VLE Algorithms for Low to Moderate Pressures

Although VLE problems of various combinations are possible, those of engineering

interest are usually Dew Point land Bubble-point calculations:
1. Bubl. P : Cal (yk) and P, given (xk) and T
2. Dew P : Cal (xk) and P, given (yk) and T
3. Bubl. P : Cal (yk) and T, given (xk) and P
4. Dew P : Cal (xk) and P, given (yk) and P

Thus, one specifies either T or P and either the liquid-phase or the vapor-phase
composition, fixing 1+(N-1) or N phase rule variables, exactly the number required by
the phase rule for vapor/liquid equilibrium calculation. All of these calculations require
iterative schemes because of the complex functionality implicit in the VLE equations. In
particular, the following relationships are available: (No of components = N)

For gas phase, fˆkV = ykφˆk P and for liquid phase, fˆkL = xk γ k f k

Since at equilibrium fˆkV = fˆkL , it follows:

yk Φ k P = xk γ k PkS ; (k = 1`,2,… N) ..(1)
We define Φ k = φˆk / φks
Thus, equation 1 may be rewritten as: yk Φ k P = xk γ k Pks ..(2)
V L ( P − Pks )
Where Φ k = (φˆk / φˆks ) exp[− k ]
RT
Bkk Pks
For a gas mixture following Virial EOS, φksat = exp[ ]
RT
P P
And for a binary, ln φ1 = ( B11 + y22δ12 ) , and φˆ2 = exp[ ( B22 + y12δ12 )]
RT RT
B ( P − P1 ) + Py2 δ12
s 2
It follows, Φ1 = exp[ 11 ] ..(3)
RT

B22 ( P − P2s ) + Py12δ12

And Φ 2 = exp[ ] ..(3a)
RT

Bk
ln Pks = Ak −
T + Ck
Now, Φ k = Φ k (T , P, y1 ,..., y N −1 ) ; and γ k = γ k (T , P, x1 ,..., xN −1 ) However, at low to moderate
pressures dependence of γk on ‘P’ is neglected (as at such conditions the liquid phase
properties are not strongly pressure dependent).

1
In all cases Eq.(1) provides the basis for calculation.
Eq.(1) : yk = xk γ k Pks / Φ k P ..(4)
or xk = yk Φ k P / γ k Pks ..(5)
Since ∑ yk = 1
∑x γk k Pks / Φ k P = 1 or P = ∑ xk γ k Pks / Φ k ..(6)
Similarly since ∑ xk = 1 = ∑ yk Φ k P / γ k Pks ; it follows that P = 1/ ∑ yk Φ k / γ k Pks ..(7)
Note that when Φ k = γ k = 1 eqn.(6) and (7) reduces to Raoult’s Law expressions.

Bubble point pressure:

1. Read T,{xk}, Antoine constant, ∈; where {xk} = ( x1, x2, ….. xN )
Set all Φk = 1.0, Evaluate {Psk}, {γk}, Calculate P using Eq.(6)
2. Calculate {yk} using Eq.(4)
3. Now evaluate {Φ k } , using appropriate Equation of State; Calculate Pnew using Eq.(6)
4. Is δP <∈ ?
5. If ‘No’, go to step ‘3’ and calculate new {yk} with last {φk}
6. If ‘Yes’, Print P, {yk}

Dew Point Pressure:

1. Read ,{yk}, Antoine constant, ∈,ζ
Set all Φk= 1.0, and all γk = 1.0; Evaluate {Psk}, Calculate P using Eq.(7); Now
evaluate {xk} by Eq.(5); Evaluate ({γk} using appropriate Liquid-phase Model;
Recalculate P using Eq.(7) (Note that here Φk= 1.0)
2. Evaluate, {Φk}, using given {yk} and last P.
3. Calculate new set of {xk} using Eq.(5).
4. Normalize xk, since xk‘s are not constrained to sum upto 1.0, i.e. each normalized xkn
xk
is given by xkn = , and compute {γk} using (xkn)
∑ xk
5. Is each δγk <ζ ?
6. If ‘No’, go to step ‘3’, use last {γk} in eq.(5)
7. If ‘Yes’, calculate ‘P’, using Eq.(7).
8. Is δP <∈ ?
9. If ‘No’, go to step (2)
10. If ‘Yes’, Print ‘P’ and {xk}.
Note: The inner loop can be omitted; it is included only to make the computational
procedure more efficient.

