(CHE60303) CHEMICAL ENGINEERING

THERMODYNAMICS AND SIMULATION

PHASE EQUILIBRIUM

1
Learning Outcomes of Chapter V

 Raoult’s law are adequate for many purposes

but are limited to low pressure.
 Two general calculational procedures for VLE
are introduced:
 - Extension of Modified Raoult’s Law
 - Equation of state

2
 Gamma/Phi Formulation of VLE
Vapour {yi}
fˆi
Defn
fugacity
of ˆ
i  fˆiv  yiˆiv P @ T, P
yi P
coefficient fˆi
fˆil  fˆiv ˆi 
Liquid {xi}
yi P

fˆi
Defn of
i  fˆil  xi  i f i @ T, P
activity xi f i
coefficient

yiˆi P  xi i f i
ˆ  Vi P  Pi sat  
V
f i  isat Pi sat exp i

P  Pi
sat

 i  sat exp 
i
 RT
i 
RT
Poynting Factor  0
yi  i P  xi i Pi sat 14.1


Gamma/Phi Formulation (eq 14.1)
ˆ
Ratio of
i  i
14.2  Considers non ideality of both
fugacity
coefficient 
i
sat
liquid and vapour phases
 Relationship of Gamma/Phi
Formulation with Raoult’s Law

Considers non ideality y i  i P  x i  i Pi sat Gamma/Phi

of both liquid and Formulation
vapour phases
i  1
Considers non ideality
Modified
of liquid phase but yi P  xi i Pi sat Raoult’s Law
vapour phase is
assumed to be ideal
i 1

Both vapour and liquid

phases are assumed to yi P  xi Pi sat Raoult’s Law

be ideal
Determination of Phi through virial
coefficients
ˆ i  Vi P  Pi sat 
 i  sat exp  
i  RT 

Poynting Factor  0
 P  
 y y 2 
ˆ 1
i  exp  Bii  j k ji   jk  14.4
ˆ RT  2 j k 
i  i
 i
sat
Bii Pisat
i sat
 exp 14.5
RT
  12  y y 2
Bii P  Pi sat  j k ji   jk  14.6

 i  exp
j k

RT
 Binary solution VIRIAL 14.7a
 
 B11 P  P1sat  Py 2212 
1  exp 
COEFFICIENTS

 RT 
 
 B22 P  P2sat  Py1212 
 2  exp  
14.7b
 RT 
  determination

PVT data Equations of State

Cubic Equations of State Generalized Correlations

(VdW, SRK, RK, PR)

Virial coefficient @ P↓ Lee/Kessler @ P↑

(from Tables)
ln  ln 0  ln 1
Pure species (pure
liquid or pure gas), ln   
Pr 0
B  B1 
i= il= iv= isat Tr or
   0 
. 1 
 0 0.422 0.172 
 B  0.083  1.6 ; B  0.139  4.2 
1

f i  i Pi exp
sat sat
l

Vi P  Pi sat   Tr Tr 

RT
lni  lni  lni
0 1

Pure species as
compressed liquid, i
@P
ln ˆ1 
P
RT

B11  y2212 
  lnˆi  lnˆi  lnˆi
P 0 1
ln ˆ2  B22  y1212
Species in solution, ˆ RT
i

𝛿12 ≡ 2𝐵12 − 𝐵11 − 𝐵22

Gamma/Phi Formulation

yi  i P  xi i Pi sat

EQUATIONS OF STATE MODELS OF EXCESS GIBBS

•Van der Waals ENERGY
• Peng Robinson • Margules
• Redlich Kwong • van Laar
• Soave Redlich Kwong • Wilson
• Lee Kessler • NRTL
• Virial • UNIQUAC
•UNIFAC
Dewpoint and Bubblepoint Calculations
 All the calculations made by the gamma/phi formulation require iteration due to its complex
functionality:

Φ i  T , P, y1 , y2 ,....., y N 1 
 i  T , x1 , x2 ,....., xN 1 
Pi sat  f T 
 At the moderate P where gamma/phi approach to VLE is appropriate  i is assumed independent of
P.
 Rearrange Eqn. (14.1) to solve for yi or xi:
x i  i Pi sat
yi  - - - - - - - - - (14.8)
i P
yi  i P
xi  - - - - - - - - - (14.9)
 i Pi sat
Because i y i  1, i x i  1, these eqns can be summed to :
x i  i Pi sat y P
1  1   i isat
i i P i  i Pi
Solved for P, they become
x i  i Pi sat 1
P (14.10) P (14.11)
i i y  / 
 i i i 1 P sat

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 BUBL P Calculations
Read T, {xi}, contants
Set all i=1.0.
Evaluate {Pisat} from Antoine, and {i} from
activity models (van Laar or Margules)
Calculate P by eqn. (14.10)

Calculate {yi} by eqn. (14.8).

Evaluate {i} by eqn. (14.6).

Calculate P by eqn. (14.10).

