03 Slides

INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS
Pre-Introduction: origins of thermodynamics
NAYEF M. ALSAIFI
Origins of thermodynamics
Question: What was the most influential invention mankind ever made?
This is a very tough

and debatable
question.
Many books have been written to answer such a question
If you go over these books, you will certainly find that STEAM ENGINE is always among the top inventions.
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Origins of thermodynamics: steam engine
Questions
 What is steam Engine?

 Why is steam engine one of the greatest invention?
 What has steam engine got to do with thermodynamics?
Heron of Alexandria
Brief History of the Steam Engine
 The first known steam engine is the one that was invented
by Heron of Alexandria 2000 years ago.
 The principal idea of the steam engine is to use heat

energy to produce mechanical motion.
 There is no useful practical application of Heron’s steam

engine, it could be considered as a toy.
Heron’s steam engine
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Heron’s steam engine
Heat effects
Familiar effects of heat:
 Evaporating a liquid
 Melting a solid
(ice, for example)
Principal idea
Un-familiar effect of heat:
Heat Energy
 Heat can produce motion
Mechanical motion (work)
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Steam engine development
1650-1715 1664-1729 1736-1819
1500 years
minor
Heron improvement Thomas Savery Thomas Newcomen James Watt
no useful practical pumping water out pumping water out made

application of coal mines of coal mines a revolution
more efficient
The history of steam engine is an extensive and fascinating one. The above modifications are just a snapshot
from the real development occurred in 18th and 19th centuries.
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Origins of thermodynamics: Watt’s steam engine
James Watt’s steam engine is the most efficient in producing useful work from heat.
(i.e. converting heat to useful work)
 In 1769, James watt received a patent for his modification of Newcomen ‘s steam Engine.
 Made a great impact on the way of life for people in agriculture, manufacturing, mining, transportation and
technology
 Propelled the Industrial Revolution in Europe.
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Steam Engine Changed the World
 If you are interested in learning about how steam engine changed the world, watch this video:
https://www.youtube.com/watch/QYDJYJ_CiOY
 Old pictures showing examples of the early practical applications of steam engine in ships, trains and cars:
Two women war workers driving a steam engine

Charles Parsons' Turbinia yacht, seen
at a site for tank trials in Lincolnshire. (Photo by
here in 1897, was the first steam
Topical Press Agency/Getty Images). 5th March
turbine-powered ship.
1918
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Steam Engine from a different perspective
In 1824, Sadi Carnot, a brilliant young engineer, studied steam engine

from a different perspective:
 Unlike previous scientists and engineers, Carnot didn’t work on the

machine parts.
 Carnot emphasised that scientists were successful to improve steam

engine based on chance but not on theory.
 He tried to answer the following questions:
Is there a limit of improving steam engine?

Sadi Carnot (1796–1832)
Can we use atmospheric air instead of water vapor?
 Carnot was the first to study steam engine THEORETICALLY. He discussed his theory
in terms of temperature, pressure and volume.
He theoretically proved that
 HEAT CANNOT COMPLETELY BE CONVERTED INTO WORK

(this statement resulted in the birth of the second law of thermodynamics)
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Origins of thermodynamics: 2nd Law of thermodynamics
 As a result of Carnot's work, Clausius and Kelvin formulated the second law of
thermodynamics.
 The second law of thermodynamics can be stated as follows:

“It is impossible to take heat from a hot reservoir and convert it
completely into work by a cyclic process without transferring a
part of it to a cold reservoir.”
Rudolf Clausius (1822-1888)
 Clausius had represented the second law of thermodynamics

mathematically.
From the second law of thermodynamics a state function called
entropy (S) was defined.
At this point, don’t worry about what we mean by a state function and entropy. However, you should
Lord Kelvin (1824-1907)
keep in mind that the second law of thermodynamics introduced a new quantity called entropy.
9 9
Origins of thermodynamics: 1st Law of thermodynamics
 Besides, the work of the second law of thermodynamics, there was extensive
work that had been carried out on the amount of energy and its
transformation.
 The work on the amount of energy and its transformation had long history. The
foundation of the law of energy amount is credited to many scientists like Mayer,
Joule and Helmholtz. Their effort had contributed to the foundation of the first law
of thermodynamics.
Julius Robert von Mayer
1814-1878
 The first law of thermodynamic could be stated as
follows:
“Energy is conserved and it can be neither created
nor destroyed, but it can only be transformed into
other types”
From the first law of thermodynamics a state

function called internal energy (U) was defined.
Hermann von Helmholtz
James Joule
1821-1894
1818-1889
10 10
Origins of thermodynamics: 2nd Law of thermodynamics
 Clausius brought together the first and second laws and made the foundations of
thermodynamics.
 Kelvin was the first to call it THERMODYNAMICS where thermo means

heat and dynamics means power or strength.
 Together (i.e. thermo and dynamics), they mean the power of heat.
Rudolf Clausius (1822-1888)
 The name found widespread acceptance and was used from that time till now. It is
clear that at that time thermodynamics was the science of heat engines.
 Later, it was found that the applications of the combination of the first and the second
laws (i.e. thermodynamics) are not limited to heat engines but they could be used in
many very useful applications and in almost all sciences.
Lord Kelvin (1824-1907)
11 11
Foundation of thermodynamics
 Therefore, thermodynamics was mainly established based on the combination of two fundamental laws:
First law of thermodynamics Second law of thermodynamics
 Nowadays, thermodynamics can be defined as follows:

Thermodynamics is the physical science that deals with the study of energy, energy
transformations and its relation to matter.
 The fist law of thermodynamics is about the conservation of energy. Energy can change from one
form to another but the total amount of energy remains always constant.
 The second law of thermodynamics could be stated as “The complete conversion of heat into
work is impossible without leaving some effect elsewhere.”. It can equivalently be stated as “Heat
does not spontaneously flow from a cold body to a hot body *”.
* This statement may look different from the first statement but if you understand the second law clearly,
you will figure out that they are equivalent. 12
What has steam engine got to do with thermodynamics?
 Back to steam engine
Do we really need to know the

history of steam engine to
understand thermodynamics?
The answer is of course NO. But, it will help you to remember a very important point
about the second law of thermodynamics:
Whatever you try to improve an engine (or any thermodynamic process), there is a
limit. That limit came from the second law of thermodynamics. It is impossible to
develop an engine with 100 % efficiency. This is the main idea of the second law of
thermodynamics.
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Zeroth law of thermodynamics
 At the beginning of the twentieth century, another law had been added. This law is related to temperature
which is a central property in thermodynamics.
 First formulated by R.H. Fowler in 1931.
 The Zeroth law of thermodynamics can be stated as:

“If object A is in thermal equilibrium with object B, and object B is in thermal equilibrium with
object C, then object C is also in thermal equilibrium with object A”
Thermometer
C
Object A Object B
 The Zeroth law is a result of thermal equilibrium.