2
Bubble-Point Temperature/Dew Temperature:
In the last two calculation procedures ‘T’ is known, which allows immediate calculation
of {Psk}. But this is not possible for Bubl T and Dew T. As we did for Raoult’s Law
VLE calculations here too we use vapour-pressure ratios, because they are weak
function of temperature. Using Equation (6), and closing ith species arbitrarily,
Pi S = P / ∑ ( xkν k / Φ k )( PkS / Pi S ) ..(8)
k

⎛ yk Φ k ⎞ ⎛ Pi s ⎞
Similarly using Eq.(7): Pi s = P ∑ ⎜ ⎟⎜ s ⎟ ..(9)
k ⎝ γ k ⎠ ⎝ Pk ⎠
In both (8) and (9) the summation is over all the species (k = 1,2,..N) including ith
species.
Bi
Now, ln Pi s = Ai − ..(10)
Ci + T
Bi
Or, T= − Ci ..(11)
Ai − lnPi s
For the purpose of starting the iteration an initial value of ‘T’ is required. For this we do
the following (as we did in the case of Raoult’s Law VLE calculations).
Bk
Tks = − Ck ..(12)
Ak − ln P

Bubble Temperature
Initial T = ∑ xk Tks ..(13)
Alternatively a Raoult’s law solution for the Bubl T may be used as initial guess so that
the range over which T is iterated is not so large and (γk) dependence on T may be
neglected.
1. Read, P, {xk}, constant, Set all Φk = 1.0; Cal. {Tsk} using Eq.(12) and T using
Eq.(13); Evaluate {Psk}, {γk} at the current T; Identify species ‘i’, calculate Psi using
Eq.(10); Now calculate Psi using Eq.(8); Calculate new T by using Eq.(11)
2. Re-evaluate {Psk} using last T; Calculate {yk} by using Eq.(4); Recalculate {Φk},
{γk} at latest T, and Psi using Eq.(10); Next recalculate Psi using Eq.(8); Now
calculate T using Eq.(11)
3. Is δT <∈ ?
4. If ‘No’, go to step ‘2’ using the last ‘T’
5. If ‘Yes’, Print {yk}, T.

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Dew Temperature
Begin iteration by initializing T= ∑y T
k k
s
..(14)
1. Read, P, {yk}, constants, ∈,ζ; Set allΦk = γk = 1.0; Cal., {Tsk} using Eq.(12); Cal. T
using Eq.(14); Evaluate {Psk}, Identify species ‘i’, compute Psi using (10); Now
calculate Psi using Eq.(9); Calculate new T by using Eq.(11); Re-evaluate (Psi ), {φk}
at last T; Calculate {xk} using Eq.(5); Using (xk), calculate (γk) at the current T;
Using {xk}, {γk}, calculate Psi using Eq.(9); Re-evaluate T using Eq.(11)
2. Evaluate (Psi), {φk} using last T
3. Calculate {xk} using Eq.(5), Normalize xkn = xk / ∑ xk ; Use normalized xk’s to
calculate {γk} at current T.
4. Is each δγk <ζ ?
5. If ‘No’ go to step ‘3’ and use the latest {γk}
6. If ‘Yes’, calculate Psi using Eq.(10) and new Psi using Eq.(9); Now calculate T using
Eq.(11)
7. If δT <∈ ?
8. If ‘No’ go to step ‘2’ and use the latest ‘T; If ‘Yes’, print T, {xk}.

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 Read T, {xk}, constants Bubble P Algorithm
Set all φk = 1.0
Evaluate {Pksat}, {γk}.
Calc. P by Eq. (6)

Calc. {yk} by Eq. (4).

Evaluate {φk}.

