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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples

Chemical Engineering 317


Additional Notes: Residual Properties and Examples
1

The Need for Departure Functions

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}.

The Departure Function Pathway

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:

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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:
&'(
*
&) +

&

&

For an ideal gas:

&./

&1

&

= " &+ %,&)- * = " %&+ . * since 0) % &+ * and 0) = " %&+*
+ )

+
)

&./

&

therefore %&+ . * = &+ %)* = 0


)

Residual Internal Energy

(Not considered in class)


Consider U = U ( T ,V )

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

Residual internal energy, UR, developed in terms of {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:

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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

Residual Entropy in terms of P, V and T

Consider an enthalpy change:


2 = 2 2 = 2

+2

Therefore need an expression for


2+,/ = 2+,/ 2+,/

+2

=2

+ 3+ . 0/ 4"
5

HR:

= 2+,/ 2+,/67

2+,/

2+,/67

But enthalpy of an ideal gas is pressure INDEPENDENT


Therefore 2+,/ = 2+,/ 2+,/67

&)

Previously: 42 = 0 4" + , " %&+ * - 4


/

&)

Therefore at constant temperature: 42 = , " %&+ * - 4


/

&)

Therefore: 2+ = 3/67 , " %&+ * - 4

4.2

Residual Enthalpy for Generalised correlation charts: Residual Enthalpy in terms of


Z, Tr and Pr
/

&)

Above we derived: 2+ = 3/67 , " %&+ * - 4


=

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

= % &+ *

Substitute above into


Therefore:

@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
;

/;

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
9:; <; =
+>

=F

9:; <; =
+>

G +BF

9:; <; =
+>

See tables E5 E8 p700-703


Generalised correlation charts for HR(0) and HR(1) from Koretsky (reproduced with permission)

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
4.3

Residual Enthalpy from EOSs

For a volume explicit EOS


/

&)

Previously Residual Enthalpy: 2+,/ = 3/67 , " % * - 4


&+
=%

Volume explicit EOS e.g. Virial EOS:

&)
&+ /

+
* !1 +
/

+ $

IJ + 0 J

Determine % * and substitute into residual functions

Remember B and C are temperature dependent, therefore also need to determine their
derivatives!

For a pressure explicit EOS


= LM",

Pressure explicit EOS:

N e.g. cubic EOSs

&)

Residual enthalpy: 2+,/ = 3/67 , " %&+ * - 4


/

If

Not that easy to work with for pressure explicit EOSs

= LM",

&/

&/

N then 4 = %&+ * 4" + %&)* 4


)

At constant temperature: 4 =

&/
%&)* 4
+

&)

&/

Substitute above into residual enthalpy equation: 2+,/ = 3/67 , " %&+ * - %&)* 4
Therefore: 2+,/ =

/
3/67 ,

&/
%&)*
+

&)

&)
&/
" %&+ * %&)* - 4
/
+

&/

&/

From cyclic relations: %&+ * %&)* = %&+ *


/

&/

&/

Therefore 2+,/ = 3/67 , %&)* + " %&+ * - 4


+

Residual Entropy

5.1

Residual Entropy in terms of P, V and T


+ 'P

Ideal gas entropy change: O

= 3+ .
5

QR

4" STU %/. *


5

Consider an entropy change:


O = O O = O

+O

+O

=O

+ 'P

+ 3+ .
5

QR

4" STU %/. *


5

Therefore need an expression for SR:


O+,/ = O+,/ O+,/

= O+,/ O+,/67

O+,/

O+,/67

&)

From Maxwell: 4O+ = %&+ * 4


/

= S" or

For an ideal gas:


Therefore 4O+
Therefore: O+,/

V/
S /

O+,/67

+
/

&)

therefore%&+ * = /

= 3/67 S

V/
/

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Back to above using Maxwell applied to a real gas: O+,/ O+,/67

Substitute into above: O+,/ =


/

/
&)
3/67 % * 4
&+ /

&)

Simplified: O+,/ = 3/67 ,/ %&+ * - 4


5.2

/
V/
3/67 S /

&)

= 3/67 %&+ * 4
/

Residual Entropy for Generalised correlation charts: Residual Enthalpy in terms of


Z, Tr and Pr
/

&)

Remember from above: O+,/ = 3/67 ,/ %&+ * - 4


+ &8
% *
/ &+ /

Therefore O+,/ = 3/67 ,/


/

Therefore O+,/ = S 3/67 ,

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
/; &+; /

See tables E5 E8 p704-707


Generalised correlation charts for SR(0) and SR(1) from Koretsky (reproduced with permission)

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples

5.3

Residual Entropy from an EOS

For a volume explicit EOS:


/

&)

Previously Residual Entropy: O+,/ = 3/67 , % * - 4


/
&+
Volume explicit EOS e.g. Virial EOS:

&)

=%

+
* !1 +
/

+ $

IJ + 0 J

Determine %&+ * and substitute into residual functions


/

Remember B and C are temperature dependent, therefore also need to determine their
derivatives!

For a pressure explicit EOS


/

&)

Residual entropy: O+,/ = 3/67 ,/ %&+ * - 4

Substitute 4 =

&/
%&)*
+
/

&/

&)

&/

Therefore: O+,/ = 3/67 ,/ %&)* %&+ * %&)* - 4


&)

&/

&/

From cyclic relations: %&+ * %&)* = %&+ *


/

&/

&/

Therefore: O+,/ = 3/67 ,/ %&)* + %&+ * - 4

&)

&/

4 into above: O+,/ = 3/67 ,/ %&+ * - %&)* 4

Class Examples

Parts from Koretsky reproduced with permission

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
6.1

Class Example 5.3: Koretsky Example 5.5

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
6.2

Class Example 5.4: Koretsky Example 5.4

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples

6.3

Class Example 5.5: Tutorial Test 2012 Question

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?

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Chemical Engineering 317 2015: Additional notes: Residual Properties and Examples
Solution
General
Let CO2 = component a ;

Let CH4 = component b

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 =

Furthermore, temperatures must be in Kelvin and pressures must be absolute. Therefore:


At State 1:

T1 = 294.05 K; P1 = 2.02+1.01325 = 3.03325 bar (303325 Pa)

At State 2:

T2 = 325.35 K; P2 = 120.2+1.01325 = 121.21325 bar (12121325 Pa)

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

H = H1R + H 2R + H ig = H1R + H 2R + CPig dT


T1

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)

Using Lee-Kesler Correlations

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

mix = yaa + ybb


ig
ig
CPig( mix ) = yaCPa
+ ybCPb

Amix = ya Aa + yb Ab , Bmix = ya Aa + yb Ab , etc.

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

Pseudo properties of mixture

Tc
K
304.2
190.6
250.242

Pc

bar
73.83
45.99
60.607

0.224
0.012
0.1233

Heat capacity parameters for ideal gas C P /R


A
5.457
1.702

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

or: H R = RTc( mix )


+
RT
RTc( mix )
c( mix )

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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

where A, B, etc. are for the mixture.

T2

BT 2 CT 3 D
= AT +
+

2
3
T T

T2

4.8619 2 1.0279 3 0.60745 105


= 3.6734 T +
T
T +

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

= ( 83.8 ) + ( 3291.3 ) + 1156.9


= 2051 J/mol

Note that this value is negative, i.e. energy has to be removed from the gas mixture.
(b)
P=

Using van der Waals


RT
a
2;
V b V

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:

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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 =

under isothermal conditions (dT = 0)

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 =

since V = represents an ideal gas condition

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

= ( 61.3 ) + ( 2901.3 ) + 1156.9


= 1683 J/mol

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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.

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