Introductory Chemical

Engineering Thermodynamics
Chapter 7 - Departure Functions

By J.R. Elliott, Jr.

 Internal Energy Departure Function
 ∂U   ∂U 
V ig

U(T,V)-U (T,V) = ∫ ∂V
  −   dV
ig

∞   T  ∂V T
FPR tells us (dU)T = T(dS)T - P(dV)T
For the ideal gas (dUig)T = T(dSig)T -P(dVig)T
ig
where (dSig)T = RdlnV and P(dV )T = RT/V dV = RT dlnV
ig
Substituting we find, (dU )T = T*R dlnV - RT dlnV = 0
 ∂U 
ig

Therefore,  ∂V  =0
 T
 ∂U  ∂S   ∂V 
Returning to the FPR,  ∂V  = T  ∂V  − P ∂V 
 T  T  T
 ∂S   ∂P 

Maxwell’s Relation ∂V  =  
  T  ∂T  V
  ∂P 
V

(U − U ) = ∫ T 
ig
 − P  dV
Finally,
∞ 
∂T  V 

If we transform to density, the expressions we get are usually easier to integrate.

Chapter 7 - Departure Functions Slide 2

 −1 ∂V −∂ρ
∴ dV = dρ ⇒ = and , at V → ∞, ρ → 0
ρ 2
V ρ
 U - U ig 
ρ
 P 1  ∂ P   dρ
⇒   = ∫  −   
 RT  0  ρRT ρR  ∂T  ρ  ρ
ρ
 U (T ,V ) − U ig (T ,V )   ∂Z  dρ  U (T , P ) − U (T , P ) 
ig
∴   = ∫ − T   =  
 RT  0  ∂T  ρ ρ  RT 
Because Uig(T,P) - Uig(T,V) = ∫ (∂Uig/∂V)T dV = 0
Example. Derive the internal energy departure function for the EOS:
Z=1+4bρ/(1-bρ)-aρ/RT
(∂Z/∂T)ρ = + aρ/RT2 ⇒ -T(∂Z/∂T)ρ = -aρ/RT
ρ
 U (T ,V ) − U ig (T ,V )   ∂ Z  dρ − a ρ ρ −a − aρ
∴   = ∫ − T   = ∫ d ρ = [ρ ]ρ
=
 RT  0  ∂ T  ρ ρ RT 0 ρ RT
0
RT

Chapter 7 - Departure Functions Slide 3

 Helmholtz Energy:Departure Function
V
 ∂A   ∂A  
ig

A(T , V ) − A (T , V ) = ∫ 
ig
 −  dV
∞ ∂V T  ∂V T 
 ∂A   ∂lnV  − RT
ig

FPR ⇒ (dA) T = − PdV ⇒ (dA)

RT
=− dV = − RTdlnV ⇒   = − RT   =
ig

 ∂V  T  ∂V  T
T
V V

 ∂A   ∂A   ∂A 
ig
RT
  = −P ⇒  −
   = − P +
Also  ∂V 
T  ∂ V T  ∂ V T V
Transform to ρ⇒dV = -V dρ/ρ
ρ
 A(T ,V ) − A ig (T ,V )   Z −1
⇒   = ∫  dρ
 RT  0 ρ 

Chapter 7 - Departure Functions Slide 4

 Gibbs energy departure function
As for the density dependent part, it is easy to see that,
G = U + PV -TS = A + PV
ρ
G (T , V ) − G id (T ,V ) A(T , V ) − A ig (T ,V )  Z −1
⇒ = + Z − 1 = ∫  dρ + Z − 1
RT RT o
ρ 
Since V and P correspond to the properties of the real gas, the pressure of the ideal gas at
T and V is P1 =RT/V. The change in Gibbs energy is
G ig (T , p) − G ig (T , V ) = RT ln( P / P1 ) = RT ln( PV / RT ) = RT ln( Z )
G (T , P ) - G ig (T , P ) G (T , P, V ) − G ig (T , V ) G ig (T , P ) − G ig (T , V ) G (T , P, V ) − G (T , V )
ig
⇒ = − = − ln( Z )
RT RT RT RT
ρ
G (T , P ) − G ig (T , P )  Z −1
⇒ = ∫  dρ + Z − 1 − ln( Z )
RT o
ρ 

Chapter 7 - Departure Functions Slide 5

 Summary of density dependent formulas for
departure functions from equations of state.

