1

UNIVERSITY OF MINNESOTA DULUTH

DEPARTMENT OF CHEMICAL ENGINEERING
ChE 3211-4211
K
y
x
i
i
i
=
(1)
Henry's Law: K H
i i
=
(2)
Raoult's Law: K
P
P
i
i
s
=
(3)
P P
i
=

(4)
VAPOR-LIQUID EQUILIBRIUM
OBJ ECTIVE
Experimentally determine the vapor-liquid equilibrium conditions for the binary methanol-water
system and correlate the results for use in the analysis of the distillation column. Explore the
conditions for which Henrys and Raoults laws are adequate to describe the vapor-liquid
equilibrium. Your results will be used in the analysis of the continuous distillation column.
INTRODUCTION
Vapor-Liquid Equilibrium Solution Theory
At equilibrium, the relationship between the compositions of species i in the vapor and
liquid phases is often defined by a K-value, or equilibrium ratio:
where x
i
and y
i
are the mole fractions of species i in the liquid and vapor phases, respectively.
Assuming ideal conditions near ambient temperature and pressure, the K-value may be described
according to Henrys and Raoults laws for dilute and concentrated solutions respectively:
where H
i
is an empirical constant, P
i
s
is the saturation vapor pressure of pure component i, and P
is the total pressure of the equilibrium vapor mixture assuming Daltons Law:
2
K
P
P
i
i i
s
=

(5)
ln ln
1 2
2
2 1
2
= = A A x x (6)
( )
[ ]
( )
[ ]
ln ln
1
1 2
2
2
1
2
1
=
+
=
A
A A
A
1+ A A
12
12 21
21
2 21 12
x x x x
(7)
A A
12 21
= +

