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When designing chemical processes, chemical engineers often need to calculate the change of a
specific state property between one state and another state (e.g. U, S, H, A, G, etc.). The
state (toestand) of a pure component in a specific phase can be fully described by any two of
the following parameters: T, P and V. In other words, the state property can be expressed as
f(T,P), f(T,V) or f(P,V). For example if U = U(T,V) then U = U(T2,V2) U(T1,V1).
In principle, departure functions fulfill the need to have a general approach, applicable to any
fluid, whereby a specific change () in a state property can be calculated by following a specific
type of pathway while describing the property either in terms of {T,V} or {T,P}. Departure
functions make use of residual properties and it is therefore important that the definition and
nature of residual properties are well-understood.
In practice, the parameters T and P are easy to measure and they are thus convenient to use.
However, many equations of state (EOS) are pressure-explicit, in other words P = P(T,V), and it is
not easy to re-arrange these equations to volume-explicit functions such as V = V(T,P).
Therefore, in order to utilize the most widely used equations of state, the best approach is quite
often to develop the state properties in terms of {T,V}.
For simplicity sake, lets consider internal energy, u, as the state property under investigation.
To avoid very complex calculations of a parameter such as cv we rather follow a pathway
consisting of three steps:
Step 1: Calculate U when isothermally changing from the real fluid of state 1 to an ideal gas
at the same {T,V} or {T , P } . In other words, the measured parameters remain constant, but the
component is changed from a real fluid to an ideal gas.
Step 2: Calculate U when changing the ideal gas from state 1 to state 2 (T and v can now
change), while remaining an ideal gas.
Note: Under ideal gas conditions, we know that cv is only a function of temperature and we can
thus change the temperature of the system while ignoring the volume-dependence of cv.
Step 3: Calculate U when isothermally changing between the state 2 ideal gas and the
equivalent real fluid of state 2 (i.e. the final state).
Following Simpsons rule, we now combine the above three steps to provide:
Therefore:
Page 1 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
This equation can be generalized to any fundamental or derived state property M, where M
could be u, s, h, a, or g. In general form:
In addition, we know that molecular attraction and repulsion forces are, per definition, ignored
for an ideal gas. Furthermore, when a real fluid is at a state where or 0, the
molecules are so far apart that attraction and repulsion forces are completely insignificant.
Therefore, it follows that:
!", $ = !",
!", $ = !",
$ or
0$
In other words, to assist with solving the problem, the internal energy of an equivalent ideal
gas can be calculated at the same temperature as the real fluid, but at zero pressure (or at
infinite molar volume).
To summarise:
The advantage of the pathway proposed above (including two departure functions) is that all
ig
calculations that relate to changes in T are performed in the ideal gas state, where cP = cvig + R .
Ideal gas heat capacities are independent of P and V, as is verified below:
&'(
*
&) +
&
&
&./
&1
&
= " &+ %,&)- * = " %&+ . * since 0) % &+ * and 0) = " %&+*
+ )
+
)
&./
&
UTR,V
UT ,V UTig,V
= UT ,v UT ,
V
= dU
when isothermal
U
=
dV
V
S
= T
P dV
V T
See Smith & VN, eq.6.31, p.205. By applying Maxwell, it follows that:
V
P
U TR,V = T
P dV
T V
Alternatively, one can simply apply equation 6.32 in Smith & VN (p.205), as follows:
UTR,V
= UT ,V UT ,
V
= dU
CV dT + T T V P dV
T
when isothermal
Now, the departure function pathway to calculate U between states 1 and 2 results in:
Page 2 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
UR
UR
2 8
1 8
6474
6474
= U 2 U 2ig U1 U1ig + U 2ig U1ig
= U 2 U1
) (
) (
V2
1
2
P
= T
P
dV
P
dV
+
CVig dT
T
V
V
T1
Residual Enthalpy
4.1
+2
+2
=2
+ 3+ . 0/ 4"
5
HR:
= 2+,/ 2+,/67
2+,/
2+,/67
&)
&)
&)
4.2
&)
8 +
/
&)
therefore %&+ *
/
/
Therefore 2+ = 3/67 ,
/
8 +
/
Therefore 2+ = 3/67 ,
8
/
8 +
/
+ &8
% *
/ &+ /
+ &8
% * -4
/ &+ /
+ . &8
%&+* - 4
/
/
Divide each side by Tc and multiply Pc above and below the line on the RHS:
9:; <; =
+>
+; . &8
%&+ *
/;
; /
= 3/ ;67 ?
