CHEG 281

Experiment 9: Determination of Vapor-Liquid Equilibrium

One of the most common chemical engineering operations is the separation of two or
more compounds based on differences in boiling points. At a given pressure a pure
compound boils at a ver well defined temperature. !i"tures of compounds boil at
temperatures intermediate between the two pure compound boiling points# the e"act
temperature depends upon the composition of the mi"ture. $nli%e the pure compounds
in which the vapor and li&uid have the same composition' boiling mi"tures will have a
different composition in the li&uid phase than in the vapor phase. (ote that for a boiling
mi"ture' the vapor and li&uid phases are at the same temperature. A plot of this behavior
is a )*E +)apor,*i&uid E&uilibrium- envelope' as shown in .igure 1. /his difference in
composition between the vapor and li&uid phases becomes the basis for separating the
compounds. /he industrial separation device is the distillation column. 0ou will stud
this in more detail in CHEG 1222 3/hermodnamics4' CHEG 1812 3!odeling 5
6imulation4' CHEG 7822 39rocess :esign4' and CHEG 7222 36eparations4.
(ot all )*E curves are as simple as that shown in .igure 1 and under certain
circumstances' the boiling point of the mi"ture can be above or below those of the pure
components when the mi"ture forms an a;eotrope. .igure 2 is such a )*E curve.
Complete separation b simple distillation is then not possible' which is wh ethanol
cannot be easil separated from water b distillation.
VLE - Furan / Carbon Tetrachloride
(1 atm)
80
100
120
140
160
180
0 0.2 0.4 0.6 0.8 1
Mole Fraction Furan
T
e
m
p

(

F

)
)*E :iagram at 1 atm for .uran < Carbon /etrachloride
.igure 1
E"periment = ,, )*E :etermination page 1 of >
"' *i&uid 9hase
' )apor 9hase
CHEG 281
)*E diagram at 1 atm for Ethanol and /oluene
.igure 2
E"perimentall' )*E data are determined in the laborator using a device that ensures
e&uilibrium between the li&uid and the vapor. One such device' to be used in this
laborator' is the Othmer still' shown in .igure 1. A volume of the material to be studied
is charged to the still and the contents heated. /he vapor is condensed and returned to the
still,pot. ?hen the temperature stabili;es' indicating thermal e&uilibrium' a sample of
both the li&uid and vapor are withdrawn and anal;ed. !aterial is then added to the still
to change the composition. @n this unit' the heating element is in the recirculation leg
from the bottom of the condenser to the still pot. @t is insulated both to conserve heat and
for user safet. /he heating rate is controlled b a )ariac +not shown-.
@n this e"periment' ou will determine the vapor,li&uid e&uilibrium envelope +at
atmospheric pressure- for binar mi"ture made from two of the following compoundsA
?ater
!ethanol
Ethanol
Compound pairs will be assigned to various teams after the semester begins.
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CHEG 281
Othmer 6till
.igure 1
Analsis of the vapor and li&uid samples will be done using the Abbe refractometer. /he
first tas% will be to build a calibration curve for the test solution. (oteA this can be done
while the initial charge is heating in the still. 0ou should use at least 12 +and preferabl
about 1>- composition samples to develop the calibration curve. @nstructions for the
Abbe refractometer are ne"t to instrument# BEA: them before using the device. Cefore
ou come to lab' ou should ma%e up a table showing the volumes +or weights- of each of
our two compounds ou will use to ma%e the individual calibration samples.
+/he Abbe refractometer is a more sophisticated version of the hand,held refractometer
used in E"periment 8. @f ou have not et done E"periment 8' please read the discussion
on refractive inde" that is part of E"periment 8.-
Construction of a proper )*E curve re&uires the use of mole fractions for composition'
not mass fractions. However' ou ma find that the calibration curves is easier to read if
it is constructed using mass fraction data. /hus' ou ma want to develop two
refractometer calibration curves D one using mole fraction data and one using mass
E"periment = ,, )*E :etermination page 1 of >
CHEG 281
fraction data. $se whichever is easier' but remember to plot our )*E curves with the
",a"is in mole fraction units.
VLE Determination
Ensure water is flowing through the condenser and that the condensate and still pot
sample valves are closed. Add about 2>2 ml of the lower boiling compound +find normal
boiling points from a reference such as 9errEs Chemical Engineers Handboo% or /he
Handboo% of Chemistr and 9hsics- to the still pot. Hoo% up the resistance heater to
the )ariac in the e"haust hood. Cefore appling power to the sstem' have the lab
instructor or /A inspect and verif our set,up. 6et the )ariac at the F>G level and appl
power to the resistance heater. @t will ta%e some time for the sstem to heat up and reach
a constant boiling rate' as evidenced b a stable temperature and a continuous flow of
condensed vapor in the recirculation leg. Even though this first sample should be a pure
compound' measure the refractive inde" of both li&uid and vapor samples and verif that
both are pure components. Becord the temperature and compare to the published value
of the normal boiling point. @f it is not the same' be prepared to e"plain wh it might
disagree. +/he normal boiling point is the temperature at which a substance boils at
atmospheric pressure.-
/o determine the )*E curvesA
1. :rain off the condensed vapor +about 18 ml- and enough li&uid from the still pot
such that the total volume removed is about 12 ml. Condensate and still pot
samples are collected in separate containers for later analsis.
2. Add about 12 ml of the higher boiling compound to the still pot and let the sstem
come to a new e&uilibrium as evidenced b a stable temperature A(: a
continuous recirculation of the condensed vapor to the still pot.
3. ?ait about > minutes after the temperature has stabili;ed and the there is
continuous recirculation flow of condensed vapor before ta%ing samples. It is
critical tat te s!stem be at equilibrium for !our data to be "alid. #ou can$t
urr! te process%
&. Cool the samples and anal;e using the Abbe refractometer. @t is critical that the
samples be at the same temperature as the calibration samples. 0ou can place
them in the water bath that cools the Abbe' but ensure that the caps are tight.
'. Bepeat steps 1 , 7 until ou have sufficient data to determine the )*E.
:etermine +before ou come to lab- our dilutions such that ou ta%e at least 12 samples
and preferabl 1> samples. 9lot all the data in form similar to .igure 1 +" is the li&uid
mole fraction' is the vapor mole fraction of one of the component-. @t is normal
practice to plot the mole fraction of the more volatile +lower boiling temperature- on the
",a"is.
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CHEG 281
0our report should contain all the data' sample calculations as appropriate' the calibration
curve' and the /,", diagram. 0ou should also discuss possible sources of error and' if
possible' compare to literature or theoretical results.
Important (ote: )is experiment can not be urried and must be done carefull! to
obtain *ood data. It ma! ta+e more tan te normal tree ours allocated for lab so
be prepared to spend extra time if necessar!.
,afet!
Consider all compounds used in this lab to be poisonous if ingested. :o not drin% an of
the compounds in this +or an- lab.
?ear safet glasses at all times
/he fumes can be harmful if ou are e"posed for long periods of time. Ce sure the
sstem is under the hood and the hood is wor%ing properl.
/he Othmer still is glass +and e"pensiveH- so be careful handling it.
:uring the distillation process' the glassware will be hot. $se caution when e"tracting
samples and wear the appropriate gloves when turning stopcoc%s or removing stoppers.
:o not put large volumes of cold fluid into the hot still. /he thermal shoc% could brea%
the apparatus. ?hen adding material to the sstem' use a pipette or sringe and add the
material slowl' inIecting it into the pool of boiling li&uid. :o not spra it on the sides of
the still.
E"periment = ,, )*E :etermination page > of >