ENGINEERING THERMODYNAMICS

UNIT I
Introductory Concepts.

Definition of THERMODYNAMICS:
 Thermodynamics is the science that includes the study of energy transformations and of the
relationships among the physical properties of the substances which are affected by these
transformations.
 The term 'Thermodynamics' was first used in a publication by Lord Kelvin in 1849. The first
thermodynamics textbook was written in 1859 by William Rankine, a professor at the University of
Glasgow.

 Scope of Thermodynamics
Although aspects of thermodynamics have been studied since ancient times, the formal study of
thermodynamics began in the early nineteenth century through consideration of the capacity of hot
objects to produce work. Today the scope is much larger. Thermodynamics now provides essential
concepts and methods for addressing critical twenty-first-century issues, such as using fossil fuels
more effectively, fostering renewable energy technologies, and developing more fuel-efficient means
of transportation. Also critical are the related issues of greenhouse gas emissions and air and water
pollution. Thermodynamics is both a branch of science and an engineering specialty. Engineers are
generally interested in studying systems and how they interact with their surroundings. To facilitate
this, thermodynamics has been extended to the study of systems through which matter flows, including
bioengineering and biomedical systems.

Areas of Application of Engineering Thermodynamics

1. Aircraft and rocket propulsion,

2. Alternative energy systems
3. Fuel cells
4. Geothermal systems
5. Wind turbines
6. Automobile engines
7. Bioengineering applications
8. Biomedical applications
9. Combustion systems
10. Compressors, pumps
11. Steam and gas turbines
12. Power production
13. Propulsion
14. Magneto hydrodynamic (MHD) converters
15. Ocean thermal, wave, and tidal power generation
16. Solar-activated heating, cooling, and power generation
17. Thermoelectric and thermionic devices
18. Cooling of electronic equipment
19. Cryogenic systems, gas separation, and liquefaction
 20. Fossil and nuclear-fuelled power stations
21. Heating, ventilating, and air-conditioning systems
22. Absorption refrigeration and heat pumps
23. Vapour-compression refrigeration and heat pumps
Thermodynamic Properties and energy relationships can be studied by two methods.
(i) Classical Thermodynamics
(ii) Statistical Thermodynamics
i. Classical and statistical Thermodynamics: It Involve studies which are undertaken without
recourse to the nature of the Individual Particles which make up a substance and to their reactions.
This is macroscopic view towards matter, and it requires no hypothesis about the detailed structure
of matter on the atomic scale.
For example, the pressure of a gas in a container is the result of momentum transfer between the
molecules and the walls of the container. However, one does not need to know the behaviour of the
gas particles to determine the pressure in the container. It would be sufficient to attach a pressure
gage to the container.
classical thermodynamics allows important aspects of system behaviour to be evaluated from
observations of the overall system. It provides a direct and easy way to the solution of engineering
problems.

ii. Statistical Thermodynamics: It is based on the statistical behaviour of large groups of

Individual particles. This is microscopic view point of matter.
The statistical thermodynamics or microscopic approach to thermodynamics, is concerned directly
with the structure of matter. The objective of statistical thermodynamics is to characterize by
statistical means the average behaviour of the particles making up a system of interest and relate
this information to the observed macroscopic behaviour of the system.
For applications involving lasers, plasmas, high speed gas flows, chemical kinetics, very low
temperatures (cryogenics), and others, the methods of statistical thermodynamics are essential.
System: A thermodynamic system is a Three dimensional region of space or an amount of matter,
bounded by an arbitrary surface.
Everything external to the system is considered to be part of the system’s
surroundings. The system is distinguished from its surroundings by a specified
boundary, which may be at rest or in motion.

Systems may be considered to be closed or open, depending on whether a fixed mass or a fixed
volume in space is chosen for study. A closed system (also known as a control mass or just
system when the context makes it clear) consists of a fixed amount of mass, and no mass can cross
its boundary. That is, no mass can enter or leave a closed system, as shown in fig. However energy
may cross the system boundary.
 Examples:

An open system, or a control volume, as it is often called, is a properly selected region in space. It
usually encloses a device that involves mass flow such as a compressor, turbine, or nozzle. Flow
through these devices is best studied by selecting the region within the device as the control volume.
Both mass and energy can cross the boundary of a control volume. The boundaries of a control volume
are called a control surface, and they can be real or imaginary.
A large number of engineering problems involve mass flow in and out of a system and, therefore, are
modelled as control volumes.
Example: A water heater, a car radiator, a turbine, and a compressor all involve mass flow and should
be analyzed as control volumes (open systems) instead of as control masses (closed systems).

 Properties: The state or physical condition of the system can be described by some parameters
called as Properties. Properties are the coordinates to describe the state of the system. Every
property has a fixed value at a particular state.
Some familiar properties are pressure P, temperature T, volume V, and mass m. The list can be
extended to include less familiar ones such as viscosity, thermal conductivity, modulus of
elasticity, thermal expansion coefficient, electric resistivity, and even velocity and elevation.

 Properties are considered to be either intensive or extensive.

 Intensive properties are those that are independent of the Size or Extent or mass of a system,
such as temperature, pressure, and density.
 Extensive properties are those whose values depend on the size—or extent—of the system.
Total mass, total volume, and total momentum are some examples of extensive properties. An
easy way to determine whether a property is intensive or extensive is to divide the system into
two equal parts with an imaginary partition, as shown in Fig. Each part will have the same
 value of intensive properties as the original system, but half the value of the extensive
properties.

 Extensive properties per unit mass are called specific properties. Some examples of specific
properties are specific volume (v = V/m) and specific total energy (e = E/m).
 Continuum: Matter is made up of atoms that are widely spaced in the gas phase. Yet it is very
convenient to disregard the atomic nature of a substance and view it as a continuous,
homogeneous matter with no holes, that is, a continuum.
 The continuum idealization allows us to treat properties as point functions and to assume the
properties vary continually in space with no jump discontinuities. This idealization is valid as
long as the size of the system we deal with is large relative to the space between the molecules.

 To have a sense of the distance involved at the molecular level, consider a container filled with
oxygen at atmospheric conditions. The diameter of the oxygen molecule is about
 3 x10-10 m and its mass is 5.3 x 10-26 kg. Also, the mean free path of oxygen at 1 atm pressure
and 20°C is 6.3 x 1028 m. That is, an oxygen molecule travels, on average, a distance of 6.3 X
1028 m (about 200 times of its diameter) before it collides with another molecule.
 Also, there are about 3 X 1016 molecules of oxygen in the tiny volume of 1 mm3 at 1 atm
pressure and 20°C. The continuum model is applicable as long as the characteristic length of
the system (such as its diameter) is much larger than the mean free path of the molecules.
 At very high vacuums or very high elevations, the mean free path may become large (for
example, it is about 0.1 m for atmospheric air at an elevation of 100 km). For such cases the
rarefied gas flow theory should be used, and the impact of individual molecules should be
considered. In this text we will limit our consideration to substances that can be modelled as a
continuum.

 State: The state of a system is the condition of the system described by the values of its properties.
 Equilibrium: If the Properties are invariant with respect to time then that state is called as an
Equilibrium state.
 Consider a system not undergoing any change. At this point, all the properties can be measured or
calculated throughout the entire system, which gives us a set of properties that completely describes
the condition, or the state, of the system. At a given state, all the properties of a system have fixed
values. If the value of even one property changes, the state will change to a different one. In the below
figure shows a system at two different states.

There are many types of equilibrium, and a system is not in thermodynamic equilibrium unless the
conditions of all the relevant types of equilibrium are satisfied. For example,
iii. a system is in thermal equilibrium if the temperature is the same throughout the entire system, as
shown in Fig. That is, the system involves no temperature differential, which is the driving force
for heat flow.
iv. Mechanical equilibrium is related to pressure, and a system is in mechanical equilibrium if there
is no change in pressure at any point of the system with time. However, the pressure may vary
within the system with elevation as a result of gravitational effects.
v. Finally, a system is in chemical equilibrium if its chemical composition does not change with
time, that is, no chemical reactions occur. A system will not be in equilibrium unless all the
relevant equilibrium criteria are satisfied.
If all the above equilibrium are satisfied then the system is said to be in Thermodynamic
Equilibrium.

State Postulate:
 The state of a simple compressible system is completely specified by two independent,
intensive properties.

Processes and cycles:

 Any change that a system undergoes from one equilibrium state to another is called a
process, and the series of states through which a system passes during a process is
called the path of the process.
  To describe a process completely, one should specify the initial and final states of the
process, as well as the path it follows, and the interactions with the surroundings.
If the process proceeds in such a way that if the final state is same as initial state then a
CYCLE is said to be completed.

 Quasi static Process

When a process proceeds in such a manner that the system remains infinitesimally
close to an equilibrium state at all times, it is called a quasi-static, or quasi-equilibrium,
process.

 Expansion or Compression Work in Quasi-Equilibrium Processes

A Quasi Equilibrium process is one in which the departure from thermodynamic equilibrium is
at most infinitesimal. All states through which the system passes in a quasi equilibrium process
may be considered equilibrium states. Because non equilibrium effects are inevitably present
during actual processes, systems of engineering interest can at best approach, but never realize, a
quasi equilibrium process.
Imagine that one of the masses is removed, allowing the piston to move upward as the gas expands
slightly. During such an expansion, the state of the gas would depart only slightly from equilibrium.
The system would eventually come to a new equilibrium state, where the pressure and all other
intensive properties would again be uniform in value. Moreover, were the mass replaced, the gas
would be restored to its initial state, while again the departure from equilibrium would be slight. If
several of the masses were removed one after another, the gas would pass through a sequence of
equilibrium states without ever being far from equilibrium. In the limit as the increments of mass
are made vanishingly small, the gas would undergo a quasi equilibrium expansion process. A quasi
equilibrium compression can be visualized with similar considerations.
TEMPERATURE AND THE ZEROTH LAW OF THERMODYNAMICS
Temperature is rooted in the notion of the “hotness” or “coldness” of objects. We use our sense of
touch to distinguish hot objects from cold objects and to arrange objects in their order of “hotness,”
deciding that 1 is hotter than 2, 2 hotter than 3, and so on. But however sensitive human touch may be,
we are unable to gauge this quality precisely.

To illustrate this, consider two copper blocks, and suppose that our senses tell us that one is warmer
than the other. If the blocks were brought into contact and isolated from their surroundings, they would
interact in a way that can be described as a thermal (heat) interaction. During this interaction, it
would be observed that the volume of the warmer block decreases somewhat with time, while the
volume of the colder block increases with time. Eventually, no further changes in volume would be
observed, and the blocks would feel equally warm. Similarly, we would be able to observe that the
electrical resistance of the warmer block decreases with time and that of the colder block increases
with time; eventually the electrical resistances would become constant also. When all changes in such
observable properties cease, the interaction is at an end. The two blocks are then in thermal
equilibrium. Considerations such as these lead us to infer that the blocks have a physical property that
determines whether they will be in thermal equilibrium. This property is called
temperature, and we postulate that when the two blocks are in thermal equilibrium,
their temperatures are equal.

Zeroth Law of Thermodynamics:

 when two objects are in thermal equilibrium with a third object, they are in thermal equilibrium
with one another.
 If we want to know if two objects are at the same temperature, it is not necessary to bring them into
contact and see whether their observable properties change with time, as described previously. It is
necessary only to see if they are individually in thermal equilibrium with a third object. The third
object is usually a thermometer.
 Any object with at least one measurable property that changes as its temperature changes can be
used as a thermometer. Such a property is called a thermometric property. The particular
substance that exhibits changes in the thermometric property is known as a thermometric substance.
 Temperature scales:
 The temperature scales used in the SI and in the English system today are the Celsius scale and the
Fahrenheit scale respectively. On the Celsius scale, the ice and steam points were originally
assigned the values of 0 and 100°C, respectively. The corresponding values on the Fahrenheit scale
are 32 and 212°F. These are often referred to as two-point scales since temperature values are
assigned at two different points.
 In thermodynamics, it is very desirable to have a temperature scale that is independent of the
properties of any substance or substances. Such a temperature scale is called a thermodynamic
temperature scale, which is developed later in conjunction with the second law of
thermodynamics.
 The thermodynamic temperature scale in the SI is the Kelvin scale, named after Lord Kelvin
(1824–1907). The temperature unit on this scale is the kelvin, which is designated by K. The lowest
temperature on the Kelvin scale is absolute zero, or 0 K.
 The thermodynamic temperature scale in the English system is the Rankine scale, named after
William Rankine (1820–1872). The temperature unit on this scale is the rankine, which is
designated by R.
 The relationship of the Kelvin, Rankine, Celsius, and Fahrenheit scales is shown in Fig. together
with values for temperature at three fixed points: the triple point, ice point, and steam point.
 By international agreement, temperature scales are defined by the numerical value assigned to the
easily reproducible triple point of water: the state of equilibrium among steam, ice and liquid
water. The temperature at this standard fixed point is defined as 273.16 Kelvins, abbreviated as
273.16 K.

 The relationship between centigrade scale and Kelvin scale is T(0C)= T(K) -273.15.
 The relationship between fahrenheit scale and Rankine scale is T(0F)= T(R) -459.67.
 The relationship between fahrenheit scale and centigrade scale is T(0F)= 1.8T(0C) +32

Constant volume Gas thermometer:

 A small amount of gas is enclosed in bulb B which is in communication via the capillary tube C
with one limb of the mercury manometer M. The other limb of mercury manometer is open to the
atmosphere and can be moved vertically to adjust the mercury levels so that mercury just touches
the Lip L of the capillary. The pressure in the bulb is used as a thermometric property and is given
by
p =po +ρmZg.
where po is the atmospheric pressure and ρm is the density of mercury.

when the bulb is brought in contact with the system whose temperature is to be measured, the bulb, in
course of time, comes in thermal equilibrium with the system. The gas in the bulb expands, on being
heated, pushing the mercury downwards. The flexible limb of the manometer is then adjusted so that
the mercury again touches the lip L. The difference in the mercury levels Z is recorded and the
pressure p of the gas in the bulb is estimated. since the volume of the trapped gas remains constant,
from the ideal gas equation
𝑉
∆𝑇 = ∆𝑃
𝑅
i.e temperature increase is proportional to pressure increase.

Point and Path functions:

 Thermodynamic quantities can be divided into two categories: point or state functions and path
or process functions.

 All properties are state functions, since the change in the value of a property depends solely on
the property values at the initial and final states, and not on the path of the process.
 A property change for a process with given end states 1 and 2 is described mathematically by
the exact differential dy, such that
2
∆𝑦 = ∫ 𝑑𝑦
1
  Quantities whose values depend on the path of the process are called process or path functions.
 Path functions are inexact differentials and hence
2
𝑍12 ≠ ∫ 𝑑𝑧
1

The two major process functions in thermodynamic studies are work and heat.

