Laboratory Exercise No.

6
Vapor-Liquid Equilibrium: The Rachford-Rice Equation

1. Objective:
The objective is to address challenges related to vapor-liquid equilibrium through problem-solving activities.

2. Intended Learning Outcomes (ILOs):

The students shall be able to:
2.1 solve vapor-liquid equilibrium problems using matlab.
2.2 solve equations for a phase separation.
2.3 predict thermodynamic properties

3. Discussion:
Vapor-liquid equilibrium (VLE) is a crucial concept in chemical engineering, particularly in the design and
operation of separation processes such as distillation and absorption. It refers to the equilibrium established
between the vapor and liquid phases of a mixture at a given temperature and pressure. Understanding VLE
is essential for predicting the composition of the vapor and liquid phases in equilibrium, which is vital for
designing separation processes with optimal efficiency.

One of the key tools used to analyze and predict vapor-liquid equilibrium behavior is the Rachford-Rice
equation. This equation was developed by J. D. Rachford Jr. and J. S. Rice in the 1950s and provides a
mathematical framework for determining the number of theoretical stages required for achieving a desired
separation in distillation processes.

The Rachford-Rice equation is based on the principle of phase equilibrium, which states that at equilibrium,
the chemical potential of each component in the liquid phase is equal to its chemical potential in the vapor
phase. Mathematically, this principle can be expressed using the Gibbs-Duhem equation, which relates the
changes in the compositions of the liquid and vapor phases:

Where xi and yi are the mole fractions of component I in the liquid and vapor phases, respectively, and γi is
the activity coefficient of component i.

The Rachford-Rice equation is derived from the Gibbs-Duhem equation by integrating over the entire
composition range. It is given by:

Where zi is the mole fraction of component i in the feed mixture, and λi is the vapor-liquid equilibrium
parameter. The parameter λ represents the degree of non-ideality in the mixture and is related to the
relative volatility of the components.
Solving the Rachford-Rice equation provides the value of \( \lambda \), which, in turn, allows for the
determination of the compositions of the vapor and liquid phases in equilibrium. This information is crucial
for designing and optimizing distillation columns, as it helps in determining the number of theoretical stages
required for achieving the desired separation efficiency.

In summary, the Rachford-Rice equation is a fundamental tool in the analysis and design of separation
processes involving vapor-liquid equilibrium. By providing a mathematical framework for predicting phase
behavior, it enables engineers to optimize the design and operation of distillation columns and other
separation units, ultimately leading to more efficient and cost-effective processes.
Distillation towers are used to separate mixtures of chemicals into two or more streams, each a relatively
pure stream of one of the chemicals. The physical process governing that separation is vapor-liquid
equilibrium.

Take a mixture of two or more chemicals in a temperature regime where both have a significant
vapor pressure. The composition of the mixture in the vapor is different from the liquid. By harnessing this
difference, you can separate two chemicals, which is the basis of distillation. To calculate this phenomenon,
there is a need to predict thermodynamic properties such as fugacity, and then perform mass and energy
balances over the system.

Phase separation is only one part of distillation process, it is the basis for the entire process. Vapor-
liquid equilibria problems are expressed as algebraic equations.

Flash distillation (sometimes called "equilibrium distillation") is a single stage separation technique. A
liquid mixture feed is pumped through a heater to raise the temperature and enthalpy of the mixture. It then
flows through a valve and the pressure is reduced, causing the liquid to partially vaporize. Once the mixture
enters a big enough volume (the "flash drum"), the liquid and vapor separate. Because the vapor and liquid
are in such close contact up until the "flash" occurs, the product liquid and vapor phases approach
equilibrium.

Simple flash separations are very common in industry, particularly petroleum refining. Even when
some other method of separation is to be used, it is not uncommon to use a "pre-flash" to reduce the load
on the separation itself.