No

Calc. P by Eq. (6) Yes

Is δP < ε Print P, {yk}

Read T, {yk}, constants.

Set all φk = 1.0, all γk = 1.0
Evaluate {Pksat}.
Dew P Algorithm
Calc. P, by Eq. (7)
Calc {xk} by Eq. (5)
Evaluate {γk }.
Calc P by Eq. (7)

Evaluate
{φk}

Calc {xk} by Eq. (5).

Normalize the xk values.
Evaluate {γk }.

No
Is each δγk < ε ?

No
Yes Print, P,
Calc. P by Eq. (7) Is δP < ε ? {xk}.
 Read P, {xk}, constants, Set all φk = 1.0. Bubble T Algorithm
Calc. {Tksat} by Eq. (12). Calc. T = Σk xkTksat.
Evaluate {Pksat}, {γk}. Identify species i.
Calc. Pisat by Eq. (8). Calc. T by Eq. (11)

Evaluate {Pksat}.
Calc. {yk} by Eq. (4).
Evaluate {φk }, {γk}.
Calc. Pisat by Eq. (10).
Calc. T by Eq. (11)

No
Is δT < ε ?

Yes

Print T, {yk}.

Read P, {yk}, constants. Set all φk = 1.0, all γk = 1.0.

Calc. {Tksat} by Eq. (12). Calc T = Σiyk Tksat
Dew T Algorithm
Evaluate {Pksat}. Identify species i.
Calc. Pisat by Eq. (9). Calc. T by Eq. (11).
Evaluate {Pksat}, {φk }. Calc {xk} by Eq. (5).
Evaluate {γk}. Calc. Pisat by Eq. (9), T by Eq. (11)

Evaluate {Pksat}, {φk }.

Calc. {xk} by Eq. (5).

Normalize the xk values.
Evaluate {γk}.

No
Is Each δγk < ε

Calc. Pjsat by Eq. (10).

Calc. T by Eq. (11).

No
Is δT < ε

Yes
Print T, {xk}
 Table I: Some Models for the Excess Gibbs Energy and Activity Coefficients for Binary Systems

Model GE/RT Binary ln γ1 and ln γ2

Name parameters
Two-suffix G E / RT = Ax1 x2 A ln γ 1 = Ax22
Margules
(One-constant) ln γ 2 = Ax12
Three- G E / RT = x1 x2 ( A21 x1 + A12 x2 ) A21 , A12 ln γ 1 = x22 [ A12 + 2( A21 − A12 ) x1 ]
suffix
Margules (Two-constant) ln γ 2 = x12 [ A21 + 2( A12 − A21 ) x2 ]
A12 A21 x1 x2 A21 , A12 A12 x1 2 A x
Van Laar G E / RT = ln γ 1 = A12 /(1 + ) ; ln γ 2 = A21 /(1 + 21 2 )2
A12 x1 + A21 x2 A21 x2 A12 x1

Conversely:
x1 ln γ 1 2 x ln γ 2 2
A12 = ln γ 1 (1 + ) ; A21 = ln γ 2 (1 + 2 )
x2 ln γ 2 x1 ln γ 1

GE Λ12 , Λ 21  Λ12 Λ 21 
Wilson = − x1 ln( x1 + x2 Λ12 ) − x2 ln( x2 + x1Λ 21 ) ln γ 1 = ln( x1 + x2 Λ12 ) + x2  − 
RT
 x1 + Λ12 x2 Λ 21 x1 + x2 
 Λ12 Λ 21 
ln γ 2 = ln( x2 + x1Λ 21 ) + x1  − 
 x1 + Λ12 x2 Λ 21 x1 + x2 
 τ G τ G    G 
2
τ 12G12 
NRTL G E / RT = x1 x2  21 21 + 12 12  ln γ 1 = x τ 21 
2 21
 + 
 x1 + x2G21 x`2 + x1G12    x1 + x2G21  ( x2 + x1G12 ) 
2 2

Where, G12 = exp( −α12τ 12 ); G21 = exp( −α12τ 21 )