 It indicates that temperature is a well-defined physical quantity.
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Results of the zeroth, first and second laws of thermodynamics
Zeroth law of thermodynamics First law of thermodynamics Second law of thermodynamics
Resulting function Resulting function Resulting function

of state of state of state
Temperature (T) Internal energy (U) Entropy (S)
What does LAW mean?
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Why thermodynamics is important for Chemical Engineers

“Thermodynamics is the study of energy, including the
conversion of energy from one into another and the
effects that adding or removing energy have on a
system.

The Role of Thermodynamics in Chemical Engineering
• In a trip to a local supermarket, one can count over 50 different household

cleaning products, over 20 different hair care products, over 25 kinds of
toothpaste, and over 40 different insect repellents—not to mention the
multitude of process.
• Many of these household products contain 10 or more ingredients, each

of which can itself be considered a chemical products.
• These various products are manufactured in factories and chemical plants

from a wide variety of raw materials.
• Chemical engineers are responsible for designing processes to

manufacture them efficiently, economically, reliably, and (in particular)
safely.

❖ Chemical engineers are responsible for designing processes to manufacture

them efficiently, economically, reliably, and (in particular) safely.
• How many different chemical reactions are necessary?

• Can all reactions be carried out in a single reactor, or is a separate piece of
equipment needed for each reaction?
• Pure products leaving the Separation processes. How close to “pure” is required?
• How are the separations to be carried out?
• Can the separations all be completed with a single piece of equipment, or are
several distinct separation steps needed?
• At what temperature and pressure does each piece of equipment operate?

❖ Thermodynamics plays a vital role in the design of processes.
• The chemical engineer must consider thermodynamic properties when addressing

questions such as
• How much raw material and energy will it take to make 10 million pounds of
a product annually?
• What methods can be used to separate this product from any by-products and
unused raw materials?
• How much energy does it take to heat this process stream to the required temperature
of 300°F?
• How can the reactor conditions be optimized for the maximum production of the
desired product while minimizing the production of undesired by-products?

Thermodynamic vocabulary
NAYEF M. ALSAIFI
"Every science requires a special language because every

science has its own ideas."
Étienne Bonnot de Condillac, French philosopher
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System, Boundary & Surroundings
System: the part of the universe under study.
Boundary: the surface bounding the system.
Surroundings: the part of the universe outside the boundary.
Boundary
System
(usually fluids)
Surroundings
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Thermodynamics systems
An isolated system: A system that doesn't exchange ENERGY (i.e. work or heat)
or MATTER with its surroundings.
A closed system: A system that exchanges ENERGY with the surroundings but doesn't exchange
MATTER.
An open system: A system that exchanges both ENERGY and MATTER with its surroundings.
An isolated system A closed system An open system 4

Thermodynamics properties
 Temperature, pressure, mass, volumes energy, entropy, density and molar volume are examples of
thermodynamic properties
 Thermodynamic properties can be classified as intensive and extensive:
Intensive properties: independent of the mass like pressure, temperature

and density
Extensive properties: dependent of the mass (their values change with
mass) like volume, energy and entropy.
A thermodynamic property is a point (or state) function NOT a path function.

Important !
However, work and heat are path functions
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Thermodynamics properties
B
From A to B through two different paths
Path 2 Path 1
Height = 200 m
Distance traveled Distance traveled

= 210 m = 600 m
A
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Thermodynamic properties
 Height (like thermodynamic property) is a point (state) function.
 Distance (like heat and work) is a path function.
 Therefore, properties such as pressure and temperature are not dependent on the path.
The change of these properties depend only on the initial and final states of the
system.
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Thermodynamic state of a system
Daily life thermodynamics
How is his condition (state)? Is he sick?
System
Butane
gas
Similarly, in thermodynamics, we specify the state of

We determine his condition by temperature and the system by thermodynamic properties like
pressure. temperature, pressure, volume, etc.
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Thermodynamic state of a system
State of the system is the condition of the system which can be specified by pressure, temperature, volume,
density, energy etc.
 Examples:
State 1 State 2
gas gas
T1 =450 K T2 =500 K
P1=2 atm P2=2 atm
This is a state This is another state
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Process
A thermodynamic process is a way for a system to change from an initial state to
a final state.
 Different categories of processes

 Isothermal process: constant temperature process.
 Isobaric process : constant pressure process.
 Isometric (or isochoric ) process: constant volume process
 Adiabatic process : heat doesn't cross the system boundary
 Reversible process (ideal process): the initial state of the system can be restored with no
observable effects in the system and its surroundings.
 Irreversible process (real process): the initial state of the system and surroundings cannot
be restored to the original conditions .
 cyclic process a process in which the initial and final states are identical
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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
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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
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
D) solid
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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?
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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?
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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

 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
 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

(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)

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

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
There is a unique temperature above which no liquid phase occurs regardless of pressure.
This is called the critical temperature (TC)
 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
There is a unique pressure above which no vapor phase occurs regardless of
temperature. This is called the critical pressure (PC).
 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
20
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.
21
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)

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

(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.
23
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
24
Temperature
Pressure-Temperature phase diagram
 The complete phase behaviour of a pure compound is given in the following diagram:
critical point
triple point
A material that is both above the critical pressure and above the critical temperature is called a supercritical fluid.
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
26
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
27
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
28
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

29
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
Pressure –volume diagram
50 50
40 40
400oC 500 oC
Pressure (MPa)
Pressure
30
(MPa)
30
supercritical critical point
20 20 saturated vapor
300oC 10 300 oC
10 saturated liquid
200oC 100 oC
0 0
1 1.5 2 2.5 3 3.5 4 1 1.5 2 2.5 3 3.5 4
Log10 [ V(cm3/mol)] Log10 (Volume) [cm3/mol]
How to turn a gas into liquid?
 Suppose a gas is defined by the state condition shown on the figure by a red point.
LNG process : https://www.youtube.com/watch?v=QgtSoEJD9HE&t=10s
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)
But remember, logically, The term “gas” is used to describe a compound that is above its critical temperature but below its critical
pressure, and the term “vapor” is used for a compound that is below its critical temperature but above its boiling temperature.
31
Phase Change
Supercritical Fluid region
critical pressure
Pressure (atm)
100
Temperature (°C)
1
Phase Change
critical pressure
50 °C
Pressure (atm)
1 150 °C
100
Temperature (°C)
2
Phase Change
Pressure (atm)
1 2 3 4 5 6
Temperature (°C)
3
Phase Change
superheated
1 6
Subcooled vapor
liquid
1 kg Liquid 1 kg Vap
2 3 4 5
Saturated Saturated
vapor vapor Saturated
Saturated vapor
Saturated
liquid liquid Saturated liquid
≈1 kg Liquid ≈1 kg Vap
0.6 kg Liq 0.4 kg Liq
4
0.4 kg Vap 0.6 kg Vap
PVT relations: virial equation of state
Copyright Dr. Nayef M. Alsaifi, 2021 NAYEF M. ALSAIFI

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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.
Copyright Dr. Nayef M. Alsaifi, 2021 2
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A day in your company
Problem
Suppose your company received a shipment of Liquefied Petroleum Gas (LPG) cylinders . Your
supervisor told you that, each cylinder is supposed to contain 6 kg. Your supervisor asked you to double
check the amount of the gas in the cylinders because similar cylinders may contain 5 kg?

