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Pub Azeotropic Published PDF
Pub Azeotropic Published PDF
2, December 2004 43
Short Communication
H.N. Njenga, Dept. of Chemistry, University of Nairobi, Box 30197, Nairobi, Kenya
ABSTRACT
Vapour-liquid equilibrium data for the ethanol-water system was obtained at 70, 80, 90,
100, 150, 300 and 500mm Hg pressure using a modified Othmer still which was integrated with a
computerized and automatic pressure control system. The pressure readings were corrected for
the effects of temperature, gravity, latitude and altitude on the height of the mercury column. The
measured temperatures were corrected for the effects of deviations between the set pressure and
the actual pressures at which the readings were taken. Azeotropic compositions at the various set
pressures were obtained from the experimental vapour-liquid equilibrium data. Using the
relationship between activity coefficient and saturated vapour pressure, azeotropic compositions
and temperatures at 80, 90, 100, 150, 300 and 500mm Hg pressures were obtained.
ethanol-water system around and below 760 accurate measurement of temperatures. The
mm Hg by fractionating mixtures whose final modification was a facility for
compositions were on either side of the simultaneous vacuum sampling of both the
suspected azeotropic compositions. They vapour and liquid phases.
obtained azeotropic compositions at various The composition in the still was
pressures by differential interpolation using originally BDH analar grade ethanol with a
density increments and relative increase in minimum purity of 99.7 % by volume. The
the amount distilled. These workers pressures mentioned above and
controlled pressure using a manostat and corresponding bubble temperatures were
obtained pressure deviations of as much as recorded and hence became the first (T,x,y)
±3mm Hg pressure. as (Tp,1,1). Subsequently the first of a
Assuming that the fugacity sequence of predetermined dilutions was
coefficient is 0 for the pressure range carried out. After equilibrium was
considered here and denoting the activity established the temperature and pressure
coefficient of component i to be γi at were read. Vapour and liquid samples were
equilibrium, then: withdrawn and their density measurements
taken. The ambient temperature and
pressure were recorded. The samples were
yiP = γixiPio (1) returned to the still after each vapour-liquid
equilibrium determination. The
where y and x are equilibrium vapour and
compositions were calculated and plotted in
liquid compositions respectively, P and Po
their respective vapour equilibrium curves
are the total and saturated vapour presures
before proceeding with the next dilution in
respectively.
the sequence. If it became necessary to go to
At the azeotrope:
a higher region of a particular curve, for
example, if from the calculations it was
yi = xi (2) found out that the azeotropic point had been
P = γiPio (3) passed and more data points were required
For a two component system: above it, some of the solution in the still was
removed and replaced with either some
absolute ethanol or concentrated ethanol
P = γ1P1o = γ2P2o (4) solution.
experimental temperatures were corrected the existence of the azeotrope. At 70, 80 and
for the difference between the corrected 90mm Hg, there was experimental scatter
pressures and the set pressures as described around x=1 and therefore no conclusion
by Njenga [13]. could be drawn at this stage on whether or
Thermodynamic consistency tests of not azeotropes existed at these pressures.
the experimental data were carried out using Detailed plots of log γ1/γ2 and log P2o/P1o
Herington’s [15] method. All seven data against x1 for the data sets at 100, 150, 300,
sets passed this test [13]. The log γ1/γ2 and and 500mm
log P2o/P1o for each data set were fitted Hg was made from around 0.6 to 1.0 liquid
against the liquid composition x1 .The mole fractions. By interpolation, more
intersection of the two curves for each data accurate estimates of the azeotropic
set indicated the azeotropic composition. compositions at these pressures were
Using this procedure, the data set at 100, obtained. Figure 1 is a detailed plot at
150, 300, and 500 mm Hg clearly indicated 500mm mercury pressure.