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 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 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 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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 (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
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 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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 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  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 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 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 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 system is
in two phase region, and flash calculation can be made. 13
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  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  K  1   1 (10.17)
i

 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 = 0.312 y2 = 0.292 y3 = 0.397
x1 = 0.035 x2 = 0.172 x3 = 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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