CHE 407: CHEMICAL ENGINEERING THERMODYNAMICS 2

VAPOR-LIQUID EQUILIBRIA
 The Phase Rule
Consider a non-reactive system under equilibrium, with π phases each
containing N species:
Number of
Total number of
Degrees of Freedom independent
= systemic intensive -
equations relating
variables
all the variables

Phase Rule Variables:

• Temperature Chemical
• Pressure potential equality
• Mole Fractions relations
 Three Dimensional Phase
Diagram for a Binary System (P-T-xy)
Upper face of the 3D surface
à Bubble Surface

Lower face of the 3D surface

à Dew Surface

Any point above the Bubble Surface

à State: Sub-cooled Liquid

Any point below the Dew Surface

à State: Super-heated vapor

Any point in between the Bubble

and Dew Surface
à State: Vapor-Liquid Mixture
 Three Dimensional Phase
Diagram for a Binary System (P-T-xy)

Consider “Lens AB”

• Constant Temperature
• Upper curve P-x1 à Bubble P Line
• Lower curve P-y1 à Dew P Line
• Line T1 – T2 à Tie Line (connects
phase compositions x1* and y1*)

Consider “Lens DE”

• Constant Pressure
• Upper curve T-y1 à Dew T Line
• Lower curve T-x1 à Dew P Line
 Two Dimensional Phase Diagram
for a Binary System (P-xy and T-xy)
 Raoult’s Law for VLE
Quantitative analysis of VLE can be performed by Raoult’s Law, which
requires two major assumptions:

1. The vapor phase behaves as an ideal gas

à Close or less to atmospheric pressure

2. The liquid phases behaves as an ideal solution

à Species involved are chemically similar (size, chemical nature)

where:
Raoult’s Law
i = 1, 2, 3 … N component

Other forms:

(for Binary System only)

 Azeotropic Mixtures
• Mixture that resulted from a very large deviation from ideality
• Azeotrope is a special class of liquid mixture that boils at a constant temperature at
a certain composition.
 VLE Calculations
1. Bubble Point Temperature Calculation
àGiven: pressure, liquid phase composition
àUnknown: temperature, vapor phase composition

For binary systems:

Psat = f(TB)

TB should be between TB1

and TB2

• Solve for TB
• Evaluate P1sat or P2sat
• Solve for y1 and y2
 VLE Calculations
2. Bubble Point Pressure Calculation
àGiven: temperature, liquid phase composition
àUnknown: pressure, vapor phase composition

For binary systems:

• Evaluate P1sat and P2sat

• Solve for P
• Solve for y1 and y2
 VLE Calculations
3. Dew Point Temperature Calculation
àGiven: pressure, vapor phase composition
àUnknown: temperature, liquid phase composition

For binary systems:

Psat = f(TD)

TB should be between TD1

and TD2

• Solve for TD
• Evaluate P1sat or P2sat
• Solve for x1 and x2
 VLE Calculations
4. Dew Point Pressure Calculation
àGiven: temperature, vapor phase composition
àUnknown: pressure, liquid phase composition

For binary systems:

• Evaluate P1sat and P2sat

• Solve for P
• Solve for x1 and x2
 VLE Calculations
5. Flash Calculation

By material balance:

Combining:

Define, EQUILIBRIUM RATIO:

Sample Calculations
1. Determine the temperature and composition of the first bubble created from a
saturated liquid mixture of benzene and toluene containing 45 mole percent benzene
at 200 kPa. Benzene and toluene mixtures may be considered as ideal.

2. Determine the pressure and composition of the first bubble created from a saturated
liquid mixture of benzene and toluene containing 45 mole percent benzene at 400 K.
Benzene and toluene mixtures may be considered as ideal.

3. Determine the temperature and composition of the first dew created from a saturated
vapor mixture of benzene and toluene containing 45 mole percent benzene at 200
kPa. Benzene and toluene mixtures may be considered as ideal.

4. Determine the temperature and composition of the first dew created from a saturated
vapor mixture of benzene and toluene containing 45 mole percent benzene at 400 K.
Benzene and toluene mixtures may be considered as ideal.
Use of K-values in VLE Calculations
Raoult’s Law Equilibrium Ratio

𝑃"% 𝑦" 𝑃
𝑦" = 𝑥 = 𝑥"
𝑃 " 𝑃"%
𝑦"
𝑦" = 𝐾" 𝑥" = 𝑥"
𝐾"
𝑦
( 𝑦" = ( 𝐾" 𝑥" ( " = ( 𝑥"
𝐾"
𝑦"
1 = ( 𝐾" 𝑥" ( =1
𝐾"

(for Bubble Calculations) (for Dew Calculations)

Sample Calculations
5. The vapor exiting the distillation column contains the following: 23% propane, 67%
isobutane, and the remaining to be n-butane. This overhead vapor will then enter a
condenser operating at 8 bar.

a) Determine the temperature at which the condenser must operate in order to

condense the overhead product completely.

b) Assuming the overhead product vapors are in equilibrium with the liquid on the top
plate of the column, determine the temperature of the overhead vapor and the
composition of the liquid on the top plate when operating at the pressure of the
condenser.

