Thermodynamics

Index

Topics Page

1. Basic Concepts & Zeroth Law of Thermodynamics 2

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2. First Law of Thermodynamics 8

3. Second Law of Thermodynamics 10

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4. Entropy Availability and Irreversibility

5. Properties of Pure Substances

6. Thermodynamic Relations & real Gas Mixtures

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 Basic Concepts & Zeroth Law of Thermodynamics

System

A system can be defined as a quantity of matter (control mass) or a region

(control volume) in space selected for the study.

SURROUNDING- Everything external to the system is known as surrounding or

the environment. Energy interaction is studied between the system and
surroundings i.e. every energy leaving the system will be absorbed by the
surrounding and vice versa.

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BOUNDARY- An imaginary or real surface that demarcates the system from
its surroundings is known as the boundary. The boundary is the surface of

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contact between the system and surrounding, thus, shared by both the system
and the surroundings. Mathematically, the boundary has no thickness, and
can neither occupy any volume in space nor contain any mass. The boundary
may either be moving or fixed.

Universe- A system and its surroundings together constitute the universe.

Everything is contained in the universe, so everything occurring whether
energy transfer or transformation or losses remains inside the universe.
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Types of System

Depending upon the mass and energy interaction.

(i) Open System – When there is mass as well as energy transfer across the
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boundary, that type of system is called an Open system. Example - air

compressor, boiler, pump, IC engine with valve open, etc. The majority of
engineering devices come under this category.
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 (ii) closed system –When in a system, the mass remains fixed or constant but
there may be energy transfer into or out of the system i.e. no mass transfer
occurs across the system boundary but only energy transfer. Example – Tea
in kettle, automobile engine with valve closed etc.

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(iii) Isolated system - When there is no mass and energy interaction taking
place between the system and the surroundings, such systems are called
isolated systems. It is of fixed mass and energy, and there is no mass or
energy interaction across the system boundary. Example – thermo-flask,
Universe
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Macroscopic v/s Microscopic Approach

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Macroscopic Approach - When a certain quantity of matter is considered,

without getting into molecular level, such systems are called Isolated systems
(also called as classical approach). Every property will be the average of that
property of each molecule passing through that space.

Microscopic Approach - When study is made on a molecular level as matter is

composed of a large number of molecules, such approach is called a
Microscopic approach. The behavior of the gas is determined by considering
the behavior of each molecule.
 CONCEPT OF CONTINUUM- The concept of the continuum is the idealization
of the continuous description of matter where the properties of the matter are
considered as continuous functions of space. The space between the
molecules (mean free path) is almost zero or negligible when compared to the
size of the system.

Extensive Properties v/s Intensive Properties

(i) Extensive Properties – The properties dependent on mass are known as

extensive properties (sometimes known as extrinsic properties). Since, the
mass of the specimen changes, the value of extensive properties will also

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change according to it.
Example – Volume, Enthalpy, Weight, etc.

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(ii) Intensive Properties – Extrinsic properties per unit mass, are intensive
properties. These properties are independent of the mass of the system (also
known as intrinsic properties). It is a system property, independent of
quantity.
Example – Pressure, Density, Viscosity, specific energy, specific enthalpy etc.

Thermodynamic Equilibrium

When no change in macroscopic properties is observed, a system is said to

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be in a state of thermodynamic equilibrium. A system will be in a state of
thermodynamic equilibrium if the following conditions are met:

(i) Mechanical Equilibrium - without the presence of an unbalanced force

within the system itself and also between the system and the surroundings.
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(ii) Chemical equilibrium - an absence of any chemical reaction or transfer of

matter from one part of the system to another.
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(iii) Thermal equilibrium - When a system exists in mechanical as well as a

chemical equilibrium when separated from its surroundings by a diathermic
wall (diathermic means ‘which allows heat to flow’).

Even when one of these conditions is not met, the system can't be in
thermodynamic equilibrium.

The thermodynamic properties are defined only for thermodynamic

equilibrium states.
 PROCESS - Any change of state that a system undergoes, from one
equilibrium state to another equilibrium state is known as a process.

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PATH - The succession of states passed through during a change of state
from an initial condition to the final required condition, is called the path of the
change of state.