Density, Specific Volume, and Specific Gravity:

 The density ρ is defined as the mass per unit volume:

𝑚𝑎𝑠𝑠 𝑚
𝜌 = 𝑣𝑜𝑙𝑢𝑚𝑒 = ,its unit is kg per m3
𝑣

 The specific volume v is defined as volume per unit mass:

𝑣𝑜𝑙𝑢𝑚𝑒 𝑉
𝑣 = 𝑚𝑎𝑠𝑠 = 𝑚 , its unit is m3 per kg
 The specific gravity of a substance is the ratio of its density to that of water at a specified
temperature, such as 4 or 20oC and one atmosphere:
𝜌
𝑆𝑝. 𝑔𝑟 = 𝜌 it has no units
𝑤𝑎𝑡𝑒𝑟
 The density of water at 4 C is close to 1.00 g/cm3 (kg/L), 1000 kg/m3, while that of liquid
o

mercury is close to 13.6 g/cm3, 13600 kg/m3.

 The specific weight w of a substance is the weight per unit volume:
𝑤𝑒𝑖𝑔ℎ𝑡 𝑊
𝑤 = 𝑣𝑜𝑙𝑢𝑚𝑒 = , its unit is N per m3
𝑉

Thermodynamic work
 Work is said to be done by a system if the sole effect on things external to the system can be
reduced to the raising of a weight.

Battery-motor System driving a fan Work transfer from a System

Sign Convention:
 When work is done by a system it is arbitrarily taken to be positive, and when work is done on
a system, it is taken to be negative.
 (a) W is positive (b) W is negative

Work interaction between a System and the Surroundings

 The symbol W is used for work transfer. The unit of work is N.m or Joule.
 The rate at which the work is done by, or upon, the system is known as power. The unit of
power is J/s or Watt.

Displacement work or pdV Work:

 Consider expansion of gas in a piston-cylinder assembly as shown in fig. 1.13.
 The expansion of the gas by outward movement of the piston can be represented on p-V
diagram as given in Fig.1.14.

pdV work Quasi-static pdV work

 The shaded area represents work done due to small movement of the piston and the total work
done by the gas during expansion process is
2
𝑊1−2 = ∫ 𝑝𝑑𝑉
1
2
 The integral ∫1 𝑝𝑑𝑉 can be evaluated, only if we know the relation between p and V or the
path of the process.
 The area under the curve 1-2 represents the work done during the process 1-2.

pdV-work in Various Quasi-Static Processes:

 Constant pressure process (isobaric or isopiestic process)
2
𝑊1−2 = ∫1 𝑝𝑑𝑉 = 𝑝(𝑉2 − 𝑉1 )
 Constant volume process (isochoric process)
2
2𝑊1−2 = ∫ 𝑝𝑑𝑉 = 0
1
 Constant Pressure Process Constant Volume Process

 Process in which pV = C
𝑉2
𝑉2 𝑃1
𝑊1−2 = ∫ 𝑝𝑑𝑉 = 𝑝1 𝑣1 𝑙𝑛 = 𝑝1 𝑣1 𝑙𝑛
𝑉1 𝑉1 𝑃2

 Process in which pVn=C, where n is a constant

𝑝1 𝑣1 𝑛 = 𝑝2 𝑣2 𝑛
𝑝1 𝑣1 𝑛
𝑝= 𝑣𝑛

𝑉 𝐶 𝑉 1−𝑛 𝑉11−𝑛 𝑉21−𝑛 𝑉11−𝑛

𝑊1−2 = ∫𝑉 2 𝑣𝑛 𝑑𝑣 = 𝐶 ⌊ 1−𝑛
2
− ⌋ = 𝑝2 𝑣2 𝑛 ∗ − 𝑝1 𝑣1 𝑛 ∗
1 1−𝑛 1−𝑛 1−𝑛
𝑝2 𝑣2 −𝑝1 𝑣1
∴ 𝑊1−2 = 𝑛−1

Process in which pV=Constant Profess in which pVn=Constant

Similarly, for process in which pv γ =C
𝑝2 𝑣2 − 𝑝1 𝑣1
𝑊1−2 =
𝛾−1
Other Types of Work Transfer
Electrical Work:
 When a current flows through a resistor, taken as a system, there is work transfer into the
system.
 It is a thermodynamic work because the current can drive a motor, the motor can drive a pulley
and the pulley can raise a weight.
 The current flow, I, in amperes, is given as
 𝑑𝑐
𝐼 = 𝑑𝑡 where C is the charge in coulombs and t is time in seconds.
 If E is the voltage potential, the work, 𝑑𝑊 = 𝐸. 𝑑𝑐 = 𝐸𝐼𝑑𝑡
𝑡
 𝑊 = 𝐸. 𝑑𝑐 = ∫𝑡 2 𝐸𝐼𝑑𝑡
1

Electrical Work
Shaft Work:
 When a shaft rotated by a motor, taken as a system, there is work transfer into the system.

Shaft work
 This is a form of thermodynamic work because the shaft can rotate a pulley which can raise a
weight.

 If T is the torque applied to the shaft and 𝑑𝜃 is the angular displacement of the shaft, the shaft
2
work is 𝑊 = ∫1 𝑇𝑑𝜃

Spring Work:
 It is common knowledge that when a force is applied on a
spring, the length of the spring changes.
 When the length of the spring changes by a differential amount dx
under the influence of a force F, the work done is
dWspring = F dx
 The displacement x is proportional to the force applied
F = kx (kN)
 where k is the spring constant and has the unit kN/m. The displacement x is measured from the
undisturbed position of the spring (that is, x = 0 when F = 0).
 Work done = [Link]

For Infinitesimal extension (dx) of spring work is  w  F .dx

2 2
 x2 x2 
Total work   Fdx   kxdx  k  2  1  (kJ)
1 1 2 2
where x1 and x2 are the initial and the final displacements of the spring, respectively,
measured from the undisturbed position of the spring.
Paddle-wheel work or Stirring Work:
 The paddle-wheel turns when the weight
is lowered.
 The paddle-wheel stirs fluid system and hence,
there is work transfer into the fluid system.
 Since the volume of the system remains
2
constant, ∫1 pdV = 0

 If m is the mass of the weight lowered through a distance dz and T is the torque transmitted by
the shaft in rotating through an angle d , the differential work transfer to the fluid is given by
2 2
dW = mgdz = 𝑇𝑑𝜃 =𝑊 = ∫1 𝑚𝑔𝑑𝑧 = ∫1 𝑇𝑑𝜃 = 0

 The total work transfer is

𝑚𝑔∆𝑧 = 𝑇∆𝜃
Flow Work:

 The flow work is significant only in a flow process or an open system.

 When mass m enters or leaves a control volume, work is required to push the fluid into or out
of the system. This term is referred to as flow work.
 A mass m in region A (Fig. 1.21) initially resides just outside a control surface.

Flow work at a Control Surface

 The normal force exerted at the control surface of area A is simply the pressure times the area,
or PA.

 Thus the rate of flow work 𝑊̇𝑓𝑙𝑜𝑤 is given by

𝑊̇𝑓𝑙𝑜𝑤 =𝑝𝐴𝑉, where V is the velocity of fluid mass m.

Since m = AV/v, therefore 𝑊̇𝑓𝑙𝑜𝑤 = 𝑝𝑚𝑣. Where v is the specific volume.

 The flow work per unit mass is 𝑝𝑣.

Work done in Stretching a Wire:
 Let us consider a wire as the system.
 If the length of the wire is changed from L to L + dL, the infinitestimal amount of work that is
done is equal to dW = - F dL, where F is the tension in the wire.
  The minus sign is used because a positive value of dL means an expansion of the wire, for
which work must be done on the wire, i.e., negative work.
 For a finite change of length.
2
𝑊 = − ∫1 𝐹𝑑𝑙
 If we limit the problem to within the elastic limit, where E is the modulus of elasticity,𝜏 is the
stress, 𝜀 is the strain, and A is the cross-sectional area, then
𝜏
𝐹 = 𝜏𝐴 = 𝐸𝜖𝐴, 𝑠𝑖𝑛𝑐𝑒 𝐸 =
𝜀
𝑑𝑙
and = .
𝐿
𝑑𝑤 = −𝐹𝑑𝐿 = −𝐸𝜖𝐴𝐿𝑑𝜀
2
𝐴𝐸𝐿
∴ 𝑊 = −𝐴𝜀𝐿 ∫ 𝜖𝑑𝜖 = −
1 2(𝜖22 − 𝜀12 )

Unrestrained or Free Expansion:

 The expansion of gas against a vacuum is called free expansion; essentially it is expansion
which is not restrained by an opposing force.
 Let us consider a gas separated from the vacuum by a partition. Let the partition be removed.
The gas rushes to fill the entire volume.

Unrestrained Expansion
 Though this free expansion process involves a change of volume yet the work transfer is zero
since the vacuum does not offer any resistance to the expansion process.
 Free expansion process is a totally irreversible process for which work transfer is zero even
though ∫ pdv is not zero.

Heat Transfer:
 Heat is defined as the form of energy that is transferred across a boundary by virtue of
temperature difference. The temperature difference is the ‘potential’ or ‘force’ and heat
transfer is the ‘flux’.
 Heat flow into a system is taken to be positive, and heat flow out of a system is taken as
negative. The symbol Q is used for heat transfer.
 Like work transfer, heat transfer is a path function and is an inexact differential.
 A process in which no heat crosses the boundary of the system is called an adiabatic process.
  Thus, an adiabatic process is one in which there is only work interaction between the system
and its surroundings.
 A wall which is impermeable to the flow of heat is an adiabatic wall, whereas a wall which
permits the flow of heat is a diathermic wall.

Specific Heat:
 The specific heat of a substance is defined as the amount of heat required to raise a unit mass of
the substance through a unit rise in temperature. The symbol c will be used for specific heat.
𝑄
𝐶 = 𝑚∆𝑇 J/kg K.
 For gases, if the process is at constant pressure, it is cp, and if the process is at constant volume,
it is cv.
 For solids and liquids, however, cp=cv=c, as they are incompressible.

Latent Heat:
 The latent heat is the amount of heat transfer required to cause a phase change in unit mass of a
substance at a constant pressure and temperature.
 There are three phases in which matter can exist; solid, liquid, and vapour or gas.
 The latent heat of fusion (Lfu) is the amount of heat transferred to melt unit mass of solid into
liquid, or to freeze unit mass of liquid to solid.
 The latent heat of vaporization (Lvap) is the quantity of heat required to vaporise unit mass of
liquid into vapour or condense unit mass of vapour into liquid.
 The latent heat of sublimation (Lsub) is the amount of heat transferred to convert unit mass of
solid to vapour or vice versa.
 Lfu is not much affected by pressure, whereas Lvap is highly sensitive to pressure.

Comparison of Heat and Work:

Similarities:
 Both heat and work are path function; they are not properties of the system and their
differentials are not exact.
 They represent energy crossing the system boundary; and hence they are a boundary
phenomenon.
 Both represent transient phenomenon; these energy interactions occur only when a system
undergoes change of state. They exist as stored energy before or after the interaction.
 Concepts of heat and work are associated not with a ‘store’ but with a ‘transfer across
boundary’.

Dissimilarities:

 There cannot be work transfer in a stable system. No such restriction exists for heat
interaction.
 Heat is energy interaction due to temperature difference only; work is by reasons other than
temperature difference.
 Heat is a low grade energy whereas work is a high grade energy.
EENGINEERING THERMODYNAMICS
 Unit – II

Learning Material
The first Law of Thermodynamics for a Control Mass Undergoing a Cycle -
Joule’s Experiment
 Consider a closed system consisting of known mass of water, m, contained in an
adiabatic vessel having a thermometer and a paddle wheel, as shown in fig.2.3.

Adiabatic Work

 Let a certain amount of work W1-2 be done upon the system by the paddle wheel.
The quantity of work can be measured by the fall of weight which drives the
paddle wheel through a pulley.
 Let the system is initially at temperature T1, the same as that of atmosphere, and
after work transfer let the temperature rise to T2. The pressure is always 1 atm.
 The process 1-2 undergone by the system is shown in fig. in generalized
thermodynamic coordinates, X, Y.

Adiabatic Work Transfer W1-2 Followed by Heat Transfer Q2-1

 Let the insulation now be removed. The system and the surroundings interact by
heat transfer till the system returns to the original temperature T1, attaining the
condition of thermal equilibrium with the atmosphere.
 The amount of heat transfer Q2-1 from the system during this process, 2-1, shown
in fig. can be estimated from Q2-1 = m cp (T2 – T1).
 The system thus executes a cycle, which consists of definite amount of work input
W1-2 to the system followed by the transfer of an amount of heat Q2-1 from the
system.
  It has been found that this W1-2 is always proportional to the heat Q2-1, and the
constant of proportionality is called the Joule’s equivalent or the mechanical
equivalent of heat.
 In the simple example given here, there are only to energy transfer quantities as
the system performs a thermodynamic cycle. If the cycle involves many more
heat and work quantities, the same result will be found. Expressed algebraically.

(∑ 𝑊) = (∑ 𝑄)
𝑐𝑦𝑐𝑙𝑒 𝑐𝑦𝑐𝑙𝑒

 This is also expressed in the form

∮ 𝑑𝑊 = 𝐽 ∮ 𝑑𝑄

 Where the symbol ∮ denotes the cyclic integral for the closed path. This is the
first law for a closed system undergoing a cycle. It is accepted as a general law of
nature. Since no violation of it has ever been demonstrated.
 The first law of thermodynamics states that during any cycle a system (Control
mass) undergoes, the cyclic integral of the heat is equal to the cyclic integral of
the work.

The First Law of Thermodynamics for a Change in State of a Control Mass

 Consider a system that undergoes a cycle in which it changes from state 1 to state
2 by process A and returns from state 2 to state 1 by process B. This cycle is
shown in Fig. on a pressure – volume diagram.

