Chemical Engineering Thermodynamics Basics

Chemical Engineering
Thermodynamics
Ms. N. DEEPA PRIYA
Assistant Professor
Department of Chemical Engineering
Kongu Engineering College
Perundurai
Thermodynamics
• Thermodynamics is a branch of science or physics concerned with

heat and temperature and their relation to energy and work
• Deals with the studies various forms of energies and their conversion
from one form to the other like electrical energy to mechanical energy,
heat to electrical, chemical to mechanical, wind to electrical etc.
Chemical Engineering Thermodynamics,

2
N. Deepa Priya, Assistant Professor, Kongu Engineering College, Perundurai.
Thermodynamics
• Thermodynamics is a physical science describing how systems change
when they interact with each other or their surroundings
• These interactions occur through transfer of energy and can be studied

either at the macroscopic scale, through changes in temperature,
pressure and volume, or at the micro-scale, by analyzing the collective
motion of their particles using statistical methods

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Nicolas Léonard Sadi Carnot
• Described as the "Father of thermodynamics”
• First to study heat engines through a scientific scope and laid the
foundations for the second law of thermodynamics through his well-
known Carnot cycle.

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Applications of Thermodynamics
• All types of vehicles that we use, cars, motorcycles, trucks, ships, aeroplanes, and many
other types work on the basis of second law of thermodynamics and Carnot Cycle. They
may be using petrol engine or diesel engine, but the law remains the same
• All the refrigerators, deep freezers, industrial refrigeration systems, all types of air-
conditioning systems, heat pumps, etc work on the basis of the second law of
thermodynamics
• All types of air and gas compressors, blowers, fans, run on various thermodynamic cycles.
• One of the important fields of thermodynamics is heat transfer, which relates to transfer of
heat between two media. There are three modes of heat transfer: conduction, convection
and radiation. The concept of heat transfer is used in wide range of devices like heat
exchangers, evaporators, condensers, radiators, coolers, heaters, etc
• Thermodynamics also involves study of various types of power plants like thermal power
plants, nuclear power plants, hydroelectric power plants, power plants based on renewable
energy sources like solar, wind, geothermal, tides, water waves etc
• Renewable energy is an important subject area of thermodynamics that involves studying
the feasibility of using different types
Chemical Engineering of renewable energy sources for domestic 5 and
Thermodynamics,
System, Surroundings & Boundary
• System: A quantity of the matter or part of the space which is under
thermodynamic study is called as system.
There are three types of system: closed system, open system and
isolated system
• Surroundings or environment: Everything external to the matter or

space, which is under thermodynamic study is called surroundings or
environment
• Boundary: The boundary that separates the system and surrounding is

called as system boundary. The system boundary may be fixed or
moving N. Deepa Priya, Assistant Professor, Kongu Engineering College, Perundurai.
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Types of Thermodynamic Systems
• Open system: The system in which the transfer of mass as well as

energy can take place across its boundary is called as an open system
Engine is an open system. In this case we provide fuel to engine and it

produces power which is given out, thus there is exchange of mass as
well as energy. The engine also emits heat which is exchanged with the
surroundings
The other example of open system is boiling water in an open vessel,
where transfer of heat as well as mass in the form of steam takes place
between the vessel and surrounding.
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• Closed system: The system in which the transfer of energy takes place
across its boundary with the surrounding, but no transfer of mass takes
place is called as closed system. The closed system is fixed mass
system
• The fluid like air or gas being compressed in the piston and cylinder
arrangement is an example of the closed system. In this case the mass
of the gas remains constant but it can get heated or cooled
• Another example is the water being heated in the closed vessel, where
water will get heated but its mass will remain same

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• Isolated system: The system in which neither the transfer of mass nor
that of energy takes place across its boundary with the surroundings is
called as isolated system
• For example if the piston and cylinder arrangement in which the fluid
like air or gas is being compressed or expanded is insulated it becomes
isolated system. Here there will neither transfer of mass nor that of
energy
• Similarly hot water, coffee or tea kept in the thermos flask is closed
system. However, if we pour this fluid in a cup, it becomes an open
system.
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Thermodynamic Equilibrium
• The two systems are said to be in thermodynamic equilibrium with
each other when they are in mechanical, chemical and thermal
equilibrium with each other
• In an isolated system when there is no change in the macroscopic

property of the system like entropy, internal energy etc, it is said to be
in thermodynamic equilibrium.