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CYCLE - A series of changes in states of a system, such that the final point of
the system coincides with the initial point is termed as a cycle.
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QUASI-STATIC PROCESS- The meaning of ‘Quasi’ is ‘almost’ and the meaning

of ‘Static’ is ‘at rest’. The characteristic feature of a quasi-static process is its
 infinite slowness. A process that is the locus of all the equilibrium states the
system passes through from an initial condition to the final desired condition
is known as a quasi-static process. Every state of the system through which it
passes during this process is an equilibrium state.

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Reversible and Irreversible Process

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A reversible process is a process that can be reversed without causing any
permanent change in the surroundings. That is, both the system and the
surroundings are returned to their initial states if the given process is
reversed. In the property diagrams, reversible processes are shown by
continuous line or curve whereas irreversible processes are shown by dotted
line or curve.

Reversible processes are actually only theoretical. They are a mere

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idealization of actual processes. Processes that are not reversible are termed
irreversible processes.

PURE SUBSTANCE- A substance that has a uniform and invariable chemical

composition throughout its mass is known as a pure substance.
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Examples: Atmospheric air, steam-water mixture, ammonia, etc.

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IDEAL GAS EQUATION - Ideal (perfect) gas equation is a unique equation of

state, which is applicable specifically to ideal gases. The molecular forces of
attraction between gas molecules are negligible in an ideal gas. The volume
of the molecules should be negligible compared to the total volume for a
perfect gas. Following is the perfect or ideal gas equation :

PV=nRT

Where:
P = Absolute Pressure = atmospheric pressure + Gauge pressure (in pascal)
 V = Volume in m3
R= Universal Gas constant = 8.314KJ/Kmol-K
T = Absolute temperature in kelvin
n = number of moles (in k-mol)

Boyle’s Law- When the temperature is kept constant, the variation of pressure
is such that for a volume of a given mass of gas it varies inversely.

Charles Law- When the pressure remains constant, then the volume occupied
by a fixed amount of gas is directly proportional to its absolute temperature. It
is the basis of temperature measurement.

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ZEROTH LAW OF THERMODYNAMICS

•
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It is the basic law of thermodynamics which defines the temperature.
It defines that “If thermal equilibrium of body P exists with a body Q and
body R separately, then there must be thermal equilibrium between Q
and R also”.
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Energy
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(i). In a thermodynamic system, Energy interaction can be in three ways

namely work, heat, and by mass.
 (ii). There is only work transfer and Heat transfer interaction between a closed
system and surroundings without any mass transfer, while work, Heat, and
mass transfer interaction all occur in the open system (because mass also
carries energy).

First Law of Thermodynamics

• The first law of thermodynamics is to relate the various form of energy

and energy interaction.
• Its states that “In a process the creation or destruction of energy is

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impossible but it can be changed from one form to another form” and it
is known as the “Conservation of energy principle”.

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• From the above statement, we can say that the energy leaving the
system must be equal to the energy supplied to the system.
Ein = Eout
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FIRST LAW FOR A CLOSED SYSTEM UNDERGOING A CYCLE

As per the first law for a closed system undergoing a cycle, net heat
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interaction in a cycle is equal to the net Work interaction.

where J is the Joule’s equivalent. This is also expressed in the form

 Fig.1: Closed System Undergoing A Cycle

1st LAW FOR A CLOSED SYSTEM UNDERGOING A CHANGE OF STATE (for a

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process):

The expression:

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The above equation is applicable only to systems undergoing cycles, and the
algebraic sum of all energy interaction across system boundaries is zero.

If both heat transfer and work transfer are involved in a change of state of the
system, then the net energy transfer will be stored or accumulated within the
system.
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If heat transferred to the system is Q and work transferred from the system is
W, during the process

Then, net energy transfer (Q – W) will be stored in the system.

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Energy in storage in not in the form of heat and work and it is simply the
energy of the system, thus referred as the internal energy of the system.
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Therefore: Q – W – ΔE

where ΔE: Increase in the energy of the system.

Q = ΔE + W

Consequences of 1st Law of Thermodynamics

(i) Heat is a path function.

 (ii) Energy-a property of the system.

(iii) Energy of isolated system is Constant.

(iv) Perpetual motion machine of first kind-PMM1 is not possible.

Second Law of Thermodynamics

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The figure shown above shows us that the heat transfer process can occur
only when it satisfies both the first and the second laws of thermodynamics.