= +

1 1
2 2
1 1
2
1
1 1
2 2
2
2
x
x
x
x
ln
ln
ln
ln
ln
ln

(8)
where P
i
is the partial pressure of species i in the vapor phase.
A common correction to equation (3) for non-ideal liquid mixtures at ambient pressures is
where
i
is the activity coefficient for species i in the liquid mixture (sometimes referred to as the
modified Raoults law). Note that equation (5) still assumes ideal gas behavior which is
generally reasonable under conditions of ambient pressure and temperature.
Several empirical and semi-theoretical equations exist for correlating liquid-phase activity
coefficients of binary mixtures. Perhaps the simplest form is the one-constant Margules
equation, given here for a binary system:
where A is an empirical constant. Equation (6) assumes symmetric curves for the activity
coefficients of the two species.
Some other equations for correlating activity coefficients are the two-constant Margules,
van Laar, and Wilson equations. The most commonly used form is the two-constant van Laar
equation:
where the constants may be obtained by solving equation (7) directly:
One approach to modeling the vapor-liquid equilibrium may consist of several models
combined for different solution conditions. For example, at low concentrations, Henrys law
may apply. At high concentrations, Raoults law may be satisfactory. A model such as
Margules may be appropriate for the intermediate compositions where neither Henrys law nor
Raoults law are adequate.
3
Figure 1. Othmer Equilibrium
Still.
REFERENCES
EQUIPMENT
1. Equilibrium still
2. Refractometer
3. 10 mL volumetric flasks
4. Sample vials
5. Digital thermometer
6. Graduated cylinders
7. Beakers
8. Syringe
CHEMICALS/MATERIALS
1. Methanol
2. Water
EXPERIMENTAL PROCEDURE
An Othmer vapor-equilibrium still is shown in Figure 1.
It consists of a boiling pot (A), central and outlet vapor tubes
(B), thermocouple (C), condenser (D), pot sampling cock (E),
and interchangeable receiver with liquid sampling cock (F).
The interchangeable receiver holds approximately 15 mL of
distillate.
Before beginning the experiment create a spreadsheet that
will calculate the mole fractions of methanol and water in a
mixture containing varying amounts of water and methanol.
In this experiment you will be starting with a mixture
containing 50 mL of water and 200 mL of methanol (mole
fraction methanol =0.64). You will be adding additional
water and removing methanol from the distillate receiver to
decrease the mole fraction of methanol for each sample point.
Using your spreadsheet calculate the amount of water to be
added and the amount of methanol to be removed to generate
5 to 6 samples containing mole fractions of methanol between
0.7 and 0.1. The minimum amount of water to be added each
time should be 25 mL. For these calculations, assume 15 mL
of liquid (pure methanol) is removed each time the
4
interchangeable receiver is drained. The total amount of liquid in the pot should not be greater
than 500 mL.
In this experiment you will generate vapor-liquid equilibrium data at each of the points you
calculated above. Make sure there is no liquid in the boiling tube (tube wound with external
resistance wire). [Note: The small amount that can not be removed with the syringe is ok.]
Remove the stopper and add 50 mL of water and 200 mL of methanol through the stoppered fill
hole. The funnel can be used to ensure there is no spillage during filling. Connect the digital
thermometer to the thermocouple and turn on. Make sure the thermocouple is immersed in the
liquid. Plug in the rheostat, turn the switch to 120 volts, and increase the power on the rheostat
to approximately 70.
It will take time to heat the mixture at the beginning. When the liquid is boiling and the
vapor is condensing it will take 6 to 8 minutes to fill the interchangeable receiver. When the
receiver is full, it will overflow into the return line. Start the stopwatch when liquid begins to
overflow into the return line. Let the mixture reflux for a minimum of 30 minutes. At the end of
the reflux period record the temperature of the liquid in the pot and collect a sample of the pot
and the distillate liquid in marked sample vials. Only a small amount has to be collected (2 to 3
mL) because the samples will be analyzed using a refractometer (see Analysis Procedure below).
Once the samples have been collected, turn off the rheostat. Let the liquid cool a few
minutes. Add water to the pot and/or remove distillate from the receiver in order to bring the
mixture in the pot to the next sample point concentration you want to analyze. [Note: distillate
removed from the receiver should be put in the waste bottle.] Turn on the rheostat and repeat the
procedure. Normally 3 to 4 sample points can be done in a 3 hour lab period. After the last
sample point is analyzed for the lab period, turn off the rheostat and let the solution cool so it is
warm to the touch. Drain the pot into the labeled one liter bottle provided in the equipment box.
Remove the remainder of the liquid in the heating tube with the syringe and add to the one liter
bottle. This will be saved for the next lab period.
At the next lab period, transfer the mixture in the one liter bottle to the sample pot and
continue with the experiment. At the end of the experiment let the mixture in the pot cool, then
remove and put in the waste bottle.
ANALYSIS PROCEDURE
Prepare 6 to 8 - 10 mL mixtures of methanol and water ranging from 0.0 to 1.0 mole fraction
methanol to generate a standard curve for the analysis of your samples. To prepare the mixtures,
weigh a 10 mL volumetric flask and its stopper using an analytical balance. With a 10 mL pipet
dispense a known volume of methanol into the 10 mL volumetric flask. Stopper the flask and
weigh it. Make up the volumetric flask short of the mark by about 5 mm with laboratory
deionized water. Stopper the flask and mix its contents by inversion. Now, make up the flask to
the mark, stopper, mix and weigh it.
Using a refractometer determine the index of refraction of each standard and also of pure
methanol and pure water. The operating instructions for the refractometer are located in the
laboratory. The refractive indices of each standard and pure liquid are plotted against the
compositions of the solutions expressed in mole fractions of methanol.
5
Measure the index of refraction of your samples. The composition of your samples can
then be determined by interpolation from the graph plotted above.
SAFETY NOTES
1. The experiment should be run in the hood.
2. Safety glasses/goggles should be worn at all times.
3. The hood safety shield should be in front of the distillation apparatus at all times.
4. The liquid in the pot is hot. Be cautious when collecting a sample from the pot.
WASTE DISPOSAL PROCEDURES
Methanol water solutions can not be disposed of in the drain. Place all waste, including standard
and sample waste, in the waste bottles provided.
08/2012
6
Department of Chemical Engineering
Stockroom Checkout slip
Vapor-liquid Equilibrium ChE 3211
Name: Date:
(print name)
Lab No.: Lab 1 Tuesday 12:00 - 4:50 PM Lab 2: Thursday 12:00 - 4:50 PM
Lab No.: Lab 3 Tuesday and Thursday morning (9:30 - 11:50 AM)
(circle one)
Equipment Out In Equipment Out In
Digital thermometer 25 mL graduated cylinder
2-50 mL beakers 200 mL graduated cylinder
Sample vials (16) 30 mL glass syringe
Funnel, long stem, plastic Stopwatch
8 - 10 mL Vol Flasks 10 mL graduated pipet
Pipet bulb 6 - Disposable pipet
Disposable pipet bulb
Name:
(Signature)