Chapter 10 - VLE From An Equation of State

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VLE from an Equation of State

By J.R. Elliott and C.T. Lira


FUGACITY IN A MIXTURE BY AN EQUATION OF STATE

dG = VdP - SdT + ∑  ∂ G ∂n


i


i  T , P ,n
dni
j ≠i

and noting,
∂ A 

dA = -PdV - SdT +  ∂n
i

i  T ,V ,n
dni
j ≠i

we may substitute
dA = dG - PdV - VdP = VdP - SdT + ∑  ∂ G ∂n
i


i  T , P ,n
dni - PdV - VdP
j ≠i

⇒ -PdV - SdT + ∑  ∂ A ∂n


i


i  T ,V ,n
dni = -PdV - SdT + ∑  ∂ G ∂n
i


i  T , P ,n
dni
j ≠i j ≠i

Equating coefficients of dni


∂ A  ∂G 
 
∂ni  T ,V ,n =   ∂ni  T ,P ,n = µi(T,P,V)
 j ≠i j ≠i

Referencing to the ideal gas state:


 ∂( A − A ig ) / RT 
ln( f$ i/yiP) = (µi(T,P)-µiig(T,P))/RT =  ∂
 - lnZ
 n i  T ,V ,n j ≠i

VLE from an Equation of State Slide 1


K-Values from an Equation of State
To apply this, consider the PR EOS as an example.
A− A
ig
A  Z + ( 1 + 2 )B  a  1 + ( 1 + 2 )bρ 
= − ln(1 − B / Z ) − ln  = − ln (1 − b ρ) − ln  
nRT B 8  Z + ( 1 − 2 )B  bRT 8  1 + ( 1 − 2 )bρ 
For “random mixing”, the probability of any “i-j interaction” is the same and goes as the product of the “i-j
concentrations”. This suggests that we could define Av = ΣΣyiyjAij and Bv = ΣyiBi letting Aij= Aii A jj by
comparison to the form of the energy equation for mixtures (discussed below). Then differentiation (as detailed
below) yields
 f$i v  Biv v  Z v + ( 1 + 2 ) B v  2Σy j Aij Biv 
ln
y P B
( v
) v Av
 = v Z − 1 − ln Z − B − v (
ln v )
B 8  Z + ( 1 − 2 ) B  v 
A v
− v
B 
 i 
Note: AL = ΣΣxixjAij and BL = ΣxiBi but the derivation of the fugacity coefficient would be the same and:
 f$i L  BiL  Z L + ( 1 + 2 )B L  2Σ x j Aij BiL 
ln L
( L
)
 = L Z − 1 − ln Z − B − L
L AL
( ln  L
+
) −
 L
− L
 B 
L
 x i P  B B 8  Z ( 1 2 ) B A
As we saw in the case of pure fluids, there is no fundamental reason to distinguish between the vapor and liquid
phases except by the initial guess for Z. The equation of state approach encompasses this lack of distinction in a
very direct way. To obtain an expression for Ki, it is convenient to define the fugacity coefficients of a mixture as
f$i v f$i L $L
≡ ϕ$ iv and ≡ ϕ$ iL ⇒ Recalling that
$f v = f$ L at equilibrium, we find that Ki = ϕ i v
yi P xi P i i ϕ$ i

VLE from an Equation of State Slide 2


UNIT III. FLUID PHASE EQUILIBRIA

FUGACITY IN A MIXTURE BY AN EQUATION


OF STATE: Density Dependent Formulas
Example. Fugacity coefficient for the virial equation
For pressures to 10 bars, a common method is to use the virial equation given by:
Z = 1 + Bρ ; where B = ΣΣyiyjBij and Bij= Bii B jj . Develop an expression for the
fugacity coefficient.

 ∂( A − Aig ) / RT  A− A
ig
dBρ A− A
ig
Bn2 1
ln( ϕ k ) =  − ln Z ; = ∫ Bρ = Bρ ⇒ = = ∑ ∑ni n j Bij
 ∂n k T ,V ,n k ≠ i nRT 0 Bρ RT V V

Note: For Bij= Bii B jj , ∑ ∑ ni n j Bij ( ∑n )( ∑ n ) ( ∑n B )


2
= i Bii j B jj = j jj

( ∑ n j B jj ) (∑ n ) ∂(∑ n B )
2
 ∂ ( A − A ) / RT  1∂ 2 B jj
ig
j j jj
  = =
 ∂ n k  T ,V ,nk ≠i V ∂n k V ∂n k