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A day in your company
Problem 2
To what pressure would a 0.1 m3 cylinder have to be filled at 20 oC if one wished to store 25 kg of
ethylene in it?

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Experimental volumetric measurements
Problems
 Equipment is costly.
 Time consuming
 Number of components is very large (hydrocarbons, ketones, alcohols, ethers, etc.)
 At some conditions, measurements are difficult to obtain.
Possible solution
 PVT relations
Before using PVT relations
 To apply PVT relations, one must first understand PVT behavior

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Volumetric properties for pure compounds
We shall study various types of PVT relations:
Equations of state
To use a certain PVT
 Ideal gas (for gases only) relation, you should always
ask yourself : “ Is this PVT
 Virial equations of state (for gases only) relation applicable for
liquids or gases?”
 Cubic equations of state (for gases and liquids)
Generalized correlations for gases
 Pitzer correlations for the compressibility factor (for gases only)

 Pitzer correlations for the Second Virial Coefficient (for gases only)
Generalized correlations for liquids

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Equation of state
 Equation of state is a relation between temperature, pressure and molar volume.
 The simplest equation of state is the ideal gas law:
PV = RT (3.1)
 Equation of state can be:
Explicit in pressure Explicit in volume
P = f(T, V) V = f(T, P)

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PVT relations: Ideal gas Ideal gas is applicable only
for gases (NOT liquids).
RT The pressure must also be
Ideal gas law V= low (≲ 1 atm).
P
Evaluation of accuracy
Example 1 Calculate the density of methane at 1.33 bar and 115 K using ideal gas law.
RT 83.14 × 115 cm3 1 1 mol

V= = = 7188.8 ρ= = 𝛒 = 2.23 kg/m3
P 1.33 mol V 7188.8 cm3
Example 2 Calculate the density of methane at 19.4 bar and 160 K using ideal gas law.
RT 83.14 × 160 cm3 1 1 mol

V= = = 685.69 ρ= = 𝛒 = 23.4 kg/m3
P 19.4 mol V 685.69 cm3
Comparison with experiment
 PVT from experiment is more reliable than PVT relations.
For example 1: For example 2:

At 1.33 bar and 115 K, ρ=2.32 kg/m3 (Experiment) At 19.4 bar and 160 K, ρ=31.1 kg/m3 (Experiment)
% error = (2.32-2.23)/2.32 *100 % ≈ 𝟒 % % error = (31.1-23.4)/31.1*100 % ≈ 𝟐𝟓 %
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Virial equation of state
 It was proposed by Kamerlingh Onnes in 1901.

 It has two different forms:
The first form is a power series expansion in reciprocal volumes (pressure-explicit form):
RT B C D (3.2)
P= 1+ + 2+ 3+ …
V V V V
where B, C, D are called second virial coefficient, third virial coefficient and fourth virial coefficient;
respectively.
The second form is a power series expansion in pressures (volume-explicit form):
RT
V= 1 + B′ P + C ′ P 2 + D′ P 3 + … (3.3)
P
where 𝐵′ , 𝐶 ′ , and 𝐷′ are called second virial coefficient, third virial coefficient and fourth virial
coefficients; respectively.

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Virial coefficients
 To use the virial equation of state, one needs to have the virial coefficients.
 Virial coefficients are function of temperature only.
 For many substances, B is available.
 For many substances, C is not known.
 Higher coefficients (D,E,..etc. ) are very difficult to obtain.

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 The virial coefficients in equation 3.2 ( i.e. B, C, D ) and equation 3.3 (i.e. 𝐵′ , 𝐶 ′ , 𝐷′ ) are related as follows:
′
B C − B2 D − 3BC + 2B3
B = ′
C = ′
D =
RT RT 2 RT 3
 If the above relations are substituted into equation 3.3, the equation is given in terms of B, C, D, etc. :
RT B C − B2 2 D − 3BC + 2B3 3
V= 1+ P+( )P + ( )P + … (3.4)
P RT RT 2 RT 3

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The first form ( pressure-explicit form)
RT B C D
P= 1+ + 2+ 3+ …
V V V V
 Truncated after two terms  Truncated after one term
RT B C RT B
P= 1+ + 2 P= 1+
V V V V V
The second form ( volume-explicit form)
RT
V= 1 + B ′ P + C ′ P 2 + D′ P 3 + …
P
RT RT
V= 1 + B′ P + C′ P2 V= 1 + B′ P
P P

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The first form ( pressure-explicit form)
RT B C D
P= 1+ + 2+ 3+ …
V V V V
RT B C RT B
P= 1+ + 2 P= 1+
V V V V V
The second form ( volume-explicit form)
RT B C − B2 2 D − 3BC + 2B 3 3
V= 1+ P+( )P + ( )P + …
P RT RT 2 RT 3
RT B C − B2 2 RT BP
V= 1+ P+( )P V= 1+
P RT RT 2 P RT

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 Re-solve examples 1 & 2 using the volume-explicit form of the virial equation of state with B:
RT BP
V= 1+
P RT
Example 3 Calculate the density of methane at 1.33 bar and 115 K using the volume explicit form of the
virial equation of state. The second virial coefficient (B) is -322.4 cm3/mol at 115 K.
RT BP 83.14 × 115 322.4 × 1.33 cm3

V= 1+ = 1− = 6866.4 𝛒 = 2.34 kg/m3
P RT 1.33 83.14 × 115 mol
virial equation of state. The second virial coefficient (B) is -162 cm3/mol at 160 K.
RT BP 83.14 × 160 162 × 19.4 cm3

V= 1+ = 1− = 523.69 𝛒 = 30.6 kg/m3
P RT 19.4 83.14 × 160 mol
Comparison with experiment
For example 3: For example 4:

At 1.33 bar and 115 K, ρ=2.32 kg/m3 (Experiment) At 19.4 bar and 160 K, ρ=31.1 kg/m3 (Experiment)
% error = (2.32-2.34)/2.32 *100 % ≈ 𝟎. 𝟖𝟔 % % error = (31.1-30.6)/31.1*100 % ≈ 𝟏. 𝟔 %
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 The previous two examples showed improvement of the virial equation of state over the ideal gas law.
However, this improvement doesn’t indicate that the virial equation of state gives always excellent
accuracy for PVT problems. Let us test the same volume-explicit equation at higher pressure to see the
problem clearly.
virial equation of state. The second virial coefficient (B) is -120.3 cm3/mol at 186 K.
RT BP 83.14 × 186 120.3 × 41.1 cm3