Demonstration of the Existence of Thermodynamic Property E

 From the first law of thermodynamics

∮ 𝛿𝑄 = ∮ 𝛿𝑊
2 1
 Considering the two separate processes, we have ∫1 𝛿𝑄𝐴 + ∫2 𝛿𝑄𝐵 =
2 1
∫1 𝛿𝑊𝐴 + ∫2 𝛿𝑊𝐵
 Now consider another cycle in which the control mass changes from state 1 to
state 2 by process C and returns to state 1 by process B, as before. For this cycle
2 1 2 1
we can write ∫1 𝛿𝑄𝐶 + ∫2 𝛿𝑄𝐵 = ∫1 𝛿𝑊𝐶 + ∫2 𝛿𝑊𝐵
Subtracting the second of these equations from the first, we obtain
2 2 2 2
∫1 𝛿𝑄𝐴 − ∫1 𝛿𝑄𝐶 = ∫1 𝛿𝑊𝐴 − ∫1 𝛿𝑊𝐶
2 2
or by rearranging, ∫1 (𝛿𝑄 − 𝛿𝑊 )𝐴 = ∫1 (𝛿𝑄 − 𝛿𝑊 )𝐶
  Since A and C represent arbitrary processes between states 1 and 2, the quantity
(𝛿𝑄 − 𝛿𝑊 ) is the same for all processes between states 1 and 2. Therefore,
(𝛿𝑄 − 𝛿𝑊 ) depends only on the initial and final states and not on the path
followed between the two states. We conclude that this is a point function, and
therefore it is the differential of a property of the mass. This property is the
energy of the mass and is given the symbol E. Thus we can write dE = 𝛿𝑄 − 𝛿𝑊
 Because E is property, its derivative is written dE. When equation is integrated
from an initial state 1 to a final state 2, we have 𝐸2 − 𝐸1 = 𝑄1−2 − 𝑊1−2
 Where E1 and E2 are the initial and final values of the energy E of the control
mass, Q1-2 is the heat transferred to the control mass during the process from state
1 to state 2, and W1-2 is the work done by the control mass during the process.
 The physical significance of the property E is that it represents all the energy of
the system in the given state. This energy might be present in a variety of forms,
such as the kinetic or potential energy of the system as a whole with respect to the
chosen coordinate frame, energy associated with the motion and position of the
molecules, energy associated with the structure of the atom, chemical energy
present in a storage battery, energy present in a charged condenser, or any of a
number of other forms.
 E = Internal energy + kinetic energy + potential energy (or)
 E = U + KE + PE
 𝑑𝐸 = 𝑑𝑈 + 𝑑 (𝐾𝐸 ) + 𝑑 (𝑃𝐸 ) = 𝛿𝑄 − 𝛿𝑊
 In words this equation states that as a control mass undergoes a change of state,
energy may cross the boundary as either heat or work, and each may be positive or
negative. The net change in the energy of the system will be exactly equal to the
net energy that crosses the boundary of the system. The energy of the system may
change in any or three ways – by a change in internal energy, in kinetic energy, or
in potential energy.
1
 The kinetic energy is expressed as 𝐾𝐸 = 𝑚𝑉 2 , where V is the velocity of the
2
system as a whole.
 The potential energy is expressed as 𝑃𝐸 = 𝑚𝑔𝑍, where Z is the altitude of the
center of gravity of the system as a whole from the datum line.

 Therefore, the fist law thermodynamics for a change of state of the system is
expressed as
𝑚(𝑉22 −𝑉11 )
𝑈2 − 𝑈1 + + 𝑚𝑔(𝑍2 − 𝑍1 ) = 𝑄1−2 − 𝑊1−2
2
 The net change of the energy of the control mass during a process is always equal
to the net transfer of energy across the boundary as heat and work.

Internal Energy – A thermodynamic Property

 Internal energy is an extensive property because it depends on the mass of the
system. Similarly, kinetic and potential energies are extensive properties.
  The symbol U designates the internal energy of a given mass of substance.
 The internal energy per unit mass, u, is the intensive property of the system.

The Thermodynamic Property Enthalpy

 Let us consider a control mass undergoing a quasi-equilibrium constant-pressure
process, as shown in fig.

Constant-Pressure Quasi-equilibrium Process

 Assume that there are no changes in kinetic or potential energy and that the only
work done during the process is that associated with the boundary (piston)
movement. Taking the gas as control mass and applying the first law as
Q1-2 = U2 – U1 + W1-2
2
 The work done can be calculated from the relation 𝑊1−2 = ∫1 𝑃𝑑𝑉
2
 Since the pressure is constant, 𝑊1−2 = 𝑃 ∫1 𝑑𝑉 = 𝑃(𝑉2 − 𝑉1 )
 Therefore, Q1-2 = U2 – U1 + P2V2 – P1V1
= (U2 + P2V2) – (U1+P1V1)
 We find that, in this very restricted case, the heat transfer during the process is
given in terms of the change in the quantity (U + PV) between the initial and final
states.
 Because all these quantities are thermodynamic properties, that is, functions only
of the state of the system, their combination must also have these same
characteristics. Therefore, we find it convenient to define a new extensive
property, the enthalpy, H = U + PV or, per unit mass, h = u + pv
 The heat transfer in a constant-pressure quasi-equilibrium process is equal to the
change in enthalpy, which includes both the change in internal energy and the
work for this particular process.
The First Law as a Rate Equation
𝑑𝑈 𝑑(𝐾𝐸) 𝑑(𝑃𝐸)
 + + = 𝑄̇ − 𝑊̇
𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝐸
 In the absence of kinetic and potential energies, = 𝑄̇ − 𝑊̇
𝑑𝑡

Energy of an isolated system

 An isolated system is one in which there is no interaction of the system with the
surroundings.
 For an isolated system dQ = 0, dW=0. Hence, application first law of
thermodynamics gives dE = 0. Therefore, E = constant.
  The energy of an isolated system is always constant.
Perpetual Motion Machine of the First Kind – PMM1
 There can be no machine which would continuously supply mechanical work
without some other form of energy disappearing simultaneously. Such a fictitious
machine is called a perpetual motion machine of the first kind, or in brief, PMM1.
A PMM1 is thus impossible.
The Constant-Volume and Constant-Pressure Specific Heats
 The specific heat at constant volume is defined as the amount of heat required to
raise the temperature of 1 kg substance by 1 degree when volume is maintained
1 𝛿𝑄
constant 𝐶𝑣 = ( ) .
𝑚 𝛿𝑇 𝑣

 Constant volume, for which the work term (P dV) is zero, so that the specific heat
1 𝛿𝑄 1 𝜕𝑈 𝜕𝑢
at constant volume can also be expressed as 𝐶𝑣 = ( ) = ( ) = ( )
𝑚 𝛿𝑇 𝑣 𝑚 𝜕𝑇 𝑣 𝜕𝑇 𝑣

 The specific heat at constant pressure is defined as the amount of heat required to
raise the temperature of 1 kg substance by 1 degree when pressure is maintained
1 𝛿𝑄
constant 𝐶𝑝 = ( )
𝑚 𝛿𝑇 𝑝

 Constant pressure, for which the work term can be integrated and the resulting PV
terms at the initial and final states can be associated with the internal energy terms,
thereby leading to the conclusion that the heat transfer can be expressed in terms
of the enthalpy change. The corresponding specific heat at constant pressure can
1 𝛿𝑄 1 𝜕𝐻 𝜕ℎ
be expressed as 𝐶𝑝 = ( ) = ( ) = ( )
𝑚 𝛿𝑇 𝑝 𝑚 𝜕𝑇 𝑝 𝜕𝑇 𝑝

Relationship between Specific Heats and Gas Constant

 The enthalpy, h = u + pv.
= u + RT
 dh = du + RdT
𝑑ℎ 𝑑𝑢
Therefore, = +𝑅
𝑑𝑇 𝑑𝑇
𝑐𝑝 = 𝑐𝑣 + 𝑅; 𝑐𝑝 − 𝑐𝑣 = 𝑅
First-Law Analysis for a Control Volume
 For an open system, mass as well as heat and work can cross the control surface,
and the mass in the control volume can change with time.
 Flow Process and Control Volume
 Applying the law of conservation of mass to the control volume with several
possible flows as
𝑑𝑚𝐶.𝑉.
= ∑ 𝑚̇𝑖 − ∑ 𝑚̇ 𝑒
𝑑𝑡
 The extension of the first law of thermodynamics becomes
𝑑𝐸𝐶.𝑉.
= 𝑄̇𝐶.𝑉. − 𝑊̇𝐶.𝑉. + 𝑚̇𝑖 (𝑒𝑖 + 𝑝𝑖 𝑣𝑖 ) − 𝑚̇𝑒 (𝑒𝑒 + 𝑝𝑒 𝑣𝑒 )
𝑑𝑡
1 1
= 𝑄̇𝐶.𝑉. − 𝑊̇𝐶.𝑉. + 𝑚̇𝑖 (ℎ𝑖 + 𝑉𝑖2 + 𝑔𝑍𝑖 ) − 𝑚̇𝑒 (ℎ𝑒 + 𝑉𝑒2 + 𝑔𝑍𝑒 )
2 2
 For a control volume with several entering and leaving mass flow rates,
𝑑𝐸𝐶.𝑉. 1 1
= 𝑄̇𝐶.𝑉. − 𝑊̇𝐶.𝑉. + ∑ 𝑚̇𝑖 (ℎ𝑖 + 𝑉𝑖2 + 𝑔𝑍𝑖 ) − ∑ 𝑚̇𝑒 (ℎ𝑒 + 𝑉𝑒2 + 𝑔𝑍𝑒 )
𝑑𝑡 2 2
The steady-State Process
 The control volume does not move relative to the coordinate frame.
 The state of the mass at each point in the control volume does not vary with time.
 As for the mass that flows across the control surface, the mass flux and the state of
this mass at each discrete area of flow on the control surface do not vary with
time.
 The rates at which heat and work cross the control surface remain constant.
𝑑𝑚𝐶.𝑉. 𝑑𝐸𝐶.𝑉.
 Therefore, = 0 and also =0
𝑑𝑡 𝑑𝑡
 The first-law for a control volume under steady-state with several entering and
leaving mass flow rates is expressed as
𝑉𝑖2 𝑉𝑒2
𝑄̇𝐶.𝑉. + ∑ 𝑚̇𝑖 (ℎ𝑖 + + 𝑔𝑍𝑖 ) = ∑ 𝑚̇𝑒 (ℎ𝑒 + + 𝑔𝑍𝑒 ) + 𝑊̇𝐶.𝑉.
2 2
 Many of the engineering applications of the steady-state model involve only on
flow stream entering and leaving the control volume. For this type of process, we
can write
𝑉𝑖2 𝑉𝑒2
𝑄̇𝐶.𝑉. + 𝑚̇ (ℎ𝑖 + + 𝑔𝑍𝑖 ) = 𝑚̇ (ℎ𝑒 + + 𝑔𝑍𝑒 ) + 𝑊̇𝐶.𝑉.
2 2
Rearranging this equation, we have
𝑉𝑖2 𝑉𝑒2
𝑞 + ℎ𝑖 + + 𝑔𝑍𝑖 = ℎ𝑒 + + 𝑔𝑍𝑒 + 𝑤
2 2
Where, q and w are heat and work interactions per unit mass flow rate.
Examples of Steady-State Processes
a) Heat Exchanger
 A heat exchanger is device in which heat transferred from one fluid to another.
One such example is the steam condenser, where steam condenses outside the
tubes and cooling water flows through the tubes, as shown in figure 2.5.
 Schematic Diagram of a Steam Condenser
 The flow through a heat exchanger is characterized by
(a) the Heat exchange process tends to occur at constant pressure and frictional
pressure drop in the tubes is neglected.
(b) there is no means for doing any work (shaft work, electrical work, etc.) and
(c) changes in kinetic and potential energies are negligibly small.
(d) no external heat interaction.
 Using the subscripts ‘s’ for steam and ‘w’ for water and applying the steady flow
energy equation for the heat exchanger, we get
𝑚̇𝑠 (ℎ𝑖 )𝑠 + 𝑚̇𝑤 (ℎ𝑖 )𝑤 = 𝑚̇𝑠 (ℎ𝑒 )𝑠 + 𝑚̇𝑤 (ℎ𝑒 )𝑤 or
𝑚̇𝑠 (ℎ𝑖 − ℎ𝑒 )𝑠 = 𝑚̇𝑤 (ℎ𝑒 − ℎ𝑖 )𝑤
b) Nozzle and diffuser
 A nozzle is a steady-state device whose purpose is to create high velocity fluid
stream at the expense of the fluid pressure.
 A diffuser is a steady-state device whose purpose is to raise the pressure of the
fluid at the expense of fluid velocity.

Schematic Diagram of a Nozzle

 The flow through a nozzle is characterized by the following features:

(a) There is no means to do any work
(b) There is little or no change in potential energy.
(c) There is usually little or no heat transfer. An exception is the large nozzle on a
liquid-propellant rocket.
 With these assumptions, the steady flow energy equation for the case of nozzle or
diffuser becomes
𝑉𝑖2 𝑉𝑒2
ℎ𝑖 + = ℎ𝑒 +
2 2
c) Steam or Gas Turbine
 A turbine is a rotary steady-state machine whose purpose is to produce shaft work
at the expense of the pressure of the working fluid. Two general classes of
turbines are steam turbines and gas turbines.

Schematic Diagram of a Turbine

 The characteristic features of flow through a steam or gas turbine are:
a) There is little or no change in potential energy.
b) There is usually little or no heat transfer.
c) There is little or no change in kinetic energy.
 With these assumptions, the steady flow energy equation for the case of turbine
becomes
𝑚̇ℎ𝑖 = 𝑚̇ℎ𝑒 + 𝑊̇𝑠ℎ𝑎𝑓𝑡
d) Rotary Compressor
 The purpose of the steady state compressor is to increase the pressure of a fluid by
putting in shaft work. The most common is a rotary type compressor (either axial
flow or radial / centrifugal flow).

Schematic Diagram of a Rotary Compressor

 The characteristic features of flow through a rotary compressor are
a) Shaft work is done on the system and the fluid is compressed; W is negative.
b) Heat is lost to the surroundings; Q is negative
c) There is little or no change in potential energy.
 With these assumptions, the steady flow energy equation may be written as
𝑉𝑖2 𝑉𝑒2
̇
𝑚̇(ℎ𝑖 + ) − 𝑄 = 𝑚̇(ℎ𝑒 + ) − 𝑊̇𝑠ℎ𝑎𝑓𝑡
2 2
If the velocity changes are neglected and the flow process is treated as adiabatic
(Q=0), then
 𝑊̇𝑠ℎ𝑎𝑓𝑡 = 𝑚̇(ℎ𝑒 − ℎ𝑖 )

e) Throttling Device
 When a fluid flows through a restricted passage, like a partially opened wall, an
orifice, or a porous plug, there is an appreciable drop in pressure, and the flow is
said to be throttled. Figure 2.8 shows the process of throttling by a partially
opened valve on a fluid following in an insulated pipe.

Flow through a Valve

 The flow through a throttling device is characterized by the following features:
a) There is no means to do any work.
b) There is little or no change in potential energy.
c) There is usually little or no heat transfer.
 With these assumptions, the steady flow energy equation may be written as
𝑉𝑖2 𝑉𝑒2
(ℎ𝑖 + ) = (ℎ𝑒 + )
2 2
 Often the velocities in throttling are so low that the kinetic energy terms are also
negligible. So
ℎ𝑖 = ℎ𝑒
 Therefore, throttling process is an isenthalpic process for which enthalpy remains
constant.
Engineering Thermodynamics

Unit – III

Page 1
 Learning Material
Limitations of First Law of Thermodynamics
 First law fixes the exchange rate between heat and work, and places no restrictions
on the direction of change.
 Processes proceed spontaneously in certain directions, but the reverse is not
automatically attainable even though the reversal of the processes does not violate
the first law.
 First law provides a necessary but not a sufficient condition for a process to occur,
and
 There does exist some directional law which would tell whether a particular
process occurs or not. Answer is provided by the second law of thermodynamics.
Thermal Reservoir
 A thermal (heat) reservoir is that part of environment which can exchange heat
energy with a system. It has sufficiently large heat capacity and its temperature is
not affected by the quantity of heat transferred to or from it.
 A thermal reservoir is thus characterized by its temperature which remains
constant.
 The reservoir which is at high temperature and supplies heat is known as heat
source. Examples are a boiler furnace, a combustion chamber and a nuclear
reactor, etc.
 The reservoir which is at low temperature and to which heat is transferred is called
the heat sink. Atmospheric air, ocean and river etc. constitute the heat sink.
Heat Engine
 A heat engine may be defined as a device that operates in a thermodynamic cycle
and does a certain amount of net positive work through the transfer of heat from a
high-temperature body to a low-temperature body
 The internal combustion engine and the gas turbine are examples of such devices.
 Another example of a heat engine is the thermoelectric power generation device.

