B.

Batch Azeotropic Distillation

You must wear goggles while running this experiment!
We need to evaluate the validity of our analytical prediction of the performance of a batch
distillation of a binary mixture which forms an azeotrope. Our method is a follows:
(1) Find the azeotropic composition, temperature, and pure component vapor pressure
data from handbook or Internet sources.
(2) Use a two parameter activity coefficient equation (van Laar, Margules, Wilson,
etc.) with the data from (1) to determine the parameters. Equilibrium vapor and
liquid compositions, x and y, can now be predicted.
(3) Obtain published data of equilibrium y versus x data for 1-propanol/water system
under 1 atm from handbook or Internet source. Compare the published data with
the predicted y versus x obtained in (2). How well do they agree, especially in the
range of concentration below the azeotropic concentration?
(4) Use the Rayleigh model for a batch distillation (available in any Unit Operations
book or Separation Processes book) to generate the plot of distillate composition
y, versus fraction of liquid distilled both experimentally and theoretically (using
published or predicted y-versus-x data). This sharpness curve is useful to
determine where cuts need to be made to achieve desired product fractions.
(Imagine that you are a moon shiner in the 15th century who wishes to produce
rich product). You may use either your predicted y versus x or published y
versus x for this purpose.
(5) Compare the experimental sharpness curve for batch distillations of mixtures
containing 5 and 20 mol % propanol. Also, compare the experimental sharpness
curve with theoretical sharpness curve.
Supplies Available: Othmer still (for equilibrium y versus x), boiling flask, heating
mantle, consenser, vials, refractometer, electronic balance, thermometers, and batch
distillation bottle. Be careful when assembling the Othmer still. Observe the structure of
the still and understand why this device is indeed an equilibrium still. Check with the
instructor before you start to run the still.
Data may be analyzed with Excel that are installed on every computer in ECS 114.
Key measurements: The composition of the binary mixture is analyzed with
refractometer. Search published data of refractive index versus concentration of 1proponal in water. Suggested source: CRC Handbook.
Questions that will Help You Design Experiment or Analyze Data:
Equilibrium Study (with Othmer Still)
(1) Can the van Laar equation be directly solved for parameters A and B based on the
published azeotropic condition? The Marqules equation? The Wilson equation?

(2) If you wish to apply the model parameters obtained in (1) to the prediction of y
versus x, what assumptions are necessary? Let us assume that the model
parameters are weak functions of temperature, can you tell that further assumption
of constant vapor-pressure ratio (of 1-propanol to water) might help the
theoretical prediction? Why? Note that the equilibrium temperature varies with
composition under 1 atm.
(3) Make plots of activity coefficient versus liquid composition and of equilibrium
vapor composition versus liquid composition based on experimental observations
and theoretical predictions.
(4) From the published data of refractive index versus concentration of 1-propanol in
water, can you tell what problem could arise if the starting mixture in the batch
still (or Othmer still) contain more than 70% by mol?
(5) How can you check if the Othmer still has reached steady state and
equilibrium?
(6) Why do we choose a binary system that has a potential to form an azeotrope?
Batch Distillation
(7) (1) Write the material balance leading to Rayleigh equation. What are its
assumptions? Should x and y in the equation be mol fraction or mass fraction?
Which is more convenient?
(8) Compare the sharpness curves generated with different starting 1-propanol
concentrations from
(a) Theoretical prediction using published y-versus-x data with the knowledge
of initial x in the still.
(b) Theoretical prediction using y-versus-x data predicted with various models
and model parameters from (1) and (2) above.
(c) Experimental data of measured y and cumulative mass of binary mixture
distilled recorded during the course of batch distillation.
(9) Do we generate waste in this experiment? Why or why not? Does distillation
destroy 1-propanol? Certainly not! Be sure to save the waste and reuse it in
further experiments.
Published Vapor-Liquid Equilibrium Data at 1 atm (partialyou may make an effort to
search more complete data)
Source 1
Y(mole frac)
0.375
0.388
0.4317
0.438
0.560
0.685

X
0.075
0.179
0.4317
0.482
0.712
0.850

Temperature (oC)
89.05
87.95
87.72 (azeotropic condition)
87.80
89.20
91.70

Source 2 The following data are published at Journal of Chemical and Engineering Data,
vol. 41, No. 3 (1996) on Page 403 . Students doing this experiment are urged to find the
original paper and study it for background of this experiment.
x

y
0
0.053
0.1
0.15
0.2
0.253
0.3
0.347
0.4
0.438
0.5
0.538
0.604
0.65
0.7
0.751
0.8
0.847
0.9
0.952
1

0
0.353
0.378
0.387
0.395
0.4
0.403
0.414
0.421
0.438
0.447
0.461
0.485
0.514
0.55
0.585
0.634
0.693
0.77
0.87
1

T (oK)
373.15
362.85
361.85
361.3
361.25
361.2
361.05
361
360.95
360.9
360.95
361
361.3
361.7
362.1
362.8
363.6
364.65
366.1
368
370.4

Source 3 You may also use ProII or HYSYS to find the equilibrium composition under 1
atm. Remember to choose appropriate liquid activity model. Note: Peng-Robinson
Equation and SRK equations of state do no apply here!