V= 1+ = 1− = 255.95 𝛒 = 62.7 kg/m3
P RT 41.1 83.14 × 186 mol
For example 5:
At 1.33 bar and 115 K, ρ=87.2 kg/m3 (Experiment)
% error = (87.2-62.7)/87.2 *100 % ≈ 𝟐𝟖. 𝟏 %
How to improve the accuracy
 To improve the accuracy of the virial equation of state, one needs to include higher virial coefficients

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Example 6 Estimate the molar volume of carbon dioxide at 333.15 K and 40 bar using:
a. the virial equation truncated after B using volume-explicit form
b. the virial equation truncated after C using volume-explicit form
c. the virial equation truncated after B using pressure-explicit form
d. the virial equation truncated after C using pressure-explicit form
e. Compare molar volumes obtained in a-d with experimental value, which is given by 588.95
cm3/mol
Given B=-93.2 cm3/mol and C=4384 cm6/mol2
Carbon Dioxide
 Sulfur dioxide at 333.15 and 40 bar !
A good chemical engineer should examine the state condition of carbon dioxide (i.e. 333.15 and 40 bar)
before starting calculations. Note that this is not a requirement in the question above but it is important to
keep this analysis in mind to be aware what you are exactly doing.
 You can know if carbon dioxide in subcooled, superheated or subcooled phase by phase diagram.
Sometimes, the vapor pressure curve needed. In other cases, you only need critical points. For instance,
the critical point of carbon dioxide is at 304.1 K and 73.8 bar. Therefore, our state condition in the
question is in superheated region (Check it).

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Carbon Dioxide
Example 6 Estimate the molar volume of sulfur dioxide at 333.15 K and 40 bar using:
a. the virial equation truncated after B using volume-explicit form
b. the virial equation truncated after C using volume-explicit form
Volume-explicit truncated after B:
RT B cm3
V= 1+ P = 599.25
P RT mol
% error = (588.95 -599.25 )/ 588.95 *100 % ≈ 𝟏. 𝟕𝟓 %
Volume-explicit truncated after C:
RT B C − B2 2 cm3
V= 1+ P+( )P = 593.04
P RT RT 2 mol
% error = (588.95 -593.04 )/ 588.95 *100 % ≈ 𝟎. 𝟕%

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Carbon Dioxide
c. the virial equation truncated after B using pressure-explicit form
RT B B PV B
P= 1+ PV = RT 1 + =1+
V V V RT V
RTV BRT (Quadratic equation)

PV 2 V2 − − =0
−V−B=0 P P
RT
cm3 cm3
RT/P ± RT/P 2 + 4BRT/P V = 581.46 and V = 110.99
V= mol mol
2
√ ×
% error = (588.95 -581.46 )/ 588.95 *100 % ≈ 𝟏. 𝟑 %

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Carbon dioxide
d. the virial equation truncated after C using pressure-explicit form
 The pressure-explicit form needs to be written in a more convenient for calculators:
RT B C RTV 2 BRTV RTC

P= 1+ + 2 3
V − − − =0 (check it)
V V V P P P
 By using a calculator, one can find three roots. Two of them are imagnariy numbers. The solution is equal to
592.12 cm3/mol
% error = (588.95 -592.12 )/ 588.95 *100 % ≈ 𝟎. 𝟓 %

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PVT relations: cubic equation of state
Copyright Dr. Nayef M. Alsaifi, 2021

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NAYEF M. ALSAIFI
Equation of state
Ideal gas PV=RT
Ideal gas assumptions
 Molecules are point masses
 No forces acting between molecules
Applicable only at low pressure

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Modification of the ideal gas law
In 1873, van der waals made two modifications to the ideal gas law:
 Accounting the size of molecules
 Considering intermolecular forces between molecules
RT a
P= − 2
V−b V
van der waals

 a and b are constants 1837-1923
 b is related to the size of the molecules
 a is a measure of the attractive forces between molecules

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van der waals equation of state is cubic in volume
The van der waals equation is given by:
RT a
P= − 2
V−b V
The equation can be re-written in an alternative form:
 Make a common denominator for the right hand side:
V2R T − a V − b
P=
V2 V − b
 Multiply the denominator to the other side and re-arrange the terms:
PV 3 − Pb + RT V 2 + aV − ab = 0
 Or
Pb + RT 2 a ab
V3 − V + V− =0
P P P
It is clear that van der waals equation of state is cubic in volume.
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Cubic equation of state
 Many equations have been proposed as a modification to van der waals equation of state. In general, they
are called cubic equations of state.
 widely used in industrial applications.
 Represent the PVT behavior of both liquids and vapors
 No volume explicit form
 Need iterative solution for V
 The most common cubic equations of state:
Redlich-Kwong (1949)
Soave-Redlich-Kwong (1972)
Peng-Robinson (1976)
 All cubic equations of state can be given in the following form:

V 3 + f1 T, P, 𝐜 V 2 + f2 T, P, 𝐜 V + f3 T, P, 𝐜 = 0
c is a constant. The constants could be a and b as shown in the previous slide.

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Cubic equation of state
 Examples of cubic equations of state:
 van der Waals (vdW) RT a

P= − 2
V−b V
Is there a difference
 Redlich-Kwong (RK) RT a
P= − between RK and SRK
V − b V(V + b) EOSs ? Yes, as you will
see later, a will be
different
 Soave-Redlich-Kwong (SRK) RT a
P= −
V − b V(V + b)
 Peng-Robinson (PR) RT a
P= −
V − b V V + b + b(V − b)
 The modifications in cubic equations of state have mainly been made in the attractive term.
 The repulsive term is the same for all cubic equations of state.
 The definition of a and b will NOT be the same. Each equation has its own a and b.
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van der waals equation in terms of Compressibility factor
 In the literature, it is a common practice to present cubic equations of state in terms of the compressibility factor.
What is the  At this stage, let us deal with the compressibility factor as a mathematical
compressibility variable , Z, defined by:
factor? PV
Z=
RT
 Let us now do a mathematical exercise by re-writing van der waals in terms of Z. It is a pure mathematical problem.
Van der waals is originally given as a cubic polynomial in V Pb + RT 2 a ab

V3 − V + V− =0
P P P
ZRT
 Start with the definition of Z and solve for V: V=
P
3 2
ZRT ZRT Pb + RT ZRT a ZRT ab
 Replace each V in the van der waals with : − + − =0
P P P P P P P
P 3
3
bP 2 aP abP 2
 Mutiply the above equation by : Z − 1+
RT
Z + 2 2 Z− 3 3 =0
R T R T
RT
aP bP
 Finally define A =
RT 2
and B = to get: Z3 − 1 + B Z 2 + AZ − AB = 0
RT