Fig. 3.1: A Simple Steam Power Cycle

Page 2
  Thermal efficiency is defined as the ratio of net work output to heat input
𝑁𝑒𝑡𝑤𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑊𝑛𝑒𝑡 𝑄𝐻 −𝑄𝐿
𝜂𝑡ℎ𝑒𝑟𝑚𝑎𝑙 = = =
𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 𝑄𝐻 𝑄𝐻

 Typical values for the thermal efficiency of real engines are about 35-50% for
large power plant, 30-35% for gasoline engines, and 35-40% for diesel engines.

Refrigerator or Heat Pump

 A refrigerator or heat pump may be define as a device that operates in a
thermodynamic cycle and transfer heat from a low-temperature space or body to a
high-temperature space or body by receiving work energy as input.
 The purpose of the refrigerator is to maintain the space at a temperature lower
than the surroundings by extracting heat from it.

Fig. 3.2: A Simple Refrigeration Cycle

 The purpose of the heat pump is to maintain the space at a temperature higher
than the surroundings by supplying heat to it.
 The “efficiency” of a refrigerator or heat pump is expressed in terms of the
coefficient of performance, which we designate as COP.
 The coefficient of performance is defined as the ratio of desired effect to the work
input.
 For a refrigerator, the desired effect is the amount of heat extracted from a low
temperature space, QL. Thus, the COP of a refrigerator is
𝑄𝐿
(𝐶𝑂𝑃)𝑅 =
𝑊
 For a heat pump, the desired effect is the amount of heat supplied to a high
temperature space, QH. Thus, the COP of a heat pump is
𝑄𝐻
(𝐶𝑂𝑃)𝐻𝑃 =
𝑊
 The relationship between COP of heat pump and COP of refrigerator is derived as
𝑄𝐻 𝑄𝐿 +𝑊 𝑄𝐿
(𝐶𝑂𝑃)𝐻𝑃 = = =1+ = 1 + (𝐶𝑂𝑃)𝑅
𝑊 𝑊 𝑊

The Second Law of Thermodynamics

 The Kelvin-Planck statement: It is impossible to construct a device that will
operate in a cycle and produce no effect other than the raising of a weight and the
exchange of heat with a single reservoir.
Page 3
  This statement ties in with our discussion of the heat engine. It states that it is
impossible to construct a heat engine that operates in a cycle, receives a given
amount of heat from a high-temperature body, and does an equal amount of work.
The only alternative is that some heat must be transferred from the working fluid
to a low-temperature body.
 This implies that it is impossible to build a heat engine that has thermal efficiency
of 100%
 The Clausius Statement: It is impossible to construct a device that operates in a
cycle and produces no effect other than the transfer of heat from a cooler body to
a hotter body.
 This statement is related to the refrigerator or heat pump. It states that it is
impossible to construct a refrigerator that operates without input of work. This
also implies that the coefficient of performance is always less than infinity.
Perpetual-Motion Machine of Second Kind
 A perpetual-motion machine of the second kind would extract heat from a source
and then convert this heat completely into other forms of energy, thus violating
the second law.

Fig. 3.3: Perpetual-Motion Machine of Second Kind

 Perpetual-motion machine of second kind has 100% thermal efficiency.
Equivalence of Kelvin Planck and Classius statement
At first Kelvin-Planck’s and classius statements may appear to be unconnected, but it can
easily be shown that they are virtually two parallel statements of the second law and are
equivalent in all respects.
The equivalence of the two statements will be proved if it can be shown that the
violation of one statement implies the violation of the second, and vice versa.
1. Let us first consider a cyclic heat pump P which transfers heat from a low
temperature reservoir (T2) to a high temperature reservoir (T1) with no other effect,
i.e., with no expenditure of work, violating classius statement. Let us assume a
cyclic heat engine E operating between the same thermal reservoirs, producing
Wnet in one cycle. The rate of working of the engine is such that it draws an
amount of heat Q1 from the hot reservoir equal to that discharged by the heat
pump. Then the hot reservoir may be eliminated and the heat Q1 discharged by the
heat pump is fed to the heat engine. So we see that the heat pump P and the heat
engine E acting together constitute a heat engine operating in cycles and producing
net work while exchanging heat only with one body at a single fixed temperature
(T2). This violates Kelvin-Planck Statement.

Page 4
 2. Let us now consider a perpetual motion machine of second kind (E) which
produces net work in a cycle by exchanging heat with only one thermal reservoir
(at T1) and thus violates the Kelvin-planck statement. Let us assume a cyclic heat
pump (P) extracting heat Q2 from a low temperature reservoir at T2 and
discharging heat to a high temperature reservoir at T1 with the expenditure of work
W equal to what the PMM2 delivers in a complete cycle. So E and P together
constitute a heat pump working in cycles and producing the sole effect of
transferring heat from a lower to a higher temperature body, thus violating the
classius statement.
Carnot Cycle and Carnot Heat Engine

A Carnot cycle is a hypothetical cycle consisting of four distinct processes: two

reversible isothermal processes and two reversible adiabatic processes. The cycle was
proposed in 1824 by a young French engineer, Sadi Carnot.

Fig. 3.4a: Essential Elements of a Heat Engine Fig. 3.4b: Carnot Heat Engine Cycle
working on Carnot Cycle on P-V plot
The sequence of operation for the different processes constituting a Carnot Cycle is:
Isothermal expansion (1 – 2): The heat is supplied to the working fluid at constant
temperature TH. This is achieved by bringing the heat source in good thermal contact
with the cylinder head through diathermic cover. The gas expands isothermally from
state point 1 to state point 2.
The heat supplied equals the work done which is represented by area under the curve 1-2
on pressure-volume plot and is given by
𝑉2 𝑉2
𝑄𝐻 = 𝑊1−2 = 𝑝𝑎 𝑉1 𝑙𝑜𝑔𝑒 = 𝑚 𝑅 𝑇1 𝑙𝑜𝑔𝑒
𝑉1 𝑉1

Page 5
Adiabatic Expansion (2-3): At the end of isothermal expansion (state point 2), the heat
source is replaced by adiabatic cover. The expansion continues adiabatically and
reversibly up to state point 3. Work is done by the working fluid at the expense of
internal energy and its temperature falls to TL at state point 3.
Isothermal Compression (3-4): After state point 3, the piston starts moving inwards and
the working fluid is compressed isothermally at temperature TL. The constant
temperature TL is maintained by removing the adiabatic cover and bringing the heat sink
in contact with the cylinder head. The compression continues up to state point 4.
The working fluid loses heat to the sink and its amount equals the work done on the
working fluid. This work is represented by area under the curve 3 - 4 and its amount is
given by.
𝑉3 𝑉3
𝑄𝐿 = 𝑊3−4 = 𝑝3 𝑉3 𝑙𝑜𝑔𝑒 = 𝑚 𝑅 𝑇3 𝑙𝑜𝑔𝑒
𝑉4 𝑉4

Adiabatic Compression (4 – 1): At the end of isothermal compression (state point 4),
the heat sink is removed and is replaced by adiabatic cover. The compression now
proceeds adiabatically and reversibly till the working fluid returns back to its initial state
point 1. Work is done on the working fluid, the internal energy increases and
temperature is raised to TH.
Since all the processes that constitute a Carnot cycle are reversible, the Carnot cycle is
referred to as a reversible cycle. The thermal efficiency of Carnot heat engine is given by
𝑛𝑒𝑡 𝑤𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑊𝑛𝑒𝑡
𝜂= =
ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 𝑄𝐻

There are no heat interactions along the reversible adiabatic processes 2 – 3 and 4 – 1,
and application of the first law of thermodynamics for the complete cycle gives.
∮ 𝛿𝑊 = ∮ 𝛿𝑄 or
𝑉2 𝑉3
𝑊𝑛𝑒𝑡 = 𝑄𝐻 − 𝑄𝐿 = 𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 − 𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒
𝑉1 𝑉4
𝑉 𝑉 𝑉
𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 2 −𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒 3 𝑇3 𝑙𝑜𝑔𝑒 3
𝑉1 𝑉4 𝑉4
Therefore, 𝜂= 𝑉 =1− 𝑋 𝑉
𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 2 𝑇1 𝑙𝑜𝑔𝑒 2
𝑉1 𝑉1

For the adiabatic expansion processes 2 – 3 and 4 – 1,

𝑇2 𝑉 𝛾−1 𝑇1 𝑉 𝛾−1
= ( 3) 𝑎𝑛𝑑 = ( 4)
𝑇3 𝑉2 𝑇4 𝑉1
𝑉3 𝑉4 𝑉3 𝑉2
Since T1 = T2 = TH and T3 = T4 = TL, we have = 𝑜𝑟 =
𝑉2 𝑉1 𝑉4 𝑉1

Substituting the above relation 3.10 in the equation 3.9, we get

𝑇3 𝑇𝐿 𝑇𝐻 −𝑇𝐿
𝜂 =1− =1− =
𝑇1 𝑇𝐻 𝑇𝐻

Following conclusions can be made with respect to efficiency of a Carnot engine:

(1) The efficiency is independent of the working fluid and depends upon the
temperatures of source and sink.
(2) The efficiency is directly proportional to temperature difference (T1 – T2)
between the source and the sink.
(3) Higher the temperature difference between source and sink, the higher will be
the efficiency.
(4) The efficiency increases with an increase in temperature of source and a
decrease in temperature of sink.
Page 6
 (5) If T1 = T2, no work will be done and efficiency will be zero.
Metallurgical considerations and the high cost of temperature resisting materials limit the
higher temperature T1. The lower temperature T2 is limited by atmospheric or sink
conditions.
Reversed Heat Engine (Carnot Heat Pump or Refrigerator)
Refrigerators and heat pumps are reversed heat engines.

Fig. 3.5: Carnot Heat Pump or Refrigerator Cycle on P-V plot

Fig. 3.5 shows the P – V plot of a Carnot heat pump (i.e. reversed Carnot heat engine).
The sequence of operation is:
1 – 4: Isentropic (reversible adiabatic) expansion of working fluid in the clearance space
of the cylinder. The temperature falls from T1 and T2.
4 – 3: Isothermal expansion during which heat QL is absorbed at temperature T2 from the
space being cooled.
3 – 2: Isentropic compression of working fluid. The temperature rises from T2 to T1.
3 – 1: Isothermal compression of working fluid during which heat QH is rejected to a
system at higher temperature.
As outlined above i.e. in the case of heat engine,
𝑉2 𝑉3
𝑄𝐻 = 𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 ; 𝑄𝐿 = 𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒
𝑉1 𝑉4
𝑉3 𝑉2
Also = , T1 = T2 = TH and T3 = T4 = TL
𝑉4 𝑉1

Therefore, for a heat pump

𝑄𝐻
(COP)Heat pump =
𝑄𝐻 −𝑄𝐿
𝑉
𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 2 𝑇1 𝑇𝐻
𝑉1
= 𝑉 𝑉 = =
𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 2 −𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒 3 𝑇1 −𝑇3 𝑇𝐻 −𝑇𝐿
𝑉1 𝑉4

For a refrigerator,
𝑄𝐿
(COP)Refrigerator =
𝑄𝐻 −𝑄𝐿
𝑉
𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒 3 𝑇3 𝑇𝐿
𝑉4
= 𝑉 𝑉 = =
𝑚𝑅𝑇1 𝑙𝑜𝑔𝑒 2 −𝑚𝑅𝑇3 𝑙𝑜𝑔𝑒 3 𝑇1 −𝑇3 𝑇𝐻 −𝑇𝐿
𝑉1 𝑉4

Page 7
Carnot Theorem
No heat engine operating in a cycle between two given thermal reservoirs, with fixed
temperatures, can be more efficient than a reversible engine (Carnot Engine) operating
between the same thermal reservoirs.

Proof of Carnot Theorem

Consider a reversible engine EA and an irreversible engine EB operating between the
same thermal reservoirs at temperatures TH and TL. For the same quantity of heat QH
withdrawn from the high temperature source, the work output from these engines is WA
and WB respectively. As such the heat given off by the reversible engine is (QH – WA)
and that from irreversible engine is (QH – WB).

(a) (b)
Fig. 3.6: Proof of Carnot Theorem

Let it be presumed that the irreversible engine EB is more efficient than the reversible
𝑊 𝑊
engine EA. Then 𝐵 > 𝐴 ; 𝑊𝐵 > 𝑊𝐴 𝑎𝑛𝑑 (𝑄𝐻 − 𝑊𝐴 ) > (𝑄𝐻 − 𝑊𝐵 )𝑖. 𝑒., work output
𝑄𝐻 𝑄𝐻
from irreversible engine is more than that from reversible engine.
Let the reversible engine EA now be made to operate as a refrigerator or heat pump; the
irreversible engine continues to operate as an engine.
Since engine EA is reversible, the magnitudes of heat and work interactions will remain
the same but their direction will be reversed. The work required to drive the refrigerator
can be withdrawn from the irreversible engine by having a direct coupling between the
two. Fig (b) shows the work and heat interactions for the composite system constituted
by the reversible engine (now operating as refrigerator) and the irreversible engine. The
net effect is
 No net interaction with the high temperature heat reservoir. It supplies and
recovers back the same amount of heat.
 The composite system withdraws (QH – WA) – (QH – WB) = (WB – WA) units of
heat from the low temperature reservoir and converts that into equivalent amount
of work output.
The combination thus constitutes a perpetual motion of the second kind in violation of the
second law. Obviously the assumption that the irreversible engine is more efficient than
the reversible engine is wrong. Hence, an irreversible engine cannot have efficiency
higher than that from a reversible engine operating between the same thermal reservoirs.
Corollaries of Carnot’s Theorem:
Corollary 1: All reversible engines operating between the two given thermal reservoirs,
with fixed temperature, have the same efficiency.
Page 8
Corollary 2: The efficiency of any reversible heat engine operating between two
reservoirs is independent of the nature of working fluid and depends only on the
temperature of the reservoirs.

The Thermodynamic Temperature Scale

 The concept of thermodynamic temperature scale may be developed with the help
of figure 3.7, which shows three reservoirs and three engines that operate on the
Carnot cycle.

