VAPOR LIQUID EQUILIBRIUM

VLE FROM K-VALUE CORRELATION

FLASH CALCULATION
 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
Raoults law is sat
Pi
Ki = (10.11)
P

and reference to Eq. (10.5) shows that for modified

Raoults law it gisP sat
Ki = i i (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 Ki
=1 (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).

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 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.

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 Example 10.4
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
P = 6.9 bar P = 10.34 bar P = 8.7 bar
follows:
Species yi Ki yi/Ki Ki yi/Ki Ki yi/Ki
Methan 0.1 20 0.005 13.2 0.008 16 0.006
e
Ethane 0.2 3.25 0.062 2.25 0.089 2.65 0.075
Propan 0.7 0.92 0.761 0.65 1.077 0.762 0.919
e
The
results given(yi/Ki)
in the 0.828two(yi/Ki)
= last columns show (yi/Ki)
= 1.174 that Eq. = 1.000
(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. 7
 (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 P = 26.54 bar

Species xi Ki Kixi Ki Kixi Ki Kixi
Methan 0.1 5.6 0.56 5.25 0.525 5.49 0.549
e
Ethane 0.2 1.11 0.222 1.07 0.214 1.1 0.22
Propan 0.7 0.335 0.235 0.32 0.224 0.33 0.231
e
Kixi = 1.017 Kixi = 0.963 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.
8

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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 = xi L + yiV ( i = 1, 2, ..., N )

Combining these equations to eliminate L gives:

zi = xi ( 1 - V ) + yiV ( 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 ( Ki - 1)

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

species:
zi K i

i 1 + V ( Ki - 1)
=1
(10.17)

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 10.5
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 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 kPaP2sat = 97.84 kPa P3sat = 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
= (0.45)(195.75) + (0.35)(97.84) +(0.20)(50.32)
= 132.40 kPa

DEW P calculation
{zi} = {yi}
By eq. (10.3),
1
Pdew = sat sat sat = 101.52 kPa
y1 P1 + y2 P2 + y3 P3

--> Because 101.52 kPa <110 kPa < 132.4 kPa, so the
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system is in two phase region, and flash calculation can
 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 ( Ki - 1)
=1

( 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 ( Ki - 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 10.6
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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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

i 1 + V ( Ki - 1)
=1 (10.17)

( 0.1 ) ( 9.0 ) + ( 0.2 ) ( 1.7 ) + ( 0.7 ) ( 0.5 ) =1

1 + 8.0V 1 + 0.7V 1 - 0.5V
By calculator, V = 0.236 mol.

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

zi K i yi
yi = xi =
1 + V ( Ki - 1) Ki

The phase compositions are:

y1 = 0.312y2 = 0.292y3 = 0.397
x1 = 0.035x2 = 0.172x3 = 0.794

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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.

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