(H − H ) = ig ρ
 ∂Z  dρ (G (T , P ) − G (T , P )) = (Z − 1) dρ + Z − 1 − lnZ
ig

∫
ρ

RT ∫o  ∂T  ρ + Z − 1
− T
RT o
ρ

(U − U ) ig ρ
 ∂ Z  dρ (A(T , V ) − A (T , V )) = (Z − 1) dρ
ig ρ

RT ∫o  ∂T  ρ
− T
RT ∫
o
ρ
(S (T , V ) − S (T , V )) =
ig ρ
  ∂Z 
( )
 dρ (S (T , P ) − S (T , P )) =
ig ρ
  ∂Z 
( )
 dρ
∫o   ∂T  p
 − T − Z − 1  ∫o   ∂T  p
− T − Z − 1 
ρ
+ lnZ
R   ρ R  

Chapter 7 - Departure Functions Slide 6

 Example 7.1. Use of PREOS to get enthalpy and entropy departures.
Propane gas undergoes a change of state from an initial condition of 5 bar and 105°C to
25 bar and 190°C. Compute the change in enthalpy and entropy.
For propane : A=-4.224; B=0.3063; C= -1.586E-4; D=3.215E-8
Tc = 369.8 K; Pc = 42.49 bar.; ω=0.152

Solution:
Path, for H(190,25) - H(105,5)
[H(190,25) - Hig(190,25)]+[Hig(190,25) - Hig(105,5)]+[Hig(105,5) - H(105,5)]
Similarly for S(190,25) - S(105,5)
[S(190,25 - Sig(190,25)]+[Sig(190,25) - Sig(105,5)]+[Sig(105,5) - S(105.5)]
I. Departure Function + II. Ideal gas + III. Departure function

I. (190,25) → (190,25)ig
190 + 273.15 = 463.15K & 25 bar ⇒ Tr = 1.25135; Pr = 0.58837

PREOS ⇒ Z=0.8891 ⇒ (H-Hig) = (-0.3869) 8.314*463.15 = -1490 J/mol

(S-Sig ) = (-0.2757) 8.314 = -2.2918 J/mol-K

Chapter 7 - Departure Functions Slide 7

 II. (190,25)ig →(105,5)ig
Hig(190,25) - Hig(105,5) = ∫Cp dT = -4.224(463-378) + 0.3063(4632-3782)/2+
(-1.586E-4) (4633-3783)/3 +(3.215E-8)(4634-3784)/4 = 8405 J/mole
Sig(190,25) - Sig (105,5) = A ln(T2/T1)+B(∆T) +C∆(T2)/2+D∆(T3)/3 - Rln(P2/P1) ;
∆Sig = -4.224 ln(463.15/378.15) + 0.3063(85) + (-1.586E-4)(4632-3782)/2 +
+ 3.215E-8(4633-3783)/3 - 8.314 ln 5 = 6.613 J/mol-K
III. (105,5)→(105,5)ig
105 + 273 = 378.15 & 5 bar → Tr = 1.02258; Pr = 0.11767
Z = 0.9574 ⇒ (H-Hig ) = (-0.1274) 8.314*378.15 = -400 J/mol
(S-Sig ) = (-0.0852) 8.314 = -0.7081 J/mol-K
∆Htot = -1490 + 8405 + 400 = 7315 J/mol
(Note: Chart ⇒ (1265 - 1095)*44 = 7480 J/mol)
∆Stot = -2.292 + 6.613 + 0.708 = 5.029 J/mol-K
(Note: Chart ⇒ (1.52-1.50)*44*4.184=3.7 J/mol-K)
Moral: The difference between the chart and the Peng-Robinson equation is significant,
but could be because of error in the Peng-Robinson equation or sensitivity to the
accuracy with which the chart can be read. Entropy is especially difficult because the
temperature and pressure effects tend to cancel and we end up with the small difference
between large numbers. In reality, the Peng-Robinson equation is only accurate to about
10% on enthalpy if compared to a highly accurate equation.