Fig. 3.7: Arrangement of heat engines to demonstrate the Thermodynamic Temperature

scale
 T1 is the highest temperature, T3 is the lowest temperature, and T2 is an
intermediate temperature, and the engines operate between the various reservoirs
as indicated. Q1 is the same for both A and C and, since we are dealing with
reversible cycles, Q3 is the same for B and C. Since the efficiency of a Carnot
cycle is a function only of the temperature, we can write
𝑄 𝑇
𝜂𝑡ℎ𝑒𝑟𝑚𝑎𝑙 = 1 − 𝑄 𝐿 = 1 − 𝑇 𝐿 = 1 − 𝜓(𝑇𝐿 , 𝑇𝐻 )
𝐻 𝐻

Where 𝜓 designates a functional relation. Let us apply this functional relation to

the three Carnot Cycles shown in figure 3.7.
𝑄1 𝑄2 𝑄1
𝑄2
= 1 − 𝜓(𝑇1, 𝑇2 ); 𝑄3
= 1 − 𝜓(𝑇2, 𝑇3 ); 𝑄3
= 1 − 𝜓(𝑇1, 𝑇3 )
𝑄1 𝑄1 𝑄2
Since =
𝑄3 𝑄2 𝑄3

It follows that 𝜓(𝑇1 , 𝑇3 ) = 𝜓(𝑇1 , 𝑇2 ) × 𝜓(𝑇2 , 𝑇3 )

Note that the left side is a function of T1 and T3 (and not of T2), and therefore the
right side of this equation must also be a function of T1 and T3 (and not of T2).
From this fact we can conclude that the form of the function 𝜓 must be such that
𝑓(𝑇1 ) 𝑓(𝑇2 )
𝜓(𝑇1 , 𝑇2 ) = ; 𝜓(𝑇2 , 𝑇3 ) =
𝑓(𝑇2 ) 𝑓(𝑇3 )

For in this way f(T2) will cancel from the product of 𝜓(𝑇1, 𝑇2 ) × 𝜓(𝑇2 , 𝑇3 ).
𝑄1 𝑓(𝑇1 )
Therefore, we conclude that = 𝜓(𝑇1 , 𝑇3 ) =
𝑄3 𝑓(𝑇3 )
𝑄𝐻 𝑓(𝑇𝐻 )
In general terms, =
𝑄𝐿 𝑓(𝑇𝐿 )

Suppose we had a heat engine operating on the Carnot cycle that received heat at
the temperature of the steam point and rejected heat at the temperature of the ice
point. The efficiency of such an engine could be measured to be 26.8%,
𝑇 𝑇𝑖𝑐𝑒 𝑝𝑜𝑖𝑛𝑡
𝜂𝑡ℎ = 1 − 𝑇 𝐿 = 1 − 𝑇 = 0.2680
𝐻 𝑠𝑡𝑒𝑎𝑚 𝑝𝑜𝑖𝑛𝑡

Page 9
 𝑇𝑖𝑐𝑒 𝑝𝑜𝑖𝑛𝑡
= 0.7320
𝑇𝑠𝑡𝑒𝑎𝑚 𝑝𝑜𝑖𝑛𝑡

This gives us one equation concerning the two unknowns TH and TL. The second
equation comes from the difference between the steam point and ice point.
Tsteam point – Tice points = 100
Solving these two equations simultaneously, we find
Tsteam point = 373.15 K and Tice point = 273.15 K
It follows that, T(oC) + 273.15 = T(K)
The Inequality of Clausius
𝛿𝑄
 The inequality of Clausius is expressed as ∮ ≤ 0.
𝑇
 The inequality of Clausius is a corollary or a consequence of the second law of
thermodynamics. It will be demonstrated to be valid for all possible cycles,
including both reversible and irreversible heat engines and refrigerators.
Consider first a reversible (Carnot) heat engine cycle operating between reservoirs at
temperatures TH and TL, as shown in Fig. 3.8. For this cycle, the cyclic integral of the
heat transfer, ∮ 𝛿𝑄, is greater than zero.
∮ 𝛿𝑄 = 𝑄𝐻 − 𝑄𝐿 > 0
Since TH and TL are constant, from the definition of the absolute temperature scale and
from the fact this is a reversible cycle, it follows that
𝛿𝑄 𝑄𝐻 𝑄𝐿
∮ = − =0
𝑇 𝑇𝐻 𝑇𝐿

Fig. 3.8: Reversible heat engine cycle for demonstration of the inequality of Clausius
If ∮ 𝛿𝑄, the cyclic integral of 𝛿𝑄, approaches zero (by making TH approach TL) and the
cycle remains reversible, the cyclic integral of 𝛿𝑄/𝑇 remains zero. Thus, we conclude
that for all reversible heat engine cycles
𝛿𝑄
∮ =0
𝑇
Now consider an irreversible cyclic het engine operating between the same TH and TL as
the reversible engine of Fig. 8.1 and receiving the same quantity of heat QH. Comparing
the irreversible cycle with the reversible one, we conclude from the second law that
Wirr < Wrev
Since QH – QL = W for both the reversible and irreversible cycles, we conclude that
(QH – QL) irr < (QH – QL) rev and therefore, (QL) irr > (QL) rev
Consequently, for the irreversible cyclic engine,

Page 10
 ∮ 𝛿𝑄 = (𝑄𝐻 − 𝑄𝐿 )𝑖𝑟𝑟 > 0
𝛿𝑄 𝑄𝐻 (𝑄𝐿 )𝑖𝑟𝑟
∮ = − <0
𝑇 𝑇𝐻 𝑇𝐿

Thus, we conclude that for all irreversible heat engine cycles

𝛿𝑄
∮ <0
𝑇
𝛿𝑄
Therefore, in general, for any heat engine or refrigerator ∮ ≤0
𝑇
The Significance of the inequality of Clausius may be illustrated by considering the
simple steam power plant cycle shown in Fig.3.9.
Heat is transferred in two places, the boiler and the condenser. Therefore,
𝛿𝑄 𝛿𝑄 𝛿𝑄
∮ = ∫( ) +∫( )
𝑇 𝑇 𝑏𝑜𝑖𝑙𝑒𝑟 𝑇 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟

Fig.3.9: A simple Steam Power Plant that demonstrates the Inequality of Clausius

Since the temperature remains constant in both the boiler and condenser, this may be
integrated as follows:
𝛿𝑄 1 2 1 4 𝑄12 𝑄34
∮ = ∫ 𝛿𝑄 + ∫ 𝛿𝑄 = +
𝑇 𝑇1 1 𝑇3 3 𝑇1 𝑇3

Let us consider a 1 kg mass as the working fluid. We have then

𝑞12 = ℎ2 − ℎ1 = 2066.3 𝑘𝐽/𝑘𝑔, 𝑇1 = 164.97𝑜 𝐶

𝑞34 = ℎ4 − ℎ3 = 463.4 − 2361.8 = −1898.4 𝑘𝐽/𝑘𝑔, 𝑇3 = 53.97𝑜 𝐶

Therefore,
𝛿𝑄 2066.3 1898.4
∮ = − = −1.087 𝑘𝐽/𝑘𝑔 − 𝐾
𝑇 164.97 + 273.15 53.97 + 273.15

Thus, this cycle satisfies the inequality of Clausius, which is equivalent to saying that it
does not violate the second law of thermodynamics.
Entropy – A Property of a System
By applying Eq.3.28 and Fig. 3.10 we can demonstrate that the second law of
thermodynamics leads to a property of a system that we call entropy.
 Entropy is a measure of molecular disorderliness of a substance.

Page 11
Let a closed system undergo a reversible process from state 1 to state 2 along a path A,
and let the cycle be completed along path B, which is also reversible.
Because this is a reversible cycle, we can write
𝛿𝑄 2 𝛿𝑄 1 𝛿𝑄
∮ = ∫1 ( ) + ∫2 ( ) = 0
𝑇 𝑇 𝐴 𝑇 𝐵
Now consider another reversible cycle, which proceeds first along path C and is then
completed along path B. For this cycle we can write
𝛿𝑄 2 𝛿𝑄 1 𝛿𝑄
∮ = ∫1 ( ) + ∫2 ( ) = 0
𝑇 𝑇 𝐶 𝑇 𝐵
Subtracting the equation 3.30 from the equation 3.29, we get
2 𝛿𝑄 2 𝛿𝑄
∫1 ( 𝑇 ) = ∫1 ( 𝑇 )
𝐴 𝐶

Fig. 3.10: Two reversible cycles demonstrating the fact that entropy is a property of a
substance
Since the ∫ 𝛿𝑄/T is the same for all reversible paths between states 1 and 2, we conclude
that this quantity is independent of the path and it is a function of the end states only; it is
therefore a property. This property is called entropy and is designated by ‘S’. It follows
that entropy may be defined as a property of a substance in accordance with the relation.
𝛿𝑄
𝑑𝑆 = ( ) (Equation 3.32)
𝑇 𝑟𝑒𝑣
 Entropy is an extensive property, and the entropy per unit mass is designated by
‘s’. The change in the entropy of a system as it undergoes a change of state may
be found by integrating Eq.3.32. Thus,
2 𝛿𝑄
𝑆2 − 𝑆1 = ∫1 ( )
𝑇 𝑟𝑒𝑣
 To perform this integration, we must know the relation between T and Q.
 Since entropy is a property, the change in the entropy of a substance in going from
one state to another is the same for all processes, both reversible and irreversible,
between these two states.
 Equation 3.33 enables us to calculate changes of entropy, but it tells us nothing
about absolute values of entropy.
 From the third law of thermodynamics, which is based on observations of low-
temperature chemical reactions, it is concluded that the entropy of all pure
substances (in the appropriate structural form) can be assigned the absolute value
of zero at the absolute zero of temperature.
 It also follows from the subject of statistical thermodynamics that all pure
substances in the (hypothetical) ideal-gas state at absolute zero temperature have
zero entropy.
Page 12
Entropy Change of a control mass during a Reversible Process
The entropy change during a reversible process 1 – 2 is given by
2 𝛿𝑄
𝑆2 − 𝑆1 = ∫1 ( )
𝑇 𝑟𝑒𝑣
The relationship between 𝛿𝑄 and T can be obtained from the thermodynamics property
relations.
The Thermodynamic Property Relations
The two important thermodynamic property relations for a compressible substance can be
derived from the first law of thermodynamics.
𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊
For a reversible process of simple compressible substance, we can write
𝛿𝑄 = 𝑇𝑑𝑆 and 𝛿𝑊 = 𝑃𝑑𝑉
Substituting these relations into the first law equation, we get
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
Since enthalpy is defined as = 𝑈 + 𝑃𝑉 , on differentiation we get
dH = dU + PdV + VdP
= 𝛿𝑄 + 𝑉𝑑𝑃
= 𝑇𝑑𝑆 + 𝑉𝑑𝑃 or
𝑇𝑑𝑆 = 𝑑𝐻 − 𝑉𝑑𝑃
These equations can also be written for a unit mass,
𝑇𝑑𝑆 = 𝑑𝑢 + 𝑃𝑑𝑣
𝑇𝑑𝑆 = 𝑑ℎ − 𝑣𝑑𝑃
Entropy Change of a Control Mass during an Irreversible Process
Consider a control mass that undergoes the cycles shown in fig. 3.11.

Fig. 3.11: Entropy Change of a Control Mass during an irreversible process

Since the cycle made up of the reversible processes A and B is a reversible cycle, we can
write
𝛿𝑄 2 𝛿𝑄 1 𝛿𝑄
∮ = ∫1 ( ) + ∫2 ( ) = 0
𝑇 𝑇 𝐴 𝑇 𝐵
The cycle made of the irreversible process C and the reversible process B is an
irreversible cycle. Therefore, for this cycle the inequality of Clausius may be applied as
Page 13
 𝛿𝑄 2 𝛿𝑄 1 𝛿𝑄
∮ = ∫1 ( ) + ∫2 ( ) < 0
𝑇 𝑇 𝐶 𝑇 𝑩
Subtracting the equation 3.34 from the equation 3.33 and rearranging, we have
2 𝛿𝑄 2 𝛿𝑄
∫1 ( 𝑇 ) > ∫1 ( 𝑇 )
𝐴 𝐶
Since path A is reversible, and since entropy is a property,
2 𝛿𝑄 2 2
∫1 ( 𝑇 ) = ∫1 𝑑𝑆𝐴 = ∫1 𝑑𝑆𝐶
𝐴
Therefore,
2 2 𝛿𝑄
∫1 𝑑𝑆𝐶 > ∫1 ( 𝑇 )
𝐶
As path C was arbitrary, the general result is
𝛿𝑄
𝑑𝑆 ≥
𝑇
2 𝛿𝑄
or 𝑆2 − 𝑆1 ≥ ∫1
𝑇
In these equations the equality holds for a reversible process and the inequality for an
irreversible process.
 Thus, If an amount of heat 𝛿𝑄 is transferred to a control mass at temperature T in
a reversible process, the change of entropy is given by the relation.
𝛿𝑄
𝑑𝑆 = ( )
𝑇 𝑟𝑒𝑣
 If any irreversible effects occur while the amount of heat 𝛿𝑄 is transferred to the
control mass at temperature T, however, the change of entropy will be greater than
that of the reversible process. We would then write
𝛿𝑄
𝑑𝑆 > ( )
𝑇 𝑖𝑟𝑟
Entropy Generation
The conclusion from the previous consideration is that the entropy change for an
irreversible process is larger than the change in a reversible process for the same 𝛿𝑄 and
T. This can be written out in a common form as an equality
𝛿𝑄
𝑑𝑆 = + 𝛿𝑆𝑔𝑒𝑛
𝑇
Provided the last term is positive,
𝛿𝑆𝑔𝑒𝑛 ≥ 0
The amount of entropy, 𝛿𝑆𝑔𝑒𝑛 , is the entropy generation in the process due to
irreversibilities occurring inside the system.
 This internal generation can be caused by the processes such as friction,
unrestrained expansions, and the internal transfer of energy (redistribution) over a
finite temperature difference.
 In addition to this internal entropy generation, external irreversibilities are possible
by heat transfer over finite temperature differences as the 𝛿𝑄 is transferred from a
reservoir or by the mechanical transfer of work.
 We can generate but not destroy entropy. This is in contrast to energy which we
can neither generate nor destroy.

Page 14
  Since 𝛿𝑄 = 0 for an adiabatic process, and the increase in entropy is always
associated with the irreversibilities.
 The presence of irreversibilities will cause the actual work to be smaller than the
reversible work. This means less work out in an expansion process and more
work input in a compression process.
Principles of the increase of Entropy
Consider the process shown in Fig. 3.12 in which a quantity of heat 𝛿𝑄 is transferred
from the surroundings at temperature T0 to the control mass at temperature T. Let the
work done during this process be 𝛿𝑊.

Fig. 3.12: Entropy Change for the Control Mass Plus Surroundings
For this process we can apply equation 3.38 to the control mass and write
𝛿𝑄
𝛿𝑆𝑐.𝑚. ≥
𝑇
For the surroundings at T0, 𝛿𝑄 is negative, and we assume a reversible heat extraction so
−𝛿𝑄
𝛿𝑆𝑠𝑢𝑟𝑟 =
𝑇0

The total net change of entropy is therefore

𝛿𝑄 𝛿𝑄
𝛿𝑆𝑛𝑒𝑡 = 𝑑𝑆𝑐.𝑚. + 𝑑𝑆𝑠𝑢𝑟𝑟 ≥ −
𝑇 𝑇0
1 1
≥ 𝛿𝑄 ( − )
𝑇 𝑇0

If T > T0, the heat transfer is from the control mass to the surroundings, and both 𝛿𝑄 and
the quantity {(1/T) – (1/T0)} are negative, thus yielding the same result.
𝑑𝑆𝑛𝑒𝑡 = 𝑑𝑆𝑐.𝑚. + 𝑑𝑆𝑠𝑢𝑟𝑟 ≥ 0
The net entropy change could also be termed the total entropy generation:
𝑑𝑆𝑛𝑒𝑡 = 𝑑𝑆𝑐.𝑚. + 𝑑𝑆𝑠𝑢𝑟𝑟 = ∑ 𝛿𝑊𝑔𝑒𝑛 ≥ 0
where the equality holds for reversible processes and the inequality for irreversible
processes.
 This is a very important equation, not only for thermodynamics but also for
philosophical thought. This equation is referred to as the principle of the increase
of entropy.
 The great significance is that the only processes that can take place are those in
which the net change in entropy of the control mass plus its surroundings increases
(or in the limit, remain constant). The reverse process, in which both the control
mass and surroundings are returned to their original state, can never be made to
occur.
Page 15
  Thus, the principle of the increase of entropy can be considered a quantitative
general statement of the second law and applies to the combustion of fuel in our
automobile engines, the cooling of our coffee, and the processes that take place in
our body.

