CH2351 Chemical Engineering Thermodynamics II

Unit – I, II
www.msubbu.in

PhasewwwEquilibria
.m
sub
bu
.in
Dr. M. Subramanian

Associate Professor
Department of Chemical Engineering
Sri Sivasubramaniya Nadar College of Engineering
Kalavakkam – 603 110, Kanchipuram (Dist)
Tamil Nadu, India
msubbu.in[AT]gmail.com
Jan-2012
 Contents

Criteria for vapor-liquid equilibrium between phases in multi

component non-reacting systems in terms of chemical potential and
fugacity, estimation of fugacity of liquid, Raoult’s law, constant
temperature and constantwpressure
ww VLE (Pxy, Txy diagrams), effect
of temperature and pressure .on ms VLE, P-T diagram, deviations from
ideality – positive and negative udeviations,
bb models for activity
u.in
coefficient, azeotropes – minimum and maximum boiling azeotropes

Jan-2012 M Subramanian
Ideal Solution

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ww
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ww
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Deviations from Ideal Solution

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Minimum Boiling Azeotrope

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Maximum Boiling Azeotrope

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x-y Diagrams

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 Raoult’s Law

ww
w.m
P = xAPAsat + xBPBsat sub
bu
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yA = xAPAsat/ P
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ww
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ww
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Effect of Temperature

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Effect of Pressure

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P-T Diagram

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 Deviation from Ideal Solution

• The activity coefficients express the departure from ideality and

thus define the excess Gibbs energy of the solution.

• Deviation from ideality is said to be positive when γ > 1 (ln γ is

positive) and negative when ww γ < 1(ln γ is negative).
w.m
sub
bu
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 Positive Deviation from Raoult’s Law

P= γΑxA pA sat+ γBxBpBsat

ww
w.m
sub
γi greater than 1 bu
.in

ln γi positive
 Negative Deviation From Raoult’s Law

P= γΑxA pA sat+ γBxBpBsat

ww
w.m
sub
γi less than 1
bu
.in

ln γi negative
 Azeotropes

• If azeotropes are not present, a fractional distillation can eventually

separate the mixture into the pure components, with the component
with the higher vapor pressure ending up as the distillate and the less
volatile component (known as the residue) left in the distillation pot.
ww
• For a minimum boiling azeotrope,
w
.m a fractional distillation can produce a
sub
distillate with the azeotropic composition
bu and a residue that is one of
the pure components, depending on the
. in composition of the starting
mixture.

• For a maximum boiling azeotrope a fractional distillation can produce

one of the pure components as the distillate, and a residue with the
azeotropic composition.
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ww
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ww
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ww
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ww
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ww
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Positive homogeneous
azeotropes in mixtures of
ethanol(1) and benzene(2).
The Pxy diagram is at 370 K, ww
w.m
and the Txy diagram is at 2.5 sub
bu
bar. Filled circles locate the .in
azeotropes.
Negative homogeneous ww
azeotropes (dots) in w.m
sub
mixtures of acetone(1) bu
.in
and chloroform(2). The
Pxy diagram is at 50°C;
the Txy diagram is at 0.75
bar.
Double Azeotrope

ww
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 VLE Calculations of Non-ideal Solutions

• Obtain γi from azeotropic composition data

• Evaluate model parameters of γi-xi models based on the above

data
ww
w.m
sub
• Make VLE calculation with yiP = γbixu.iPisat
in
 ww
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sub
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The equilibrium flash of a multi-

component liquid is also an
isenthalpic process and may be
visualized as a simple distillation
process using a single equilibrium
stage.
 VLE Problems
Problem Knowns Unknowns
Name to find
Bubble P T, xi P, yi
Dew P T, yi www. P, xi
ms
ub
Bubble T P, xi bu T, yi
.in

Dew T P, yi T, xi

Flash T, P, zi xi, yi, nv/n

 Henry’s Law & Raoult’s Law
• As early as in 1803 William Henry showed empirically that the vapor
pressure of a solute i is proportional to the concentration of solute i:

where xi is the mole fraction solute and kH,i is known as the Henry’s
law constant.
ww
w.m
su
bb demonstrated that at low
• More than 80 years later François Raoult
u.in
concentrations of a solute, the vapor pressure of the solvent is simply

where xi is the mole fraction solvent and pi* is the vapor pressure of the
pure solvent.

• Raoult’s and Henry’s laws are often termed ‘limiting laws’. This use
reflects that real solutions often follow these laws at infinite dilution
only.
 ww
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Comparison of Raoult’s law and Henry’s law

 Schematic illustrations of the saturated
ww vapor pressures above two different
w.m
non-ideal
sub solutions.
bu
.in
The continuous solid curves represent
the behavior of the real solutions, the
dashed lines represent Raoult’s law and
short solid lines represent Henry’s law.
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