  G 
2
τ 21G21 
b
τ 12 = 12 ; τ 21 = 21
b ln γ 2 = x1 τ 12 
2 12
 + 
  x2 + x1G12  ( x1 + x2G21 ) 
2
RT RT

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Table II: Expressions for the Molar Excess Gibbs Energy and Activity Coefficients of Multi-component
Systems Using only Pure Component and Binary Parameters

Name Molar excess Gibbs energy Activity coefficient for component i

Wilson GE N  N   N  xΛ
∑
= − xi ln  x j Λ ij  ∑ ln γ i = 1 − ln  ∑ x j Λ ij  − ∑ k ki
 k ∑ x j Λ kj
RT  j 
i    j
j
N

NRTL ∑τ ji G ji x j N
 N

GE ∑τ ji G ji x j ∑k xkτ kj Gkj
N
= ∑x j
N x j Gij  
+∑ N
N
RT ln γ i = τ ij − N 
j
i
∑G ki xk N
k
∑G k
x
ki k
k
∑k Gkj xk  ∑k Gkj xk 



Regular Solution (RS) Model

For a binary solution the relevant expressions are:
G E / RT = ( x1V1 + x2V2 ) Φ1Φ 2 (δ1 − δ 2 ) ⇒ ln γ 1 = V1Φ 22 (δ1 − δ 2 ) ; ln γ 2 = V2 Φ12 (δ1 − δ 2 )
2 2 2

xiVi
where, Φ i = volume fraction = ; Vi = molar volume of pure ith species, Vm = ΣxiVi , and δi = solubility
Vm

parameter for ith species. The solubility parameter is given by, δ i =

(∆U ) ≅ (∆H
i
vap
i
vap
− RT )
Vi Vi

∆Uivap, ∆Hivap = molar internal energy, and enthalpy of vapourisation of ith species in the mixture

For Multicomponent Mixtures

( )
x jV j
∑Φ δ ;Φ = ∑ x V
2
R T ln γ i = Vi δ1 − δ ; δ = j j j (where, j → runs over all the species).
j j j
j

Relations for Activity Coefficients:

∂ (nG E / RT ) (i.e., ln γ i is a partial molar property w.r.t to excess Gibbs free energy GE/RT); thus
1. ln γ i =
∂ni T , P,n j ≠1

in table I the expressions for lnγi is obtained by applying the above operation on the expression for GE/RT
2. Since ln γ i is a partial molar property the Gibbs Duhem Relation applies: Σxi d ln γ i = 0
3. lim γ i = γ i∞ (infinite dilution activity coefficient)
xi → 0

4. lim γ i = 1 (for pure components, activity coefficient is unity)

xi →1

2
Low to Moderate Pressure VLE:
Gas phase: fˆ = y φˆ P ; Liquid phase: fˆ = x γ f
k
V

k k k
L

k k k

At equilibrium: fˆ = fˆ , or y φˆ P = x γ f k
V

k
L

k k k k k

Fugacity for liquid phase:

V (P − P ) l sat

f (T , P) = φ P exp[
i i
sat
] i
sat i i

RT
Phase equilibria relation: y Φ P = x γ P k k k k k
S
..(1)
We define Φ = φˆ / φ k k
s

V (P − P ) L s

Where Φ = (φˆ / φˆ )exp[ −

k
] k
s

k
k k
..(2)
RT
The Pontying factor in equation 2 is usually ~ 1 for
low to moderate pressure range, hence:
Φ = (φˆ / φ )
k k
s

k
..(3)
s
B P
By Virial EOS, φ = exp[ ] k
sat kk k
..(4)
RT
For binary:
P P
ln φ
= 1
( B + y δ ) ;φˆ = exp[
11
( B + y δ )] 2

2 12 2 22
2

1 12
..(5)
RT RT

B ( P − P ) + Py δ s 2

Using eqns 3 – 5, Φ = exp[ ] 1

11 1 2 12

RT

B ( P − P ) + Py δ s 2

And Φ = exp[ 2
] 22 2 1 12

RT