Entropy Change of a Solid or Liquid

Writing the first thermodynamic property relation,
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑃𝑑𝑣
Since change in specific volume for a solid or liquid is very small,
𝑑𝑢 𝑑𝑇
𝑑𝑠 ≈ ≈𝑐
𝑇 𝑇
For many processes involving a solid or liquid, we may assume that the specific heat
remains constant, in which case equation 3.47 can be integrated. The result is
𝑇2
𝑠2 − 𝑠1 = 𝑐 𝑖𝑛
𝑇1

Where, C is the specific heat in J/kg -K.

Entropy Change of an Ideal Gas

Writing the first thermodynamic property relation,
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑃𝑑𝑣
𝑃 𝑅
For an ideal gas, du = Cv dT and =
𝑇 𝑉
𝑑𝑇 𝑑𝑣
Therefore, ds = cv +𝑅
𝑇 𝑉
Upon integration, we have
2 𝑑𝑇 𝑣2
𝑠2 − 𝑠1 = ∫1 𝑐𝑣 + 𝑅 𝑙𝑛
𝑇 𝑣1

Where, cv is the specific heat at constant volume in J/kg –K.

Similarly,
𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑃
𝑣 𝑅
For an ideal gas, dh = cp dT and =
𝑇 𝑃
𝑑𝑇 𝑑𝑃
Therefore, ds = cp −𝑅
𝑇 𝑃
Upon integration, we have
2 𝑑𝑇 𝑃2
𝑠2 − 𝑠1 = ∫1 𝑐𝑝 − 𝑅 𝑙𝑛
𝑇 𝑃1

Where, cp is the specific heat at constant pressure in J/kg –K.

Entropy as a Rate Equation
𝑑𝑆 1 𝛿𝑄 𝛿𝑆𝑔𝑒𝑛
= +
𝛿𝑡 𝑇 𝛿𝑡 𝛿𝑡
High and Low Grade Energy
High Grade Energy: High Grade Energy is the energy that can be completely
transformed into shaft work without any loss and hence is fully utilizable. Examples are

Page 16
mechanical and electric work, water, wind and ideal power; kinetic energy of jets; animal
and manual power.
Low Grade Energy: Low Grade Energy is the energy of which only a certain portion
can be converted into mechanical work. Examples are heat or thermal energy; heat from
nuclear fission or fusion; heat from combustion of fuels such as coal, wood, oil, etc.
Available and Unavailable Energy
 The portion of thermal energy input to a cyclic heat engine which gets converted
into mechanical work is referred to as available energy.
 The portion of thermal energy which is not utilizable and is rejected to the sink
(surroundings) is called unavailable energy.
 The terms exergy and anergy are synonymous with available energy and
unavailable energy, respectively. Thus Energy = exergy+anergy.
The following two cases arise when considering available and unavailable portions of
heat energy
Case 1: Heat is withdrawn at constant temperature

Fig. 3.13: Available and Unavailable Energy: Heat Withdrawn from an Infinite Reservoir
Fig.3.13 represents a reversible engine that operates between a constant temperature
reservoir at temperature T and a sink at temperature T0. Corresponding to heat Q
supplied by the reservoir, the available work Wmax is given by
𝑊𝑚𝑎𝑥 𝑇−𝑇0
𝜂= =
𝑄 𝑇
Therefore,
𝑇−𝑇0 𝑇 𝑄
Wmax = Available energy = 𝑄 [ ] = 𝑄 [1 − 0 ] = 𝑄 − 𝑇0 = 𝑄 − 𝑇0 𝑑𝑠
𝑇 𝑇 𝑇
Unavailable energy = 𝑇0 𝑑𝑠
Where 𝑑𝑠 represents the change of entropy of the system during the process of heat
supply 𝑄.
Case 2: Heat is withdrawn at varying temperature.
In case of a finite reservoir, the temperature changes
as heat is withdrawn from it (Fig. 3.14), and as such
the supply of heat to the engine is at varying
temperature. The analysis is then made by breaking
the process into a series of infinitesimal Carnot
cycles each supplying 𝛿𝑄 of heat at the temperature
T (different for each cycle) and rejecting heat at the
constant temperature T0. Maximum amount of work
(available energy) then equals
Fig. 3.14: Available and Unavailable Energy:
Heat Supply at varying Temperature
Page 17
 𝑇
Wmax = ∫ [1 − 0 ] 𝛿𝑄
𝑇
𝛿𝑄
=∫ 𝛿𝑄 − ∫ 𝑇0
𝑇
𝛿𝑄
=∫ 𝛿𝑄 − 𝑇0 ∫ = 𝑄 − 𝑇0 𝑑𝑠
𝑇
It is to be seen that expressions for both the available and unavailable parts are identical
in the two cases.
Loss of Available Energy due to Heat Transfer through a Finite Temperature
Difference
Consider a certain quantity of heat Q transferred from a system at constant temperature
T1 to another system at constant temperature T2 (T1>T2) as shown in Fig. 3.15.

Fig. 3.15: Decrease in Available Energy due to Heat Transfer through a Finite Temperature
Difference
Before heat is transferred, the energy Q is available at T1 and the ambient temperature is
T0 .
𝑇
Therefore, Initial available energy, (𝐴𝐸 )1 = 𝑄 [1 − 0 ]
𝑇1

After heat transfer, the energy Q is available at T2 and again the ambient temperature is T0.
𝑇
Therefore, Final available energy, (𝐴𝐸 )2 = 𝑄 [1 − 0 ]
𝑇2
𝑇 𝑇
Change in available energy = (𝐴𝐸 )1 − (𝐴𝐸 )2 = 𝑄 [1 − 0 ] − 𝑄 [1 − 0 ]
𝑇1 𝑇2
−𝑄 𝑄
= 𝑇0 [ + ] = 𝑇0 (𝑑𝑆1 + 𝑑𝑆2 ) = 𝑇0 (𝑑𝑆)𝑛𝑒𝑡
𝑇1 𝑇2
𝑄 𝑄
Where 𝑑𝑆1 = − , 𝑑𝑆2 = and (𝑑𝑆)𝑛𝑒𝑡 is the net change in the entropy of the
𝑇1 𝑇2
combination to the two interacting systems. This net entropy change is called the entropy
change of universe or entropy production.
Since the heat transfer has been through a finite temperature difference, the process is
irreversible, i.e., (dS)net>0 and hence there is loss or decrease of available energy.
The above aspects lead us to conclude that:
 Whenever heat is transferred through a finite temperature difference, there is
always a loss of available energy.
 Greater the temperature difference (T1–T2), the more net increase in entropy and,
therefore, more is the loss of available energy.
 The available energy of a system at a higher temperature is more than at a lower
temperature, and decreases progressively as the temperature falls.

Page 18
  The concept of available energy provides a useful measure of the quality of
energy. Energy is said to be degraded each time it flows through a finite
temperature difference. The second law may, therefore, be referred to as law of
degradation of energy.
Availability
 The work potential of a system relative to its dead state, which exchanges heat
solely with the environment, is called the availability of the system at that state.
 When a system and its environment are in equilibrium with each other, the system
is said to be in its dead state.
 Specifically, a system in a dead state is in thermal and mechanical equilibrium
with the environment at T0 and P0.
 The numerical values of (T0, P0) recommended for the dead state are those of the
standard atmosphere, namely, 298.15 K and 1.01325 bars (1 atm).
Availability of Non-flow or Closed System
Consider a piston-cylinder arrangement (closed system) in which the fluid at P1, V1, T1,
expands reversibly to the environmental state with parameters P0, V0, T0. The following
energy (work and het) interactions take place:
 The fluid expands and expansion work Wexp is obtained. From the principle of
energy conservation, 𝛿𝑄 = 𝛿𝑊 + 𝑑𝑈, 𝑤𝑒 𝑔𝑒𝑡 ∶ −𝑄 = 𝑊𝑒𝑥𝑝 + (𝑈0 − 𝑈1 )
The heat interaction is negative as it leaves the system.
Therefore 𝑊𝑒𝑥𝑝 = (𝑈1 – 𝑈0 )– 𝑄
 The heat Q rejected by the piston-cylinder
assembly may be made to run a reversible heat
engine. The output from the reversible engine
equals
𝑇
Weng = 𝑄 [1 − 0 ] = 𝑄 − 𝑇0 (𝑆1 − 𝑆0 ) (Equ.3.60)
𝑇1

The sum total of expansion work Wexp and the engine

work Weng gives maximum work obtainable from the
arrangement.

Fig. 3.16: Availability of a Non-Flow System

𝑊𝑚𝑎𝑥 = [(𝑈1 – 𝑈0 )– 𝑄] + [𝑄– 𝑇0 (𝑆1 – 𝑆0 )]
= (𝑈1 – 𝑈0 )– 𝑇0 (𝑆1 – 𝑆0 )
The piston moving outwards has to spend a work in pushing the atmosphere against its
own pressure. This work, which may be called as the surrounding work is simply
dissipated, and as such is not useful. It is given by
𝑊𝑠𝑢𝑟𝑟 = 𝑃0 (𝑉0 − 𝑉1 )
The energy available for work transfer less the work absorbed in moving the environment
is called the useful work or net work.
Therefore, Maximum available useful work or net work,

Page 19
 (Wuseful)max = Wmax - Wsurr
= (U1 – U0) – T0(S1 – S0) – P0(V0 – V1)
= (U1 + P0V1 – T0S1) – (U0 + P0V0 – T0S0)
= A1 – A 0
Where A = (U+P0V – T0S) is known as non-flow availability function. It is a composite
property of the system and surroundings as it consists of three extensive properties of the
system (U, V and S) and two intensive properties of the surroundings (P0 and T0).
When the system undergoes a change from state 1 to state 2 without reaching the dead
state, then
(Wuseful)max = Wnet = (A1 – A0) – (A2 – A0) = A1 – A2

Availability of Steady Flow System

Consider a steady flow system and let it be assumed that the following fluid has the
following properties and characteristics:
Internal energy U, specific volume V, specific enthalpy H, pressure P, velocity C and
location Z.
The properties of the fluid would change when flowing through the system. Let subscript
1 indicate the properties of the system at inlet and subscript 0 be used to designate the
fluid parameters at outlet corresponding to dead state. Further let Q units of heat be
rejected by the system and let the system deliver Wshaft units of work.
𝐶12 𝐶02
𝑈1 + 𝑃1 𝑉1 + + 𝑔𝑍1 − 𝑄 = 𝑈0 + 𝑃0 𝑉0 + + 𝑔𝑍0 + 𝑊𝑠ℎ𝑎𝑓𝑡
2 2
Neglecting potential and kinetic energy changes,
U1 + P1V1 – Q = U0 + P0V0 + Wshaft
H1 – Q + H0 + Wshaft
Therefore, Shaft work Wshaft = (H1 – H0) – Q

The heat Q rejected by the system may be made to

run a reversible heat engine. The output from this
engine equals
𝑇
Weng = Q [1 − 0 ] = 𝑄 − 𝑇0 (𝑆1 − 𝑆0 ) (Equation 3.67)
𝑇1

Therefore, Maximum available useful work or net

work
Wnet = Ws + Weng =(H1 – H0) – Q + Q – T0(S1 – S0)
= (H1 – T0 S1) – (H0 – T0 S0)
= B1 – B0 (Equation 3.68) Fig. 3.17: Availability of a Steady flow System

Where B = (H – T0S) is known as the steady flow availability function. It is composite

property of system and surroundings involving two extensive properties H and S of the
system and one intensive property T0 of the surroundings.
When the system changes from state 1 to some intermediate state 2, the change in steady
flow availability function is given by
Page 20
 dB = (B1 – B0) – (B2 – B0) = B1 – B2
Helmholtz and Gibb’s Functions
For a non-flow process, the maximum work output from the system when T1 = T2 = T0, is
given by
𝑊𝑚𝑎𝑥 = (𝑈1 – 𝑇1 𝑆1 ) – (𝑈2 – 𝑇2 𝑆2 ) = 𝐴1 – 𝐴2
 The term (U – TS) is called the Helmholtz function and is defined as the
difference between the internal energy and the product of temperature and entropy.
 The maximum work of the process is equal to the decrease in Helmholtz function
of the system.
In the case of flow process, the maximum work output from the system when T1 = T2 =
T0 and neglecting kinetic and potential energies, is given by
Wmax = (U1 + P1V1 – T1S1) – (U2 + P2V2 – T2S2)
= (H1 – T1S1) – (H2 – T2 S2) = G1 – G2
 The term (H – TS) is called Gibb’s function and is defined as the difference
between enthalpy and product of temperature and entropy.
 The changes of both Helmholtz and Gibb’s functions are called free energy i.e.,
energy that is free to be converted into work. Further, both the Helmholtz and
Gibb’s functions establish a criterion for thermodynamic equilibrium. At
equilibrium, these functions are at their minimum values.
Maxwell Relations
The Maxwell relations can be derived from the different forms of the thermodynamic
property relations discussed earlier such as
𝑑𝑢 = 𝑇𝑑𝑠 − 𝑃𝑑𝑣; 𝑑ℎ = 𝑇𝑑𝑠 + 𝑣𝑑𝑃;
𝐴 = 𝑈 − 𝑇𝑆 (𝑜𝑟) 𝑎 = 𝑢 − 𝑇𝑠 and 𝐺 = 𝐻 − 𝑇𝑆 (𝑜𝑟) 𝑔 = ℎ − 𝑇𝑠
These relations are exact differentials and are of the general form 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦.
For exact differentials, we have
𝜕𝑀 𝜕𝑁
( ) =( ) .
𝜕𝑦 𝑥 𝜕𝑥 𝑦

Therefore using this relationship we can derive the following equations:

𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑣
( ) = −( ) ; ( ) = −( )
𝜕𝑣 𝑠 𝜕𝑠 𝑣 𝜕𝑃 𝑠 𝜕𝑠 𝑃
𝜕𝑃 𝜕𝑠 𝜕𝑣 𝜕𝑠
( ) = −( ) ; ( ) = −( )
𝜕𝑇 𝑣 𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇

These four equations are known as the Maxwell Relations for a simple compressible
fluid.
Third Law of Thermodynamics (Nernst Law)
At absolute zero temperature, the entropy of all homogeneous crystalline (condensed) substances
in a state of equilibrium becomes zero. the molecules of a substance in solid phase continually
oscillate, creating an uncertainty about their position. These oscillations, however, fade as the
temperature is decreased, and the molecules supposedly become motionless at absolute zero.
This represents a state of ultimate molecular order (and minimum energy). Therefore, the
entropy of a pure crystalline substance at absolute zero temperature is zero since there is no
Page 21
uncertainty about the state of the molecules at that instant. This statement is known as the third
law of thermodynamics. The third law of thermodynamics provides an absolute reference point
for the determination of entropy. The entropy determined relative to this point is called absolute
entropy, and it is extremely useful in the thermodynamic analysis of chemical reactions. Notice
that the entropy of a substance that is not pure crystalline (such as a solid solution) is not zero at
absolute zero temperature. This is because more than one molecular configuration exists for such
substances, which introduces some uncertainty about the microscopic state of the substance.

