VAPOR-LIQUID BEHAVIOR OF TWO-PHASE

SYSTEMS

Calculations involving Equilibrium:

- Bubble point calculations

- Dew point calculations

- Flash calculations

- Determination of Phase

V, yi

P
F, zi

L, xi
x z y

zi = mole fraction of any component in total feed

yi = mole fraction of any component in vapor phase
xi = mole fraction of any component in liquid phase
F = total moles of feed
V = total moles of vapor
L = total moles of liquid
Equilibrium vaporization ratio (equilibrium constant) is defined as:

yi
Ki =
xi

How to calculate Ki ?

Ki from Ideal Gas & Ideal Mixture

Partial pressure of component i = P yi

Partial pressure of component i, according to Henry’s Law = Po xi

yi P o
P yi = Po xi à Ki = =
xi P

Equilibrium constant is independent on compositions.

Ki from Chart à see Fig. 6.7 (Campbell) or GPSA Data book.

Ki from Tables à see Table 6.1 (Campbell)

Ki from Equations of State models (=f(P,T,x))

yi φiL
Ki = = V φ = fugacity coefficient
xi φi ;

Ki from Equations of State models and activity coefficient models

y i γ iLυ i
Ki = = V γ = activity coefficient
xi φi ;

f iLo
υi = = fugacity coefficient of any component
P
as a pure liquid

APPLICATION

Bubble point calculations

Given: Pressure, liquid compositions à Find bubble point temperature

or Temperature, liquid composition à Find bubble point pressure

Requirement:

∑ y = ∑K x = ∑K z
i i i i i = 1. 0

Procedure of calculation:

1. Assume a temperature for the known pressure (or assume pressure if

temperature is known)
 2. Find K at pressure and temperature known and assumed

3. Calculate ∑K x i i

4. If ∑K x
i i = 1.0 the assumed temperature or pressure is right. If not,

repeat step 1-3 until ∑K x i i = 1.0

Example:

Determine the bubble point temperature of the mixture shown at 4.0 MPa.

Comp. zi Ki Ki zi
CO2 1.25 1.25 1.56
H2S 0.50 0.29 0.15
Try at –30 oC
C1 21.36 3.80 81.17
C2 36.78 0.41 15.08
C3 10.21 0.10 1.021
iC4 6.38 0.039 0.25
nC4 9.84 0.026 0.26
iC5 2.63 0.009 0.024
nC5 4.01 0.007 0.028
C6 3.90 0.0018 0.007
C7+ 3.14 0.0002 0.00063
99.55
Dew point calculations

Given: Pressure, vapor compositions à Find dew point temperature

or Temperature, vapor composition à Find dew point pressure

Requirement:

yi zi
∑x = ∑K = ∑K
i = 1.0
i i

Procedure of calculation:

1. Assume a temperature for the known pressure (or assume pressure if

temperature is known)

2. Find K at pressure and temperature known and assumed

yi
3. Calculate ∑K
i

yi
4. If ∑K = 1.0 the assumed temperature or pressure is right. If not,
i

yi
repeat step 1-3 until ∑K = 1.0
i

Example:

Determine the dew point temperature of the mixture shown at 4.0 MPa.
 Comp. zi Ki zi/ Ki
CO2 1.25 4.45 0.281
H2S 0.50 2.58 0.194
Try at 144 oC
C1 21.36 6.69 3.19
C2 36.78 2.96 12.44
C3 10.21 1.61 6.34
iC4 6.38 1.02 6.28
nC4 9.84 0.86 11.24
iC5 2.63 0.61 4.28
nC5 4.01 0.53 7.55
C6 3.90 0.30 12.92
C7+ 3.14 0.089 35.29
100.00

Flash calculation

Given: Pressure, temperature, and the amount of feed and its compositions

à Find the amounts of vapor and liquid, and the compositions of each.

V, yi

F, zi

L, x i
Overall balance: F=V+L

For each component: F zi = L xi + V yi

For convenience, let F = 1 mol, then zi = L xi + V yi

Ly i  1  L  
zi = + Vyi = Vyi     + 1

Ki   Ki  V  

zi
V yi =
 1  L 
1 +   
 Ki  V 

zi
V = V ∑ yi = ∑
or  1  L 
1 +   
 Ki  V 

Similarly, we can derive:

zi
L = L ∑ xi = ∑
V 
Ki   + 1
L

Procedure of calculation:

1. Find K at known pressure and temperature

2. Assume V, L, V/L, or L/V

3. Solve flash equation

 4. If assumed V or L is satisfied, calculation is complete. If not, repeat

step 1-4

Example:

Determine the analyses and quantities of vapor and liquid for a flash of the

mixture shown at 4.0 MPa and 100 oC.

Try for a V/L = 4.06

Comp. zi Ki Li xi Vi yi
CO2 1.25 3.75 0.08 0.39 1.17 1.46
H2S 0.50 2.02 0.05 0.28 0.45 0.56
C1 21.36 6.24 0.81 4.10 20.55 25.61
C2 36.78 2.25 3.63 18.35 33.15 41.32
C3 10.21 1.08 1.90 9.60 8.31 10.36
iC4 6.38 0.62 1.82 9.23 4.56 5.68
nC4 9.84 0.52 3.18 16.10 6.66 8.30
iC5 2.63 0.33 1.13 5.74 1.50 1.87
nC5 4.01 0.27 1.91 9.66 2.10 2.62
C6 3.90 0.14 2.48 12.55 1.42 1.76
C7+ 3.14 0.033 2.77 14.00 0.37 0.46
19.77 100.00 80.24 100.00
Determination of Phase

It is often necessarily to determine whether the fluid in a line is all gas, all

liquid or two phase.

zi
1. If ∑K zi i and ∑K are both greater than 1.0 à a two-phase
i

system exists.

2. If ∑K zi i is less than 1.0 à the system is all liquid.

zi
3. If ∑K is less than 1.0 à system is all vapor.
i