Use the DePriester diagram for estimation of K-values.

Sample Calculations
a) Determine the temperature at which the condenser must operate in order to
condense the overhead product completely.

Solution: 1 = ( 𝐾" 𝑥" at an assumed Temperature

Trial 1: T = 111oF
Component xi Ki xi*Ki
Propane 0.23 1.81 0.4163
Isobutane 0.67 0.82 0.5494
n-Butane 0.1 0.59 0.059
1.0247
Sample Calculations
a) Determine the temperature at which the condenser must operate in order to
condense the overhead product completely.

Solution: 1 = ( 𝐾" 𝑥" at an assumed Temperature

Trial 1: T = 111oF Trial 2: T = 109oF

Component xi Ki xi*Ki Component xi Ki xiKi
Propane 0.23 1.81 0.4163 Propane 0.23 1.8 0.414
Isobutane 0.67 0.82 0.5494 Isobutane 0.67 0.79 0.5293
n-Butane 0.1 0.59 0.059 n-Butane 0.1 0.59 0.059
1.0247 1.0023
Sample Calculations
b) Assuming the overhead product vapors are in equilibrium with the liquid on the top
plate of the column, determine the temperature of the overhead vapor and the
composition of the liquid on the top plate when operating at the pressure of the
condenser.
𝑦"
Solution: ( = 1 at an assumed Temperature
𝐾"

Trial 1: T = 109oF
Component yi Ki yi/Ki
Propane 0.23 1.8 0.127777778
Isobutane 0.67 0.79 0.848101266
n-Butane 0.1 0.59 0.169491525
1.145370569

Trial 2: T = 123oF
Component yi Ki yi/Ki
Propane 0.23 2.05 0.112195122
Isobutane 0.67 0.94 0.712765957
n-Butane 0.1 0.7 0.142857143
0.967818222
Sample Calculations
b) Assuming the overhead product vapors are in equilibrium with the liquid on the top
plate of the column, determine the temperature of the overhead vapor and the
composition of the liquid on the top plate when operating at the pressure of the
condenser.
𝑦"
Solution: ( = 1 at an assumed Temperature
𝐾"

Trial 1: T = 109oF Trial 3: T = 120oF

Component yi Ki yi/Ki Component yi Ki yi/Ki
Propane 0.23 1.8 0.127777778 Propane 0.23 2 0.115
Isobutane 0.67 0.79 0.848101266 Isobutane 0.67 0.9 0.744444444
n-Butane 0.1 0.59 0.169491525 n-Butane 0.1 0.68 0.147058824
1.145370569 1.006503268

Trial 2: T = 123oF
Component yi Ki yi/Ki
Propane 0.23 2.05 0.112195122
Isobutane 0.67 0.94 0.712765957
n-Butane 0.1 0.7 0.142857143
0.967818222
Sample Calculations
6.

Component Pi,sat Ki zi V=0.70 V=0.90 V=0.834

Benzene 234.11 2.601 0.3333 0.4088 0.3552 0.3713

Ethylbenzene 47.35 0.526 0.3333 0.2624 0.3058 0.2900

Toluene 99.56 1.106 0.3333 0.3432 0.3366 0.3387

1.0145 0.9976 1.0000
 VLE BY MODIFIED RAOULT’S LAW
à Liquid phase exhibits non-ideality
à For low to moderate pressures so that the vapor phase is assumed to
substantially behave as an ideal gas
à Use of activity coefficient in the Raoult’s Law