• The second law also asserts that energy has a quality attached to it and
its preservation is a major concern of engineers. In the above example,
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it can be seen that the energy contained in the hot container (present at
a higher temperature) has a higher quality (ability to work) compared to
the energy stored (at a lower temperature) in the surroundings.
• The second law is also used in the determination of the theoretical
limits of the performance of the general engineering systems like heat
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engines and refrigerators etc.

Thermal Energy Reservoirs

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• Thermal energy reservoirs are hypothetical bodies that have a relatively

large thermal energy capacity (mass × specific heat). They can supply
or absorb infinite amounts of heat without undergoing any change in
temperature. Lakes, atmosphere, seas are examples of thermal
reservoirs.
• As a two‐phase can absorb and release large quantities of heat while
remaining at a constant temperature, therefore it can be modeled as a
reservoir.
 • A reservoir that supplying energy in the form of heat is called a source
and the one absorbing energy in the form of heat is known as the sink.

Heat Engines

• Heat engines perform the work of conversion of heat into work. The
working of heat engines is described as follows :

o receiving heat from a high‐temperature source (oil furnace,

nuclear reactor, etc.)
o conversion of a part of this heat to work

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o rejection of the remaining waste heat to a low‐temperature sink
o cyclic operation

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• Thermal efficiency: Ratio of the network generated to the total heat

supplied to the engine.
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 • The thermal efficiencies of work‐developing systems are low. The
thermal efficiency of ordinary spark‐ignition automobile engines is
about 20%, thermal efficiency of diesel engines is about 30%, and that
of a power plant is in the range of 40%.

The Second Law: Kelvin‐Planck Statement

• The Kelvin Planck statement is "it is impossible for any device that
operates on a cycle to receive heat from a single reservoir and produce
a net amount of work." In other words, its impossible for a heat engine
to attain a thermal efficiency of 100%.

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The figure above shows a heat engine that violates the Kelvin‐Planck
statement of the second law and such a heat engine cannot be built.
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Refrigerators and Heat Pumps

• Naturally, heat flows from higher temperature regions to lower

temperature ones. It is not possible for the reversal of this process to
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occur by itself.
• Special devices are used for the transfer of heat from a lower
temperature region to a higher temperature one namely refrigerators
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and heat pumps.

• Refrigerators and heat pumps are cyclic devices where the working
fluids used in the cycles are called refrigerants.
• Refrigerators and heat pumps are more or less the same devices;
differing in their objectives only. A refrigerator maintains the
refrigerated space at a lower temperature whereas a heat pump
absorbs heat from a lower temperature source and supplies the heat to
a warmer medium.
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Coefficient of Performance (COP)

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The performance of heat pumps and refrigerators is expressed in terms
of the coefficient of performance (COP) which is expressed as:

• Mathematically, it can be seen that:

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COPHP = COPR + 1
• Air conditioners perform nearly the same task refrigerators perform but
the refrigerated space is a room or a building.
• The Energy Efficiency Rating (EER) is the ratio of the quantity of heat
removed from the cooled space to the power consumed by the unit.
Most air conditioners have an EER in the range of 8 to 12 (with COP of
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2.3 to 3.5).

The Second Law of Thermodynamics: Clausius Statement

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• The Clausius statement is - "It is impossible to construct a device that

operates in a cycle and produces no effect other than the transfer of
heat from a lower‐temperature body to a higher‐temperature body."
• A refrigerator can only operate when its compressor is driven by an
external power source.
• Kelvin‐Planck and Clausius's statements of the second law both being
negative statements, cannot be proved.
 • The two statements of the second law are equivalent and therefore any
device violating the Kelvin‐Planck statement also violates the Clausius
statement and vice versa.

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The violation of the Kelvin‐Planck statement leads to the violation of
the Clausius statement is being shown in the above figure.

Note:
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• A perpetual‐motion machine of the first kind (PMM1) is a device that
violates the first law of thermodynamics (by generating energy).
• A perpetual‐motion machine of the second kind (PMM2) is a device that
violates the second law of Thermodynamics.
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Read also: Zeroth and First Law of Thermodynamics Notes for Mechanical
Exams
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Reversible and Irreversible Process

• A reversible process is a process that can be reversed without causing

any permanent change in the surroundings. That is, both the system and
the surroundings return to their initial states if the given process is
reversed. In the property diagrams, reversible processes are shown by
continuous line or curve whereas irreversible processes are shown by
dotted line or curve.
 Reversible processes are actually only theoretical. They are a mere
idealization of actual processes. Processes that are not reversible are
termed irreversible processes.