Page 22
ENGINEERING THERMODYNAMICS
 Unit – IV
Objectives:

 To introduce the students to Properties of Pure substances, various Phase diagram

like P-v, P-T, T-s and h-s and steam tables.

Syllabus:

Pure substance, phase, phase transformation, P-V, P-T, T-S and h-s diagrams of a pure
substance (water), Triple point, critical point, P-V-T surface, Dryness fraction, steam
tables, Mollier diagram, Determination of steam Properties using steam tables and
mollier chart, Various Thermodynamic Processes, and energy transfer, measurement of
steam quality- Steam calorimetry, clausius- clapeyron equation,
Outcomes:
Students will be able to
 Evaluate properties of substances at saturation points, at mixtures of phases and
Draw phase diagram (P-V, P-T, T-S and h-s) of substances.

 Define triple point, critical point, Dryness fraction.

 Analyse heat and work quantities by using steam tables and Mollier chart.

 Evaluate quality of steam by using Various steam calorimeters.

 Evaluate Latent heat by using Phase transformations using Clausius- clapeyron

equation.
 UNIT IV

PROPERTIES OF PURE SUBSTANCES

4.1 Pure substance

 A Pure substance is a substance of constant chemical composition

throughout its mass. It is a one component system and it may exist in one
or more phases.
Or
A substance that has a fixed chemical composition throughout is called a
Pure substance. Water, nitrogen, helium, and carbon dioxide, for example
are all pure substances.

 A pure substance does not have to be of a single chemical element or

compound. A mixture of various chemical elements or compounds also
qualifies as a pure substance as long as the mixture is homogeneous.
Air for example, is a mixture of several gases, but is often considered to be
pure substance because it has a uniform chemical composition. However a
mixture of oil and water is not a pure substance. Since oil is not soluble in
water, it will collect on top of water, forming two chemically dissimilar
regions.

 A mixture of two or more phases of a pure substance is still a pure

substance as long as the chemical composition of all the phases is same.
A mixture of ice, liquid water for example is a pure substance because both
phases have the same chemical composition.

 A mixture of liquid air and gaseous air is not a pure substance since the
composition of liquid air is different from the composition of gaseous air,
and the mixture is no longer chemically homogeneous.

We know that substance exists in different phases. At room

temperature and pressure, copper is a solid, mercury is a liquid, and
nitrogen is a gas. Under different conditions each may appear in different
phase. Even though there are three principle phases- solid, liquid, and gas-
a substance may have several phases within a principle phase, each with a
 different molecular structure. For example carbon may exist as diamond,
graphite in solid phase. Helium has two liquid phases; Iron has three solid
phases. Ice may exist at seven different phases at high pressures.

 A phase is identified as having a distinct molecular arrangement that is

homogeneous throughout and separated from others by easily identifiable
boundary surfaces.

 Intermolecular bonds are strongest in solids, and weakest in gases. One

reason is that molecules in solid are closely packed together, where as in
gases they are separated by relatively large distances.

 The molecules in a solid are arranged in a three – dimensional pattern

(lattice) that is repeated throughout. Because of the small distances between
the molecules in a solid, the attractive forces of molecules on each other are
large and keep the molecules in fixed positions. The attractive forces
between the molecules turn to repulsive forces as the distance between the
molecules approaches to zero, thus preventing the molecules from piling up
on top of each other. Even though the molecules in a solid cannot move
relative to each other, they continuously oscillate about their equilibrium
positions. The velocity of the molecules during these oscillations depends
on the temperature. At sufficiently high temperatures, the velocity of the
molecules may reach a point where the intermolecular forces are partially
overcome and groups of molecules break away. This is the beginning of
Melting (change of Phase from Solid to Liquid) process.

Fig. 4.1 The molecules in a solid are kept at their positions by the large spring like intermolecular
forces.

 The molecular spacing in the liquid phase is not much different from that
of solid phase, except the molecules are no longer at fixed positions relative
to each other and they can rotate and translate freely. In liquids the
 intermolecular forces are weaker relative to solid, but still relatively strong
compared with gases.

 In the gas phase the molecules are far apart each other, and molecular
order is nonexistent.

 4.2 Phase change process of pure substance

There are many practical situations where two phases of a pure substance
coexist in equilibrium. Water exists as a mixture of liquid and vapor in the
boiler and condenser of a steam power plant. The refrigerant turns from liquid
to vapor in the freezer of a refrigerator.
As a familiar substance water is used to demonstrate the basic principles
involved.

 Compressed liquid and saturated liquid

Consider a piston cylinder device containing liquid water at 200C and 1 atm.
Pressure (fig. 4.2 a). let this is state [Link] these conditions, water exists in
the liquid phase, and it is called a compressed liquid or a sub cooled liquid,
meaning that it is not about to vaporize. Heat is now transferred to water until
its temperature rises to say 400C. As the temperature rises, the liquid water
expands slightly, and so its specific volume increases. To accommodate this
expansion, the piston moves up slightly. The pressure in the cycle remains
constant at 1 atm during this process. Water is still a compressed liquid at this
state since it has not started to vaporize.
 As more heat is transferred, the temperature is keeps rising until it reaches
say 1000C (fig.4.2 b). Let this is state 2. At this point water is still a liquid but
any heat addition will cause some of the liquid to vaporize. That is a phase
change process from liquid to vapor is about to takes place. A liquid is about to
vaporize is called saturated liquid. Therefore state 2 is a saturated liquid
state.

 Saturated vapor and super heated vapor

Once boiling starts, the temperature stops rising until the liquid is
completely vaporized. That is, the temperature will remains constant
during the entire phase-change process if the pressure is held constant.
During the boiling process, the only change we will observe is a large
increase in volume and a steady decline in the liquid level as a result of
more liquid turning to vapor.
Mid way about complete vaporization, the cylinder contains equal
amounts of liquid and vapor (fig. 4.2 c). Let this is at state 3. As we continue
transferring heat, the vaporization process continues until the last drop of
liquid is vaporized. At this point the entire cylinder is filled with vapor (fig
4.2 d). Let this is state 4. Any heat loss from this vapor will cause some of
the vapor to condense (phase change from vapor to liquid). A vapor that is
about to condense is called Saturated Vapor.
Therefore state 4 is a saturated vapor state. A substance at states between 2
and 4 is referred to as a saturated liquid- vapor mixture since liquid and
vapor phases coexists in equilibrium at these states.
Once the phase change process is completed, we are back to single
phase region again (this time vapor phase) and further transfer of heat
results in an increase in both the temperature and the specific volume. At
state 5, the temperature of the vapor is let us say 3000C (fig. 4.2e), and if we
transfer some heat from vapor, the temperature may drop somewhat but no
condensation will takes place as long as the temperature above 1000C (for
p=1atm). A vapor that is not about to condense (i.e not saturated vapor) is
called a super heated vapor. [see T-υ diagram of water at constant
pressure, Fig. 4.2f]
 Fig.4.2 f T-υ diagram for the heating process of water at constant pressure of 1 atm

 4.3 Saturation Temperature and saturation Pressure:

The statement “water boils at 1000C” is incorrect. The correct
statement is “water boils at 1000C at 1 atm pressure.” The only reason
water started boiling at 1000C was because we held the pressure constant at
1 atm (101.325 kPa). If the pressure inside the cylinder were raised to 500
kPa by adding weights on top of the piston, water would start boiling at
151.80C. That is, the temperature at which water starts boiling depends on
the pressure; therefore, if the pressure is fixed, so is the boiling
temperature.
 At a 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. At a pressure of 101.325 kPa, Tsat is 99.970C.
Conversely, at a temperature of 99.970C, Psat is 101.325 kPa.

 Saturation tables that list the saturation pressure against the temperature
(or the saturation temperature against the pressure) are available for
practically all substances. A partial listing of such a table is given for water.
 This table indicates that the pressure of water changing phase (boiling
or condensing) at 250C must be 3.17 kPa, and the pressure of water
must be maintained at 3976 kPa (about 40 atm) to have it boil at 2500C.
Also, water can be frozen by dropping its pressure below 0.61 kPa.

 It takes a large amount of energy to melt a solid or vaporize a liquid. The

amount of energy absorbed or released during a phase-change process is
called the latent heat. More specifically, the amount of energy absorbed
during melting is called the latent heat of fusion and is equivalent to the
amount of energy released during freezing.

 Similarly, the amount of energy absorbed during vaporization is called the

latent heat of vaporization and is equivalent to the energy released
during condensation. The magnitudes of the latent heats depend on the
temperature or pressure at which the phase change occurs. At 1 atm
pressure, the latent heat of fusion of water is 333.7 kJ/kg and the latent
heat of vaporization is 2256.5 kJ/kg.

 During a phase-change process, pressure and temperature are obviously

dependent properties, and there is a definite relation between them, that is,
Tsat =f (Psat). A plot of Tsat versus Psat, such as the one given for water in
the following fig. 4.3 is called a liquid–vapor saturation curve. A curve of
this kind is characteristic of all pure substances.
 From the figure it is clear that Tsat increases with Psat. Thus, a substance
at higher pressures boils at higher temperatures. In the kitchen, higher
boiling temperatures mean shorter cooking times and energy savings.

 4.4 Property Diagrams for Phase – change processes

4.4.1 The T-υ diagram

 The phase-change process of water at 1 atm pressure was described in
detail in section 4.2 and the plot on T-v diagram in Fig. 4.2f. Now we
repeat this process at different pressures to develop the T-v diagram.

 Let us add weights on top of the piston until the pressure inside the
cylinder reaches 10bar. At this pressure, water has a somewhat smaller
specific volume than it does at 1 atm pressure. As heat is transferred to the
water at this new pressure, the process follows a path that looks very much
like the process path at 1 atm pressure, as shown in Fig. 4.4, but there are
some noticeable differences.

 First, water starts boiling at a much higher temperature (179.90C) at this

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

 As the pressure is increased further, this saturation line continues to shrink,

as shown in Fig. 4.4, and it becomes a point when the pressure reaches
220.6 bar 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 vapor
states are identical.

 The temperature, pressure, and specific volume of a substance at the critical

point are called, respectively, the critical temperature Tcr, critical
pressure Pcr, and critical specific volume vcr. The critical-point properties
of water are Pcr = 220.6bar , Tcr = 373.950C, and vcr = 0.003106 m3/kg.
For helium, they are 2.3 bar, -267.850C, and 0.01444 m3/kg.

 At pressures above the critical pressure, there is not a distinct phase change
process (Fig. 4.4a). Instead, the specific volume of the substance continually
increases, and at all times there is only one phase present. Eventually, it
resembles a vapor, but we can never tell when the change has occurred.
Above the critical state, there is no line that separates the compressed
liquid region and the superheated vapor region. However, it is customary
to refer to the substance as superheated vapor at temperatures above the
critical temperature and as compressed liquid at temperatures below the
critical temperature.
 The saturated liquid states in Fig. 4.4 can be connected by a line called the
saturated liquid line, and saturated vapor states in the same figure can be
connected by another line, called the saturated vapor line. These two lines
meet at the critical point, forming a dome as shown in Fig. 4.4b.

 All the compressed liquid states are located in the region to the left of the
saturated liquid line, called the compressed liquid region. All the
superheated vapor states are located to the right of the saturated vapor line,
called the superheated vapor region. In these two regions, the substance
exists in a single phase, a liquid or a vapor.

 All the states that involve both phases in equilibrium are located under the
dome, called the saturated liquid–vapor mixture region, or the wet
region.
 4.4.2 The P-υ Diagram
 Consider a unit mass of ice at -100C and 1atm contained in a piston-
cylinder machine. Let the ice be heated slowly so that its temperature is
always uniform.
The changes which occur in the mass of water would be traced as the
temperature is increased while the pressure is held constant. Let the state
changes of water be plotted on p-υ coordinates. The distinct regimes of
heating are as shown in following fig. 4.5a

 1-2 : The temperature of ice increase from -100C to to 00C. The volume of
ice would increase. At state 2 i.e at 00C, the ice would start melting.
 2-3 : Ice melts into water at constant temperature of 00C. At state 3
melting process ends. There is a decrease in volume which is peculiarity
of water.
 3-4 : The temperature of water increases, upon heating from 00c to 1000C.
the volume of water increase because of thermal expansion.
 4-5 : The water starts boiling at state 4 and boiling ends at state 5. This
phase change from liquid to vapor occurs at a constant temperature of
1000C. (the pressure is being constant at 1 atm). There is large increase in
volume.
 5-6 : The vapor is heated to say 2500C (state 6) . The volume of vapor
increases from υ5 to υ6.
 Water existed in the solid phase between 1 and 2, in the liquid phase
between 3 and 4, and in the gas phase beyond 5. Between 2 and 3, the solid
changes into the liquid phase by absorbing the latent heat of fusion and
between 4 and 5, the liquid changes into vapor phase by absorbing the
latent heat of vaporization, both at constant temperature and pressure.

 The states 2, 3, 4, 5 are known as saturation states. A saturation state is a

state from which a change of phase may occur without a change of pressure
or temperature. State is a saturated solid state because a solid can change
into liquid at constant pressure and temperature from state 2. States 3 and
4 are both saturated liquid states. In state 3, liquid is saturated with respect
to solidification, where as in state 4, the liquid is saturated with respect to
vaporization. State 5 is a saturated vapor state, because from state 5, the
vapor can condense into liquid without a change of pressure or
temperature.

 If the heating of ice at -100C to steam at 2500C were done at constant

pressure of 2 atm, similar regimes of heating would have been obtained
with similar saturation states 2,3,4,5. (see Fig. 4.5 b for water and 4.5 c for
any other substance)

 All saturated solid states 2 at various pressures are joined by a line and it is
called saturated solid line.

 Similarly, all the saturated liquid states 3 with respect to solidification, all
the saturated liquid states 4 with respect to vaporization, and all the
saturated vapor states 5 are joined together. The line passing through all
 the saturated liquid states 3 and 4 is known as saturated liquid line and the
line passing through all the saturated vapor states 5, is the saturated
vapor line.

 The saturated liquid line with respect to vaporization and the saturated
vapor line inclined towards each other and form a vapor dome. The two
lines meet at the critical state.

