Phase behavior and

equilibrium calculation
Chapter 25
Outlines

• Phase behavior of pure component systems.

- P-T diagram and critical properties
- P-v-T diagram
• Phase behavior of mixtures (multicomponent systems)
- P-T diagram and critical properties
- Retrograde phenomenon.
• VLE – Data and computations
- Importance
- K factors
- Calculation of dew and bubble points
Equilibrium flash calculations
 Single component

Definition of Basic Terms

Vapor Pressure: The pressure that the vapor phase

of a fluid exerts over its own liquid at equilibrium at
a given temperature.
Dew Point: The pressure and temperature condition
at which an infinitesimal quantity of liquid (a
droplet) exists in equilibrium with vapor.
Bubble Point: The pressure and temperature
condition at which the system is all liquid, and in
equilibrium with an infinitesimal quantity (a bubble)
of gas.
 Two very important thermodynamic points bound the vapor
pressure curve: the Critical Point at its upper end and the Triple
Point at its lower end

Properties of The Critical Points Tc, Pc for pure components

✓ Temperature and pressure for which liquid and vapor are no longer
distinguishable.
✓ For T > Tc, liquid and vapor will not co-exist, no matter what the
pressure is.
✓ For P > Pc, liquid and vapor will not co-exist, no matter what the
temperature is.
P-T diagram for single components

✓ Starting at point A and moving towards point C at constant

pressure, we add heat to the system. By adding this heat, we
cause a temperature increase in the system (Temperature at C >
Temperature at A).
✓ At point C, which lies above the vapor pressure or boiling point
curve, we encounter a phase change. During this transition, from
liquid to vapor, we will notice that the heat that we add to the
system does not cause any temperature increase.

✓ Up to this point, we saw that the heat added before the system
reached the phase transition was used to raise the temperature of the
substance. However, the heat that we are adding right now, during
the phase transition, is not causing any temperature increase (hence it
is said to be hidden heat or latent heat of vaporization).
✓ Therefore, we differentiate between two kinds of heat: sensible heat
and latent heat.
Sensible Heat: Its main purpose is to cause an increase in
temperature of the system.
Latent Heat: It serves only one purpose: to convert the liquid into
vapor. It does not cause a temperature increase.
Phase behavior for mixtures P-v-T diagram

The line connecting all of the bubble and dew points will generate the bubble and

dew point curve, both of which meet at the critical point.

Notice that the critical point does not represent a maximum in the P-V diagram of

a mixture. Also note that bubble point pressures and dew point pressures are no

longer the same.

Phase behavior for mixtures P-T diagram

• Bubble and dew point curves coincide together in the single component system.

• In multicomponent systems, the bubble point curve will shift to the upper left (higher pressures) and dew point curve

will shift to the lower right (lower pressures) — both of them meeting at the critical point.
• Cricondenbar (Pcc):
✓ The highest pressure in the two-phase
envelope.
✓ For P > Pcc, liquid and vapor cannot co-exist
at equilibrium no matter what the temperature
is
• Cricondentherm (Tcc):
✓ The highest temperature in the two-phase
envelope.
✓ For T > Tcc, liquid and vapor cannot co-exist Source: Hydrocarbon Phase Behavior - Production Technology (production-technology.org)

at equilibrium no matter what the pressure is.

 Retrograde phenomenon

• Two cases of isothermal compression for two different temperatures T1 and

T2. Notice that these temperatures are such that T1 < Tc and Tc < T2 < Tcc.

• The isothermal compression at T = T1. At point A, we are in an ALL VAPOR

condition (0 % liquid) and we are starting to cross over into the two-phase

region. As we compress from point A to B, more and more liquid is formed

until the entire system has been condensed (point B). We went all the way

from 0 % liquid to 100 % liquid, as we expected, by compressing the vapor.

Retrograde phenomenon
Retrograde gas-condensate
reservoir: if the reservoir
temperature between critical
temperature and Cricondentherm
temperature

11
• In the second case (Tc < T2 < Tcc), we have a different behavior. At point C we are starting in an ALL VAPOR condition (0

% liquid); by increasing pressure, we force the system to enter the two-phase region. Thus, some liquid has to drop out; we

expect that as the pressure keeps increasing, we will produce more and more liquid. That is true to some extent… BUT, look

at the final point of our journey, point D: although we are producing liquid, our final condition (dew point) requires us to

have 0 % liquid in the system again.

• This is telling us that, as we are entering the two-phase region, we will start to produce some liquid; but, there will be a point

(of maximum liquid yield) where that liquid will start to vaporize (point C’). In other words, even though we are

compressing the system, liquid will vaporize and not condense. That is why we call this a retrograde (contrary to

expectation) behavior.

• It is also important to see that a similar behavior is to be expected within the region Pc < P < Pcc. In this case, we talk about

retrograde vaporization since we will be moving from a 100 % liquid to another 100 % liquid condition (both on the bubble

point curve) in an isobaric heating.

Gas state:
it may be define as a homogeneous fluid of low density and low viscosity, which has neither
independent shape nor volume.

