculation of the
number of variables that need to be specified to fix the
values of all other intensive properties of a system.
Numerical values for thermodynamics properties are
essential to calculate heat and work quantities for
industrial processes.
From the first and second laws, fundamental relations
can be developed and calculation of values of intensive
properties from P V T and heat-capacity data is
possible.

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 Property Relations for Homogeneous Phases

For a closed system of n moles undergoing reversible process, the

first law gives:
= +

Since = () and = ()

= (6.1)

This equation is applicable to a closed system where there is a

change between equilibrium states, for both reversible and
irreversible system (since all properties in the equation are state
functions).
P, V, T, U, and S are the fundamental thermodynamic properties.
Additional thermodynamic properties arise only by definition in
relation to these primary properties.

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 Property Relations for Homogeneous Phases

Definition of additional thermodynamic properties:

Enthalpy: + (2.11)

Helmholtz energy: (6.2)

Gibbs energy: (6.3)

Expand and substitute = into the

relations yield:
= + (6.4)
= (6.5)
= 6.6

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 Property Relations for Homogeneous Phases

In molar/specific forms:

= (6.7)

= + (6.8)

= (6.9)

= (6.10)

These fundamental property relations are valid for a

homogeneous fluid of constant composition.

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 Maxwells Equations
Maxwells Equations can be formed by application of
the criterion of exactness for a differential equation.
If = (, ):

+


or = + (6.11)

where ;



since ;




since = (6.12)

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 Maxwells Equations
Similar technique is used to derive other thermodynamic relations

= + =

= = (6.13)

= + = (6.14)

= = (6.15)

= = (6.16)

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 Homogeneous Phase: (, ) and(, )
The most useful property relations for enthalpy and entropy of a
homogeneous phase result when these properties are expressed
as functions of T and P.
Since (, ):

= + and = +


By definition, From Maxwells equation,

= (2.20) =


= = = + +

= + = +


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 Homogeneous Phase: (, ) and(, )
Since S(, ):

= +

By definition:

= =

= (6.21)

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 Homogeneous Phase: (, )
From the enthalpy equation, +
Internal energy is given by =

=



Since:

= +



=



Since:

=



= (6.22)

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 Homogeneous Phase: Ideal-Gas State
The ideal-gas state is an example of equation of state:

= = =


From Equation (6.20),


= +


= (6.23)

From Equation (6.21),

=


= (6.24)

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 Homogeneous Phase: Liquids
Alternative forms of enthalpy and entropy of liquids can be
expressed in terms of volume expansivity, and isothermal
compressibility, .
By definition:
1 1
;


= + = + 1


= =



= =

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 Homogeneous Phase: (, ) and(, )
Temperature and volume often are more convenient variables
than temperature and pressure
Since =

= and =

By definition, From Maxwells equation,

= = =


= + = +

= + = +

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 Homogeneous Phase: (, ) and(, )
Alternative forms:

= =

= + = +

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 Example 6.1
Determine the enthalpy and entropy changes of liquid water for a
change of state from 1 bar and 25oC (298.15 K) to 1000 bar and
50oC (323.15 K). Data for water are given in the following table.

t(oC) T (K) P (bar) CP (J mol-1 K-1) V (cm3/mol) (K-1)

25 298.15 1 75.305 18.071 25610-6
25 298.15 1000 18.012 36610-6
50 323.15 1 75.314 18.234 45810-6
50 323.15 1000 18.174 56810-6

Weak function of T Weak function of P

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 Example 6.1
Determine the enthalpy and entropy changes of liquid water for a
change of state from 1 bar and 25oC (298.15 K) to 1000 bar and
50oC (323.15 K). Data for water are given in the following table.
Solution
Since H and S are state functions, choose the following path:

Figure 6.1:
Calculational path

Since CP is a weak function of T and both V and are weak

functions of P, mean values can be used in calculations, thus avoid
integration.
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 Example 6.1
Solution

= + 1 ; =

= 2 1 + (1 2 ) (2 1 )
2
= ln (2 1 )
1
At P = 1 bar,
75.305 + 75.314
= = 75.310 J mol1 K 1
2
At T= 50oC,
18.234 + 18.174
= = 18.204 cm3 mol1 = 18.204 106 m3 mol1
2
458 + 568
= 106 = 513 106 K 1
2

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 Example 6.1
Solution
Substitution into the equation for gives:
= 2 1 + 1 2 2 1
[1 513 106 323.15 ](18.204)(1000 1)
= 75.310 323.15 298.15 +
10 cm3 bar J 1
= 3400 J mol1

2
= ln (2 1 )
1
323.15 513 106 (18.204)(1000 1)
= 75.310 ln
298.15 10 cm3 bar J 1
= 5.13 J mol1 K 1

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