Chapter 7 - Departure Functions Slide 8

 Example 7.6. Use of Referenced PREOS to get enthalpy and entropy
Propane gas undergoes a change of state from an initial condition of 5 bar and 105°C to
25 bar and 190°C. Compute the change in enthalpy and entropy by using a common
reference state of 230K and 0.1MPa.
For propane : A = -4.224; B = 0.3063; C = -1.586E-4; D = 3.215E-8
Tc = 369.8 K; Pc = 42.49 bar.; ω=0.152

Solution: In this example, we are directed to use a reference state such that, for enthalpy:
H2 - H1 = (H2 - Href) - (H1 - Href), and for entropy: S2 - S1 = (S2 - Sref) - (S1 - Sref). Note the
equivalence of this procedure to the way steam tables are computed. Furthermore, the
computation of H2 - Href or S2 - Sref is entirely equivalent to the procedure given in
Example 7.1.
1. REF: Enter the values of Tc , Pc , ω, A, B, C, D and define the T, P, and root of
interest.
2. Press PVTF to enter the pressure and temperature and choose the root of interest.
E.g. at 463.15 K and 2.5 MPa, V = 1369 cm3/mole
3. Press UHSG to compute internal energy, enthalpy, entropy, and Gibbs free energy.
E.g. at 463.15 K and 2.5 MPa, H2 - Href = 36901 J/mole; S2 - Sref = 109.15 J/mole-K
4. Repeat at 378.15 K and 0.5 MPa, H1 - Href = 29586 J/mole; S1 - Sref = 104.13 J/mole-K
5. Subtract ⇒ ∆H = 36901-26756 = 7315 and ∆S = 109.15-104.13 = 5.02 J/mole-K

Chapter 7 - Departure Functions Slide 9

 Example 7.3 Enthalpy departure for PREOS
Obtain a general expression for the enthalpy departure function of the PREOS.
Solution: In the previous example we were able to obtain both pressure-explicit and
density-explicit equations. Therefore, we could solve the problem two different ways.
For the PREOS, we can only solve one way.
1 aρ / RT
Z= −
(
(1 − bρ ) 1 + 2bρ − b 2 ρ 2 )
 ∂Z  ρT / R  − a 1  da  
−T  = +  
∂
 ρT (
1 + 2b ρ − b ρ )
2 2  2
T T  dT  

[ ( )]
2
a = ac 1 + κ 1 − T / Tc ; ac ≡ 0.45724
R 2Tc 2
Pc
where κ = 0.37464 + 1.54226 ω - 0. 26993 ω 2
  T   − κ 1 −1 / 2 
da
dT 

= ac 2 1 + κ 1 −
Tc
 

  2
T 

T
da
[ (
⇒ dT = − a c 1 + κ 1 − T / Tc κ T / Tc)]( )
  Tc
 ∂Z 
−T  =
bρ  −a
−
ac
− 1[ (
+ κ 1 − T / Tc )](
κ T / Tc

≡) bρ
F (Tr )
 (1 + 2bρ − b 2 ρ 2 )
2 2  
 ∂T  ρ 1 + 2bρ − b ρ  bRT bRT
F(Tr) is shorthand. Also B ≡ bP/RT ⇒ bρ = B/Z and A ≡ aP/R2T2 ⇒ a/bRT = A/B