• Some of the factors causing irreversibility’s in a process are listed

below:

o Friction
o Unrestrained expansion and compression
o mixing
Heat transfer (finite ΔT)

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o Inelastic deformation
o Chemical reactions

The Carnot Cycle

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The execution of the processes that make up a heat engine cycle
greatly affects the efficiency of the cycle.
The maximum efficiency could be attained if all the processes involved
are made reversible and the best known reversible cycle is the Carnot
cycle.
• Reversible cycles are practically not possible due to the irreversibility’s
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involved.
• The reversible cycles give us an idea of the upper limits on the
performance of real cycles.
• The Carnot cycle has four processes:
o 1‐2 Reversible isothermal expansion
o 2‐3 Reversible adiabatic expansion
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o 3‐4: Reversible isothermal compression

o 4‐1: Reversible adiabatic compression
The thermal efficiency of a heat engine (reversible or irreversible) is
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provided by the following expression :

• For the Carnot cycle, it is:

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Fig above shows P‐v diagram for the Carnot cycle.

An irreversible (real) cycle operating between the same two thermal

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reservoirs has an efficiency which is always lesser than the Carnot
cycle.

The Carnot Refrigeration and Heat Pump Cycle

• A refrigerator or heat pump operating on the reversed Carnot cycle is

called a Carnot Refrigerator, or a Carnot heat pump.
• The COP (Coefficient of Performance) of any refrigerator or heat pump
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(reversible or irreversible) is given by:

• COP of all reversible refrigerators or heat pumps can be calculated by:

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Also, similar to heat engine, one can conclude:

 Entropy Availability and Irreversibility

Entropy

The Clausius Inequality

• The first law is just a balance of energy.

• The second law states an inequality ie an irreversible process is less
efficient than a reversible process.
• One of such important inequalities is that of the Clausius inequality in
Thermodynamics according to which the cyclic integral of δQ / T is

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always less than or equal to zero.
• It is valid for all cycles, be it reversible or irreversible.
• The basis for the definition of a new property called entropy is formed

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by the Clausius inequality.
For an internally reversible process, the cyclic integral of δQ / T is zero.
If the cyclic integral of a quantity is zero, it means that it depends on the
state only and not the process path. Hence, it is a property.
For an irreversible process, the value of entropy change for a closed
system is greater than the value of integral of dQ/T evaluated for that
process.
• If the energy exchange takes place, δQ will be the energy transfer from
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the surroundings to the system.
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TEMPERATURE-ENTROPY PLOT

Now dQrev, = TdS

 Thus, area under the T -S plot on S axis will give the heat transfer in a
reversible process.

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Fig.: Area under a reversible path on the T-s plot

THE INCREASE OF ENTROPY PRINCIPLE:

Let us assume a cycle that is made up of two processes as shown below:

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process 1-2, which is an arbitrary process (reversible or irreversible),

and process 2-1, which is internally reversible in nature, as shown in the Figure
below,
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 Fig.: Combination of reversible & irreversible process

where the equality is for the internally reversible process and the inequality for
the irreversible process.

It should be kept in mind that the entropy generation Sgen is always a positive
quantity or zero. Its value is process-dependent, and thus it is not a property
of the system.

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For an isolated system,
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dQ = 0 since no energy interaction occurs between the system and the
surrounding.

Therefore, for an isolated system

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dSiso ≥ 0

For a reversible process,

dSiso = 0
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implies, S = constant

For an irreversible process

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dSiso > 0

Entropy change of the system:

Entropy charge of the system is summation entropy change due to internal

irreversibility and entropy change due to external interaction

dS = (dS)Irr, + (dS)EI
 T-dS EQUATION

........(1)

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........(2)

Note:

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Equation (1) & (2) are applicable for both reversible process as well as the
irreversible process because it contents all properties.