NO
Is P< ? (tolerance)
YES
Print P, {yi}
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 DEW P Calculations
Read T, {yi}, contants
Set all i=1.0, all i=1.0.
Evaluate {Pisat} from Antoine.
Calculate P by eqn. (14.11).
Calculate {xi} by eqn. (14.9).
Evaluate {i}.
Calculate P by eqn. (14.11).

Evaluate {i} by eqn. (14.6).

Calculate {xi} by eqn. (14.9).

Normalize the x with xi=xi/ixi.
Evaluate {i}.
YES
Is each i < ?
NO
Calculate P by eqn. (14.11).

Is P < ?
YES NO
11 Print P, {xi}
 BUBL T Calculations
Read P, {xi}, constants
Set all i=1.0.
Calculate {Tisat} by Antoine). Calculate T=ixiTisat.
Evaluate {Pisat}, {i}. Identify species j.
Calculate Pjsat by eqn. (14.13). Calculate T by eqn. (14.15).

Evaluate {Pisat}.
Calculate {yi} by eqn. (14.8).
Evaluate {i} by eqn. (14.6); {i}.
Calculate Pjsat by eqn. (14.13).
Calculate T by eqn. (14.15).

NO
Is T< ?
YES
Print T, {yi}
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 DEW T Calculations
Read P, {yi}, constants
Set all i=1.0, all i=1.0.
Calculate {Tisat} by eqn. (14.12). Calculate T=iyiTisat.
Evaluate {Pisat}. Identify species j.
Calculate Pjsat by eqn. (14.14). Calculate T by eqn. (14.15).
Evaluate {Pisat}, {i}. Calculate {xi} by eqn. (14.9).
Evaluate {i}. Calculate Pjsat by eqn. (14.14), T by eqn. (14.15).

Evaluate {Pisat}, {i} by eqn. (14.6).

Calculate {xi} by eqn. (14.9).

Normalize x with xi=xi/ixi.
Evaluate {i}.

Is each i < ? NO

YES
Calculate Pjsat by eqn. (14.14).
YA
Calculate T by eqn. (14.15)
NO
Is T < ?
YES
13 Print T, {xi}
 FLASH CALCULATIONS
 Flash calculations using gamma/phi formulation of VLE makes the calculations
become more complex. However the primary equation is unchanged:
L (mol frac of liq)+V(mol frac of vapor)=1
zi K i
yi  (i  1, 2, ......, N) - - - - - - - (10.16)
1  VK i  1

 With xi=yi/Ki, an alternative equation is:

zi
xi  (i  1, 2, ......, N ) - - - - - - - (14.16)
1  V K i  1

 Both sets of mole fractions must sum to unity  ixi= iyi=1. Thus if
summation eq 10.15 is taken for all species and subtract unity from this sum,
the difference Fy is zero:
zi K i
Fy   1  0 - - - - - - - - - (14.17)
i 1  V K i  1

 Similar treatment to Eqn. 14.16 yield the difference Fx=0:

zi
Fx   1  0 - - - - - - - - - (14.18)
i 1  V K i  1

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 Read T, P, {zi}, constants

DEW P calculation with {yi}= {zi}.

BUBL P calculation with {xi}= {zi}.

Is Pdew < P < Pbubl ? NO

Stop

Estimate {i}; {i}; V.

Evaluate {Ki} by eqn. (14.22).

Evaluate F and dF/dV by eqns. (14.19) and (14.20).
Evaluate {xi} by eqn. (14.16) and {yi} by yi=Kixi.
Evaluate {i} and {i} by eqn. (14.6).

Are V, each xi and each yi NO

< ?

YES

Print V, {xi}, {yi}.

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VLE / Flash Calculations
o BUBBLEPOINT CALCULATIONS:
 BUBBLE P (Specify xi & T; Find yi & P)
 BUBBLE T (Specify xi & P; Find yi & T)
o DEWPOINT CALCULATIONS:
 DEW P (Specify yi & T; Find xi & P)
 DEW T (Specify yi & P; Find xi & T)
o FLASH CALCULATIONS:
 ISOTHERMAL FLASH
 ADIABATIC FLASH

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VLE calculations on simulation software (UNISIM,
ProII, DESIGN II and etc)

BASIS MANAGER ENVIRONMENT

COMPONENT FLUID PKGS HYPOTHETICAL

Adding Specifying methods Adding components not

components for i & i in the library list

SIMULATION ENVIRONMENT (PFD VIEW)

CONDITIONS COMPOSITIONS PROPERTIES

Specifying T, P, Vapour Specifying mole / mass Properties of

fraction (Vf) fractions / flows components specified
18 eg. Critical values
 VLE calculations on simulation software (UNISIM,
HYSYS, PROII, DESIGN II and etc)

CONDITIONS COMPOSITIONS

Specifying T, P, Vapour Specifying mole / mass

fraction (Vf) fractions / flows

VLE / Flash Calculations

P-T FLASH BUBBLE T BUBBLE P DEW T DEW P

{Vf, xi, yi} {T, yi} {P, yi} {T, xi} {P, xi}

Specify: Specify: Specify: Specify: Specify:

T, P, Total P, xi , Vf=0 T, xi , Vf=0 P, yi , Vf=1 T, yi , Vf=1

compositions
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