Flash and Phase Separation

Putting some water in an open pan on the stove, initially at room temperature. The partial pressure of
water in the air (at equilibrium) will equal the vapor pressure of water at that temperature. Now, heat the
pan. The vapor pressure increases, since it increases as the temperature rises. If the partial pressure of
water at the pan temperature exceeds the partial pressure of water in the room temperature (usually set by
humidity), the water will evaporate.
Next, imagine doing the same thing with a mixture of two chemicals in a closed vessel. The closed
vessel is one with a piston that can move so the pressure inside remains constant. The two chemicals have
different boiling points,and different vapor pressures at a given temperature. As you increase the
temperature of the vessel, the relative amount of each chemical in the vapor changes, because one is more
volatile than the other. At temperatures below the bubble point, Tbubble, the mixture is entirely a liquid. At
temperatures above the dew point, Tdew, the mixture is entirely a vapor. At temperatures in between, both
liquid and vapor co-exist. The composition of the liquid and vapor are not the same, however. Thus, as you
gradually increase the temperature from a low value, some vapor forms, and this vapor is richer in the more
volatile component. As the temperature increases further, more and more vapor forms. Finally, as the last
drop of liquid evaporates, all the material is in the vapor phase, which has the same composition as
the original liquid. However, between the bubble point and dew point, the composition of the liquid and
vapor are changing as the temperature increases, and it is this change that there is a need to calculate.
There is another scenario that, unfortunately, is purely imaginary. In that scenario, as the temperature
increases, chemical one evaporates completely when the temperature reaches its boiling point. As the
temperature increases further, the boiling point for the second chemical is reached, and it all evaporates.
You wish it did happen this way! Despite the fact that in real life the separation of the two chemicals is
never complete in either liquid or vapor phase, it is still a useful phenomenon and forms the basis for
distillation.
This laboratory exercise looks first at equations governing an isothermal flash, and then shows how
one can predict the thermodynamic quantities that is needed to solve the isothermal flash problem.

ISOTHERMAL FLASH – DEVELOPMENT OF EQUATIONS

Consider the flow sheet shown in below:

Figure 1. Flash Phase Separator

Suppose you know the temperature, pressure, and overall composition of the inlet stream. The mole
fractions of the chemicals in the inlet are called {zi}. In the phase separator, however, the liquid and vapor
are separated. The mole fraction of the chemicals in the vapor phase are called {yi} and those in the liquid
phase are called {xi}. When the vapor and liquid are in equilibrium, you can relate the mole fractions of
each chemical in the vapor and liquid by the equation:

The members of the set {Ki} are called K-values, and they can be predicted from thermodynamics.
For now, assume that their values are known.
To derive the equation governing the phenomenon, you first sum the mole fractions of vapor and liquid over
all components.
 2

Then, subtract those two equations:

Next, substitute the equilibrium expression and rearrange to obtain:

Next, make a mass balance for each component over the phase separator. F is the total molar flow
rate, V is the molar flow rate of the vapor, and L is the molar flow rate of the liquid. The mole balance is
then

Divide by F and define v’ as the fraction of the feed that is vapor:

By using the equilibrium expression again, you can write this as

Solve for the mole fractions in the liquid:

Put that expression into Eq. 4 to obtain the final equation:

 9

This is called the Rachford–Rice equation. Notice that, if the K-values and inlet compositions {zi} are
known, this is a nonlinear equation to solve for v’. Once the value of v’ is known, one can calculate the
value of the liquid compositions, {xi}, and vapor compositions, {yi}, using Eqs. 1 and 3. The mole balance is
then complete.

4. Resources:
Matlab
5. Procedure:
1. Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the fraction of
the stream that is vapor and the mole fraction of each chemical in the vapor and liquid streams.
Table 1 shows the flow rates and K-values at 180 o F and 70 psia, using a basis of one mole per
unit of time.
TABLE 1. Mole Fractions and K-values for Vapor–Liquid
Mole Fraction Phase Equilibrium, K-value
Propane 0.1 6.8
n-Butane 0.3 2.2
n-Pentane 0.4 0.8
n-Octane 0.2 0.052
1

2. The function (filename: vpequil.m) for Procedure 1 contains:

%vapor-liquid equilibrium
% using Eq. 9
function y=vpequil(v)
z=[0.1 0.3 0.4 0.2]
K=[6.8 2.2 0.8 0.052]
sum1=0.;
for i=1:4
num=(K(i)-1)*z(i)
denom=1+(K(i)-1)*v
sum1=sum1+num/denom
end
y=sum1
3. Using the MATLAB command window, issue the command vpequil(0.2). Show the results.
4. Verify if the program is correct by using calculator. Show the results. Do they give the same
answers.
5. Now, add semi-colons at the end of each line of the m-file and save it. Issue fzero command in the
MATLAB command window:
>>fzero(@vpequil,0.2)
Show the results.
6. Determine the mole fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using
MATLAB by creating an m-file (filename: yourSurname_le08_p06. Show the results.
 7. The following stream is at 100 psia and 178 oF. Calculate the fraction that is vapor by solving the
Rachford–Rice equation using MATLAB by creating a function file (filename: vpequil7.m) and
issuing fzero command in MATLAB command window. Determine the mole fraction of each
chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file
(filename: yourSurname_le08_p07. Show the results. Show the results.