APPLICATIONS OF ENTROPY PRINCIPLE:

For every irreversible process, there is an increase of entropy of the universe,

and this entropy increase determines the extent of the irreversibility of the
process. The higher the entropy increase of the universe; the higher will be the
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irreversibility of the process.

Some of the applications of the entropy principle are illustrated in the

following.

(A) Heat transfer through a Finite Temperature Difference.

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(B) Two fluids mixing with each other.

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(C) Maximum Work that can be obtained from Two Finite Bodies at
Temperatures T1 and T2 interacting in a reversible manner.

The sources of energy can be divided into two groups i.e., high grade energy
(mechanical work, electrical energy, water power, wind power) and low grade
energy (heat or thermal energy, heat derived from nuclear fission or
combustion of fossil fuels). That part of the low grade energy which is
available for, conversion is referred to as available energy, while the part
which is not available is known as unavailable energy.
 Availability: When a system is subjected to a process from its original state to
dead state the maximum amount of useful work that can be achieved under
ideal conditions is known as available energy or availability of the system.

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Wmax = AE = Qxy – T0(Sy-Sx)

Unavailable Energy: UAE = T0(Sy-Sx)

where, Sx and Sy are the entropy at x and y, respectively.

The Available Energy (AE) is also known as exergy and the Unavailable Energy
(UAE) as anergy. The energy which cannot be utilised for doing useful work is
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called unavailable energy. Irreversibility is equivalent to energy destroyed,
hence also known as energy destruction consider the example given below.
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DECREASE IN AVAILABILITY WHEN HEAT TRANSFER THROUGH FINITE

TEMPERATURE DIFFERENCE
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Consider a reversible heat engine operating between T1 and T0.

Q1 = T1. Δs

W = AE= (T1 – T0)Δs om

Let us now consider heat Q1 is transferred through a finite temperature
difference.

Q1 = T1 Δs = T’1 . Δs’
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Δs’ > Δs

Q2 = T0 Δs → Initial UAE

Q’2 = T0 Δs’ ⇒ Afterward UAE

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Q’2 > Q2
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W’ =Q’1 – Q’2

W’ = T’1 Δs’ – T0Δs’

W’ = (T’1 – T0) Δs’

W = (T1 – T0) Δs

Hence increase in UAE and the shaded portion represent increase in UAE.
 SECOND LAW EFFICIENCY: Second law efficiency is the ratio of the exergy
recovered to the exergy spent. OR It is the ratio of actual work produced to the
max work produced under reversible condition. Consider the case of heat
engine.

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The second law efficiency is measure of the performance of a device relative
to its performance under reversible conditions.
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EXERGY OF A CLOSED SYSTEM : Consider a piston cylinder device that

contains a fluid of mass m at temperature T and pressure P. The system is
then allowed to undergo a differential change of state during which volume
changes by dV and heat is transferred from the system to surroundings.
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For change of exergy from state 1 to state 2.

Φ1 = (E1 – E0) + P0(V1 – V0) – T0(S1 – S0)

Φ2 = (E2 – E0) + P0(V2 – V0) – T0(S2 – S0)

Φ1 – ϕ2 = Energy at state 1 – Energy at state 2

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Φ1 – ϕ2 = (E1 – E2) + P0 (V1 – V2) – T0(S1 – S2)

EXERGY OF OPEN SYSTEM: A flowing fluid has an additional form of energy,

called flow energy, which is the energy needed to maintain flow in Pipe.
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Wflow = PV
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Exergy associated with system is

Φflowing fluid = ϕnon flow fluid + ϕflow

 Φflowing fluid = (E1 – E0) + P0(V1 – V0) – T0(S1 – S0) +P1V1 – P0V0

Φflowing= U1- U0 + (KE)1 - (KE)0 + (PE)1 – (PE)0 + P1V1 – P0V0 – T0 (S1 – S0)

Φflowing fluid = (U1 + P1V1) – (U0 + P0V0) – T0(S1 – S0) + (KE)1 – (KE)0 + (PE)1 –
(PE)0

Φflowing = (H1 – H0) – T0 (S1 – S0) + (KE)1 – (KE)0 + (PE)1 – (PE)2

Properties of Pure Substances

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• A pure substance is a material with homogeneous and invariable
composition.
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Pure substances can have multiple phases, an ice water mixture is still
a pure substance but an air-steam is not a pure substance.