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• Mechanical equilibrium: When there are no unbalanced forces within
the system and between the system and the surrounding, the system is
said to be under mechanical equilibrium
• The system is also said to be in mechanical equilibrium when the

pressure throughout the system and between the system and
surrounding is same
• Whenever some unbalance forces exist within the system, they will get
neutralized to attain the condition of equilibrium. Two systems are said
to be in mechanical equilibrium with each other when their pressures
are same

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• Chemical equilibrium: The system is said to be in chemical
equilibrium when there are no chemical reactions going on within the
system or there is no transfer of matter from one part of the system to
other due to diffusion
• Two systems are said to be in chemical equilibrium with each other

when their chemical potentials are same.

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• Thermal equilibrium: When the system is in mechanical and
chemical equilibrium and there is no spontaneous change in any of its
properties, the system is said to be in thermal equilibrium
• When the temperature of the system is uniform and not changing

throughout the system and also in the surroundings, the system is said
to be thermal equilibrium. Two systems are said to be thermal
equilibrium with each other if their temperatures are same
• For the system to be thermodynamic equilibrium it is necessary that it

should be under mechanical, chemical and thermal equilibrium. If any
one of the above condition are not fulfilled, the system is said to be in
non-equilibrium
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• State of the system: The present status of the system described in
terms of properties such as pressure, temperature, and volume is called
the state of system
• For Eg: In a thermos flask there is 250 ml of water at 50 degree

Celsius, this is the state of the system, thermos flask. If the values of
the properties of the system changes, the state of the system also
changes. Suppose we pour out 100 ml of water and its temperature
also reduces, the state of this system is also said to have changed.

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• State : Any condition of the system is known as the state of the system.
• Process : Change of state is called process.
• Process path : The infinite states through which the system passes while
going from initial to final state is called as the process path.
• Thermodynamic Process :
When the system undergoes change from one thermodynamic state to
final state due change in properties like temperature, pressure, volume etc, the
system is said to have undergone thermodynamic process
• Various types of thermodynamic processes are: isothermal process,

adiabatic process, isochoric process, isobaric process and reversible process

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• Isothermal process: When the system undergoes change from one
state to the other, but its temperature remains constant, the system is
said to have undergone isothermal process
• For instance, in our example of hot water in thermos flask, if we

remove certain quantity of water from the flask, but keep its
temperature constant at 50 degree Celsius, the process is said to be
isothermal process
• Another example of isothermal process is latent heat of vaporization of

water. When we heat water to 100 degree Celsius, it will not start
boiling instantly. It will keep on absorbing heat at constant
temperature; this heat is called latent heat of vaporization. Only after
absorbing this heat water at constant temperature, water will get
converted into steam
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• Adiabatic process: The process, during which the heat content of the
system or certain quantity of the matter remains constant, is called as
adiabatic process
• Thus in adiabatic process no transfer of heat between the system and

its surroundings takes place
• The wall of the system which does not allows the flow of heat through
it, is called as adiabatic wall, while the wall which allows the flow of
heat is called as diathermic wall

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• Isochoric process: The process, during which the volume of the
system remains constant, is called as isochoric process
• Heating of gas in a closed cylinder is an example of isochoric process

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• Isobaric process: The process during which the pressure of the system
remains constant is called as isobaric process
• Example: Suppose there is a fuel in piston and cylinder arrangement.

When this fuel is burnt the pressure of the gases is generated inside the
engine and as more fuel burns more pressure is created. But if the
gases are allowed to expand by allowing the piston to move outside,
the pressure of the system can be kept constant
• The constant pressure and volume processes are very important. The
Otto and diesel cycle, which are used in the petrol and diesel engine
respectively, have constant volume and constant pressure processes. In
practical situations ideal constant pressure and constant pressure
processes cannot be achieved
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• Reversible process: It is kind of process which can be reversed in ay
direction following the same path and without leaving any effect on
the system and the surroundings. (All the three conditions should be
satisfied)
• Both the system and the surroundings are returned to their initial state
at the end of the reverse process
• This is possible when the net heat and work exchange is zero

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• Rapid process: It is a process which takes place at a faster rate so that
during the process the properties at one part of the system differ from
that at the other part of the system
• When a system undergoes a rapid change in state, the equilibrium of

the system is distributed during the process and the state of the system
stays away from equilibrium

