CHE553 Chemical Engineering Thermodynamics

3/23/2015

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.
Ki

yi
xi

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 Raoults law is
Ki

(10.10)

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.

Pi sat
P

(10.11)

and reference to Eq. (10.5) shows that for modified Raoults law
it is
Ki

i Pi sat
P

(10.12)

CHE553 Chemical Engineering Thermodynamics

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According to Eq. (10.10), yi = Kixi. Summation with iyi = 1 yields

K x
i

Equations (10.11) and (10.12) together with Eq. (10.10)

represent alternative forms of Raoults law and modified Raoults
law.
Raoults 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 Raoults law.

(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

K
i

(10.14)

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

to find the set of K-values that satisfies Eq. (10.14).

Example 10.4

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:

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.

P = 6.9 bar

P = 8.7 bar

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

P = 10.34 bar

Species

(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
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the last column of the table.

CHE553 Chemical Engineering Thermodynamics

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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.

b) When the system is at its bubblepoint, the given mole fractions

becomes values of xi. In this case we find by trial the value of P
for which the K-values satisfy Eq.(10.13). Results for several
values of P are given in the following table.
P = 26.2 bar

P = 27.6 bar

Species

xi

Ki

Kixi

Ki

Kixi

Ki

Kixi

Methane

0.1

5.6

0.56

5.25

0.525

5.49

0.549

Ethane

0.2

1.11

0.222

1.07

0.214

1.1

0.22

Propane

0.7

0.335

0.235

0.32

0.224

0.33

0.231

Kixi = 1.017

Kixi = 0.963

P = 26.54 bar

Kixi = 1.000

Equation (10.13) is satisfied when P = 26.54 bar. This is the

bubblepoint pressure. The composition of the bubble of vapor is
given by yi = Kixi as shown in the last column.
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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:

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

yi

zi K i

1 V K 1 1

i 1, 2, ..., N

Combining these equations to eliminate L gives:

zi x i 1 V y iV

i 1, 2, ..., N

(10.16)

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

L V 1

zi x i L y i V

zi K i
1 V K i 1

(10.17)

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

of V which satisfies this equation.

(10.15)

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CHE553 Chemical Engineering Thermodynamics

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Example 10.5
Solution:
Determine whether the system is in two phase region (Pdew<P<Pbubl), then
only flash calculation can be made.

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 Raoults 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 kPa
P3sat = 50.32 kPa

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),
Pdew

13

1
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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Example 10.6
By eq. (10.11), Ki = Pisat/P;
K1 = 1.7795
K2 = 0.8895
Substitute known values into eq. (10.17),

K3 = 0.4575

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?

zK
i 1 V i Ki 1 1
i

0.451.7795 0.35 0.8895 0.20 0.4575

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),
yi

zi K i
1 V K i 1

y1 = 0.5087
x1 = 0.2859

xi

y2 = 0.3389
x2 = 0.3810

yi
Ki
y3 = 0.1524
x3 = 0.3331

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Solution:
The given pressure lies between the dewpoint and bubblepoint
pressures established for this system in Ex. 10.4. The system
therefore consists of two phases. With K-values from Fig. 10.13,
the procedure is to find that value of V for which Eq. (10.17) is
satisfied.
Species

zi

Ki

Methane

0.1

9.0

Ethane

0.2

1.7

Propane

0.7

0.5

zi K i

1 8.0V

1 0.7V

1 0.5V

zi K i
1 V K i 1

xi

yi
Ki

The phase compositions are:

y2 = 0.292
x2 = 0.172

y3 = 0.397
x3 = 0.794

(10.17)

0.1 9.0 0.2 1.7 0.7 0.5

yi

y1 = 0.312
x1 = 0.035

1 V K 1 1
i

By eq. (10.16) and eq. (10.10),

By calculator, V = 0.236 mol.

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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.

PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303

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