Pure Substance:

A substance that has a fixed chemical composition throughout is called

a pure substance i.e., water, nitrogen, helium, and CO2.
Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
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Saturation Temperature and Saturation Pressure:

• At given pressure, the temperature at which a pure substance changes

phase is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.

Example: For water at a pressure of 101.325 kPa, Tsat is 100oC, conversely at a

temperature of 100oC, psat is 101.325 kPa.
 Latent Heat:

• The amount of energy absorbed or released during a phase change

process is called the latent heat.
• The amount of energy absorbed during melting is called the latent heat
of vaporization.
• Similarly, the amount of energy absorbed during vaporization is called
latent heat of vaporization and is equivalent to the energy released
during condensation.

Liquid-Vapour Saturation Curve:

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From the following figure, it is clear that Tsat increases with psat. Thus, a
substance at higher pressure will boil at higher temperatures.

Tsat = f(psat)
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• In the kitchen, higher boiling temperature means shorter cooking time

and energy saving.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer time to cook at
higher altitudes than it does at sea level.

Property Diagrams for Phase-change Process

The T-V Diagram:

 • The specific volume of the saturated liquid is larger and the specific
volume of the saturated vapour is smaller than the corresponding
values at 1 atm pressure. That is, the horizontal line that connects the
saturated liquid and saturated vapour states is much shorter.

• As the pressure is increased further, this saturation line will continue to

get shorter as shown in figure and it will become a point when the
pressure reaches 22.09 MPa for the case of water. This point is called
the critical point and it is defined as the point at which the saturated
liquid and saturated vapour state are identical.

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• At pressure above the critical pressure, there will not be a distinct phase
change. Instead, the specific volume of the substance will continually
increase and at all times there will be only one phase present. It is

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customary to refer to the substance as superheated vapour at
temperature above the critical temperature and as compressed liquid at
temperatures below the critical temperature.
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Triple Phase:

• When all three phases of a pure substance co-exist in equilibrium. It is

called triple phase.
• Triple phase states form a line called the triple line.
• The triple line appears as a point on the p-T diagram and therefore is
often called the triple point.
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• No substance can exist in the liquid phase in stable equilibrium at
pressure below the triple point pressure.
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•
freezing.
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The same can be said for temperature for substance that contract on

Substances at high pressure can exist in the liquid phase at

temperatures below the triple point temperature.

The p-T Diagram:

• Solid – Liquid = Fusion

Liquid – Vapour = Vaporisation
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• Solid – Vapour = Sublimation
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Enthalpy
 • Enthalpy is a measure of the total energy of a thermodynamic system.
• It includes energy required to create a system and the amount of energy
required to make room for it by displacing its environment and
establishing its volume and pressure.
• For certain type of processes particularly in power generation and
refrigeration.
o Enthalpy (H )= U + pV(kJ) Or
o per unit mass h = u + pV(kJ/kg)

Saturated Liquid and Saturated Vapour States:

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• Subscript f → properties of saturated liquid
• Subscript g → properties of saturated vapour
• Vf → specific volume of saturated liquid
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Vg → specific volume of saturated vapour
Vfg → difference between Vg and Vfnthal
Vfg = Vg - Vf
hfg → enthalpy of vaporisation or latent heat of vaporisation (amount of
energy need to vaporise a unit mass of saturated liquid at a given
temperature of pressure).
The magnitude of latent heat depends on temperature and pressure at
which phase change occurs.
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• For example at 1 atm pressure, the latent heat of fusion of water is
333.7 kJ/kg and latent heat of vaporization is 2257.1 kJ/kg.
• At below triple point pressure, substance begins to change directly gas.
• Enthalpy of vaporization decreases as the temperature or pressure
increases and become zero at the critical point.
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Saturated Liquid Vapour Mixture:

• During vaporisation process, a substance exists as part liquid and part

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vapour.
• A new property quality x is the ratio of mass of vapour to the total
mass of the mixture.

Quality or dryness fraction:

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mtotal = mliquid + mvapour = mf + mg

where, mf = mass of the saturated liquid, and mg = mass of the saturated

vapour

Quality has significance for saturated mixtures only.

