ChE Cal 2

Lecture set 1
by
Engr. Rowie Carpio
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Introduction

PHASE DIAGRAM

Phase diagram

Phase diagram

Phase diagram

Phase diagram of water

Phase diagram

Phase diagram

Definition of terms
Vapor pressure
or equilibrium vapor pressure
or saturation pressure
is the pressure exerted by a vapor in thermodynamic
equilibrium with its condensed phases (solid or liquid) at a
given temperature in a closed system.
is an indication of a liquid's evaporation rate. It relates to the
tendency of particles to escape from the liquid (or a solid).
corresponds to a point on the vapor-liquid curve for a
substance at a given temperature T.
is the pressure for a corresponding to temperature at which a
liquid boils into its vapor phase.
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Definition of terms
Vapor pressure (continuation)
a substance with a high vapor pressure at normal
temperatures is often referred to as volatile.
A highly volatile substance is much more likely to
be found as vapor than is a substance with low
volatility, which is more likely to be in condensed
phase (liquid or solid)
High vapor pressure high volatility
Low boiling point high volatility
Example: acetone is more volatile than liquid
water at room temperature
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Definition of terms
Vapor pressure (continuation)
increases non-linearly with temperature (for any
substance)

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Definition of terms
Boiling point temperature
or saturation temerature
corresponds to the temperature on the vapor-liquid equilibrium
curve for a substance at a given pressure
normal boiling point is the boiling point of a substance at P = 1 atm
Melting point
or freezing point
corresponds to the temperature on the solid-liquid equilibrium
curve for a substance at a given pressure
Sublimation point
corresponds to the temperature on the solid-vapor equilibrium
curve for a substance at a given pressure
Triple point
the point at which solid, liquid and vapor phases can all co-exist
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Definition of terms
Critical point
or critical state
the point at which the vapor-liquid equilibrium
terminates.
at critical T , critical P and critical V
on the PT diagram corresponds to the highest P and T
at which two phases (liquid-vapor) can co-exist.
Supercritical fluid
any substance at a temperature and pressure above
its critical point, where distinct liquid and gas phases
do not exist.
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Definition of terms

Gas vs. Vapor

Vapor
gaseous substance below its critical temperature
which can be condensed by compressing or
increasing the pressure.
Gas
or noncondensable 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

In the absence of empirical data ( i.e. steam table),
vapor pressure can be estimated using the
following:
1. Antoine equation
2. Cox vapor pressure chart
3. Clausius-clapeyron

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Estimation of Vapor pressure

1. Antoine equation

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Estimation of Vapor pressure

2. Cox vapor pressure chart

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Estimation of Vapor pressure

3. Clausius-Clapeyron equation

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Estimation of Vapor pressure

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Estimation of Vapor pressure

Alternatively, Clausius-Clapeyron equation

If the Hvap is known, and is constant within the range of the

temperature given

Note: Antoine equation is more accurate than Clausius-Clapeyron

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Gibbs phase rule

Degrees of freedom (DOF)
Is the number of intensive variables that must
be specified (or fixed) to define a system.
DOF = 2+C P, C=number of components,
P=number of phases
Intensive variables do not depend on the size of the
system. Example: molar volume, density, temp,
pressure
Extensive variables depend on the size of the system.
Example: mass, volume
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Gibbs phase rule

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Gibbs phase rule

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Application of Gibbs phase rule

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Application of Gibbs phase rule

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Application of Gibbs phase rule

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Application of Gibbs phase rule

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Introduction

PHASE EQUILIBRIUM

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Definition of term

Equilibrium
A condition in which all acting influences are
canceled by others, resulting in a stable,
balanced, or unchanging system.

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Phase equilibrium

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Phase Equilibrium
Why study?
Many processes in chemical engineering do not
only involve a single phase.
Example:
brewing a cup of coffee or tea,
absorption of SO2,
distillation to recover methanol or ethanol from
aqueous solution from aqueous solution
L-L extraction
Adsorption
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Phase equilibrium systems

Solid-liquid
Solid-vapor
Gas-liquid
Vapor-liquid
Liquid-liquid

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GAS-LIQUID SYSTEMS - 1 condensable component

Example: Air-water system

System of multiple components of which only 1 may

condense at a given process conditions.
evaporation, drying, humidification involve
transfer of species from the liquid to the gas
phase.
condensation, dehumidification involve transfer
of species from the gas to the liquid phase

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GAS-LIQUID SYSTEMS - 1 condensable component

Water molecules begin to evaporate, as
the mole fraction of water increase in the
gas phase, so as the partial pressure of
water. Eventually, the net amount of
water molecules entering to gas phase
approaches zero. Such that no change
occurs in the amount or concentration of
either phase. At such condition, the:

Note:
air (or any gas) can only hold so
much water vapor (or any vapor)
If the air (or any gas) and liquid water
(or any liquid substance) are at
equilibrium, the air must be saturated
with water vapor .