• Ideal gas low:

• The ideal gas law, also called the general gas equation, is the equation of state of a
hypothetical ideal gas.
• PV=nRT
• n=m/M
𝑃𝑀
• Ꝭ=
𝑅𝑇
• Specific gravity of a gas:
Ꝭ 𝑃𝑀𝑔/𝑅𝑇 Mg Mg
• g= = = =
Ꝭ𝑎𝑖𝑟 𝑃𝑀𝑎𝑖𝑟/𝑅𝑇 M𝑎𝑖𝑟 29
 Mixture of ideal gases:

• Dalton’s Law, or the Law of Partial Pressures, states that the total pressure exerted by a
mixture of gases is equal to the sum of the partial pressures of the gases in the mixture.
Ptotal=PA+PB+...etc

Pi=yi*P
• Apparent molecular weight:
M=σ𝑛𝑖=1 𝑌i𝑀i

Example:
Compute the apparent molecular weight of air given its composition:

Component Composition
Nitrogen 0.78
Oxygene 0.21 Ma=(0.78*28.01)+(0.21*32)+(0.01*39.94)=28.97lb/lbmole
Argon 0.01
Vapor Liquid equilibrium – importance
We use vapor liquid equilibrium calculations in the following:
1. Reservoir calculation
2. Two phase pipeline flow calculations
3. Inlet separation calculations.
4. Distillation calculations.
5. Absorption calculations

K – factor
Phase equilibrium, Raoult’s Law
𝑦𝑖 𝑃𝑇𝑜𝑡𝑎𝑙 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
Where:
𝑦𝑖 = mole fraction of vapor phase.
𝑥𝑖 = mole fraction of liquid phase.

𝑃𝑖𝑠𝑎𝑡 = 𝑓 𝑇𝑜𝑛𝑙𝑦
- Works well for compounds that are simple and very similar in nature.
- Works well when 𝑥𝑖 is close to 1.
Application of K : bubble point and dew point calculation, flash calculation.

Bubble point determination:

if= ƩKiNi < 1 all liquid
if= ƩNi/Ki< 1 all vapor
if both ƩKiNi and ƩNi/Ki all greater than 1 then the system is two
phase
Example
Component mol fra
Calculate the dew point temperature and bubble point C1 0.8

temperature at 1500kPa of the natural gas shown in the table. C2 0.1

C3 0.05
i-C4 0.05

Solution using Raoult’s law (Assume ideal gas vapor and liquid phases)

𝑃𝑖𝑠𝑎𝑡
𝐾𝑖 =
𝑃 𝑠𝑎𝑡 in bar, and 𝑇 in K 𝑃𝑡

𝑃𝑖𝑠𝑎𝑡 = 10^ 𝐴− 𝐵/ 𝑇+𝐶

A B C
C1 3.9895 443.028 -0.49
C2 3.9384 659.739 -16.719
C3 4.5368 1149.36 24.906
i-C4 4.3281 1132.108 0.918
Bubble point temperature Given P, x and required T, y

P, kPa =1500

To be calculated by trial and error using

solver
T3 = 163.53

T1 = 160 T2 = 170 Psat, kPa ki ki*x

1871.559 1.248 0.998
Component x Psat, kPa ki ki*x Psat, kPa ki ki*x 27.832 0.019 0.002
2.737 0.002 0.000
Methane 0.8 1629.555 1.086 0.869 2376.401 1.584 1.267
0.278 0.000 0.000
1.000
Ethane 0.1 21.569 0.014 0.001 43.076 0.029 0.003

Propane 0.05 2.093 0.001 0.000 4.363 0.003 0.000

iso butane 0.05 0.196 0.000 0.000 0.506 0.000 0.000

1 0.871 1.270
Dew point temperature Given P, y and required T, x

P, kPa =1500

To be calculated by trial and error using solver

T3 = 264.239

T1 = 270 T2 = 262 Psat, kPa ki y/k

Component y Psat, kPa ki y/k Psat, kPa ki y/k
20406.382 13.604 0.059
Methane 0.8 22165.234 14.777 0.054 19741.723 13.161 0.061 1874.788 1.250 0.080
364.543 0.243 0.206
Ethane 0.1 2155.654 1.437 0.070 1772.649 1.182 0.085
114.425 0.076 0.655
1.000
Propane 0.05 435.916 0.291 0.172 339.414 0.226 0.221

iso butane 0.05 141.031 0.094 0.532 105.236 0.070 0.713

1 0.828 1.079
Determination of K and Pk for multicomponent hydrocarbon at high
pressure > 1000 psia
• The k value for multicomponent hydrocarbon system at high pressure
depends on composition
• The second observation is that, at high pressures, the K values of all
components in a mixture tend to converge to unity at the same pressure.
This pressure is called the convergence pressure.
• Convergence pressure: it is the critical pressure of the mixture which has
a critical temperature. Also known as the pressure for the system at a
given temperature when vapor-liquid separation is no longer possible.
• There are different correlations to calculate convergence pressure and then
K value for multicomponent hydrocarbon in high pressure.
• KH2S=0.4KC3+0.6KC2
• 𝐾𝐶𝑂2 = 𝐾𝐶1 𝐾𝐶2
• How to determine 𝑷𝑲 ( as suggested by GPA):
1. Assume the liquid phase composition ( if there is no guide, use the total feed composition)
2. Identify the lightest hydrocarbon component which present in a concentration of at least 0.1%mole in the
liquid phase.
3. Calculate the mass average critical T and critical P for the remaining heavier components to form a pseudo
binary system.( as a short method, you can use only Tpc)
4. Trace the critical locus of the binary consisting of the light component and pseudo heavy component. When
the average pseudo heavy component is between two real hydrocarbons, an interpolation of the two critical
loci must be made.
5. Read the convergence pressure (Pk) at the system temperature from the figure.
6. Using the convergence pressure determined from step 4 together with the system temperature and system
pressure, obtain K values for the components from the appropriate convergence pressure K-charts.
7. If the liquid composition was assumed, calculate it using the K-values and overall system composition.
8. If the differences between the assumed and calculated Pk are significant repeat the entire procedure.
Where A1=(P-Pa)/(Pk-Pa)A2

Pa=atmospheric pressure
A2 from 0.5-0.8
• Please read chapter 25 on GPSA
• And print pages from 25.9-25.24