Engi-3434

Chemical Engineering Thermodynamics

Dr. Charles Xu @ Chemical Engineering, Lakehead University

7-1. Vapor-Liquid Equilibrium

There are two sealed round-bottom flasks contain bromine (Br2) vapor (brown color). (a) The flask on the left has been immersed in an ice-water bath. (b) The flask on the right has been immersed in a hot-water bath.

Compare (1) the flask color vs. the flask temperature, and (2) the amount of liquid in the flask vs. its temperature.

Problems To Be Solved
For a mixture of substances at equilibrium, (1) the equilibrium compositions of each species in vapor and liquid phases; (2) Dependence of the equilibrium compositions on P and T.

Knowledge We Have So Far

1. EOS for pure substances (liquid or vapor) 2. Generalized correlations to calculate the compressibility factors (Z) of pure fluids 3. Saturation vapor pressure versus temperature (Antoines Equation) for pure substances:

ln Pi

sat

/ kPa = Ai

Bi t / C + C i

(Table B.2 in Appendixes)

4. Clapeyron equation to calculate the enthalpy change (latent heat) of phase change of a pure substance dP Sat (4.11) H = TV 5. Phase rule: F = N + 2 (no reactions)

dT

7.1 Measures of Composition

Mole fraction of species i in liquid: liq

xi = ni Number of moles of species i in the liquid = n liq Total number of moles of all speceies in the liquid

x
i

=1

Mole fraction of species i in vapor:

yi = nivap Number of moles of species i in the vapor = vap Total number of moles of all speceies in the vapor n

y
i

=1

Molar concentration of species i in liquid (mol/m3):

C iliq = xi mole fraction of species i in liquid = V Molar volume of the liquid (m 3 /mol)

Molar mass (mean molecular weight) of the liquid (kg/mol): M liq = xi M i where M i = molecualr weright of species i (kg/mol)
i

7.2 Qualitative Behavior of VLE (VaporLiquid Equilibrium)

Homework: read section 10.3 on the textbook

7.2.1 Qualitative Behavior of VLE

Pxy Diagram at Constant Temperature
C4H8O (a) (b) (a) Solution of tetrahydrofuran (1) and carbon tetrachloride (2) at 30C CCl4 CHCl3 (b) Solution of chloroform (1) and tetrahydrofuran (2) at 30C C4H8O Azeotrope: A point where x1=y1, i.e., the liquid does not change composition as it evaporates. Separation of the azeotrope solution is thus impossible by distillation!

x1 y1

7.2.1 Qualitative Behavior of VLE

Pxy Diagram at Constant Temperature (Contd)
(c)
Bubble point curve

(d)

Bubble point: With a subcooled liquid, as pressure decreases, first bubble appears at this point! Dew point: With a superheated vapor, as pressure increases, first drop of liquid appears at this point!

Dew point curve

C4H4O (c) Solution of furan (1) and carbon tetrachloride (2) at 30C CCl4 (d) Solution of ethanol (1) and toluene (2) at 65C

7.2.1 Qualitative Behavior of VLE

Pxy Diagram at Constant Temperature (Contd)
Consider a mixture of two species (1 and 2) of overall composition z1: n1 total number of moles of species 1 in all phases present z1 = = n1 + n2 total number of moles of speceies 1 and 2 in all phases present

Sub-cooled Liquid (L)

P-x1 P-y1

P1sat

P = pressure of the vapor = pressure of the liquid = pressure of the total system

L+V

Three Regions: Sub-cooled liquid (L) Superheated vapor (V) Liquid-vapor co-existing (L+V) Superheated Vapor (V) Two Lines: Bubble point curve (P-x1) Dew point curve (P-y1)

P2sat

Two Points: 0 x1 or y1 x2 = 1 x1 and y2 = 1 y1

sat 1.0 When x1 = 0 (i.e., x2 = 1), P = P2

When x1 = 1, P = P1sat

7.2.1 Qualitative Behavior of VLE

Pxy Diagram at Constant Temperature (Contd) Consider a mixture of two At P = PA: only liquid phase exists, z1 = x1A,
species (1 and 2) of overall composition z1:
PA PB PC PD PE Sub-cooled Liquid (L) A B C L+V P-x1 P-y1 y1A is meaningless. At P = PE: only vapor phase exists, z1 = y1E, x1E is meaningless. At P = PB: bubble point. If reducing the pressure P from PA, the first bubble will P1sat be observed at P . B

C C D E

P2sat
Superheated Vapor (V)
y1E

At P = PD: dew point. If increasing the pressure P from PE, the first dew will be observed at PD. At P = PC: two phases co-exist, x1C< z1 & y1C > z1. The number of moles of species-1 in vapor (n1vap) and its number of moles in liquid (n1liq) can be determined by the lever rule:
n1
vap liq