Chapter 7 - Departure Functions Slide 10

  ∂Z  d (bρ ) d (bρ )
bρ bρ
bρ
∫o  ∂T T bρ =
− ∫( ( ) =
T
o
1 + 2bρ − b ρ
2 2
F
)Tr
bρ

F (Tr )   1 − 2  bρ (1 + 2 ) + 1 

l =
bρ
(
F (Tr ) 1 + 1 + 2 bρ 
ln 
)
 n  
8   1 + 2  bρ (1 − 2 ) + 1  0  
8  1 + 1( − 2 bρ

 )
bp
B
bρ

= RT = bρ ⇒ ∫ − T  
 ∂Z  d (bρ ) F (Tr )  Z + 1 + 2 B 
= ln 
( )
Note Z p 0  ∂ T  T b ρ 8  Z + 1 −( 2 B

 )
ρRT
(H − H ) = Z − 1 +
ig
1
ln 
(1 + 2 )B   − a − a [1 + κ (1 −
Z +
)] 
Tr κ Tr 
(1 − 2 )B   bRT bRT
c

nRT 8 Z + 

l
( 2 )B  A 1 + κ Tr 
Z + 1+
= Z - 1 - n 
( 2 )B  B 8  α 
 Z + 1-

Chapter 7 - Departure Functions Slide 11

 Example 7.4 Gibbs Departure for PREOS.
Obtain a general expression for the Gibbs energy departure function of the PR-EOS.
1 aρ / RT
Z= −
(
(1 − bρ ) 1 + 2bρ − b 2 ρ 2 )
1 1 − bρ aρ / RT bρ aρ / RT
Z −1 = − − = −
(
1 − bρ 1 − bρ 1 + 2bρ − b 2 ρ 2 ) ( )
(1 − bρ ) 1 + 2bρ − b 2 ρ 2
(G (T , p ) − G (T , p )) = (Z − 1) dρ + Z − 1 − lnZ
id ρ

nRT ∫
o
ρ
(
1 + 1 + 2 b ρ 
a )
=ln(1-bρ) – lnZ + Z – 1 + bRT 8 ln  1 + 1 - 2 bρ 
( )
 
(
Z + 1+ 2 B A)
=ln(Z-B)- ln  Z + 1 - 2 B  B 8
( )
 

Chapter 7 - Departure Functions Slide 12

 Example 7.7 Liquefaction revisited
2
Reevaluate the liquefaction of methane considered Precool 3
previously using the methane chart by performing Compressor
8
the analogous calculations with the PR EOS. 1 Heat Exch
Natural gas, assumed here to be pure methane, is 7 4
liquefied in a simple Linde process. Compression is Flash Throttle
to 60 bar and precooling is to 300K. The separator is Drum 5

maintained at a pressure of 1 bar and unliquefied gas 6

at this pressure leaves the cooler at 295 K. What
fraction of the gas is liquefied in the process?
Tc =190.6; Pc =4.60MPa; ω=.008; Cp ≈ Cp (200K) ≈ 28.45 J/mol-K
Solution: To facilitate comparison to chart, set the reference enthalpies equal.
satL sat
Let: Href=H (1bar) = 4538J/mol (283.6 J/g as given on chart, T (1bar)=111.0K).
300
H 60 (
= H 60
300
− id H 60
300
+ ) ( id 300
H 60 ) (
− id H 1111 + id
)
H 1111 − H 1satL + H ref
= -0.4334(8.314)300+28.45(300-111)+8.9453(8.314)111 + 4538 = 17089 J/mole
H 8 = H 1295 = (H 1295 − id H 1295 ) + ( id H 1295 − id H 1111 ) + ( id H 1111 − H 1satL ) + H ref
= 0 + 28.45(295-111) + 8255 + 4538 = 18028J/mole
H6 ≡ 4538 E-Bal ⇒ H3 = qH8 + (1-q)H6 ⇒ q=0.9304 ⇒ 6.96% liquefied
This compares to 7.13% when we read the chart to the best of our ability.

Chapter 7 - Departure Functions Slide 13