June 12, 2012

Multiphase Systems
Chapter 6
• Why Study?
- Phase change operations such as freezing,
melting, evaporation, condensation
Example:
Multiphase
p Systems
y 1. brewing g a cup
p of coffee or tea,,
2. absorption of SO2,
3. distillation to recover methanol or ethanol
from aqueous solution
„Dr.
M. A. A. Shoukat Choudhury
4. L-L extraction
„Email:shoukat@buet.ac.bd
„Website: http://teacher.buet.ac.bd/shoukat/
5. Adsorption

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6.1 Single Component Phase Equilibrium Phase Diagram of water

• Phase diagram – A plot of one system variable
against another that shows the conditions at which
the substance exists as solid, liquid and gas.
• Phase Diagram of water
- Boiling point Gas
- normall boiling
b ili point
i t
- melting/freezing point
- sublimation point
- triple point
- critical temperature and pressure – above which
two phases (liquid-vapor) never coexist.

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Difference of vapor and gas
• Vapor:
- Gaseous substance below its critical
temperature which can be condensed by
compressing or increasing the pressure
• Gas :
- Gaseous substance above its critical
temperature which cannot be condensed by
compressing or increasing the pressure
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Estimation of Vapor Pressure
• Clapeyron Equation / Clausius-Clapeyron
Equation
• Antoine Equation
• Cox’s Chart
• Clapeyron Equation / Clausius-Clapeyron Equation
„Example 6.1-1 Vapor Pressure Estimation using Clausius
„-Clapeyron Equation:
„If the vapor pressure of benzene is 40 mm Hg at 7.6 oC
„and 60 mm Hg at 15.4 oC, find the vapor pressure at 42.2
„oc using Clausius-Clapeyron Equation
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June 12, 2012
Vapor Pressure
• Definition: Vapor pressure (also known as equilibrium vapor
pressure) is the pressure of a vapor in equilibrium with its non-
vapor phases.
• All liquids and solids have a tendency to evaporate to a gaseous
form, and all gases have a tendency to condense back into their
original form (either liquid or solid). At any given temperature,
for a particular substance, there is a pressure at which the gas
of that substance is in dynamic equilibrium with its liquid or
solid forms. This is the vapor pressure of that substance at that
temperature.
• The equilibrium vapor pressure is an indication of a liquid's
evaporation rate. It relates to the tendency of molecules and
atoms to escape from a liquid or a solid.
• Higher the vapor pressure, the more volatile the compound is.
5 6/12/2012 ChE 201/shoukat@buet.ac.bd „Source : wikipedia 6
Antoine Equation
• log10 p* = A - B/ (T + C)
• p* = 10^(A - B/ (T + C))
T is in oC
p* is in mm Hg
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Cox’s Chart for Vapor Pressure Estimation Water Vapor

Pressure Table

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Water Vapor Gibbs Phase Rule

Pressure Table
• How many intensive variables must be
specified to define a system?
• DOF = 2 + C – P, C=number of components,
P=number of phases
• intensive variables – do not depend on the
size off the
h system. Example:
l molar
l volume,
l
density
• Extensive variables – depend on the size of
the system. Example: mass, volume
• Calculate DOF for various regions of water
phase diagram.
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Gas-Liquid Systems – One Condensable Components Example 6.3.2

Examples – evaporation, drying, humidifications,
A stream of air at 100 oC and 5260 mm Hg contains
condensations, dehumidifications 10% water by volume.
Bone
BDA dry air
+ water a) Calculate the dew point and the degree of
„P, T
superheat of the air
Water b) Calculate the percentage of vapor that condenses
and the final composition of the gas phase if the air
•Raoult’s Law: pi= yi P = pi*
is cooled to 80 oC at constant pressure.
•Saturated: pi= yi P = pi*
c) Calculate the percentage of vapor that condenses
•Superheated: pi= yi P < pi*(T)
and the final composition of the gas phase, if the air
•Dew point: if the superheated vapor is cooled
is compressed isothermally to 8500 mm Hg.
•at constant pressure, the temperature at which
•the first dew forms
•Degrees of superheat: Ti - Tdp
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Gas-Liquid Systems – Multi-Component systems Bubble Point Temperature (for solution)

• Bubble point: When a liquid solution is slowly heated at
A, B, C „P, T constant pressure, the temperature at which the first
A+B+C bubble forms is the bubble point of the solution at the
given pressure.
• Raoult’s Law: pA= yA P = xA pA*
- works good for xA is close to 1 (i.e., the solution is
almost pure A)
- mixtures of structurally similar liquids (straight
(straight-chain
chain
alcohols, aromatic hydrocarbons,...)
1. pentane, hexane, heptane, 2. methanol, ethanol, propanol
3. benzene, toluene, xylene
• Henry’s Law: pA= yA P = xA HA(T)
- HA is Henry’s constant for A at temp. T
- works good for xA is close to 0 (i.e., the dilute
solution
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Dew Point Temperature Graphical Representations of VLE

Dew point: When a vapor is slowly cooled at constant
pressure, the temperature at which the first liquid droplet
forms is the dew point temperature at the given pressure.

