31/10/2018

31 October 2018

Phase Diagrams and VLE Calculations

PHASE EQUILIBRIUM

How do we determine
these compositions?

1
 31/10/2018

PHASE DIAGRAM

PHASE DIAGRAM

Hypothetical Experiment!

2
 31/10/2018

PHASE DIAGRAM

Hypothetical Experiment!

PHASE DIAGRAM

ESTIMATION OF VAPOR PRESSURES

 Antoine Equation
B
ln P sat = A -
T +C

3
 31/10/2018

GIBBS PHASE RULE

EXAMPLES
Find the number of degrees of freedom:
 An aqueous solution of sucrose
 An aqueous solution of sucrose and ribose
 Solid sucrose and an aqueous solution of sucrose and ribose
 An aqueous sucrose solution and water vapor
 Solid sucrose, an aqueous sucrose solution, and water vapor

GIBBS PHASE RULE

4
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

 Consider an ethanol solution in water

-- NBP of water (1): 100oC
-- NBP of ethanol (2) : 78.4oC
-- Specify at least 2 DF to
define system

VAPOR-LIQUID EQUILIBRIUM

Definition of terms
¤ Subcooled liquid – liquid existing below its boiling point
¤ Superheated vapor – vapor heated above its boiling point

¤ Saturated liquid – liquid whose T and P are such that any increase in
T (at constant P) or any decrease in P (at constant T) causes it to
vaporize
¤ Saturated vapor – vapor whose T and P are such that any decrease in
T (at constant P) or any increase in P (at constant T) causes it to
condense

5
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

Definition of terms
¤ Bubble point – the temperature or pressure where the first vapor
bubble forms

¤ Dew point – temperature or pressure where the first drop of

liquid forms

VAPOR-LIQUID EQUILIBRIUM

T-xy DIAGRAM for a binary system Saturated

vapor
Superheated 
vapor

Subcooled liquid

Saturated liquid

6
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

T-xy DIAGRAM for a binary system

Saturated
vapor
Superheated 
vapor
F = L +V
V F L z 1F = x 1L + y1V

L FV V LF L VF
= = =
V FL F LV F VL
Subcooled liquid

Saturated liquid

VAPOR-LIQUID EQUILIBRIUM

T-xy DIAGRAM for a binary system

Saturated
vapor
Superheated 
vapor
F = L +V
z 1F = x 1L + y1V

L FV V LF L VF
= = =
V FL F LV F VL
Subcooled liquid

Saturated liquid

7
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

T-xy DIAGRAM for a binary system

Saturated
vapor
Superheated 
vapor
F = L +V
z 1F = x 1L + y1V

L FV V LF L VF
= = =
V FL F LV F VL
Subcooled liquid

Saturated liquid

VAPOR-LIQUID EQUILIBRIUM

T-xy DIAGRAM for a binary system

Saturated
vapor
Superheated 
vapor

F = L +V
z 1F = x 1L + y1V
Subcooled liquid

Saturated liquid

8
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

P-xy DIAGRAM for a binary system

Subcooled liquid
Total Saturated liquid

Superheated 
vapor

Saturated
vapor

VAPOR-LIQUID EQUILIBRIUM

 Consider an ethanol solution in water

-- NBP of water (1): 100oC
-- NBP of ethanol (2) : 78.4oC
-- Specify at least 2 DF to
define system

9
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

RAOULT’S LAW
ASSUMPTIONS:
 The vapor phase is an ideal gas.
-- The law can only apply for low to moderate pressures.

 The liquid phase is an ideal solution.

-- The law has approximate validity only when the species that
comprise the system are chemically similar.
-- Valid when xi is close to 1 (liquid is almost pure i)

VAPOR-LIQUID EQUILIBRIUM

RAOULT’S LAW
Ideal Solution

 Mathematically: Pi = yi P = xi Pisat

10
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

How do we
determine
these
compositions?