Gas phase is said to be saturated with

water, referred to as saturated gas
And, the water in the gas phase is
referred to as saturated vapor.

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GAS-LIQUID SYSTEMS - 1 condensable component

Raoults Law for 1 condensable component.

For a condensable component i, at equilibrium (at saturation), the partial
pressure of i in the gas mixture must equal the vapor pressure of the
pure i liquid at the temperature of the system.
Raoults law:

The limiting case for a single condensable component

Where,
Pi = partial pressure of the component i in the gas phase
yi = mole fraction of component i in the gas phase
P = total pressure of the gas mixture
pi* = vapor pressure of the component I as liquid at the temperature of the system.

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GAS-LIQUID SYSTEMS - 1 condensable component

Raoults Law for 1 condensable component.
Raoults law:
Notes:
Pi = pi* , saturated gas
Pi < pi* , the vapor present in the gas is said to be superheated vapor
Dew point: if the superheated vapor is cooled at constant
pressure, the temperature at which the first dew forms.
Degrees of superheat: Ti-Tdp ,
where, Ti = actual temperature,
Tdp = dew point temperature
.

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GAS-LIQUID SYSTEMS - 1 condensable component

Definition of term
Saturation
A phase at equilibrium is saturated with a chemical species if it
holds as much of the species as it maximally can.
example, air at a given temperature and pressure will only hold so
much water vapor. If more water vapor were somehow
introduced into the air, condensation would occur and the extra
water vapor would come out of the air as liquid water.
In general, when a gas that is saturated with a species A is in
contact with a liquid of pure A, the rate at which molecules of A
evaporate from the liquid into the gas equals the rate at which
molecules of A from the gas condense into the liquid.
In general, when a gas that is saturated with a species A, it means
contains all the species A it can hold (maximum) at the a given T
and P.

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GAS-LIQUID SYSTEMS - One condensable component

Definition of terms

Partial saturation
is the condition at which the vapor is not in equilibrium
with the liquid phase, and the partial pressure of the
vapor is less than the vapor pressure of the liquid at the
given temperature.
Partial pressure
In a mixture of gases, each gas has a partial
pressure which is the pressure that the gas would have if
it alone occupied the same volume at the
same temperature.
The total pressure of a gas mixture is the sum of the
partial pressures of each individual gas in the mixture.

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GAS-LIQUID SYSTEMS - 1 condensable component

Saturated Gas

Humidity

specific term use to refer to the air-water

vapor system.
Saturation

refers to any gas-vapor combination.

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Means of expressing saturation

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GAS-LIQUID SYSTEMS - 1 condensable component

Things to consider!!

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Example 1:
Use of Raoults law

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Example 2
A stream of air at 100 deg C and 5260 mm Hg contains 10%
water by volume. Calculate:

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Example 2
A stream of air at 100 deg C and 5260 mm Hg contains 10%
water by volume. Calculate:

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Example 2
A stream of air at 100 deg C and 5260 mm Hg contains 10%
water by volume. Calculate:

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Example 2
A stream of air at 100 deg C and 5260 mm Hg contains 10%
water by volume. Calculate:

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Example 2
A stream of air at 100 deg C and 5260 mm Hg contains 10%
water by volume. Calculate:

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Example 3
What is the minimum number of cubic meters of dry air
at 20oC and 100 kPa necessary to evaporate 6.0 kg of
ethyl alcohol if the total pressure remains constant at
100 kPa and the temperature remains 20oC?
Assume that the air is blown through the alcohol to
evaporate it in such a way that the exit pressure of the
air-alcohol mixture is at 100 kPa.

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Example 4

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Seatwork 1

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Seatwork 2

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Seatwork 3

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Seatwork 4

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Seatwork 5

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Seatwork 6

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Example 5
Calculate the volume of 150 Kg humid air at
30oC, 30% RH, at 1 atm

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Example 6

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Example 7

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