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van der waals in different forms
Van der waals can be given in three equivalent forms:
 Original form:
RT a
P= − 2
V−b V
Why is the point from
presenting the equation in
three different forms?
 A polynomial in terms of V:
Pb + RT 2 a ab
V3 − V + V− =0
P P P
 A polynomial in terms of Z:
Z 3 − 1 + B Z2 + AZ − AB = 0
It is just a matter of convenience. One form will
A=
aP
B=
bP be sufficient. Choose whatever form you like.
RT 2 RT
All cubic equations of state can be written in the above three forms. The first and third forms are more common.
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Cubic equations of state
Cubic equations of state in the original and the Z forms
van der Waals Redlich-Kwong Soave-Redlich-Kwong
RT a RT a RT a
P= − 2 P= − P= −
V−b V V − b V(V + b) V − b V(V + b)
Z 3 − 1 + B Z 2 + AZ − AB = 0 Z 3 − Z 2 + (A − B − B2 )Z − AB = 0 Z 3 − Z 2 + (A − B − B2 )Z − AB = 0
All these equations

of state contain P, T,
V, a and b. The
Peng-Robinson question is how to
define a and b?
RT a
P= −
V − b V V + b + b(V − b)
Z 3 + B − 1 Z 2 + A − 2B − 3B2 Z − AB + B2 + B3 = 0

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Can you explain in your own words why the 2-Phase segment of the P-v isotherm should correspond to one single point in the P-T diagram?
What about the critical point in the P-T diagram? Which P-v isotherm could that correspond to?
a and b in cubic equations of state
 To determine a and b, let us proceed in two steps:
Step 1 review some basic mathematics : slope and inflection point
Slope
 As an example, let us focus on a simple function: y = x 3
y Slope
dy dy
= 3𝑥 2
dx dx
B
0 dy
Find the slope at 𝐴 = 3𝑥 2 = 3(−1)2 = 3
dx
-1 A
dy
Find the slope at B = 3𝑥 2 = 3(0)2 = 0
dx
-1 0 x
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 To understand what a and b are, we have to study two steps:
Step 1 let us review some basic mathematics : slope and inflection point
 As an example, let us focus on a simple function: y = x 3
Inflection point
y
 Two conditions must be satisfied:
B I. The point at which the second derivative of a function is
0 equal to zero or undefined
-1 A II. To have an inflection point we must check that the sign of

the second derivative is different on each side of the point.
-1 0 x
𝑑2y 𝑑2y
Is point B an inflection point? = 6x =6 0 =0 II is also satisfied (check it) YES
d𝑥 2 d𝑥 2
𝑑2y 𝑑2y
Is point A an inflection point? = 6x = 6 −1 = −6 NO
d𝑥 2 d𝑥 2
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Step 2 Study the critical isotherm behavior at the critical point
∂P
 At the critical point, the slope of the critical isotherm on P-V diagram is zero: ∂V T
=0
∂2 P
 At the critical point, the critical isotherm on a P-V diagram has an inflection point: ∂V 2 T
=0
 The above partial derivatives is a mathematical definition of the critical point.
critical isotherm
V
 van der Waals used these partial derivatives to determine a and b in terms of critical constants (Tc & Pc ).

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How van der Waals find a & b
 Based on the definition of the critical point, we now know that
∂P 𝜕2P
=0 (1) =0 (2)
∂V T
∂𝑉 2 T
 Determining the derivatives based on the van der waals equation of state gives the following two equations:
∂P RT 2a ∂2 P 2RT 6a
=− + 3 = −
∂V T
V−b 2 V ∂V 2 T
V−b 3 V4
 At the critical point, T = Tc , P = Pc and V = Vc . Apply (1) and (2), we obtain:
RTc a RTc 2a 2RTc 6a

Pc = − 2 0 =− + 0 = −
(Vc − b) Vc Vc − b 2
Vc 3 Vc − b 3
Vc 4
 Now, we have three equations with three unknowns (Tc , Pc & Vc ). Solve the three equations simultaneously to get:
8𝑎 𝑎
Vc = 3b Tc = Pc =
27𝑏𝑅 27𝑏2
 From the above three equations, it could be shown that:
27 R2 Tc2 1 R Tc
a= b=
64 Pc 8 Pc

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Limitation of VDW CEOS
• The value of ‘b’ is not

constant but varies with
pressure and temperature.
• The value of Vc is not equal
to 3b, but it is equal to “b”,
in some cases and in other
cases equal to 2b.
• The value of Z= RTC/PCVC is
not equal to 8/3 but it is
usually more than 3 for
most of the gases
Solution of Cubic EOS
Volume roots from cubic equations of state
Problem statement temperature and pressure are given for a certain substance, estimate molar volume roots.
 The molar volumes are obtained by iterative methods: hand calculations or calculators.
 Examples of iterative methods by hand calculations: see the next four slides.
 Example of iterative methods by calculator: see the last slide in this file.
 The use of calculators can simplify the problem. Particularly, if one makes cubic equations of state
in the polynomial form.
 Bear in mind that the cubic EOS has a maximum of three roots. The roots are not necessarily to be all real.
It depends on the temperature in the problem statement. One needs to compare T with Tc as follows:
 One positive real root (supercritical fluid)
If T > Tc
 Two imaginary numbers (non-physical)
If T = Tc  Three equal real values (the critical molar volume)
If T < Tc Three real roots:

 The highest positive real root represents the molar volume of the vapor state
 The lowest positive real root represents the molar volume of the liquid state
 The third real root has no physical meaning
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Volume roots from van der Waals EOS: hand calculations
 Check the phase of the substance at the given temperature and pressure (superheated, subcooled, etc.)
 Use Table B1 in the appendix and get the values of the critical constants (Tc , Pc ).
27 R2 Tc2 1 R Tc
 Estimate a and b from their own definitions: a= b=
8 Pc
64 Pc
 Follow the following iterative procedure to estimate molar volume of vapor (or vapor-like) phase:
RT
Initial guess V0 =
P
RT a (Vn − b)
The iterative formula Vn+1 = +b− n = 0, 1, 2, … . .
P P Vn 2
 Follow the following iterative procedure to estimate molar volume of liquid (or liquid-like) phase:
Initial guess V0 = b
RT + bP − Vn P n = 0, 1, 2, … . .
The iterative formula Vn+1 = b + Vn 2
a

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Volume roots from Redlich-Kwong EOS: hand calculations
 Use Table B1 in the appendix and get the values of the critical constants (Tc , Pc ).
0.42748R2 Tc2.5 0.08664R Tc
 Estimate a and b from their own definitions: a= b=
Pc T Pc
RT
Initial guess V0 =
P
RT a (Vn − b)
The iterative formula Vn+1 = +b− 𝑛 = 0, 1, 2, … . .
P P Vn Vn + b
RT + bP − Vn P
The iterative formula Vn+1 = b + Vn (Vn + b) 𝑛 = 0, 1, 2, … . .
a