8. The following stream is at 126 psia and 178 oF. Calculate the fraction that is vapor by solving the
Rachford–Rice equation using MATLAB by creating a function file (filename: vpequil8.m) and
issuing fzero command in MATLAB command window. Determine the mole fraction of each
chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file
(filename: yourSurname_le08_p08.m) Show the results.
Mole Fraction Phase Equilibrium, K-value
Methane 0.1 16
Ethane 0.2 2.65
Propane 0.7 0.762

9. A feed F is split into a vapor product V and a liquid product L in a flash tank. The feed is 50%
pentane, 30% hexane and 30% cyclohexane ( all I mole %). Kpentane = 1.685 , Khexane = 0.742 and
Kcyclohexane = 0.532. Determine the fraction that is vapor by solving the Rachford-Rice equation using
MATLAB by creating a function file (filename: vpequil9.m) and issuing fzero in MATLAB command
window. Determine the mole fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8)
using MATLAB by creating an m-file (filename:yourSurname_le08_p09.m). Show the results.

10. The exit gas from ammonia reactor is at 250 bar and contains 61.5% H 2, 20.5% N2 and 18% NH3.
The gas is cooled to 25 0 C (partly condensed), and is then separated in a flash drum into a
recycled vapor stream V and a liquid product L containing most of the ammonia. KNH3 = 0.0393,
KH2 = 60.8 and KN2 = 35.6 . Calculate the fraction that is vapor by solving the Rachford–Rice
equation using MATLAB by creating a function file (filename: vpequil10.m) and issuing fzero
command in MATLAB command window. Determine the mole fraction of each chemical in the
vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file (filename:
yourSurname_le08_p10.m) Show the results.

Course: Laboratory Exercise No.:

Group No.: Section:
Group Members: Date Performed:
1. Date Submitted:
2. Professor:
3. Engr. Crispulo G. Maranan
4.
5.
6. Data and Results:
Procedure Results
1
2
3
4
5
6
7
8
9
10

7. Conclusion:
9. Assessment (Rubric for Laboratory Performance):
TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES
RUBRIC FOR MODERN TOOL USAGE
(Engineering Programs)
Student Outcome (e): Use the techniques, skills, and modern engineering tools necessary for engineering
practice in complex engineering activities.
Program: Chemical Engineering Course: __________ Section: _______ ____Sem SY ________
Performance Unsatisfactory Developing Satisfactory Very Satisfactory Score
Indicators 1 2 3 4
1. Apply Fails to identify Identifies Identifies modern Recognizes the
appropriate any modern modern techniques and is benefits and
 techniques, techniques to techniques but able to apply constraints of
skills, and perform fails to apply these in modern
modern discipline- these in performing engineering tools
tools to specific performing discipline-specific and shows
perform a engineering discipline- engineering task. intention to apply
discipline- task. specific them for
specific engineering engineering
engineering task. practice.
task.
2. Demonstrate Fails to apply Attempts to Shows ability to Shows ability to
skills in any modern apply modern apply fundamental apply the most
applying tools to solve tools but has procedures in appropriate and
different engineering difficulties to using modern effective modern
techniques problems. solve tools when solving tools to solve
and modern engineering engineering engineering
tools to problems. problems. problems.
solve
engineering
problems.
3. Recognize Does not Recognizes Recognizes the Recognizes the
the benefits recognize the some benefits benefits and need for benefits
and benefits and and constraints of and constraints of
constraints constraints of constraints of modern modern
of modern modern modern engineering tools engineering tools
engineering engineering engineering and shows and makes good
tools. tools. tools. intention to apply use of them for
them for engineering
engineering practice.
practice.
Total Score
Mean Score = (Total Score / 3)
Percentage Rating = (Total Score / 12) x 100%
Evaluated by: Engr. Crispulo G. Maranan
Printed Name and Signature of Faculty Member Date: