INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS
Volumetric properties of pure fluids : Phase behavior
NAYEF M. ALSAIFI
Motivation
methane
Suppose “methane” is available in the above cylinders at 80 oC and 100 bar, do you
think the methane is in:
A) gas phase
B) liquid phase
C) a mixture of gas and liquid
D) solid
2
Motivation
methane
What if the state conditions of the methane in the cylinders are 20 oC and 300 bar, do you think the methane
is in:
A) gas phase
B) liquid phase
C) a mixture of gas and liquid
D) solid
3
Motivation
methane
What if the cylinders contain a mixture of methane, ethane and propane at 20 oC and 300 bar, do you think
the mixture is in:
A) gas phase
B) liquid phase
C) a mixture of gas and liquid
D) solid
4
Motivation
If natural gas is transported in pipeline at very high pressure and low temperature, the natural gas
becomes a solid. The solid is called gas hydrates and it causes serious problem in industry because
gas hydrates blocks pipelines.
What are the exact pressure, temperature and compositions at which natural
gas may form gas hydrates?
5
Motivation Motivation
It is a common practice in industry to convert gases into liquids for ease of storage or transport.
An example: liquid natural gas (LNG)
Liquefied Natural Gas
How to turn gases into liquids?
6
Thermodynamics & macroscopic properties
How to answer the previous questions?
To answer the previous questions, one must understand the PHASE BEHAVIOUR of pure components
and mixtures.
Phase behavior is the behavior of vapor, liquid, and solids as a function of pressure, temperature,
and composition
The importance of the relationships between the macroscopic properties ( temperature, pressure and density (or
molar volume)) is clear from the previous questions.
For instance, understanding the relationships among them is a key for understanding the phase behaviour.
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Title of Chapter 3: Volumetric properties of pure fluids
What do we mean with volumetric properties?
Entropy, internal energy, enthalpy, density, isothermal compressibility, molar volume, excess
volume, etc. are examples of thermodynamic properties.
Some of these properties can be classified as volumetric properties which can be defined as
properties that are related to volume such as density, isothermal compressibility,
volumetric expansivity, partial molar volume etc.
How are volumetric properties obtained?
Volumetric Measurements ( experimental volumetric measurements )
Thermodynamic models (e.g. PVT relations)
Volumetric properties
give information on how thermodynamic properties vary with pressure or density at
constant temperature.
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Phase Behaviour
Phase Behaviour
“Phase behavior is the behavior of vapor, liquid, and solids as a function of pressure,
temperature, and composition” CURTIS H. WHITSON
Pressure-temperature diagram for pure compounds
(P-T diagram)
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Phase behaviour: pure Compound
A pure compound ( or a single component) is the substance that has a fixed chemical composition
such as water, air, or methanol.
A phase (liquid, gas or solid) is the part of a system that is uniform in physical and chemical properties
Gas This is a phase (gas)
Coexisting phases (here gas and liquid) are separated from each other
by definite boundary surface
Liquid
This is another phase (liquid)
A pure compound may exist in different phases: only liquid, only vapor, only solid or mixed phases (vapor-
liquid, liquid-liquid etc.).
The most common diagrams that are used to describe the behaviour of pure substance is
pressure-temperature diagram and pressure-density diagram. 10
Let’s start with a simple question !
What is the boiling point of water?
11
Pressure-temperature (P-T) phase diagram
Incomplete statement
The boiling point of water is equal to 100°C.
Complete statement
The boiling point of water is equal to 100°C only at 1 atm.
Normal boiling point*
The boiling point of any compound at 1 atm is called normal boiling point.
What if the pressure decreases?
In the southern region of Saudi Arabia in Abha city, there is Al Sooda mountain which stands 3000
meters high, the pressure is about 0.7 atm. If one boils water at the top of Al Sooda, he will notice
that the boiling point of water is about 90 °C.
If the pressure is decreased, the boiling point will decrease
What if the pressure increases?
If the pressure is 15 atm, water boils at 200 °C
If the pressure is 80 atm, water boils at 300 °C
Therefore, there is a definite pressure corresponds to each boiling point of water. This
pressure is called the vapour pressure.
* normal boiling points of some compounds are given in the appendix. 12
Pressure-temperature (P-T) phase diagram
To summarize what was in the previous slide about water boiling temperature and its corresponding vapor
pressure:
Pressure (atm) Temperature (°C)
0.7 90
The temperatures
The vapor pressure are also called
1 100
are also called saturated
saturated pressure 15 200 temperatures
80 300
Please note that these data were given in the previous slide
Vapor pressure curve
(vaporization curve
Pressure (atm)
15 or
saturation curve)
1
100 200
Temperature (°C)
The vapor pressure curve ( vaporization curve or saturation curve) gives values of temperature and pressure
where the liquid and vapor states of water can coexist at equilibrium. 13
An overview about equilibrium state
What do we mean by “equilibrium”?
Equilibrium is the state at which no changes will occur with time if the
system is left at constant pressure and temperature.
Figure A
60 oC
Vapor-liquid equilibrium
Vapor
Take the vapor-liquid system in Figure A. For example, If you control
the temperature to be 60 oC everywhere in the system and leave it for
long time, the rate of evaporation eventually will be equal to the rate of
condensation. The pressure will also be uniform everywhere inside the Liquid
system. 60 oC
14
Pressure-temperature (P-T) phase diagram
Other pure substances show similar behaviour of the P-T vapor pressure curve. For example: n-octane
60 oC 100 oC 150 oC
n-octane n-octane
n-octane
Psat= 0.104 atm Psat = 0.463 atm Psat = 1.88 atm
Vapor pressure curve
(vaporization curve
Pressure (atm)
1.88 or
saturation curve)
0.463
0.104
60 100 150
15
Temperature (°C)
Where does the vapor pressure curve end?
A thought experiment: measurement of vapor pressure at different temperature. Start the measurement
from 60 oC and increase the temperature gradually.
0.104 atm 0.463 atm 1.00 atm 1.88 atm 12.4 atm 22.8 atm 24.574 atm 26 atm
60 oC 100 oC 125.68 oC 150 oC 250 oC 295 oC 295.55 oC 298 oC
critical point
Fluid region
critical pressure
24.574
22.8 critical point
Pressure (atm)
Vapor pressure curve
1.88 (vaporization curve)
0.463
0.104 critical temperature
60 100 150 295 295.55 298 16
Temperature (°C)
Where does the vapor pressure curve end?
A thought experiment: If you decrease the pressure, vapor and liquid will continue to coexist
at equilibrium at lower temperature. Until, a new phase(solid) will coexist with the vapor and
liquid. The point at which vapor, liquid and solid coexist at equilibrium is called triple point.
30 oC 60 oC 100 oC 125.68 oC 150 oC
-56.78 oC
2.11E-05 atm 0.0243 atm 0.104 atm 0.463 atm 1.00 atm 1.88 atm
Triple point
critical pressure
24.574
Pressure (atm)
22.8 critical point
Vapor pressure curve
1.88
(vaporization curve)
0.0243
2.11E-05 critical temperature
Triple point
-56.78 30 150 295 295.55 298
17 17
Temperature (°C)
Critical and triple points for some pure compounds
The critical point is the point at which the liquid and vapor phases are not distinguishable.
Substance Temperature (oC) Pressure (atm)
water 373.95 217.67
methane -82.55 45.39
ethane 32.15 48.08
The “triple point” is the point at which the liquid, solid, and vapor phases can exist
together at equilibrium.
Substance Temperature (oC) Pressure (atm)
water -273.14 0.00604
methane -182.47 11.7
ethane -183.26 8E-4
The vapor pressure curve is the line that connects the critical point with triple point.
18 18
What about other substances?
Note all substances show similar vaporization curve.
At 1 atm, 1-butanol boils at 118 oC, benzene boils at 80.1 oC and acetone boils at 56 oC.
What does that imply?
That means 1-butanol has the strongest intermolecular forces (that hold
molecules together) and acetone has the weakest intermolecular forces. In
other words, acetone is the most volatile component and 1-butanol is the
least volatile.
Normal boiling points of some compounds
1-butanol benzene acetone
117.6 oC
80 oC
56.2 oC
1.0 atm 1.0 atm 1.0 atm 19
Some examples on vapor pressure
Example Generate the vapor pressure curve of 1-butanol using Antoine equation.
From Table B.2, 1-butanol constants are given by A = 15.3144, B = 3212.43 and C = 182.739
The Antoine equation is valid in this table for a temperature range from 37 to 138 oC.
t (oC) Psat (kPa)
37 2.004
40 2.440
50 4.534
60 8.007
70 13.52
Note that the critical temperature of 1-butanol is 289.95 oC. That means
the Antoine equation in Table B2 doesn’t cover the whole range of the 80 21.93
vapor pressure curve because the vapor pressure curve terminates at 90 34.33
the critical point.
100 52.07
Generate a table of Psat vs. t by selecting random temperature values. 110 76.76
For each temperature, you can calculate the vapor pressure as shown
in the table. 120 110.3
130 154.9
Finally, one can easily plot Psat vs. t . 138 200.1
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Some examples on vapor pressure
Example What is the boiling point of 1-butanol at 5 bar?
5 bar = 500 kPa
From Table B.2, 1-butanol constants are given by A = 15.3144, B = 3212.43 and C = 182.739
B B
ln P sat = A − t= −C 𝑡 = 170.28 ℃
t+C A − ln P sat
Example What is the boiling point of 1-butanol at 50 bar?
Be careful !