;
Remember A = A 7 !"
&8
Therefore %&+ *
;
/;
9:; <; =
+>
$ + BA !"
&8C
= % &+ *
@4
9: =
+>
/
/;
&8 5
B % &+ *
;
expression:
+ . &8C
9:; <; =
= 3/ ;67 ? /; % &+ * @ 4
;
/;
/;
+>
= 3/ ;67 ?
;
+; .
&8C
D% &+ *
/;
; /
+ . &8 5
&8 5
+ B % &+ * E@ 4
;
/;
+ B 3/ ;67 ? /; % &+ * @ 4
;
/;
Page 3 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
9:; <; =
+>
=F
9:; <; =
+>
G +BF
9:; <; =
+>
Page 4 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
4.3
&)
&)
&+ /
+
* !1 +
/
+ $
IJ + 0 J
Remember B and C are temperature dependent, therefore also need to determine their
derivatives!
&)
If
= LM",
&/
&/
At constant temperature: 4 =
&/
%&)* 4
+
&)
&/
Substitute above into residual enthalpy equation: 2+,/ = 3/67 , " %&+ * - %&)* 4
Therefore: 2+,/ =
/
3/67 ,
&/
%&)*
+
&)
&)
&/
" %&+ * %&)* - 4
/
+
&/
&/
&/
&/
Residual Entropy
5.1
= 3+ .
5
QR
+O
+O
=O
+ 'P
+ 3+ .
5
QR
= O+,/ O+,/67
O+,/
O+,/67
&)
= S" or
V/
S /
O+,/67
+
/
&)
therefore%&+ * = /
= 3/67 S
V/
/
Page 5 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Back to above using Maxwell applied to a real gas: O+,/ O+,/67
/
&)
3/67 % * 4
&+ /
&)
/
V/
3/67 S /
&)
= 3/67 %&+ * 4
/
&)
8
/
W8
/
as well as
8 +
/
&)
&+ /
and % * =
8
/
+ &8
% * -4
/ &+ /
+ &8
+ / %&+* - 4
/
Divide RHS above and below the line with Tc and Pc:
Similar to above it can be proven that:
:; <;
=F
:; <;
:; <;
=
= 3/67 F
G +BF
:; <;
W8
/;
+; &8
% * G4
/; &+; /
Page 6 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
5.3
&)
&)
=%
+
* !1 +
/
+ $
IJ + 0 J
Remember B and C are temperature dependent, therefore also need to determine their
derivatives!
&)
Substitute 4 =
&/
%&)*
+
/
&/
&)
&/
&/
&/
&/
&/
&)
&/
Class Examples
Page 7 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
6.1
Page 8 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
6.2
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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Page 10 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Page 11 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
6.3
Question
A mixture of carbon dioxide (75.2 mass %) and methane must be compressed on a plant near
the sea from a pressure of 2.02 bar(gauge) and temperature of 20.9 oC to a pressure of
120.2 bar(gauge) at a temperature of 52.2 oC. You want to calculate the energy difference
(in J/mol) between these two states. However, you are not sure which equation of state will
describe the gas behaviour adequately and therefore perform the calculations by
a. Firstly applying the Lee-Kesler correlations and
b. By using the simple van der Waals equation of state.
c. To what extent do the answers differ and what is your opinion regarding the accuracy of
the two methods?
Page 12 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Solution
General
Let CO2 = component a ;
Firstly remember that we have to work with mole fractions, instead of mass fractions.
0.752 / 44.01
= 0.525
0.752 / 44.01 + 0.248 / 16.043
yb = 0.475
ya =
At State 2:
The difference in enthalpy between State 1 and State 2 can be calculated by following a useful
hypothetical path that includes two residual enthalpy values (i.e. a departure function pathway).
T2
The two residual enthalpy value can be calculated according to Lee Kesler correlations (section a
of the question), or the van der Waals equation of state (section b of the question).
(a)
Obtain physical property data for CO2 and CH4, from Appendix in the textbook. For the gas
mixture, we need to calculate pseudo properties according to Kays rule, as follows:
Pc(mix ) = ya Pca + yb Pcb
Tc( mix ) = yaTca + ybTcb
Kays rule is not necessarily correct, but it is the best mixing rule that you have at this stage when
applying the Lee-Kesler correlations. The physical property data from the textbook, and the
calculated pseudo-properties, are summarised in the following table.