0 x x1C 1D
x2 = 1 x1 and y2 = 1 y1

z1

y1C

y1B 1.0

x1A x1B y1D

n1 n1

vap

+ n1
liq

= =

z -x C' C = 1 1C and y1C -x1C C' C" y -z CC" = 1C 1 y1C -x1C C' C"

n1
vap

+ n1

liq

7.2.2 Qualitative Behavior of VLE

Txy Diagram at Constant Pressure
(a) T (b)

x1

y1
xi

Dew Point

(a) tetrahydrofuran (1) and carbon tetrachloride (2) at 1atm

L+V T2sat T at P D C TC

T
(b) Solution of chloroform (1) and tetrahydrofuran (2) at 1atm

TB Sub-cooled Liquid (L)

Superheated Vapor (V) D C C T-y1 B T-x1

Bubble Point

T1sat at P 1.0

x1C

z1

y1C

7.3 Raoults Law

Two Major Assumptions:

7.3.1 Simple Models for Vapor/Liquid Equilibrium for Solutions Raoults Law

1. The vapor phase is considered as an ideal gas valid thus only for low to moderate pressure vapors 2. The liquid phase is considered as an ideal solution valid for the solutions whose comprising species are chemically similar, e.g., solutions of isomers, solutions of similar compounds such as n-hexane / n-heptane, ethanol/propanol, benzene/toluene, acetone (CH3COCH3)/acetonitrile (CH3CN), etc.

Raoults Law:

Raoult, Franois Marie (18301901), French physicist and chemist

y i P = xi Pi sat (i = 1, 2, .... , N)
Pi sat = Saturated vapor pressure of species i

(10.1)

where: P = total pressure of the system = pressure of the vapor or liquid phase.

Note: when the temperature T > Tc (critical temp), Roaults Law is not valid since P sat does not exist at T > Tc.
i

7.3.1 Simple Models for Vapor/Liquid Equilibrium for Solutions Raoults Law (contd) Bubble-point and Dew-point Calculations
Bubble P Calculations: to calculate {yi} and P, given {xi} and T Bubble T Calculations: to calculate {yi} and T, given {xi} and P

yi P = xi Pi sat (i = 1, 2, .... , N) x P sat yi = i i P

y
i

=1

P = xi Pi sat
i

(10.2)

Dew P Calculations: to calculate {xi} and P, given {yi} and T Dew T Calculations: to calculate {xi} and T, given {yi} and P

yi P = xi Pi sat (i = 1, 2, .... , N) yP xi = isat Pi

x
i

=1

P=

1 yi / Pi sat
i

(10.3)

Modified Raoults Law

Recall that, Raoults law is valid only if:
1. The vapor phase is considered as an ideal gas (e.g., low to moderate pressure gases). 2. The liquid phase is considered as an ideal liquid.

The modified Raoults law may be used if the vapor phase consists of low to moderate pressure gases, while the liquid phase is NOT an ideal solution:

y i P = xi i Pi sat (i = 1, 2, .... , N)

(10.5)

where: P = total pressure of the system = pressure of the vapor/liquid phases. Pi sat = Saturated vapor pressure of species i i = activity coefficient, accounting for the deviation from the solution ideality Bubble P/T Calculations: calculate {yi} and P/T, Given {xi} and T/P P = xi i Pi sat (by y i = 1 )
i
i

Dew P/T Calculations: calculate {xi} and P/T, Given {yi} and T/P
P= 1 (by xi = 1 ) i y i /( i Pi sat )
i

Example 7.1
Binary system acetonitrile CH3CN (1)/nitromethane CH3NO2 (2) conforms closely to Raoults law. Vapor pressure for the pure species are given by the following Antoine equations: 2945.47 2972.64 sat sat ln P1 / kPa = 14.2724 ln P2 / kPa = 14.2043 t / C + 224.00 t / C + 209.00
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75C. (b) Prepare a graph showing T vs. x1 and T vs. y1 for a pressure of 70 kPa. (c) Calculate the bubble-P and dew-P for the solution of overall composition z1 = 0.5 at 75C. (d) Calculate the bubble-T and dew-T for the solution of overall composition z1 = 0.5 at 70 kPa.

