SKF 2213 Chemical Engineering

Thermodynamics
Chapter 3: Volumetric Properties of Pure Fluids
-Introduction to volumetric properties
-PVT behaviour of pure substances
-Volumetric properties from equations of state:
oIdeal gas equation
oVirial equation
oGeneric cubic equations
-Volumetric properties from generalized correlations:
oGases
oLiquid
-Volumetric properties from thermodynamic Tables
and Diagrams
It is expected that students have the ability to:
-Determine the state/phase of a given fluid at given conditions.
-Calculate the volumetric properties using the equations of state and
generalized correlations for a given system.
-Identify the applicability and limitation of every equation of state.
-Determine the volumetric properties from thermodynamic tables and
diagrams.
The phase rule [2.7/pg29]
Degrees of Freedom (F)
The number of independent variables that must be fixed to established
its intensive state (J. Willard Gibbs)
F=2-+N
is number of phase
N is number of species
For example, a system contains water vapor
F=2-1+1=2
So, the degree of freedom is 2
This means we are free to specify 2 thermodynamics variable (e.g. T and
P), the rest of thermodynamic properties (e.g. U, H, V etc.) will depend on
these two variables
PVT behaviour of pure substances: PT diagram
PVT behaviour of pure substances: PV diagram
From PV diagram we know that there are
correlations between PVT for a pure
substance.
V for gas is highly dependent on T and P.
i.e. gas is highly compressible.
V for liquid phase, however, is almost
independent of T and P
i.e. incompressible liquid
The correlation for PVT is known as equation
of state (EOS)
6
Single Phase Region (1) [pg 68]
This equation is mostly applicable for liquid
phase
F=2
Let say V=V(T,P)
dV =
cV
cT
|
\

|
.
|
P
dT +
cV
cP
|
\

|
.
|
T
dP
dV
V
=
1
V
cV
cT
|
\

|
.
|
P
dT +
1
V
cV
cT
|
\

|
.
|
P
dP
dV
V
= |dT kdP
So
| =
1
V
cV
cT
|
\

|
.
|
P
is volume expansivity
k =
1
V
cV
cT
|
\

|
.
|
P
is isothermal compressibility
T
P
Single Phase Region (2)
For small change of T and P, reasonable approximation can
be made if and is assumed constant, so
If we assume incompressible liquid:
and is 0, hence V or is 0,
V and is constant.

ln
V
2
V
1
= | T
2
T
1
( )
k P
2
P
1
( )
Example 3.1 [pg 69]
The simplest form of EOS:
Ideal Gas
For gas phase only.
PV=RT
Developed by Boyle, Charles and Gay-
Lusaac in the 18th century.
Valid at low pressure.
Assume no interaction among molecules.
From degree of freedom,
we say U(T,P), H(T,P),
but P has no effect on U and H of an ideal gas
so we write U(T) and H(T).
9
In general
Ideal gas EOS is valid at low pressure.
In many cases, gas at pressure up to several
bar can be assumed as ideal gas.
To confirm this assumption, always check
compressibility factor Z as in PV=ZRT.
For ideal gas, Z=1
Caution:
At 0
o
C and 100 atm
CO
2
: Z = 0.202 non-ideal gas
N
2
: Z = 0.9848 almost like ideal gas
10
Virial Equation of State
Only for gas phase
Z =
PV
RT
= 1+ ' B P + ' C P
2
+ ' D P
3
+ ..... 3.11
( )
Z =
PV
RT
= 1+
B
V
+
C
V
2
+
D
V
3
+ ..... 3.12
( )
where,
' B =
B
RT
' C =
C B
2
RT ( )
2
' D =
D 3BC + 2B
3
RT ( )
3
B
'
,C
'
,D
'
,.......and
B,C,D,....... are virial coefficients
Virial Equation of State (2)
Truncated forms are recommended for application at low to
moderate pressures.
It is suggested that for P up to 15 bar, truncation to two terms will
give reasonable approximation.
Z =
PV
RT
= 1+ ' B P
Also for P up to 50 bar, truncation to three terms will give
reasonable approximation.
Z =
PV
RT
= 1+ ' B P + ' C P
2
Heat Capacity
13
For ideal gas
Heat capacity at constant pressure Cp
Heat capacity at constant volume Cv
Cp=Cv+R
Ideal Gas Isothermal process
Energy balance for ideal gas in a closed system.
cQ +cW = dU
ig
+ dE
K
+ dE
P
cQ +cW = 0
cQ = cW = PdV =
RT
V
dV
Q = W = RT ln
V
2
V
1
= RT ln
P
2
P
1
For isothermal process (T=0), dU
ig
=dH
ig
=0
Ideal Gas Isobaric process
Isobaric Process (P=0)
cQ+ cW = dU
ig
+ dE
K
+ dE
P
cQ PdV = dU
ig
cQ= dU
ig
+ PdV = dH
ig
Q= C
P
ig
dT
}
AH
ig
= C
P
ig
dT
}
AU
ig
= C
V
ig
dT
}
cW = PdV
W = P(V
2
V
1
) = R(T
2
T
1
)
dH
ig
= dU
ig
+ dPV
dH
ig
= dU
ig
+ PdV +VdP
Energy balance for ideal gas in a closed system,
Note:
Ideal Gas Isochoric process
Isochoric Process (V=0)
cQ+ cW = dU
ig
+ dE
K
+ dE
P
cQ= dU
ig
Q= C
v
ig
dT
}
AH
ig
= C
P
ig
dT
}
AU
ig
= C
V
ig
dT
}
cW = PdV
W = 0
Energy balance:
Ideal Gas Adiabatic process (1)
Adiabatic Process (Q=0)
AH
ig
= C
P
ig
dT
}
AU
ig
= C
V
ig
dT
}
cQ +cW = dU
ig
+ dE
K
+ dE
P
cW = dU
ig
W = C
v
ig
AT
Let =
C
p
C
v
=
C
v
+ R
C
v
=1+
R
C
v
so
C
v
=
R
1
W =
RAT
1
=
R(T
2
T
1
)
1
=
P
2
V
2
P
1
V
1
1
(eqn 3.33)
dH
ig
= dU
ig
+ dPV
C
p
dT = C
v
dT + RdT
Note:
Ideal Gas Adiabatic process (2)
cW = dU
ig
PdV = C
v
ig
dT
RT
V
dV = C
v
ig
dT
R
C
v
ig
dV
V
=
dT
T
R
C
v
ig
ln
V
2
V
1
= ln
T
2
T
1
T
2
T
1
=
V
1
V
2
|
\

|
.
|
R
C
v
ig
we could also show that
P
2
P
1
=
V
1
V
2
|
\

|
.
|
C
P
ig
C
v
ig
or PV

= constant
Substitute into eqn 3.33, we get rev. work
W =
RT
1
1
P
2
P
1
|
\

|
.
|
1 ( )

1





(

(
(
(

AH
ig
= C
P
ig
dT
}
AU
ig
= C
V
ig
dT
}
Adiabatic Process (Q=0), another approach:
Adiabatic Process (Q=0)
TV
-1
=const
TP
(1-)/
=const
PV

=const
Ideal Gas Polytropic process
Adiabatic
isochoric
Isothermal
Isobaric
Prove equation 3.37 for constant heat capacity.
Example 3.3
Calculate W, Q, U, H for each of the 3 processes
and for the entire cycle. Given Cv=(3/2)R, Cp=(5/2)R
Assignment
Problems 3.3 & 3.8 (pg. 111-112)
Prove 3.13 a-c?