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• It has no meaning in the compressed liquid or superheated region.
• Its value lie between 0 (saturated liquid) and 1 (saturated vapour).
• The properties of the saturated liquid are the same whether it exists
alone or in a mixture with saturated vapour.
• During vaporization process, only the amount of saturated liquid
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changes not its properties. The same can be said about a saturated
vapour.
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Quality :

• Vav = (1-x)Vf + xVg or Vav = Vf + xVg

• Uav = Uf + Ufg
• hav = hf + xhfg
 Superheated Vapour :

Since, the superheated region is a single phase region (vapour phase only)
temperature and pressure are no longer dependent properties and they can
conveniently be used as the two independent properties.

Superheated vapour is characterised by:

• Lower pressures (p < psat at a given T)

• Higher temperatures (T < Tsat at a given p)
• Higher specific volumes (U > Vg at a given p or T)

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• Higher internal energies (U > Ug at a given p or T)
• Higher enthalpies (h > hg at a given p or T)

INTRODUCTION om
Thermodynamic Relations & real Gas Mixtures

The properties such as temperature pressure, volume and mass can be

calculated directly.

The substances properties such as density (ρ) and specific volume(v) can be
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estimated using some simple relations.

However, energy, enthalpy (h) and entropy (s) are not very easy to determine
because they are not measurable or can not be easily expressed in terms of
measurable properties through some simple relations :
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1. Maxwell’s Equations
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These are the set of equations that establish the relation between the partial
derivatives of properties P, V, T, and S of a simple compressible system.

dU = TdS – PdV

dH = TdS + VdP

Helmholtz function

F = U – TS (availability of closed system)

 Gibb’s function

G = H – TS (availability of open system)

For all real processes, the value of the Helmholtz function & Gibbs function
decreases & attains a min value at equilibrium.

Helmholtz function

F = U – TS (availability of closed system)

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Gibb’s function

G = H – TS (availability of open system)

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For all real processes the value of Helmholtz function & Gibbs function
decreases & attains a min value at equilibrium.

Hence Four Maxwell’s relations are,

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COEFFICIENT OF VOLUME EXPANSION (β)

It is rate of change of volume with respect to temperature at constant

pressure.
 ISOTHERMAL COMPRESSIBILITY (KT)

It shows the rate of change of volume with respect to pressure at a constant

temperature or at isothermal conditions.

2. T-dS Equation

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This is known as the first Tds equation

This is known as the second TdS equation.

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T = Positive
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Cp –Cv = +ve

Cp > Cv

3. Energy Equation
 Joule Thompson Coefficient (µ)

When a fluid passes through the porous plug, capillary tube, or valve, its
pressure decreases. The throttling process is isenthalpic in nature. The
temperature behavior of the fluid during throttling is described by the joule
Thompson coefficient(µ),

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Fig:1
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 Fig:2

Important points:

1. Joule Thomson coefficient is +ve in cooling region i.e slope of

isenthalpic curve on T – P diagram is +ve in cooling region,
2. μ is –ve in heating region i.e the slope of isenthalpic curve on T – P
diagram is –ve in the heating region,
3. There is nothing as a heating or cooling region for an ideal gas & the
value of the joule Thomson coefficient is zero everywhere.

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4. Clausius Clapeyron Equations

Clausius Clapeyron equations is a relationship between saturation pressure,

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temperature, and enthalpy of vaporization and the specific volume of two
phases involved. This equation helps in calculations of properties in two-
phase regions.
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Fig:3
 The above equation is called the Clausius Clapeyron equation. It helps to
determine enthalpy change associated with phase change by measuring
pressure, temperature, and volume.

Gas Constant

• It has been experimentally observed that the ideal gas relation given

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closely approximately the p-V-T behaviour of real gases at low densities.
• At low pressure and high temperature, the density of a gas decreases
and the gas behaves as an ideal gas under these conditions.

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where, Ru = Universal gas constant, M = Molar mass, R = Gas constant.

Compressibility Factor
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• Compressibility factor (correction factor) is measurement of deviation
of gases from ideal gas behaviour.
• Compressibility factor (z):
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• It can also be expressed as

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• For ideal gases ⇒ z = 1

• For real gases ⇒ z is away from unity (> 1 or < 1)

Van der wall’s Equation of State:

 • Two effects: Inter molecular attraction forces:

and b accounts for volume occupied by the gas molecules.

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