Solution: (a) At t = 75C, the given Antoine Eqs give the saturated pressures of the two species:

P = xi Pi
i

P1
sat

sat

/ kPa = 83.21

and
sat 1 1

P2
sat 2

sat

/ kPa = 41.98

(10.2)

P =x P

+ x2 P

= x1 P1sat + (1 x1 )P2sat

(A)

Now the calculation is very simple. Select x1 between 0 and 1.0, calculate P with Eq. (A), then
sat . The following table is thus constructed: y1 with Eq. (10.1): y = x1 P1 1

x1 0.0 0.2 0.4

y1 0.0000 0.3313 0.5692

P /kPa 41.98 50.23 58.47

x1 0.6 0.8 1.0

y1 0.7483 0.8880 1.0000

P /kPa 66.72 74.92 83.21

The following graph showing P-x1 and P-y1 is obtained by plotting the data in the table.

50

0.33

(b) P = 70 kPa is fixed.

Example 7.1 (contd)

We know that x1 and y1 varies with T that is bounded by the two saturation temperatures t1sat and t2sat for the two species under a fixed P. By rearranging the Antoine equations given, t1sat and t2sat for the two species at P are calculated: Bi Bi sat ln Pi / kPa = Ai t isat / C = Ci t / C + C i Ai ln P / kPa
At 70 kPa, t1
sat

/ C = 69.84

and

t2

sat

/ C = 89.58

Now the calculation is very simple. Select a temperature t between t1sat = 69.84C and t2sat = 89.58C, calculate P1sat and P2sat with the given Antoine equations, then calculate x1 by the modified Eq. (A), i.e.,

P = x 1 P1sat + (1 x1 )P2sat

(A)

x1 =

P P2sat P1sat P2sat

(A)

Then, calculate y1 with Eq. (10.1): y1 = t /C 89.58 (t2sat) 86 82 x1 0.0000 0.1424 0.3184 y1 0.0000 0.2401 0.4742 t /C 78 74

x1 P1sat . The following table is thus constructed: P

x1 0.5156 0.7378 1.0000 y1 0.6759 0.8484 1.0000

69.84 (t1sat)

The following graph showing T-x1 and T-y1 is obtained by plotting the data in the table.

Example 7.1 (contd)

(c) Calculate the bubble-P and dew-P for the solution of overall composition z1 = 0.5 at 75C. From the figure, under the bubble-P for the solution z1 = 0.5, x1 = z1 = 0.5. Thus the bubble pressure calculation is

P = xi Pi sat
i

(10.2)

P = x1 P1sat + (1 x1 ) P2sat = 0.5 83.21 + (1 0.5)41.98 = 62.595kPa

From the figure, under the dew-P for the solution z1 = 0.5, y1 = z1 = 0.5. Thus the dew pressure calculation is

P=
P=

1 yi / Pi sat
i

(10.3)

1 1 = = 55.81kPa y1 y2 0.5 (1 0.5) + + sat sat 83.21 41.98 P1 P2

Example 7.1 (contd)

(d) Calculate the bubble-T and dew-T for the solution of overall composition z1 = 0.5 at 70 kPa. From the figure, at the bubble-T for the solution z1 = 0.5, x1 = z1 = 0.5. Thus the bubble-T calculation is

P = xi Pi sat
i

(10.2) (B)

P = x1 P1sat + (1 x1 ) P2sat

where P is fixed at 70 kPa, but P1sat and P2sat are dependent on temperature (here is the bubble-T) by the 2945.47 Antoine equations. 14.2724

P1

sat

/ kPa = e

t / C + 224.00

P2
70 kPa = 0.5e

sat

/ kPa = e

2972.64 14.2043 t / C + 209.00

Now, eq. (B) becomes

2945.47 14.2724 t / C + 224.00

+ (1 0.5)e

2972.64 14.2043 t / C + 209.00

Use goal-seek in Excel or other method to find the t (bubble-T) that satisfy the above equation.

The result is: Bubble-T =78.3C

Example 7.1 (contd)

To Calculate the dew-T for the solution of overall composition z1 = 0.5 at 70 kPa. From the preceding figure, at the dew-T for the solution z1 = 0.5, y1 = z1 = 0.5. Thus the bubble pressure calculation is

P=

1 yi / Pi sat
i

(10.3)

P=

1 (1 y1 ) y1 + sat P1 P2sat

(D)

where P is fixed at 70 kPa, but P1sat and P2sat are dependent on temperature (here is the dew-T) by the Antoine equations.

P1

sat

/ kPa = e

2945.47 14.2724 t / C + 224.00

and

P2

sat

/ kPa = e
1 + e

2972.64 14.2043 t / C + 209.00

Now, eq. (D) becomes

70 kPa = e

0.5
2945.47 14.2724 t / C + 224.00

(1 0.5)
2972.64 14.2043 t / C + 209.00

Use goal-seek in Excel or other method to find the t (dew-T) that satisfy the above equation.

The result is: Dew-T =81.5C