Take a look first at Table B.1, the critical pressure is 44.23 bar. Above this pressure, 1-butanol doesn’t
coexist in two phases. In fact, one should check this first (even for the previous example before finding
the boiling point.
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Back to vaporization curve: subcooled liquid
Suppose you want to boil water ( initially at T= 20 °C) where P= 1 atm. (Remember water boils at
100 °C when P= 1 atm).
Let’s represent this process graphically on PT diagram.
State 1 (20 °C, 1 atm) State 2 (100 °C, 1 atm)
Vapor pressure curve
liquid (vaporization curve)
Pressure (atm)
15
State 1 State2
1
20 100 200
Temperature (°C)
At a given pressure if a liquid is available at temperature less than its saturation temperature, then the liquid is
called a subcooled liquid. (Remember, water has a saturation temperature equals to 100 °C at 1 atm)
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Subcooled liquid means liquid is not ready yet to vaporize
Back to vaporization curve: superheated vapor
If you continue heating until you reach vapor region (state 3), the vapor is called superheated
vapor
Vapor pressure curve
(vaporization curve)
Pressure (atm)
15
State 1 State2 state 3
1
vapor
20 100 200
Temperature (°C)
Superheated vapor means if you take out little amount of heat, you still remain in the vapor phase.
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Pressure-Temperature phase diagram
Any point on the vapor pressure curve indicates that the system exists in two phases (vapor and liquid) at
equilibrium.
Vapor
Pressure
Two phases
at equilibrium
Liquid
Temperature
Any point below the vapor pressure curve indicates that the system exists in vapor phase only.
Pressure
Only vapor phase
Vapor
Vapor
Temperature
Any point above the vapor pressure curve indicates that the system exists in liquid phase only.
Pressure
Liquid Only liquid phase
Liquid
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Temperature
Pressure-Temperature phase diagram
The complete phase behaviour of a pure compound is given in the following diagram:
critical point
triple point
25
Solid and liquid coexist at equilibrium
Solid exists at equilibrium with liquid and the curve is called fusion curve.
Example: ice and water
Fusion curve
critical point
liquid
Solid
Pressure
vapor
triple point
Temperature
Change from Solid to liquid is called melting
Change from liquid to solid is called freezing
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Solid and vapor coexist at equilibrium
Solid exists at equilibrium with vapor and the curve is called sublimation curve .
Fusion curve
Critical point
liquid
Solid
Pressure
triple point
vapor
Sublimation curve
Temperature
Change from solid to vapor is called sublimation
Change from vapor to solid is called deposition
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Pressure-density (P-density) diagram
Let’s consider octane again but this time, let’s measure liquid and vapor density.
Saturated density of vapor (rV) =3.5E-6 mol/cm3
60 oC
Psat= 0.104 atm
n-octane
Saturated density of liquid (rL) =0.00586 mol/cm3
T Psat rV (mol/cm3) rL (mol/cm3)
( C)
o (atm)
60 0.104 3.5E-6 0.00586
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Pressure-density (P-density) diagram
Let’s now consider the measurements of liquid and vapor density at different temperatures up to the critical
temperature. Then, plot pressure vs. density.
60 oC 100 oC 125.68 oC 150 oC 250 oC 295 oC 295.55 oC
0.104 atm 0.463 atm 1.00 atm 1.88 atm 12.4 atm 22.8 atm 24.574 atm
critical point
T Psat rV rL
o
( C) (atm) (mol/cm3) (mol/cm3)
60 0.104 3.5E-6 0.00586
100 0.463 1.49E-5 0.00556
125.68 1 3.5E-5 0.00535 pressure Saturated
liquid density
150 1.88 6.01E-5 0.005143 Saturated
Vapor density
250 12.4 0.000448 0.003987
295.55 24.574 0.00203 0.00203
Critical density density
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Pressure-density diagram
A thought experiment: let’s start with a gas at point X. If you increase its pressure gradually at constant
temperature, its density increases. At some point, a slight change in pressure would cause a sudden increase in
density from point Y to Z. Point Y represents saturated gas while point Z corresponds to saturated liquid. The
change from Y to Z corresponds to condensation. Between Y and Z, the system is in two phases. If you
continue increase the pressure after Z, the system will be in the subcooled region (compressed liquid).
isotherms
X Vapor Critical point
T > Tc
T = Tc
Vapor Pressure
Y saturated
vapor
saturated M
Z Liquid T < Tc
liquid
GAS Co-existence region
Y Z LIQUID
M Liquid X
density 30
How to turn a gas into liquid?
Suppose a gas is defined by the state condition shown on the figure by a red point.
100
Two ways to turn the gas at this point 80
into a liquid:
Pressure (bar)
60
By increasing the pressure
By decreasing the temperature 40
liquid
20
0
Gas
80 100 120 140 160 180 200 220 240 260 280 300
Temperature (K)
31