VLE Calculations

Straightforward solution
¤ Bubble P calculations
¤ Dew P calculations

Iterative solution – requires a loop in the solution until the guess

and the final answer achieves the same value (convergence)
¤ Bubble T calculations
¤ Dew T calculations

11
 31/10/2018

Bubble P Calculations

¤ Required: y, P
¤ Given: x, T
¤ For species i: x i Pi sat  y i P
n sat
x i Pi sat xP
 yi   i i 1
P i 1 P

 i i P
x P
i 1
sat

Bubble P Calculations

¤ Required: y, P
¤ Given: x, T
¤ Algorithm:
– Compute for all Psat’s using the T given (use Antoine if parameters are given)
– Compute for the bubble pressure
n

x P
i 1
i i
sat
P

– Compute for all y’s using:

x i Pi sat
 yi
P

12
 31/10/2018

Dew P Calculations

¤ Required: x, P
¤ Given: y, T
¤ For species i: x i Pi sat  y i P
yP n
yiP
x i  isat  1
Pi i 1 Pi sat

1
n
P
yi

i 1 Pi
sat

Dew P Calculations

¤ Required: x, P
¤ Given: y, T
¤ Algorithm:
– Compute for all Psat’s using the T given (use Antoine if parameters are given)
– Compute for the dew pressure
1
n
P
yi

i 1 Pi
sat

– Compute for all x’s using:

yiP
 xi
Pi sat

13
 31/10/2018

Example

Assuming the validity of Raoult’s Law, do the following calculations

for benzene(1)/toluene(2) system:
¤ Given x1 = 0.33 and T = 100 deg C, find y1 and P

B
Use the following data: ln P sat [kPa ] = A -
T [C] + C

For benzene: A = 13.7819, B = 2726.81, C = 217.572

For toluene: A = 13.9320, B = 3056.96, C = 217.625

Solution

¤ Given x1 = 0.33 and T = 100 deg C, find y1 and P

– Bubble P calculation!

¤ Step 1: Calculate for the Psat of all components at the given T

æ 2726.81 ÷ö
P1sat = exp çç13.7819 - ÷÷ = 180.4528 kPa
çè 100 + 217.572 ø
æ 3056.96 ö÷
P2sat = exp çç13.9320 - ÷ = 74.2597 kPa
çè 100 + 217.625 ÷ø

14
 31/10/2018

Solution

¤ Step 2: Compute for the bubble pressure using the formula:

n

x P
i 1
i i
sat
P

P = x 1P1sat + x 2P2sat
P = (0.33)(180.4528 kPa ) + (0.67 )(74.2597 kPa )
P = 109.3034 kPa

Solution

¤ Step 3: Compute for the bubble composition using the equation:

x i Pi sat
yi 
P

x 1P1sat (0.33)(180.4528 kPa )

y1 = = = 0.5448
P 109.3034 kPa
y2 = 1 - y1 = 0.4552

15
 31/10/2018

Bubble T Calculations

¤ Required: y, T
¤ Given: x, P
n

 i i P
x P
i 1
sat

¤ Iterative solution

Bubble T Calculations

¤ Required: y, T
¤ Given: x, P
¤ Algorithm
– Determine the initial T1sat and T2sat from the given P. Use Antoine
equation if parameters are given.
– Determine an initial guess Told using:
T0 = å x iTisat
– Determine the old values of P1sat and P2sat from the computed Told. Use
Antoine equation if parameters are given.

16
 31/10/2018

Bubble T Calculations

¤ Algorithm sat
– Determine the value of alpha using: a =
P1

P2sat
P
– Determine a new P2sat using: P2,sat
new =
x 1a + x 2

– Determine Tnew from the new P2sat. Use Antoine equation if the
parameters are given.
– Compare Told and Tnew. If different, repeat entire process by solving a new
alpha using the value of Tnew. Terminate the loop if Told and Tnew achieves
the same value.

Bubble T Calculations

¤ Algorithm

Guess T Calc 𝛼 Calc 𝑃

Calc new
Converge
T

17
 31/10/2018

Dew T Calculations

¤ Required: x, T
¤ Given: y, P 1
n
P
yi

i 1 Pi
sat

¤ Iterative solution

Dew T Calculations

¤ Required: x, T
¤ Given: y, P
¤ Algorithm
– Determine the initial T1sat and T2sat from the given P. Use Antoine
equation if parameters are given.
– Determine an initial guess Told using:
T0 = å yiTisat
– Determine the old values of P1sat and P2sat from the computed Told. Use
Antoine equation if parameters are given.