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• Quasi-static process: When a process proceeds in such a manner that
the system remains infinitesimally close to equilibrium state at all
times, it is called quasi-static process
• A quasi-equilibrium process can be viewed as a sufficiently slow

process that allows the system to adjust itself so that properties at one
part of the system do not change any faster than those at the other parts

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• Cyclic process: When the system undergoes a number of changes in
states and returns back to the initial state, the system is said to have
undergone cyclic process

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Properties of the system
• The characteristics by which the physical condition of the system is
described are called as properties of system (Any characteristic of the
system is known as the property of the system)
• Some examples of these characteristics are: temperature, pressure,

volume etc and are called as properties of system
• Properties are classified as:

• Intensive and Extensive properties
• Specific and Molar properties
• Point and Path properties
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Extensive and Intensive Properties of the
System
EXTENSIVE PROPERTIES INTENSIVE PROPERTIES
• The properties of the system that • These properties do not depend on
depend on the mass or quantity of the the quantity of matter of the system
system are called extensive properties
• Some of the examples of intensive
• Some examples of extensive properties are: freezing point
properties are: mass, volume, temperature, boiling point,
enthalpy, internal energy, entropy etc temperature of the system, density,
specific volume etc
All specific properties are intensive (intrinsic) properties. Eg: Specific volume, specific enthalpy, specific entropy etc.
Chemical Engineering Thermodynamics, 25
Specific and Molar Properties of the System
SPECIFIC PROPERTIES MOLAR PROPERTIES

• The extensive properties per unit • The extensive properties per unit
mass are called specific properties mole are called the molar properties
• Eg: Specific Volume, Specific Heat • Eg : Molar Volume, Molar Heat

Capacity, Specific Internal Energy Capacity, Molar Internal Energy

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Path and Point Properties of the System
PATH PROPERTIES POINT PROPERTIES

• If the change in thermodynamic • If the change in a thermodynamic
property depends on the path property is independent of the path
followed by the system, the property followed by the system, and is
is called path property dependent only on the initial and
final conditions (state) of the system,
then the property is called a point
• Eg: Heat and Work property
• Eg : Internal Energy, Enthalpy

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Chemical Engineering Thermodynamics, 28
PATH FUNCTION POINT FUNCTION
• Dependent on path taken to establish • Independent of path taken to
property or value establish property or value
• Need multiple integrals and limits of • Can integrate using final and initial
integration in order to integrate values
• Multiple steps result in different • Multiple steps result in same value

value
• Based on established state of system
• Based on how state of system was (temperature, pressure, amount,
established and identity of system)
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Zeroth Law
• When two systems A and B are separately in thermal equilibrium with

a third system C, then the two systems A and B are also in thermal
equilibrium with each other

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First Law
• Although energy assumes many forms, the total quantity of energy is
constant, and when energy disappears in one form, it appears
simultaneously in other forms
• The first law applies to the system and its surroundings; not to the
system alone
• For any process the first law requires,
∆(Energy of the system)+ ∆(Energy of surroundings)=0

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• Mathematically,
∆U=Q+W
∆U = total change in internal energy of a system

Q=heat exchanged between a system and its surroundings
W=work done by or on the system

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Perpetual Motion of Machine of First Kind (PMM – 1):
• A machine which would continuously supply mechanical work without

absorbing energy in any other form is called perpetual motion of machine of first
kind. (According to First Law, PPM-1 is not possible)
• A perpetual motion machine of the first kind produces work without the input
of energy. It thus violates the first law of thermodynamics: the law of
conservation of energy.
Limitations of First Law of Thermodynamics:
• First law of thermodynamics does not give direction to the occurrence of any
process.
• It is the second law which clearly gives an idea about the direction of occurrence
of various processes. Chemical Engineering Thermodynamics,
33
Process Sign of heat (Q) Sign of Work (W)
Work done by the system N/A -
Work done onto the system N/A +
Heat released from the system-

exothermic (absorbed by - N/A
surroundings)

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Example 1
• A gas in a system has constant pressure. The surroundings around the
system lose 62 J of heat and does 474 J of work onto the system. What
is the internal energy of the system?
Chemical Engineering Thermodynamics, N. Deepa Priya,

35
Assistant Professor, Kongu Engineering College, Perundurai.
• To find internal energy, ΔU, we must consider the relationship between
the system and the surroundings
• Since the First Law of Thermodynamics states that energy is not

created nor destroyed we know that anything lost by the surroundings
is gained by the system
• The surrounding area loses heat and does work onto the system.
Therefore, q and w are positive in the equation ΔU=q+w because the
system gains heat and gets work done on itself
ΔU = (62J) + (474J); ΔU = 536J

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Example 2
A system has constant volume (ΔV=0) and the heat around the system
increases by 45 J.
• What is the sign for heat (q) for the system?
• What is ΔU equal to?
• What is the value of internal energy of the system in Joules?