Mass
fraction
M
g/mol
44.010
16.043
CO2
CH4
Mole
fraction
0.752
0.248
0.5250
0.4750
Tc
K
304.2
190.6
250.242
Pc
bar
73.83
45.99
60.607
0.224
0.012
0.1233
B x 103
1.045
9.081
3.6734
4.8619
C x 106
D x 10-5
-1.157
-2.164
-1.0279
-0.60745
In order to use the Lee-Kesler correlations in the Appendix, we require reduced temperatures
and pressures for the gas mixture at each state, i.e.
Tr( mix ) =
T
Tc( mix )
Pr( mix ) =
Pc( mix )
The calculated pseudo-reduced temperatures and pressures, as well as the correlation values
obtained from the Appendix, are indicated in the table below. Note that one has to interpolate
between Tr = 1.15 and Tr = 1.2 to obtain correct values for State 1. Furthermore, for each state:
( )
( )
HR
HR
HR
=
+
,
RTc( mix ) RTc(mix )
RTc( mix )
( )
( )
0
1
HR
HR
Page 13 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Tr (pseudo)
State 1
State 2
Pr (pseudo)
1.1751
1.3001
(HR)0/RTc
0.0500
2.0000
(HR)1/RTc
-0.0375
-1.56
-0.0225
-0.178
HR/RTc
-0.04027
-1.58195
HR
J/mol
-83.79
-3291.27
We now have the two residual values and only need to calculate the enthalpy change in the ideal
gas condition ( H ig ) when changing the temperature from T1 to T2.
T2
CPig( mix )
T1
dT
T2
T1
( A + BT + CT
+ DT 2 ) dT
T2
BT 2 CT 3 D
= AT +
+
2
3
T T
T2
2 103
3 106
T
T1
= 139.15
CPig( mix )dT = R [....]T2 = 8.314 139.15 = 1156.9 J/mol
T2
T1
Therefore:
T2
H = H 1R + H 2R + CPig dT
T1
Note that this value is negative, i.e. energy has to be removed from the gas mixture.
(b)
P=
a=
27R 2Tc2
;
64 Pc
b=
RTc
8Pc
Since this is a mixture, we need to calculate the a and b parameters for the mixture as follows:
amix = aa ya2 + 2 ya yb aa ab + ab yb2
bmix = ya ba + ybbb
27 8.3142 304.22
= 0.36550
64 73.83 105
27 8.3142 190.62
ab =
= 0.23035
64 45.99 105
amix = 0.2974
aa =
8.314 304.2
= 4.282 10 5
8 73.83 105
8.314 190.6
bb =
= 4.307 105
8 45.99 105
bmix = 4.294 10 5
ba =
Derive the equation for residual enthalpy (for van der Waals) from first principles:
Page 14 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
H = H (V ,T )
H
H
dH =
dV +
dT
V T
T V
H
V dV
T
V =
V
H R = H H ig = H =
H = U + PV
dH = dU + d ( PV )
= dW + dQ + PdV + VdP
= PdV + TdS + PdV + VdP
= VdP + TdS
P
S
V V + T V dV
T
T
V =
V
HR =
P
P
= V
+T
dV
V T
T V
123
V =
Maxwell
V
Now determine the partial derivatives from van der Waals, and then integrate:
RT
a
2
van der Waals
V b V
2a
RT
P
V = V 3
2
T
(V b )
P=
R
P
T = V b
V
2a
VRT
TR
+
2
dV
2
(V b ) V b
V
V =
V
H R =
2a
=
RT ln (V b )
+ RT ln (V b )
V
V
2a RTb
=
+
V V b
HR =
RTb 2a
V b V
For each state, calculate the specific volume (V) from the van der Waals equation by iteration,
while using bmix and amix. Then apply the equation above (in block) to calculate the residual
enthalpy for each state.
V1 = 0.007981 m3 /mol
V2 = 0.000149 m3 /mol
H 1R = 61.3 J/mol
H 2R = 2901.3 J/mol
T2
H = H 1R + H 2R + CPig dT
T1
Page 15 of 16
Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
(c)
Comparison
There is a 22% difference between the answers from the Lee-Kesler and van der Waals
calculations. Van der Waals is the most simple, non-ideal equation of state and generally not
very accurate. One would expect the Lee-Kesler equation, which is a 4-parameter virial equation
of state, to be notably more accurate. Furthermore, one has to remember that the mixing rules,
as applied here, may not be very accurate. In short, approximately 2000 J/mol energy needs to
be removed from the gas mixture.
Page 16 of 16