CHE553 (CHEMICAL ENGINEERING

THERMODYNAMICS)

CHAPTER 1: VAPOR
LIQUID EQUILIBRIUM

EDITED BY: MEOR MUHAMMAD HAFIZ SHAH BUDDIN

CONTENT – PART 3

VLE FROM K-VALUE CORRELATION

FLASH CALCULATION

COURSE LEARNING OUTCOME

■ Identify and apply the concept of equilibrium
■ Calculate dew point and bubble point pressure or
temperature, vapor and liquid compositions at equilibrium
2
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VLE FROM K-VALUE CORRELATION

■ K-value or equilibrium ratio Ki is a measure of the tendency of a given

chemical species to partition itself between liquid and vapor phases.

yi
Ki  (10.10)
xi

■ It serve as a measure of the “lightness” of a constituent species, i.e.,

of its tendency to favor the vapor phase.
■ When Ki is greater than unity, species i exhibits a higher
concentration in the vapor phase; when less, a higher concentration
in the liquid phase, and is considered a “heavy” constituent.
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■ The use of K-values allow elimination of one set of mole fractions {yi}
or {xi} in favor of the other.
■ Reference to Eq. (10.1) shows that the K-value for Raoult’s law is

Pi sat
Ki = (10.11)
P

and reference to Eq. (10.5) shows that for modified Raoult’s law it is

 i Pi sat
Ki = (10.12)
P
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■ According to Eq. (10.10), yi = Kixi. Summation with iyi = 1 yields

K x
i
i i =1
(10.13)
■ For bubblepoint calculations, where the xi are known, the problem is
to find the set of K-values that satisfies Eq. (10.13).
■ Alternatively, Eq. (10.10) can be written, xi = yi/Ki. Summation with ixi
= 1 yields
yi
i K = 1 (10.14)
i

■ For dewpoint calculations, where the yi are known, the problem is to

find the set of K-values that satisfies Eq. (10.14).
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■ Equations (10.11) and (10.12) together with Eq. (10.10) represent

alternative forms of Raoult’s law and modified Raoult’s law.
■ Raoult’s law expresses K-values as functions of just T and P,
independent of the composition of the liquid and vapor phases. This
allows K-values to be calculated and correlated as functions of T and
P.
■ For mixtures of light hydrocarbons and other simple molecules, in
which the molecular force fields are relatively uncomplicated,
correlation of this kind have approximate validity.
■ Figures 10.13 and 10.14, show monographs for the K-values of light
hydrocarbons as functions of T and P, prepared by Dadyburjor. They
do allow for an average effect of composition, but the essential basis
is Raoult’s law.
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Example 4
For a mixture of 10 mole % methane, 20 mole % ethane, and 70
mole % propane at 10oC (283.15K), determine the
(a) dewpoint pressure
(b) bubblepoint pressure
The K-values are given by Fig. 10.13.
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Solution:
(a) When the system is at its dewpoint, only an insignificant amount of
liquid is present, and the given mole fractions are values of yi. For
the given temperature, the K-values depend on the choice of P, and
by trial we find the value for which Eq. (10.14) is satisfied. Results
for several values of P are given as follows:

P = 6.9 bar P = 10.34 bar P = 8.7 bar

Species yi Ki yi/Ki Ki yi/Ki Ki yi/Ki
Methane 0.1 20 0.005 13.2 0.008 16 0.006
Ethane 0.2 3.25 0.062 2.25 0.089 2.65 0.075
Propane 0.7 0.92 0.761 0.65 1.077 0.762 0.919
(yi/Ki) = 0.828 (yi/Ki) = 1.174 (yi/Ki) = 1.000

The results given in the last two columns show that Eq. (10.14) is
satisfied when P = 8.7 bar. This is the dewpoint pressure, and the
composition of the dew is given by the values of xi = yi/Ki listed in the last
column of the table.
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FLASH CALCULATIONS
■ An important application of VLE is the flash calculation.
■ The name ‘flash’ originates from the fact that a liquid at a pressure
equal to or greater than its bubblepoint pressure “flashes” or partially
evaporates when the pressure is reduced, producing a two phase
system of vapor and liquid in equilibrium.
■ P, T-flash calculation refers to any calculation of the quantities and
compositions of the vapor and liquid phases making up a two-phase
system in equilibrium at known T, P, and overall composition.
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■ Consider a system containing one mole of nonreacting chemical

species with an overall composition represented by the set of mole
fractions {zi}. Let L be the moles of liquid, with mole fractions {xi}, and
let V be the moles of vapor, with mole fraction {yi}. The material
balance equations are:

L + V =1

zi = x i L + y i V ( i =1, 2, ..., N )

■ Combining these equations to eliminate L gives:

zi = x i (1− V ) + y iV ( i = 1, 2, ..., N ) (10.15)

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■ Substituting xi = yi/Ki, and solving for yi yields:

zi K i
yi = (10.16)
1+ V ( K i −1)

■ Because iyi = 1, eq. (10.16) is summed over all species:

zi K i
i 1+ V ( K −1) = 1 (10.17)
i

■ The initial step in solving a P, T-flash problem is to find the value of V

which satisfies this equation.
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Example 5
The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80oC
(353.15K) and 110 kPa has the overall composition, z1 = 0.45,
z2 = 0.35, z3 = 0.20. Assuming that Raoult’s law is appropriate to this
system, determine L, V, {xi}, and {yi}. The vapor pressures of the pure
species at 80oC (353.15K) are:
P1sat = 195.75 kPa P2sat = 97.84 kPaP3sat = 50.32 kPa
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Solution:
Determine whether the system is in two phase region (Pdew<P<Pbubl),
then only flash calculation can be made.

BUBL P calculation
{zi} = {xi}
By eq. (10.2),
Pbubl = x1P1sat + x2P2sat + x3P3sat
= 132.40 kPa

DEW P calculation
{zi} = {yi}
By eq. (10.3),
1
Pdew = sat sat sat = 101.52kPa
y1 P1 + y 2 P2 + y3 P3

Because 101.52 kPa <110 kPa < 132.4 kPa, so the system is in two
phase region, and flash calculation can be made.
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By eq. (10.11), Ki = Pisat/P;

K1 = 1.7795 K2 = 0.8895 K3 = 0.4575
Substitute known values into eq. (10.17),
zi K i
i 1+ V ( K −1) = 1
i

( 0.45)(1.7795 ) ( 0.35 )( 0.8895 ) ( 0.20 )( 0.4575 )

+ + =1
1+ 0.7795V 1 − 0.1105V 1 − 0.5425V
Solution for V by calculator yields V = 0.7367 mol
Thus, L = 1 – V = 0.2633 mol
By eq. (10.16) and eq. (10.10),
zi K i yi
yi = xi =
1+ V ( K i −1) Ki

y1 = 0.5087 y2 = 0.3389 y3 = 0.1524

x1 = 0.2859 x2 = 0.3810 x3 = 0.3331
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Example 6
For the system described in Ex. 10.4, what fraction of the system is
vapor when the pressure is 13.8 bar and what are the compositions
of the equilibrium vapor and liquid phases?
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REFERENCE
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to
Chemical Engineering Thermodynamics. Seventh Edition. Mc Graw-
Hill.