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Volume roots from Soave-Redlich-Kwong EOS : hand calculations
 Use Table B1 in the appendix and get the values of the critical constants (Tc , Pc , 𝜔).
2
 Estimate 𝑇𝑟 , then 𝜅 and 𝛼: κ = 0.48 + 1.574ω − 0.176ω2 α = 1 + κ 1 − Tr
0.42748 α R2 Tc2 0.08664R Tc

 Estimate a and b from their own definitions: a=
Pc
b=
Pc
RT
Initial guess V0 =
P
RT a (Vn − b)
P P Vn Vn + b
RT + bP − Vn P
The iterative formula Vn+1 = b + Vn (Vn + b) 𝑛 = 0, 1, 2, … . .
a

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Volume roots from Peng-Robinson EOS : hand calculations
 Use Table B1 in the appendix and get the values of the critical constants (Tc , Pc , 𝜔).
2
 Estimate 𝑇𝑟 , then 𝜅 and 𝛼: κ = 0.37464 + 1.54226ω − 0.26992ω2 α = 1 + κ 1 − Tr
0.45724 α R2 Tc2 0.07780R Tc

 Estimate a and b from their own definitions: a=
Pc
b=
Pc
RT
Initial guess V0 =
P
RT a Vn − b
P P Vn + (1 − 2)b Vn + (1 + 2)b
RT + bP − Vn P
The iterative formula Vn+1 = b + Vn + (1 − 2)b (Vn + (1 + 2)b)
a
𝑛 = 0, 1, 2, … . .

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Example on Redlich-Kwong EOS: hand calculations
Example Estimate the molar volumes of saturated liquid and saturated vapor for n-octane at 2.15 bar and 427.85 K.
 The question says that the system is at saturation.
 From Table B1, Tc = 569.4 K and Pc = 24.97 bar

0.42748R2 Tc2.5 0.08664R Tc
 Estimate a and b from their own definitions: a= = 4.426 × 107 ? b= = 164.26 ?
Pc T Pc
(Note that a & b are not dimensionless; they have units. Try to get rid of ? and obtain the correct units)
Vapor molar volume Liquid molar volume
RT cm3 cm3
Initial guess V0 = = 16545 Initial guess V0 = 164.26
P mol mol
RT a V0 − b cm3 RT + bP − V0 P cm3
V1 = +b− = 15489 V1 = b + V0 V0 + b = 208
P P V0 V0 + b mol a mol
RT + bP − V1 P cm3
RT a V1 − b cm 3 V2 = b + V1 V1 + b = 226
V2 = +b− = 15408 a mol
P P V1 V1 + b mol RT + bP − V2 P cm3
V3 = b + V2 V2 + b = 235
a mol
RT a V2 − b cm3
…
V3 = +b− = 15401
P P V2 V2 + b mol
RT a V3 − b cm3 V6 = b + V5 V5 + b = 243
V4 = +b− = 15401 a mol
P P V3 V3 + b mol
V7 = b + V6 V6 + b = 243
a mol
All rights reserved
Example on PR EOS by calculator
Example Estimate the molar volumes of oxygen at 327.15 K and 200 bar using Peng-Robinson EOS?
 Let us try to find the molar volumes starting from the compressibility factor (Z) form:
Z 3 + B − 1 Z 2 + A − 2B − 3B2 Z − AB + B2 + B3 = 0
 For oxygen the critical constants and acentric factor are given by: Tc = 154.9 K, Pc = 50.43 bar and ω = 0.022.
 Therefore,
2
κ = 0.37464 + 1.54226ω − 0.26992ω2 = 0.40844 α = 1 + κ 1 − Tr = 0.66401
0.45724 α R2 Tc2 0.07780R Tc

a= = 9.9850 × 105 b= = 19.868
Pc Pc
aP bP
A= = 0.26994 B= = 0.14609
RT 2 RT
 The only unknown in the above highlighted (in yellow) equation is Z. If we use calculator, we get the following roots:
Z=0.96002 V= 130.56 cm3/mol

Z=-0.05306 + 0.11306i ZRT V= -7.2155 + 15.376i
V=
Z=-0.05306 - 0.11306i P V= -7.2155 - 15.376i
 Note that 327.15 K and 200 bar is in the supercritical fluid.

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Another form of Generic cubic equation of state
• Generic cubic equation of state: generic form from which all

special cases can be derived using the table on the next slide
RT a(T )
p= −
V − b (V + b )(V + b )
• where:
• ε and σ : pure numbers, same for all substances
• α(Τ) and b: substance dependent
• Example: when a(Τ) = α and ε = σ = 0, we get the

Van der Waals EoS
Generic cubic EoS parameters
RT a(T )  (T )R 2TC2 RTC
p= − a(T ) =  b=
V − b (V + b )(V + b ) pC pC
• For RK, SRK, and PR EoS, the α(Τ) is a function of reduced temperature (Tr)
and acentric factor (ω)
Another form of Generic cubic equation of state
Z −
• For vapor-like root (VG )(largest root): Z = 1 +  − q
(Z +  )(Z +  )
Pr  (Tr )
where:  =  and: q =
Tr Tr
• This equation is typically solved by numerical iteration
• Starting value is Z = 1, substituted in the right side of the equation
• for Liquid-like root (VL )(smallest root): 1+  − Z 

Z =  + (Z +  )(Z +  ) 
• Also solved by numerical  q 
iteration
• Start iteration at Z = β
• Once Z is found → V = ZRT/p
Generic cubic EoS parameters
• Also for the generic cubic EoS the parameters a and b can be
expressed in terms of the critical parameters:
 (T )R 2TC2 b=
RTC
a=
pC pC
• where: Ψ and Ω: pure numbers
• Example: when α(Τ) = 1 and Ψ = 27/64 and Ω = 1/8,

we get the Van der Waals EoS
• Practice Problem # 3.6, 3.29, 3.42, 3.50, 3.59, 3.79 from textbook
PVT relations: Corresponding State Theory

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Corresponding theory
 One way to obtain a generalized PVT correlation is to utilize the theorem of corresponding state.
 In this lecture, the theorem of corresponding state is introduced; then it is applied to construct
generalized correlations for gases and liquids:
Generalized correlations for gases
Pitzer correlations for the compressibility factor

Pitzer correlations for the Second Virial Coefficient
Pitzer correlations for the Third Virial Coefficient

All rights reserved
Corresponding theory: Generalized correlation !
Question What does correlation mean? What is generalized correlation?
 Correlation means how two or more variables are related. For example, how P, V and T are related.
 If one variable changes and causes a change in another variable, we say that the two variables are
correlated.
 Correlation may imply how to choose the best relationship that fits data. For example, how to find
the best relationship for PVT (i.e. PVT relation) that can fit experimental data.
 “Generalized correlation” indicates a general correlation that is applicable for different types of
compounds. For example, a PVT correlation for methane is not necessarily applicable for ethane,
propane etc. However, if they can apply for methane, ethane, propane, we can call it a generalized
correlation.
 Can we describe any correlation by “generalized”? No, what makes the PVT correlation
generalized is the corresponding state theory.