∂ ( ∑n )=
(∑n )
B jj
Bkk ⇒ ln( ϕ k ) =
2
( ∑ y B ) − ln Z
j
B kk B jj − ln Z = 2 ρ
∂n k V j j jk

VLE from an Equation of State Slide 3


UNIT III. FLUID PHASE EQUILIBRIA
Example. Fugacity coefficient for the van der Waals EOS
The VdW EOS provides a simple but fairly accurate representation of key EOS concepts
for mixtures. The main tricks developed for this EOS are the same for other EOS’s but
the algebra is a little simpler.
1 aρ
Z= −
1 − bρ RT
where a= ΣΣyiyjaij ; aij= a ii a jj
b= Σyibi
Develop an expression for the fugacity coefficient.
Solution
 ∂( A − A ig ) / RT 
ln(ϕ k ) =   − ln Z
 ∂n k  T ,V ,n
k ≠i
bρ bρ
A− A ig
d ( bρ )  bρ a  d ( bρ ) a
= ∫ ( Z − 1) = ∫ − bρ  = − ln(1 − bρ) − bρ
nRT 0 bρ 0  1 − bρ bRT  bρ bRT
A− A
ig
= − n ln (1 − bρ) −
an 2
= − n ln (1 − bρ) −
∑ ∑ ni n j aij
RT V RT V RT

VLE from an Equation of State Slide 4


 ∂( A − A ig ) / RT  n  ∂bρ  1 ∂( ΣΣni n j a ij )
  = − ln(1 − bρ) +  −
 ∂n k  T ,V ,nk ≠i 1 − b ρ ∂
 k  V RT
n ∂n k

bρ =
n (∑ y j bj ) = (∑n j bj ) ⇒ ∂bρ = b k

V V ∂n k V
∑ ∑n n a ( ∑n )( ∑ n ) ( ∑n )
2
Note: For aij= a ii a jj , i j ij = i aii j a jj = j a jj

( ∑n )
2
∂ ( ΣΣni n j a ij ) ∂
( ∑n )
j a jj
= = 2 a kk a jj
∂n k ∂n k j

n  bk  2 Σn j a kj bk ρ 2 ρΣ x j a kj
ln( ϕ k ) = − ln( 1 − bρ ) +  − − ln Z = − ln( 1 − bρ ) + − − ln Z
1 − bρ  V  VRT 1 − bρ RT

B a A a jk A jk bk Bk
bρ ≡ ; ≡ ; ≡ ; ≡
Z bRT B a A b B
2Σx j Akj
ln( ϕ k ) = − ln( Z − B ) +
Bk

Z−B Z

VLE from an Equation of State Slide 5


UNIT III. FLUID PHASE EQUILIBRIA
Example. Fugacity coefficient for the PREOS
1 aρ 1
Z= −
1 − bρ RT ( 1 + 2bρ − b 2 ρ 2 )
where a= ΣΣyiyjaij ; aij= a ii a jj
b= Σyibi
Develop an expression for the fugacity coefficient.
Solution
 ∂( A − A ig ) / RT 
ln(ϕ k ) =   − ln Z
 ∂n k  T ,V ,n
k ≠i

From our integration for the pure fluid,


 A − A ig  a  1 + ( 1 + 2 )bρ 
  = − ln (1 − bρ) − ln  
 nRT  bRT 8  1 + ( 1 − 2 )bρ 

{[ ]}
 A − A ig 

 RT 
 = − n ln(1 − bρ) −
an 2
nbRT 8
] [
ln 1 + ( 1 + 2 )bρ − ln 1 + ( 1 − 2 )bρ

VLE from an Equation of State Slide 6


  ∂bρ   ∂bρ  
 ( 1 + 2 )  ( 1 − 2 ) 
 ∂( A − A ig ) / RT  n  ∂bρ  an 2  ∂
 k 
n ∂
 k 
n
  = − ln(1 − bρ) +  −  − 
 ∂n k  T ,V ,nk ≠i 1 − b ρ ∂
 k  nbRT
n 8  1 + ( 1 + 2 )bρ 1 + ( 1 − 2 )bρ 
 
 
  ∂an 2   ∂nb  
   
 1 + (1 + 2 )bρ   ∂n k  an 2  ∂n k  
− ln  −
 1 + (1 − 2 )bρ  nbRT 8 RT 8 ( nb) 
 2

 
 

bρ =
n (∑ x j bj ) = (∑ n j bj ) ⇒ ∂bρ = b k

V V ∂n k V

∑ ∑n n a = ( ∑n )( ∑n ) ( ∑n )
2
Note: For aij= a ii a jj , i j ij i aii j a jj = j a jj

