Chapter 15 Section 10.

3- not resp for reproducing deriv

Excel/PrMix.xlsx
Excel/PrFug.xlsx - explore fugacity calc by PREOS;
Excel/Virial.xlsx - explore fugacity calc by virial EOS.
Objectives: See Objective Handout

Two EOSs
Virial - can do vapor phase for VLE
vdW, PR - can do vapor &/or liquid phase for VLE

15.1 Random mixing rules

EOS used to represent PVT, and thus H, U, G, A. From
composition dependence of props, find component props.
EOS keeps same overall form/parameters as for pure fluids, but
parameters depend on composition using ‘mixing rules’ for
1
parameters.
van der Waals Virial
1 a
Z = --------------- – ------- Z = 1 + BP
-------
1 – b RT RT
ig ig
U – U - = – ------ a- G – G - = BP
------------------ ------------------ -------
RT RT RT RT
• The probability of finding a (1) molecule is the fraction of (1)
atoms, x1
• The probability of a (1)-(1) interaction is a conditional
probability. -- probability of finding a second interacting
molecule of a certain type given the first is a certain type --
the product of the individual probabilities.
The probability of a (1)-(1) interaction is x12.
The probability of a (2)-(2) interaction is x22.
2
 The probability of a (1)-(2) interaction is x1x2 and the
probability of a (2)-(1) interaction is also x1x2.
If the attractive interactions are characterized by a11, a22, and
a12, the mixing rule for a is given by:
0.1

U  U   a    ( x a  2 x1 x 2 a12  x a )
ig 2
1 11
2
2 22

mixing rule is called a quadratic mixing rule

For Cubic EOS:
n n n
a = Â Â x i x j aij b = Â x i bi
i =1 j =1 and i =1
aij = ( ai a j )1/ 2 (1 - k ij ) ;
kij is binary interaction coefficient a12 NOT a for mix
x’s used as generic
composition variable
3
For Virial EOS:
n n B12 is cross coefficient
B =   x i x j B ij NOT virial coeff for mix
i = 1j = 1 ex 10.1 shows B12 calc

V = RT
------- + B
P V
Ex 15.1 B, V for mixture virial.xls Vis=x1V1 + x2V2

Fugacity and Phase Equilibria y

Chap 9 Chap 10 Chap 15
pure ideal EOS
vapor fi = P ˆf = y ̂ V P
fˆi = y i P
ig
i i i

liquid sat ˆf = x ̂ L P
fi  Pi ˆf is  x P sat
i i i i
i i

4
 V L
ˆ ˆ
For EOS calculation, use f i = f i , without simplification

fˆi
̂ i  -------- , fugacity coefficient for component in mixture
yi P ˆf ig
i
So, if we can characterize
ln ̂ i = ln ˆf i – ln y i P (difference)
Then
ˆf = y ̂ V P
i i i
get  i from departure function:

5
 ̂ i  1
̂ i   i
Departure
̂ i =  i Functions
Ideal
Gas Model
fˆ =  y P
i i i ˆf V = ̂ V y P
i i
fˆi = y i P i
Ideal
Solution ˆf L = ̂ L x P
Model i i i
Real
Solution
Model

6
 i ig
 i ˆ      ig
f i – i   G – G    RT 
ln  -------- = ----------------------- =  -------------------------------------------
 y i P RT  n i  T P n j  i

G–G
ig
BP nB-
P-  --------- section 10.3
------------------- = ------- ------
RT RT RT  n 1  T, P, n 2
example,
binary: ln ̂ 1 =   2y 1 B 11 + 2y 2 B 12 – B P    RT  15.14
ˆf V = ̂ V y P ch 6 ch 9 mix rule
i i i
OR if (A - A ig
) =f(T,V)
̂ i
Ê ˆf ˆ Ê ∂ ( A - A
ig
) TV / RT ˆ
ig
= (i -i )/RT = Á
i
ln Á
yi P ˜¯ Ë ∂ ni ˜¯ - lnZ
Ë T ,V , n jπi

example (see Example 15.5 and 15.5 )

7
( A  Aig )TV
  ln 1 b 
a
a 1 (1 2)b
f FG IJ
RT
ln
bRT 8 1 (1 2)b H K
 n a
2 
 = --n- , and also need  ------------ and  nb
---------
V  n 1  T, V, n 2 n 1  T, V, n 2

becomes:
bk  ab k    1 + 2   1 – 2  
ln  ̂ k  = – ln  1 – b   – ln Z + --------------- – ------------------  ------------------------------------- – ------------------------------------- 
1 – b  bRT 8  1 +  1 + 2 b  1 +  1 – 2 b  
2  x j a jk
a 1 +  1 + 2 b 
b k ln -------------------------------------
– ------------------ -------------------
j
- – -----
bRT 8 a b 1 +  1 – 2 b 

or Eqn. 15.34
Bk 2  x j A jk
A B k ln Z +  1 + 2 B-
ln  ̂ k  = – ln  Z – B  + ------  Z – 1  – ----------- --------------------
j
- – ------ ----------------------------------
B B 8 A B Z +  1 – 2 B

8
355

350

345
kij=0
340
kij=0.076
BP
335

330
0 0.2 0.4 0.6 0.8 1
x,y adjust kij to adjust BP
methanol + benzene

9
Iteration Procedure:
L V
x i ̂ i P = y i ̂ i P

depends on x, T, P depends on y, T, P
L
̂ i
Ki = ------
V
̂ i
use strategy of Table 9.2 - see flowsheets of pg 336, Appendix C

See PRFUG.xls to see how calc of  i is done.

10
 kij
Component zi Tc (K) Pc (MPa)
nitrogen methane n-heptane
nitrogen 0.5 126.1 3.394 0.040 - - -
methane 0.5 190.6 4.604 0.011 0 - -
n-heptane 0 540.3 2.736 0.349 0 0 -

Current State Roots

T (K) 100 Z V fugacity component fugacity coeff component fugacity(MPa) mixture
3
P (MPa) 0.4119 cm /gmol MPa nitrogen methane n-heptane nitrogen methane n-heptane A 0.1362835
answers for three 0.861016 1737.919 0.36145609 0.92073498 0.83635927 0.21245832 0.189625 0.172248 0 B 0.0125858
3
root region 0.109979 221.9863 R(cm MPa/molK)
0.01642 33.14242 0.16875299 1.79139529 0.09369748 6.5075E-16 0.368938 0.019297 0 8.314
& for 1 root region #NUM! #NUM! #NUM! #NUM! #NUM! #NUM! #NUM! #NUM! #NUM!

A
Tr Pr
ac a b A B nitrogen methane n-heptane
nitrogen 0.793021 0.121361 0.435899 1.09772403 148073.842 162544.215 24.031 0.09686 0.011906 0.0968597 0.132926 0.662394
methane 0.524659 0.089466 0.391572 1.22753847 249385.092 306129.793 26.777 0.182422 0.013266 0.1329261 0.182422 0.909041
n-heptane 0.185082 0.150548 0.880011 2.25426114 3372204.1 7601828.66 127.728 4.529913 0.06328 0.6623942 0.909041 4.529913

11
 90
Ideal solution
80
70
P(bars) 60
50 PR - EO S
40 k ij=0
30
20
10
0
0 0.2 0.4 0.6 0.8 1

x N2 ,yN2

nitrogen + methane

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