All rights reserved
Corresponding theory: Let’s learn by an example
 A simple way to understand the theorem of corresponding state is to follow the following example.
 Experimental PVT data for nitrogen, oxygen, argon and xenon are obtained from NIST*:
nitrogen oxygen argon xenon
Recall The compressibility factor (Z), reduced temperature, reduced pressure are respectively given by:
PV T P
Z= Tr = and Pr =
RT Tc Pc

All rights reserved
 Plot PV/RT vs. T for nitrogen, oxygen, argon and xenon on the same figure.
PV/RT
 Conclusion: nitrogen, oxygen, argon and xenon show similar trend but with different
PV/RT values at any specific temperature.

All rights reserved
 Let us make a slight change by dividing the temperature values for any component with its own critical temperature.
Then plot PV/RT vs. T/Tc for the three components.
 Critical temperature of methane, ethane and propane are given in the following table:
nitrogen oxygen argon xenon

Tc (K) 126.2 154.6 150.7 289.7
PV/RT
T/Tc
 Conclusion: Methane, ethane and propane show almost identical curves. The PV/RT values at any
specific T/Tc are equal for all components. 6
 Let us repeat what we have done so far with pressure (not temperature).
PV/RT
Figure A Figure B
P P/Pc
 Figure A shows that nitrogen, oxygen, argon and xenon show similar trend but with different PV/RT values at any
specific pressure.
 Figure B shows that methane, ethane and propane show almost identical curves. The PV/RT values at any specific
P/Pc are equal for all components.
All rights reserved
Theorem of corresponding states
 From the previous slides, it was noticed that nitrogen, oxygen, argon and xenon have almost the same
compressibility factor at the same reduced temperature and reduced pressure.
 The above conclusion was deduced by van der waals long time ago*. He noticed that the vapor pressure and
coexistence curves in reduced coordinates must be the same for all fluids.
 van der Waals’s conclusion became known as the theorem of corresponding states.
Do you think if one

Do you think Z vs. obtain PVT data from
reduced volume may van der waals EOS,
follow the same the theorem is still
behavior found with valid?
reduced temperature
and pressure?
Check it yourself using the given data Check it yourself by obtaining the PVT data from van der waals EOS
Copyright Dr. Nayef M. Alsaifi, 2021 *Fink, Johannes Karl, Physical Chemistry in Depth, 2009. 8
All rights reserved
Theorem of corresponding states
 It sounds an interesting theorem but the question is what one may get from this theory?
Tr Pr Z
 Think about it: all fluids have the same Z with the same Tr and Pr. Let us assume
the data are similar to the data in the Table.
0.51509 0.005125 0.98808
0.55471 0.011351 0.97856
0.59433 0.022393 0.96493
 The data can be used to develop ONE general correlation applicable for all fluids:
0.63395 0.040306 0.94669
0.67358 0.067396 0.92346
Z = f(Tr , Pr )
0.7132 0.10615 0.89494
0.75282 0.15917 0.86078
 If T and P are given, one can easily find Z. Therefore, if Z is obtained, one can 0.79244 0.22919 0.82048
find V:
0.83207 0.31901 0.77323
ZRT
V= 0.87169 0.43165 0.71749
P
0.95093 0.73932 0.56355
0.99055 0.94436 0.4213
 Indeed, this is what K. S. Pitzer did. Therefore, we can say Pitzer developed generalized correlations
using the corresponding state theory.
9
 For simple fluids ( such as argon, oxygen, krypton, etc.), the corresponding state theory for the compressibility needs
only two parameters (Two-parameter law of corresponding states):
“All fluids, when compared at the same reduced temperature and pressure, have approximately the same
compressibility factor, and all deviate from ideal-gas behavior to about the same degree.”
 For complex fluids, the corresponding state theory for the compressibility needs one more parameter (Three-parameter
law of corresponding states):
“All fluids having the same value of ω, when compared at the same Tr and Pr, have about the same value of Z, and
all deviate from ideal-gas behavior to about the same degree.”
Question Why do we need one more parameter (w)? Does the corresponding state theory fail for complex fluids?
The calculation of the thermodynamic properties using the corresponding state theory for non-spherical (or polar
components) deviates form those of spherical molecules. This is why the acentric factor was invented to make a
correction for the deviation.
10
Acentric factor
 The acentric factor was proposed by Pitzer in 1955
 The acentric factor can be found in books and handbooks. Table B1 in the Appendix gives acentric factor
for many compounds.
 One can also estimate the acentric factor from the following equation:
Substance Acentric factor
methane 0.012
ω = −1 − log10 Prsat Tr =0.7
ethane 0.100
propane 0.152
 The acentric factor is zero for simple substances such as argon and krypton.
n-butane 0.200
n-pentane 0.252
 The acentric factor is non-zero for non-spherical substances. n-hexane 0.301
n-heptane 0.350
 The value of acentric factor may approach one for severely non-spherical substances.
 The table on the right gives some values of acentric factor. Notice the change of the values
compared to the size of component.
11
PVT relations: Corresponding State Theory

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 Generalized correlations are developed based on theorem of corresponding states.
 They are called “generalized correlations” because they are applicable to all substances.
 The compressibility factor is determined from the following equation: Z = Z0 + ωZ1
T P
 Z & Z are functions of reduced temperature and reduced pressure:
0 1 Tr = Pr =
Tc Pc
 The values of Z0 & Z1 could be obtained from Tables and Figures.
 The most widely used method is Lee and Kesler method, where Z 0 & Z1 can be taken from figures (e.g.
Figure 3.11) or tables. For tables, see Appendix D.1 and D.2 :
PV
 If Z is estimated, the definition of Z is used to estimate the required variable: Z= 2
RT
Example Determine Z0 and Z1 from Tables D.1 and D.2 at Pr= 0.2 and Tr=0.35.
 At the given reduced temperature and pressure, Z0 is equal to 0.0522.
 At the given reduced temperature and pressure, Z1 is equal to -0.0185.
3
Application and limitations: Lee and Kesler correlation
Lee-Kesler correlation is a Pitzer-type correlation, one should be aware about the applications and limitations:
 It can be used at high pressures.
 It is accurate for non-polar gases and slightly polar gases.
 It not accurate for highly polar gases (e.g. ketones and esters)
 It not accurate for gases that associate (e.g. acids, alcohols and water)
 It can be used for subcooled liquid (not high accurate)
 Don’t use it close or at the saturation conditions.
4
Application and limitations
Problem Determine the molar volume of n-butane at 510 K and 25 bar?
Z = Z 0 + ωZ1
 Find the critical constants : Tc = 425.1 K Pc = 37.96 bar
 Determine the reduced temperature and reduced pressure from Appendix G:

T P
Tr = Tr = 510/425.1=1.2 Pr = Pr = 25/37.96=0.659
Tc Pc
 Find the acentric factor value from Appendix G: ω = 0.2
 Determine Z0 and Z1 from Appendix D.1 & D.2:
Z 0 =0.865 and Z1 =0.038. By using the highlighted yellow equation above, Z is given by:
Z = 0.865 + 0.2 ∗ 0.038 = 0.873
ZRT 0.873 ∗ 83.14 ∗ 510

 Calculate V V= = = 1480 cm3 /mol
P 25
5
What if the pressure is the unknown variable
 If the pressure is the unknown, the reduced pressure cannot be obtained. Thus, an iterative
procedure is necessary.
Problem statement T and V are given, estimate P
Procedure:
1. Give an initial guess for pressure by:
ZRT
P=
V
and assume Z=1
2. Now, pressure is known and new Z can be found from:
Z = Z 0 + ωZ1
3. Use the new Z in step 1 and continue until not change occurs.
 Apply the above procedure on n-butane if you know its temperature (510 K) and molar volume
(1480 cm3 /mol) to find the pressure? (Answer is 25 bar) 6
More applications for the corresponding state theory
It is awesome to make
a generalized equation
for all fluids.
Can I apply this generalized

approach to find the virial
coefficients (B, C,..)?
Answer is YES. It is possible to create correlations to estimate virial coefficients

based on the corresponding state theory.
Extension of Pitzer correlation for:
 Pitzer correlations for the Second Virial Coefficient

 Pitzer correlations for the Third Virial Coefficient
7
Pitzer correlations for the Second Virial Coefficient
 The virial equation of state (volume-explicit form) is given by: Can we apply the corresponding
state theory to the virial equation
RT BP of state? Why not !
V= 1+
P RT
 First write the virial equation of state in terms of compressibility factor
BP
Z= 1+
RT
 Write the above equation in terms of reduced pressure and reduced temperature.
T
Tr = T = Tr Tc BP Pr
Tc Z=1+ = 1+B
P RT Tr
Pr = P = Pr Pc
Pc
BPc
B=
RTc
Pr
Z= 1+B
Tr
 Question How to determine B ?

8
How to determine 𝐵
 Pitzer and coworkers suggested the following correlation:
B = B0 + ωB1
0.422 0.172
B0 = 0.083 − B1 = 0.139 −
Tr1.6 Tr4.2
 Therefore, if B is found, the compressibility factor can be obtained from
Pr
Z= 1+B
Tr
 Remember: if the virial equation of state is truncated after the first term, it is only applicable to moderate
pressures.
9
Pitzer correlations for the third Virial Coefficient
 If the third viral coefficient is included, the virial equation of state can be given as:
2
Pr Pr
Z= 1+B +C
Tr Z Tr Z
 The C can be given as Pitzer-type correlation:
C = C0 + ωC1
0.00313 0.02432 0.05539 0.00242

C0 = 0.01407 − + C1 = −0.02676 + −
Tr10.5 Tr Tr2.7 Tr10.5
10
Pitzer correlations for the Virial Coefficients
I used the virial EOS before I know the

corresponding state theory. I don’t know what
the point of using the corresponding state
theory with the virial EOS
 Let us take an example for calcification. In a previous lecture, we have solved the following
question:
 Suppose, we don’t know the value of B, how you can solve it the questions.
BRTc
 One way to get the B is to use B= and B = B0 + ωB1
Pc
 To get B0 and B1, you only need reduced temperature (see the definitions of B0 and B1 in the pervious slides).
11
Revisited the virial equation of state
Example Estimate the second virial coefficient for methane at 115 K. Compare it
with the one obtained from experiment -322.4 cm3/mol.
12
Revisited the virial equation of state
 A method to calculate the second virial coefficients
BRTc
B=
Pc
 A method to calculate the third and third virial coefficients
C R2 Tc2
C =
Pc2
13
 To estimate the molar volumes of saturated liquids, one popular equation is Rackett equation:
1−Tr 2/7
V sat = Vc Zc
 The critical constants are given in Appendix B (Table B. 1)
Example Calculate the saturated liquid of propane at T=190 and compare the results to
The experimental value which is 70.433 cm3/mol?
From Table B1 Vc = 200 cm3/mol Tc=369.8 K Zc=0.276
T
Tr = = 190/369.8 = 0.514
Tc
2/7
V sat = 200 ∗ (0.276) 1−0.514 = 70.161 cm3/mol
% error = 0.39 14

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INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS

Pre-Introduction: origins of thermodynamics

This is a very tough

Many books have been written to answer such a question

 What is steam Engine?

 The principal idea of the steam engine is to use heat

 There is no useful practical application of Heron’s steam

Heron’s steam engine

Familiar effects of heat:

Mechanical motion (work)

1650-1715 1664-1729 1736-1819

no useful practical pumping water out pumping water out made

Two women war workers driving a steam engine

In 1824, Sadi Carnot, a brilliant young engineer, studied steam engine

 Unlike previous scientists and engineers, Carnot didn’t work on the

 Carnot emphasised that scientists were successful to improve steam

 He tried to answer the following questions:

Is there a limit of improving steam engine?

He theoretically proved that

 HEAT CANNOT COMPLETELY BE CONVERTED INTO WORK

 The second law of thermodynamics can be stated as follows:

 Clausius had represented the second law of thermodynamics

From the first law of thermodynamics a state

 Kelvin was the first to call it THERMODYNAMICS where thermo means

First law of thermodynamics Second law of thermodynamics

 Nowadays, thermodynamics can be defined as follows:

 Back to steam engine

Do we really need to know the

 First formulated by R.H. Fowler in 1931.

 The Zeroth law of thermodynamics can be stated as:

 The Zeroth law is a result of thermal equilibrium.

Zeroth law of thermodynamics First law of thermodynamics Second law of thermodynamics

Resulting function Resulting function Resulting function

What does LAW mean?

• In a trip to a local supermarket, one can count over 50 different household

• Many of these household products contain 10 or more ingredients, each

• These various products are manufactured in factories and chemical plants

• Chemical engineers are responsible for designing processes to

❖ Chemical engineers are responsible for designing processes to manufacture

• How many different chemical reactions are necessary?

❖ Thermodynamics plays a vital role in the design of processes.

• The chemical engineer must consider thermodynamic properties when addressing

"Every science requires a special language because every

Étienne Bonnot de Condillac, French philosopher

System: the part of the universe under study.

Boundary: the surface bounding the system.

Surroundings: the part of the universe outside the boundary.

An isolated system A closed system An open system 4

 Thermodynamic properties can be classified as intensive and extensive:

Intensive properties: independent of the mass like pressure, temperature

A thermodynamic property is a point (or state) function NOT a path function.

Distance traveled Distance traveled

 Height (like thermodynamic property) is a point (state) function.

 Distance (like heat and work) is a path function.

Daily life thermodynamics

How is his condition (state)? Is he sick?

Similarly, in thermodynamics, we specify the state of

This is a state This is another state

 Different categories of processes