∂ ( ∑n a )
2

∂ (an ) ∂ ( ΣΣni n j a ij )
( ∑n )
2
j jj
= = = 2 a kk a jj
∂n k ∂n k ∂n k j

VLE from an Equation of State Slide 7


bk ρ abk ρ  (1 + 2 ) (1 − 2 ) 
ln( ϕ k ) = − ln( 1 − bρ ) − ln Z + −  − 
1 − bρ bRT 8  1 + (1 + 2 )bρ 1 + (1 − 2 )bρ 
a  1 + (1 + 2 )bρ  2 Σx j a jk bk 
− ln  − 
bRT 8  1 + (1 − 2 )bρ  a b
Note:
bk ρ abk ρ (1 + 2 ) (1 − 2 ) b  bρ abρ  1  bk
− − ]= k  −  = { Z − 1}
b  1 − bρ bRT 8  1 + 2bρ − b 2 ρ 2  b
[
1 − bρ bRT 8 1 + (1 + 2 )bρ 1 + (1 − 2 )bρ
 1 + (1 + 2 )bρ  2Σx j a jk bk 
ln( ϕ k ) = − ln( 1 − bρ ) − ln Z + { Z − 1} −
bk a
ln  − 
b bRT 8  1 + (1 − 2 )bρ  a b
B a A a jk A jk bk Bk
bρ ≡ ; ≡ ; ≡ ; ≡
Z bRT B a A b B
 Z + (1 + 2 ) B  2Σx j A jk Bk 
ln( ϕ k ) = − ln( Z − B ) +
Bk A
{ Z − 1} − ln  − 
B B 8  Z + (1 − 2 ) B  A B

VLE from an Equation of State Slide 8


Example 10.6. Bubble point pressure from PR EOS
Use the PREOS(kij = 0) to determine the bubble point pressure of equimolar solution of
nitrogen+methane at 100K.
Solution:
Initial guess P ≈ Σx i Pi ≈ .5*7.851+.5*.340 = 4.1 bars; y1is = .5*7.851/4.1=.96
vap

p=4.1,y1=.963 p=4.5,y1=.944 p=4.24,y1=.945


Comp Tc Pc ω Tb x K y K y K y
N2 126.2 33.94 .040 77 .5 1.95 .970 1.796 .898 1.893 .9467
CH4 190.2 46.00 .011 112 .5 .115 .057 .1046 .052 .1097 .0548
1.027 0.950 1.0015
Note: y1 for next guess is computed from estimate of y1 of current guess. For example,
0.944=0.970/1.027, and 0.945=0.898/0.950. Note how quickly the estimate for y1
converges to the final estimate of 0.945.

VLE from an Equation of State Slide 9


Example 10.7. Flash of PREOS solutions
A distillation is to produce overhead products having the following compositions:
Propane Isobutane n-Butane
zi 0.23 0.67 0.10
Suppose only a partial condensation at 320 K and 8 bars. What fraction of
liquid would be condensed according to the PREOS (kij=0)?
Solution: Refer back to the same problem for an ideal solution for guess.
L/F = 0.75 ⇒ x = {0.1829,0.7053,0.1117} and y = {0.3713,0.5624,0.0648}
L/F= L/F= L/F=
0.75 0.90 0.867
Co Tc Pc ω zi Ki Di Di Di xi yi
C3 369.8 42.49 0.152 0.23 1.729 -0.142 -0.1563 -.1528 .2097 .3625
iC4 408.1 36.48 0.177 0.67 0.832 0.118 0.1146 0.1153 .6853 .5700
nC4 425.2 37.97 .193 0.10 0.640 0.040 0.0373 0.0378 .1050 .0673
0.016 -0.004 0.0002 1.000 .9998
For comparison, L/F = 0.87 (PR) vs. 0.75 (IS)
Propane Isobutane n-Butane
Ki (PR) 1.727 0.833 0.641
Ki (IS) 2.03 0.80 0.58

VLE from an Equation of State Slide 10


Phase Envelope for PREOS
Use the PREOS(kij=0) to determine the phase envelope of nitrogen+methane at 150K.
Plot P vs. xN2, yN2 and compare the results from PREOS to the results from the "short-cut"
result.
Solution: use the last guess as the initial guess for the next guess. Above 0.5 mole
fraction, increment xN2 by 0.02 each time or you will not converge.
100
Pressure (bars)
50
0

0 0.2 0.4 0.6 0.8 1


x N2 ,y N2

VLE from an Equation of State Slide 11

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