𝑃 = ( 𝑥" 𝛾" 𝑃"%,- Bubble Calculations

𝑦" 𝑃 = 𝑥" 𝛾" 𝑃"%,-
𝑦" 𝑃 Dew Calculations
1= (
𝛾" 𝑃"%,-
gamma1 gamma2 P x1 x2 gamma1 gamma2
1.0000 1.0000 51.0883 0.6887 0.3113 1.1133 1.6905
1.1133 1.6905 63.6398 0.7706 0.2294 1.0600 1.9297
1.0600 1.9297 62.9914 0.8011 0.1989 1.0448 2.0348
1.0448 2.0348 62.9041 0.8116 0.1884 1.0401 2.0734
1.0401 2.0734 62.8938 0.8152 0.1848 1.0385 2.0867
1.0385 2.0867 62.8926 0.8163 0.1837 1.0380 2.0911
1.0380 2.0911 62.8925 0.8167 0.1833 1.0379 2.0926
1.0379 2.0926 62.8925 0.8169 0.1831 1.0378 2.0931
1.0378 2.0931 62.8925 0.8169 0.1831 1.0378 2.0933
 T A gamma1 gamma2 P1sat P2sat P
336.00 1.0137 1.0231 2.0801 94.6897 123.9971 121.0319
335.50 1.0163 1.0231 2.0840 92.8212 121.9410 118.8422
335.00 1.0190 1.0232 2.0880 90.9835 119.9119 116.6853
334.50 1.0216 1.0233 2.0919 89.1763 117.9095 114.5608
334.00 1.0242 1.0233 2.0959 87.3992 115.9336 112.4684
333.50 1.0268 1.0234 2.0998 85.6517 113.9839 110.4077
333.00 1.0294 1.0234 2.1038 83.9335 112.0603 108.3782
332.50 1.0320 1.0235 2.1078 82.2442 110.1623 106.3797
332.00 1.0346 1.0236 2.1118 80.5834 108.2899 104.4117
331.50 1.0373 1.0236 2.1158 78.9508 106.4427 102.4740
331.45 1.0375 1.0236 2.1162 78.7891 106.2594 102.2818
331.40 1.0378 1.0236 2.1166 78.6276 106.0763 102.0900
331.35 1.0380 1.0236 2.1170 78.4664 105.8935 101.8985
331.30 1.0383 1.0236 2.1174 78.3055 105.7109 101.7072
331.25 1.0386 1.0236 2.1178 78.1449 105.5286 101.5163
331.20 1.0388 1.0236 2.1182 77.9845 105.3465 101.3257
331.15 1.0391 1.0237 2.1186 77.8245 105.1646 101.1353
Alternative Solution:

T A gamma1 gamma2 P1sat P2sat alpha P1sat T

336.0000 1.0137 1.0231 2.0801 94.6897 123.9971 0.7636 79.2758 331.6002
331.6002 1.0367 1.0236 2.1150 79.2758 106.8110 0.7422 78.0966 331.2350
331.2350 1.0386 1.0236 2.1179 78.0966 105.4738 0.7404 77.9974 331.2040
331.2040 1.0388 1.0236 2.1181 77.9974 105.3611 0.7403 77.9890 331.2014
331.2014 1.0388 1.0236 2.1182 77.9890 105.3515 0.7403 77.9883 331.2012
331.2012 1.0388 1.0236 2.1182 77.9883 105.3507 0.7403 77.9882 331.2011
331.2011 1.0388 1.0236 2.1182 77.9882 105.3506 0.7403 77.9882 331.2011
 𝑦" 𝑃
1= (
𝛾" 𝑃"%,-
T gamma1 gamma2 A P1sat P2sat x1 x2 gamma1 gamma2 P1sat P2sat = 1?
333.13 1.0000 1.0000 1.0287 84.3774 112.5579 0.4804 0.5196 1.3484 1.2910 65.3618 112.5579 0.7746
332.63 1.3484 1.2910 1.0313 82.6807 110.6533 0.3636 0.6364 1.5658 1.1576 65.1307 110.6533 0.7877
332.13 1.5658 1.1576 1.0340 81.0125 108.7743 0.3195 0.6805 1.6696 1.1197 64.7182 108.7743 0.7989
331.63 1.6696 1.1197 1.0366 79.3726 106.9206 0.3059 0.6941 1.7047 1.1091 64.4699 106.9206 0.8122
331.13 1.7047 1.1091 1.0392 77.7605 105.0920 0.3058 0.6942 1.7049 1.1090 64.3363 105.0920 0.8274
330.63 1.7049 1.1090 1.0418 76.1759 103.2882 0.3121 0.6879 1.6885 1.1138 64.2603 103.2882 0.8436
330.13 1.6885 1.1138 1.0444 74.6185 101.5090 0.3217 0.6783 1.6642 1.1214 64.2102 101.5090 0.8605
329.63 1.6642 1.1214 1.0470 73.0877 99.7542 0.3332 0.6668 1.6358 1.1308 64.1705 99.7542 0.8780
329.13 1.6358 1.1308 1.0497 71.5834 98.0236 0.3461 0.6539 1.6053 1.1418 64.1335 98.0236 0.8959
328.63 1.6053 1.1418 1.0523 70.1050 96.3168 0.3602 0.6398 1.5733 1.1544 64.0949 96.3168 0.9143
328.13 1.5733 1.1544 1.0549 68.6524 94.6337 0.3753 0.6247 1.5404 1.1687 64.0517 94.6337 0.9330
327.63 1.5404 1.1687 1.0575 67.2251 92.9740 0.3914 0.6086 1.5069 1.1848 64.0013 92.9740 0.9520
327.13 1.5069 1.1848 1.0601 65.8227 91.3376 0.4086 0.5914 1.4727 1.2031 63.9410 91.3376 0.9714
326.63 1.4727 1.2031 1.0627 64.4449 89.7241 0.4271 0.5729 1.4382 1.2237 63.8678 89.7241 0.9910
326.60 1.4382 1.2237 1.0629 64.3630 89.6280 0.4379 0.5621 1.4188 1.2365 63.8787 89.6280 0.9925
326.57 1.4188 1.2365 1.0630 64.2812 89.5320 0.4444 0.5556 1.4073 1.2444 63.8790 89.5320 0.9937
326.54 1.4073 1.2444 1.0632 64.1995 89.4361 0.4486 0.5514 1.4001 1.2496 63.8752 89.4361 0.9949
326.51 1.4001 1.2496 1.0634 64.1179 89.3402 0.4515 0.5485 1.3952 1.2531 63.8699 89.3402 0.9961
326.48 1.3952 1.2531 1.0635 64.0364 89.2445 0.4537 0.5463 1.3916 1.2559 63.8638 89.2445 0.9973
326.45 1.3916 1.2559 1.0637 63.9549 89.1488 0.4554 0.5446 1.3886 1.2581 63.8574 89.1488 0.9985
326.42 1.3886 1.2581 1.0638 63.8735 89.0532 0.4570 0.5430 1.3860 1.2601 63.8507 89.0532 0.9996
326.39 1.3860 1.2601 1.0640 63.7923 88.9577 0.4584 0.5416 1.3836 1.2619 63.8440 88.9577 1.0008
326.36 1.3836 1.2619 1.0641 63.7111 88.8623 0.4598 0.5402 1.3813 1.2637 63.8371 88.8623 1.0020
326.33 1.3813 1.2637 1.0643 63.6300 88.7669 0.4612 0.5388 1.3791 1.2654 63.8301 88.7669 1.0031
326.30 1.3791 1.2654 1.0645 63.5489 88.6717 0.4625 0.5375 1.3769 1.2672 63.8230 88.6717 1.0043
Alternative Solution:
T gamma1 gamma2 A P1sat P2sat alpha x1 x2 gamma1 gamma2 P1sat T
333.13 1.0000 1.0000 1.0287 84.3774 112.5579 0.7496 0.4804 0.5196 1.3484 1.2910 65.3618 326.9637
326.96 1.3484 1.2910 1.0610 65.3618 90.7985 0.7199 0.4599 0.5401 1.3812 1.2638 63.9762 326.4578
326.46 1.3812 1.2638 1.0636 63.9762 89.1738 0.7174 0.4587 0.5413 1.3831 1.2623 63.8596 326.4149
326.41 1.3831 1.2623 1.0639 63.8596 89.0369 0.7172 0.4589 0.5411 1.3828 1.2625 63.8497 326.4112
326.41 1.3828 1.2625 1.0639 63.8497 89.0252 0.7172 0.4591 0.5409 1.3825 1.2627 63.8489 326.4109
326.41 1.3825 1.2627 1.0639 63.8489 89.0242 0.7172 0.4592 0.5408 1.3824 1.2629 63.8488 326.4109
 BINARY ACTIVITY COEFFICENT MODELS
Empirical Models:
à The molar excess Gibbs energy is expressed as:

à Activity coefficients are estimated by:

Examples: two- and three- suffix Margules Equations, the van Laar Equation
 BINARY ACTIVITY COEFFICENT MODELS
Local Composition Models:

à Assume that the bulk (or mean) concentration of species in solution is

very different from the local concentration

à Local concentrations are dependent on the interactions between

molecules and a radial distribution function

Examples:
• Wilson Equation
• NRTL – Non-Random Two-Liquid
• UNIQUAC - Universal Quasi-Chemical
 BINARY ACTIVITY COEFFICENT MODELS
Group Contribution Models:

à These models are based on the molecular structure.

à The activity coefficients are estimated by the additive contributions of the

functional groups comprising the molecule.

Examples:
• UNIFAC – Unified Activity Coefficient
• Modified UNIFAC – Dortmund
• ASOG - Analytical Solutions of Groups
TWO-SUFFIX MARGULES EQUATION
à simplest empirical model
à molar excess Gibbs energy is proposed in the form:

For a binary mixture, Gex /RT is generally expressed as a function of composition

using a Redlich-Kister type expansion:

à THEREFORE, i = 1.

à By applying these to the general equation for activity coefficient estimation at

constant T and P:
 ILLUSTRATIVE EXAMPLE
Mara et al. (1997) obtained the following set of vapor-liquid
equilibrium data for the 1-propanol (1) and 2-pentanol (2) system at 313.5 K:

If the two-suffix Margules equation represents this system, calculate the

parameter A. The vapor pressures of 1-propanol and 2-pentanol at 313.5 K
are 6.970 kPa and 2.261 kPa, respectively.
END.