18
 31/10/2018

Dew T Calculations

¤ Algorithm sat
– Determine the value of alpha using: a =
P1

P2sat
æ y1 ö
÷
– Determine a new P2sat using: P2,sat = P ç
ççè + y 2÷
new
a ÷ø

– Determine Tnew from the new P2sat. Use Antoine equation if the
parameters are given.
– Compare Told and Tnew. If different, repeat entire process by solving a new
alpha using the value of Tnew. Terminate the loop if Told and Tnew achieves
the same value.

Dew T Calculations

¤ Algorithm

Guess T Calc 𝛼 Calc 𝑃

Calc new
Converge
T

19
 31/10/2018

Example

Assuming the validity of Raoult’s Law, do the following calculations

for benzene(1)/toluene(2) system:
¤ Given y1 = 0.33 and P = 120 kPa, find x1 and T

B
Use the following data: ln P sat [kPa ] = A -
T [C] + C

For benzene: A = 13.7819, B = 2726.81, C = 217.572

For toluene: A = 13.9320, B = 3056.96, C = 217.625

Solution

¤ Given y1 = 0.33 and P = 120 kPA, find x1 and T

– Dew T calculation!

¤ Step 1: Determine T1sat and T2sat using the given P and the
Antoine equation.
2726.81
ln (120 kPa ) = 13.7819 - sat
 T1sat = 85.5952C
T1 + 217.572
3056.96
ln (120 kPa ) = 13.9320 - sat
 T1sat = 116.6696C
T2 + 217.625

20
 31/10/2018

Solution

¤ Step 2: Determine an initial guess for T using:

T0 = å x iTisat

T0 = y1T1sat + y 2T2sat
T0 = (0.33)(85.5952C) + (0.67 )(116.6696C)
T0 = 106.4150C

Solution

¤ Step 3: Determine alpha using the value of T0 and:

P1sat
a = sat
P2

æ B1 ÷ö
exp ççA1 - ÷
P1sat çè T + C 1 ÷÷ø 213.8943
a = sat = = = 2.3807
P2 æ B2 ÷ ö 89.8465
exp ççA2 - ÷÷
çè T + C 2 ÷ø

21
 31/10/2018

Solution

¤ Step 4: Determine new P2sat using: æ y1 ö÷

P2,sat = P ç
ççè + y 2÷
new
a ø÷

æ 0.33 ö÷
P2,sat = (120 kPa ) ç
ççè + 0.67 ÷ = 97.0338 kPa
new
2.3807 ø÷

¤ Step 5: Determine Tnew from new P2sat using Antoine equation.

3056.96
ln (97.0338) = 13.9320 -  Tnew = 109.0801C
Tnew + 217.625

Solution

¤ Step 6: Compare old T with new T. Repeat process if values are

not the same. Terminate if values converge.
– T0 = 106.4150 deg C
– Tnew = 109.0801 deg C
– Since the two values are different, we repeat with computing a new alpha.
We now use the new T = 109.0801 deg C.

22
 31/10/2018

Solution

¤ Iteration Table:

Told P1sat P2sat alpha P2sat Tnew

106.4151 213.8948 89.84675 2.380663 97.03402 109.0802
109.0802 229.0984 97.03402 2.361011 97.17247 109.1299
109.1299 229.3901 97.17247 2.360649 97.17505 109.1309
109.1309 229.3955 97.17505 2.360642 97.1751 109.1309

VAPOR-LIQUID EQUILIBRIUM

 Flash Calculations
A liquid at a pressure equal to or greater than its bubble P “flashes”
or partially evaporates when the pressure is reduced, producing a
two-phase system of vapor and liquid in equilibrium

Involves calculation of quantities and compositions of the vapor

and liquid phases making up a two-phase system in equilibrium at
known T, P, and overall composition (zi)

23
 31/10/2018

VAPOR-LIQUID EQUILIBRIUM

 Flash Calculations
Consider a system containing one mole of non-reacting chemical
species with an overall composition zi.

Let L = moles of liquid and V = moles of vapor

L +V = F
xi L + yiV = z i F

APPLICATION

DISTILLATION
TOTAL

24
 31/10/2018

APPLICATION

Distillation column

25