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Answer
• negative (q<0)
• ΔU=q + (-PΔV) = q+ 0 = q
• ΔU = -45J

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The Phase Rule
Number of variables that may be independently fixed in a system at
equilibrium = Difference between total number of variables that
characterize the intensive state of the system and number of
independent equation
F = 2-π+N
Where : F – degrees of freedom

π – No of phase
N – No of chemical species
• Degrees of freedom : The number of independent variables that must

be arbitrarily specified in order to fix the intensive state of a
thermodynamic systems is the degrees of freedom, F 39
• Phase rule variables are intensive (does not depend on mass)
properties
• Phase rule variables are independent of the masses of phases and of

the total mass of the system
• Phase rule gives same information for a large and very small system
• Composition of the total system is not important
• Composition of each phase is important

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Applications of Phase Rule

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43
Heat Capacity

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Specific Heat Capacity

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Chemical Engineering

• Thermodynamics is a branch of science or physics concerned with

Chemical Engineering Thermodynamics,

• These interactions occur through transfer of energy and can be studied

Chemical Engineering Thermodynamics,

• Described as the "Father of thermodynamics”

Chemical Engineering Thermodynamics,

• Surroundings or environment: Everything external to the matter or

• Boundary: The boundary that separates the system and surrounding is

• Open system: The system in which the transfer of mass as well as

Engine is an open system. In this case we provide fuel to engine and it

Chemical Engineering Thermodynamics,

• In an isolated system when there is no change in the macroscopic

Chemical Engineering Thermodynamics,

• The system is also said to be in mechanical equilibrium when the

Chemical Engineering Thermodynamics,

• Two systems are said to be in chemical equilibrium with each other

Chemical Engineering Thermodynamics,

• When the temperature of the system is uniform and not changing

• For the system to be thermodynamic equilibrium it is necessary that it

• For Eg: In a thermos flask there is 250 ml of water at 50 degree

Chemical Engineering Thermodynamics,

• Process : Change of state is called process.

• Various types of thermodynamic processes are: isothermal process,

Chemical Engineering Thermodynamics,

• For instance, in our example of hot water in thermos flask, if we

• Another example of isothermal process is latent heat of vaporization of

• Thus in adiabatic process no transfer of heat between the system and

Chemical Engineering Thermodynamics,

• Heating of gas in a closed cylinder is an example of isochoric process

Chemical Engineering Thermodynamics,

• Example: Suppose there is a fuel in piston and cylinder arrangement.

Chemical Engineering Thermodynamics,

• When a system undergoes a rapid change in state, the equilibrium of

Chemical Engineering Thermodynamics,

• A quasi-equilibrium process can be viewed as a sufficiently slow

Chemical Engineering Thermodynamics,

Chemical Engineering Thermodynamics,

• Some examples of these characteristics are: temperature, pressure,

• Properties are classified as:

SPECIFIC PROPERTIES MOLAR PROPERTIES

• Eg: Specific Volume, Specific Heat • Eg : Molar Volume, Molar Heat

Chemical Engineering Thermodynamics,

PATH PROPERTIES POINT PROPERTIES

• Eg : Internal Energy, Enthalpy

Chemical Engineering Thermodynamics,

• Multiple steps result in different • Multiple steps result in same value

• When two systems A and B are separately in thermal equilibrium with

Chemical Engineering Thermodynamics,

• For any process the first law requires,

∆(Energy of the system)+ ∆(Energy of surroundings)=0

∆U = total change in internal energy of a system

Chemical Engineering Thermodynamics,

• A machine which would continuously supply mechanical work without

Limitations of First Law of Thermodynamics:

Work done by the system N/A -

Work done onto the system N/A +

Heat released from the system-

Chemical Engineering Thermodynamics,

Chemical Engineering Thermodynamics, N. Deepa Priya,

• Since the First Law of Thermodynamics states that energy is not

ΔU = (62J) + (474J); ΔU = 536J

Chemical Engineering Thermodynamics,

Chemical Engineering Thermodynamics,

Where : F – degrees of freedom

• Degrees of freedom : The number of independent variables that must