CCB 1064: Professor Saibal Ganguly

Lecture Set 8A: Vapor-Liquid Equilibria for Multi-component Systems

Professor Dr. Saibal Ganguly
Universiti Teknologi PETRONAS May2012

CCB 1064: Professor Saibal Ganguly

Lecture Set 8: OBJECTIVES

At the end of the lecture, students should be able to:
Non-ideal gas Equation of State Use Raoults law & Hendry law to predict the partial pressure of a solute and a solvent Calculate the composition of multi-component systems at equilibria between the liquid and vapor phases Understand Partial Saturation & Humidity

CCB 1064: Professor Saibal Ganguly

Recap: Vapour Pressure Definition

The vapour pressure of a species is a measure of its volatility. Higher vapour pressures or higher volatility means that the species tend to exist in the vapour phase than the liquid phase.

CCB 1064: Professor Saibal Ganguly

Recap: Vapour Pressure

Antoine Equation (for ideal species):

Log10 p*

B T C

A, B, C Antoine constants, T (C), p* = Vapour pressure (mmHg)

Antoine Constants are given in Tabular form in text books and reference books

CCB 1064: Professor Saibal Ganguly

Raoults Law
Raoults Law is used primarily for a component whose mole fraction approaches to unity. Partial pressure is given as,

yi P

pi

px

* i i

P = p1+p2+. = x1p1* + x2p2* +

CCB 1064: Professor Saibal Ganguly

Equilibrium Constant
The ratio of yi and xi is known as equilibrium constant or partition coefficient, K.

Ki

yi xi

This equation provides good estimate of K values at low pressures for components below their critical temperatures, but yields values too large for components above the critical temperatures, at high pressures and or for polar compounds

CCB 1064: Professor Saibal Ganguly

Equilibrium Constant
The equilibrium constant, Ki can be used to calculate the following: 1. Bubble point temperature of a liquid mixture given the total pressure and liquid composition. 2. Dew point temperature of a vapor mixture given the total pressure and vapor composition. 3. Equilibrium vapor-liquid composition over the range mole fractions from 0 to 1 as a function of temperature given the total pressure

CCB 1064: Professor Saibal Ganguly

Example 1
Determine the composition of the first vapor (saturated condition/ equilibrium) formed if a liquid mixture of 4.0% n-hexane in n-octane vaporised at 1 atm. Given the Antoine equation constants as below:
A n-hexane (C6) n-octane (C8) 15.8737 15.9798 B 2697.55 3127.60 C -48.784 -63.633

CCB 1064: Professor Saibal Ganguly

2697.55 0.040 exp 15.9787 48.784 T 3127.60 0.960 63.633 T

760 exp 15.8737 T 393.3K

p* (C6 ) 3114mmHg p* (C8 ) 661mmHg yC 6

* pC 6 xC 6 ptot

3114 (0.040) 0.164 760

yC 8 1 0.164 0.836

CCB 1064: Professor Saibal Ganguly

Raoults Law (Equilibrium/saturated condition)

yiPi = p*i(T) yiPi < p*i(T) - Superheated vapour yiPi = p*i(Tdp) - Dew point

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CCB 1064: Professor Saibal Ganguly

Example 2:
Derive the model equations for a flash drum (a single equilibrium stage separator) using the partition coefficient or equilibrium constant K.

yi Fx Fi

1 (F L) ( L / Ki )
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CCB 1064: Professor Saibal Ganguly

Example 3:
Calculate the fraction of liquid that will remain at equilibrium when a mixture of 68.6% hexane and 31.4% toluene is vaporized at 80 degree C and 1 atm pressure. Vapor pressure data at 80 degree C are 1020 mm Hg (hexane) and 290 mmHg (toluene)

Answer: L/F = 0.745

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CCB 1064: Professor Saibal Ganguly

Henrys Law
Henry Law is used for a component whose mole fraction approaches zero, such as a dilute gas dissolved in as liquid. Partial pressure is given as,

The value Hi when xi approaches to zero can be obtained from handbooks. Mole fraction in vapor phase is given as,

pi

H i xi

yi

pi ptot

H i xi ptot

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CCB 1064: Professor Saibal Ganguly

Example 4
Determine the partial pressure of CO2 when it is dissolved in water at 40oC having H=69,600 atm/mol fraction. Given xCO2=4.2 x10-6.

Answer: PCO2=69,600(4.2x10-6)=0.29 atm

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CCB 1064: Professor Saibal Ganguly

End of Lecture Set 8A

THANK YOU
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