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Solubility

• The solubility of a solid in a liquid is the

maximum amount of that substance that can
be dissolved in a specified amount of the
liquid in the equilibrium. The solubility
strongly depends on temperature.
• Saturated
• Supersaturated
• Solubility curve

Figure 6.5-1 (p. 266)

Solubilities of inorganic solutes.
Elementary Principles of Chemical Processs, 3/E by Richard M. Felder and
6/12/2012 ChE 201/shoukat@buet.ac.bd 19 Ronald W. Rousseau
Copyright © 2005 by John Wiley & Sons, Inc. All rights reserved.

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Solubility Curves Problem 6.78

• A solution containing 100 lbm KNO3 / 100 lbm

H2O at 80 oC is fed to a cooling crystallizer
operated at 25 oC. Slurry from the crystallizer
is fed to a filter where the crystals are
separated from the solution. Determine the
production rate of crystals (lbm crystals/ lbm
of feed) and the solid-liquid mass ratio (lbm
crystals/ lbm of liquid) in the slurry leaving
the crystallizer. The solubility of KNO3 is 40 g
KNO3 / 100 g H2O at 25 oC.

„o C
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6.78 solution Weather Report

„What kind of humidity?

„What is its meaning?

„Courtesy: The Daily Star, April 27, 2009

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Gas-Vapor Systems Definitions of Various Humidity

™- Saturation refers to any gas - vapor system
™- Humidity refers to air – water system
• % relative saturation/humidity
sr or hr = „pi
„X 100%
„pi*(T)

• Molal saturation
sm or hm = „pi
„P - pi

• Absolute Saturation or humidity

sa or ha = „Pi Mi
„(P- pi)Mdry
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Definitions of Various Humidity Problem 6.27

• Percentage saturation/humidity On a hot summer day the temperature is 35 oC,
„sm
sp or hp = „X 100% and barometric pressure is 103 kPa, and the
* „sm
relative humidity is 90%. An air conditioner
draws in outside air, cools it to 20 oC, and
„pi
delivers it at a rate of 12500 L/h. Calculate the
„P - pi „pi* „x 100% rate of moisture condensation (kg/h) and the
„=
„P – pi* volumetric flow rate of the air drawn from the
outside

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6.27 Solution Problem 6.38

Stack gas is emerging from a furnace at 300
oC and 105 kPa. It contains CO at a partial
2
pressure of 80 mm Hg and no CO, O2,
methane or ethane. The fuel gas fed to the
furnace containing methane and ethane is
burned with air.
air Calculate the mole fraction of
methane in the fuel and the dew point
temperature of the stack gas.

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Example 6.4.3

• Do Yourself

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Problem 6.44
Sulfur trioxide (SO3) dissolves in and reacts with water to form an
aqueous solution of sulfuric acid (H2SO4). The vapor is in equilibrium
with the solution contains both SO3 and H2O. If enough SO3 is added, all
of the water reacts and the solution becomes pure H2SO4. If still more
SO3 is added, it dissolves to form a solution of SO3 in H2SO4, called
oleum or fuming sulfuric acid. The vapor in equilibrium with oleum is
pure SO3. A 20% oleum by definition contains 20 kg of dissolved SO3
and 80 kg of H2SO4 per hundred kg of solution. Alternatively oleum
composition can be expressed as % SO3 by mass, with constituents of
the oleum considered to be SO3 and H2O.
• a) Prove that a 15.0% oleum contains 84.4% SO3
• b) Suppose a gas stream at 40 oC and 1.2 atm containing 90 mol% SO3
and 10% N2 contacts a liquid stream of 98% H2SO4 (aq), producing
15% oleum at the tower outlet. Tabulated equilibrium data indicate that
the partial pressure of SO3 in equilibrium with this oleum is 1.15 mm Hg.
Calculate i) the mole fraction of SO3 in the outlet gas if this gas is in
equilibrium with the liquid product at 40 oC and 1 atm, and ii) the ratio
of (m3 gas feed)/(kg liquid feed).

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Who is he?

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