 To the left of the saturated solid line is the solid region. Between the
saturated solid line and saturated liquid line with respect to solidification,
there exists a solid – liquid mixture (S+L) region. Between two saturated
liquid lines is the compressed liquid region. The liquid – vapor mixture
region (L+V) exists within vapor dome between the saturated liquid and
saturated vapor lines. To the right of the saturated vapor region is the
vapor region. The triple point is a line on the p-υ diagram where all the
three phases’ solid, liquid, and gas exist in equilibrium.

 At a pressure below the triple point line, the substance cannot exist in
liquid phase, and the substance when heated, transforms from solid to
vapor (known as sublimation) by absorbing the latent heat of sublimation
from the surroundings. The region below the triple point line is therefore
solid- vapor mixture region.
 4.4.3 P-T diagram
 If the heating of ice at -100C to steam at 2500C at the constant pressure of 1
atm is considered,
1-2 is solid heating (ice), 2-3 is melting of ice at 00C, 3-4 is the liquid
heating, 4-5 is the vaporization of water at 1000C, and 5-6 is the heating in
the vapor phase. The process will be reversed from state 6 to state 1 upon
cooling. The curve passing through 2,3 is fusion curve, and the curve
passing through 4,5 is called vaporization curve. If the vapor pressure of a
solid is measured at different temperatures, and these are plotted, the
sublimation curve will be obtained. (see Fig.4.6a and 4.6 b)
 The fusion curve, the vaporization curve and the sublimation curve meet at
triple point.
 The slopes of the sublimation and vaporization curves for all substances are
positive. The slope of fusion curve for most substances is positive, but for
water it is negative.
 The temperature at which a liquid boils is very sensitive to pressure, as
indicated by the vaporization curve which gives the saturation
temperatures at different pressures, but the temperature at which a solid
melts is not such a strong function of pressure, as indicated by the small
slope of the fusion curve.
 4.4.4 P-V-T Surface

 All the points on the surface represent equilibrium states. All states along
the path of a quasi-equilibrium process lie on the P-v-T surface since such a
process must pass through equilibrium states. The single-phase regions
appear as curved surfaces on the P-v-T surface, and the two-phase regions
as surfaces perpendicular to the P-T plane. This is expected since the
projections of two-phase regions on the P-T plane are lines.

 All the two-dimensional diagrams we have discussed so far are merely

projections of this three-dimensional surface onto the appropriate planes .A
 P-v diagram is just a projection of the P-v-T surface on the P-v plane, and a
T-v diagram is nothing more than the bird’s-eye view of this surface.

 Projections on planes
4.5 T-S diagram

 The heating of the system of 1kg of ice at -50C to steam at 2500C is again
considered, the pressure being maintained at 1 atm. The entropy increase of
the system in different regimes of heating as flows.
 The entropy changes are shown in fir 4.8a. The curve 1-2-3-4-5-6 is the
isobar of 1 atm. If during the heating process, the pressure had been
maintained at 2 atm, a similar curve would be obtained.
 Most often liquid –vapor transformations only are of interest, and liquid,
vapor, and the transition zones are shown in fig. 4.8b.
 4.6 h-s Diagram

 From the first and second laws of Thermodynamics, the following property
relation was obtained.

Tds  dh  vdp
 h 
 s   T
p
 This equation forms the basis of h-s diagram of pure substance, also called
Mollier Diagram. The slope of isobar on h-s coordinates is equal to the
saturation temperature (in Kelvin) at that pressure. If the temperature
remains constant, the slope will remain constant. If the temperature
increases, the slope of isobar will increase.

 Consider the heating of a system of ice at -50C to steam at 2500C, the

pressure being maintained at 1 atm. The slope of the isobar of 1 atm on the
h-s coordinates (fig 4.9a) first increases as the temperature of ice increase
from -50C to 00C (1-2). It’s slope then remains constant as ice melts into
water at the constant temperature of 00C ( 2-3). The slope of isobar again
increases as the temperature of water rises from 00C to 1000C (3-4). The
slope again remains constant as water vaporizes into steam at the constant
temperature of 1000C (4-5). Finally the slope of isobar continues to increase
as the temperature of the steam increases to 2500C (5-6) and beyond.

 Similarly isobars of different pressures can be drawn on the h-s diagram.

Fig 4.9b shows phase diagram on h-s co-ordinates. Fig. 4.9 C shows h-s
diagram for water.
 4.7 Quality or dryness fraction

 For a two- phase liquid – vapor mixture, the ratio of mass of vapor present
to the total mass of mixture is its quality. [See Fig 4.10].

 For saturated liquid x =0 and for dry saturated vapor x =1.

 In fig 4.10, m and n represents Saturated liquid (x=0) and saturated Vapor
(x=1) states respectively. a,b,c represents constant dryness fraction lines
corresponding to x=0.25, x=0.5, x=0.75 respectively.
 m vapor 
x=  
 mliquid +m vapor 
 Where mvapor is the mass of vapor, and mliquid is the mass of liquid.

 Let V be the total volume of a liquid- vapor mixture of quality x, Vf is the

volume of saturated liquid, and Vg is the volume of saturated vapor, the
corresponding masses be m , m f , mg respectively.
 Now, m  m f  mg
 V = Vf + Vg.
mv  m f v f  mg vg where v, v f , vg be the specific volume of mixture,
specific volume of liquid, specific volume of vapor respectively.
mv  m f v f  mg vg
mv  (m  mg )v f  mg vg
 m  m
v  1  g  v f  g vg
 m m
v  (1  x)v f  xvg
Similarly

s  (1  x)s f  xsg
h  (1  x)h f  xhg
 u  (1  x)u f  xug
Where s, h, and u refer to the mixture of quality x, suffix f and g indicate
the conditions of saturated liquid and saturated vapor respectively.
v  (1  x)v f  xvg
v  v f  x (v g  v f )
v  v f  x(v fg ) [ v fg  vg  v f ]
Similarly
h  h f  x(h fg )
s  s f  x( s fg )
u  u f  x(u fg )

4.8 Super heated vapor

 When the temperature of the vapor is greater than the saturation

temperature corresponding to given pressure, the vapor is said to be super
heated. (state 1 in fig.4.11)
 The difference between the temperature of the super heated vapor and the
saturation temperature at that pressure is called the super heat or degree
of super heat.
 Degree of super heat = Tsup  Tsat
 Sub cooling
 When the temperature of the liquid is less than the saturation temperature
at the given pressure, the liquid is called Sub cooled liquid or Compressed
liquid.
OR

When the liquid is cooled below its saturation temperature at a certain

pressure it is said to be sub cooled.
Degree of sub cooling = Tsat-T2 [From fig 4.11]

4.9 Measurement of steam quality

Introduction

 The state of a pure substance gets fixed if two independent properties are
given. A pure substance is thus said to have two degrees of freedom. Of all
thermodynamic properties, it is easiest to measure the pressure and
temperature of the substance.
 Therefore, when pressure and temperature are independent properties, we
can measure them to determine the state of a substance. This is done in the
compressed liquid region or super heated region.
 If the substance is in the saturated state or two-phase region, the measured
values of pressure and temperature could apply equally well saturated
liquid point f, saturated vapor point g, or the mixtures of any quality. Of
the two properties p and t only one is independent, other is dependent
property.
 In order to fix up the state of the mixture, apart from either pressure or
temperature, one more property such as specific volume, enthalpy or
composition of the mixture (quality) is required to be known.
 Since it is relatively difficult to measure specific volume of a mixture,
devices such as calorimeters are used for measurement of quality or
enthalpy of mixture.
 In the measurement of quality, the object is always to bring the state of the
substance from two-phase region to a single phase or superheated region,
where both pressure and temperature are independent, and measured to fix
the state, either by adiabatic throttling or electric heating.

4.9.1 Throttling Calorimeter

 In the throttling calorimeter, a sample of wet steam of mass m and at

pressure p1 is taken from the steam through a perforated sampling tube as
shown in fig. 4.14. Then it is throttled by a partially opened valve to a
pressure p2, measured by mercury manometer, and temperature T2, so that
after throttling the steam is in the super heated region. The process is
shown on T-S and h-s diagrams in Fig. 4.13. The steady flow energy
equation gives the enthalpy after throttling as equal to enthalpy before
throttling.

h1  h2
h f 1  x1h fg1  h2
  h  hf 1 
x1   2 
 h fg1 
 With p2, and T2 being known h2 can be found out from the super heated
steam table. The values of h f 1 and h fg1 are taken from the saturated steam
table corresponding to pressure p1.

 To be sure that steam after throttling is in the single-phase or super heated

region, a minimum of 50C super heat is desired.

4.9.2 Combined Separating and throttling calorimeter

 When the steam is very wet and the pressure after throttling is not low
enough to take the steam to the super heated region, then a combined
separating and throttling calorimeter is used for measuring the quality.
Steam from the main is first passed through a separator (fig. 4.15), where
some part of the moisture separates out due to the sudden change in
direction and falls by gravity, and the partially dry vapor is then throttled
and taken to the super heated region. In the fig. 4.15 process 1-2 represents
the moisture separation from the wet sample of steam at constant pressure
p1, and process 2-3 represents throttling to pressure p2.
h3  h2  h f 1  x2 h fg1.
 Therefore, the quality of steam after partial moisture separation can be
evaluated.
 If m kg of steam is taken through the sampling tube in t seconds. m1 kg of
it is separated, and m2 kg is throttled and then condensed to water and
collected, then m=m1+[Link] at state 2, the mass of dry vapor will be x2 m2 .
Therefore the quality of the sample of the steam at state 1, x1 is given by
Mass of dry vapor at state 1
Mass of (liquid-vapor) mixture at state 1

x2 m2
=
m1  m2

4.10 Clausius Clayperon Equation

 During Phase transitions like melting, vaporization and sublimation, the

temperature and pressure remains constant, while the entropy and volume
change. If x is the fraction of initial phase I which has been transformed to
final phase f, then
 s  (1  x) s (i )  xs ( f )
v  (1  x)v (i )  xv ( f )
Where s and v are linear functions of x.

 For first order phase transition, the heat transferred per mole( or per kg) is
the latent heat given by
l  T s ( f )  s (i) 
Which indicates the change in entropy.

dg   sdT  vdp
 g 
s   
 T  p
 g 
v 
 p T
 A phase change of the first order is known as any phase change that satisfies
the following requirements.
 1. There are changes of entropy and volume.
2. The first-order derivatives of Gibbs function changes discontinuously.

 Let us consider the first-order phase transition of one mole of substance

from phase i to phase f.
Using the first Tds equation
 P 
Tds  cv dT  T   dv
 T v
 For the phase transition which is reversible isothermal and isobaric and
P
integrating over the whole change of phase, and since   is independent
 T v
of v
 P  ( f ) (i)
T s ( f )  s (i)   T   v  v 
 T 
P s  s 
(f) (i)
l
  ( f ) (i) 
T v  v  T v ( f )  v(i) 
The above equation is known as clausius-clapeyron equation

The clausius-clapeyron equation can also be determined in another way.

For a reversible process at constant pressure, temperature, the Gibbs
function remains constant.
Therefore, for the first –order phase change at T and p

g (i )  g ( f )
And for a phase change at T+dT, and P+dP

g (i )  dg (i )  g ( f )  dg (f)
Subtracting
dg (i )  dg (f)
 s (i ) dT  v (i ) dp
 s (f) dT  v (f) dp
P s  s 
(f) (i)
l
  ( f ) (i) 
T v  v  T v ( f )  v (i) 
ENGINEERING THERMODYNAMICS
 Unit V
Objectives:

 To introduce the students to Ideal gas and real gas behavior, gravimetric and volumetric
behavior of mixture of gases.

Syllabus:
Perfect Gas Laws – Equation of State, specific and Universal Gas constants –various Non-flow
processes, Heat and Work Transfer, changes in Internal Energy Enthalpy and Entropy ,
Throttling and Free Expansion Processes, Joule-Thompson coefficient – work Transfer during
Flow processes – Deviations from perfect Gas Model – Vander Waals Equation of State, Law of
Corresponding States, Compressibility charts.
Mixtures of perfect Gases – Mole Fraction, Mass fraction Gravimetric and volumetric Analysis –
Dalton’s Law of partial pressure, Avogadro’s Laws of additive volumes, Equivalent Gas constant
and Molar Internal Energy, Enthalpy, specific heats and Entropy of mixture of perfect Gases.,
Outcomes:
Students will be able to
 Distinguish between Ideal, real gas behaviors and work and heat Interactions in various
Non-flow processes.
 Define universal and characteristic gas constants.
 Define Dalton’s Law, Avogadro’s Law of additive volumes, Equivalent gas constant.
 Calculate the changes in Internal energy, enthalpy and entropy of Ideal gases and gas
mixtures.
 Evaluate mole fraction, mass fraction, molar Internal energy, enthalpy and specific heats
of mixtures.
 5.1. Equation of state of a Gas

 The functional relationship among the properties, pressure P, molar specific volume v , and
temperature T is known as equation of state, which may be expressed in the form ,

f ( P, v ,T)=0.

 If two of these properties of a gas are known, the third can be evaluated from the equation of
state.
 In thermodynamics we distinguish between
a) Perfect gases
b) Ideal gases
c) Real gases
(a) Perfect Gas
pv
The equation  const was derived assuming that Molecules of a gas are point masses.
T
There are no attractive nor repulsive forces between the molecules.
Perfect gas is one which obeys the above equation.
 Various forms of writing perfect gas equation of state.
(i) pv  RT where P is absolute pressure
v is molar specific volume.
R is universal gas constant.
T is absolute temperature.
R = m.R where m is molecular weight. and R is characteristic gas constant.
_
R  Molecular  weight  m   R
_
R
R
Molecular  weight  m 

Substitute this value in the above equation, we get

(ii) pv  mRT .
 m
(iii) But n  where m is the mass of the gas and n is number of moles.

Substituting this value we get
m
(iv) pv  .RT .
n

p ( nv )  mRT

(v) pV  mRT Where V is the total volume and

(vi) pV  nRT is also obtained.

(vii) pv  RT Where v is specific volume and R is characteristic gas constant.

R is universal gas constant. Its value is 8.314kJ/kmol.K.

R
R is characteristic gas constant. =
m
8.3143 kJ
Rair   0.287 .
28.96 kgK
8.3143 kJ
Ro2   0.262 .
32 kgK
 A perfect gas has constant specific heats.
 An Ideal gas is one which obeys the above equation, but whose specific heats are functions
of temperature alone.
(b) Ideal Gas:
m
 A hypothetical gas which obeys the law pv  RT or pv  RT at all pressures and
n
temperatures is called an Ideal Gas.
 Real gases do not confirm to this equation of state with complete accuracy. As
p  0 or T   the real gas approaches Ideal behavior.
( c) Real Gases
 Real gases deviate from ideal behavior because real gases have intermolecular forces and real
gases have volume.
 If there were no intermolecular forces, gases could not be made into liquids and solids
because they would not stick together.
 Conditions of low temperature, low volume, high number of moles, and high pressure puts
molecules close together, which makes the factors of intermolecular forces and gas volume
to become important.
AVAGADRO’S LAW
It states that the volume of a [Link] of all gases at the pressure of 760mm Hg and
temperature of 00 C is the same and is equal to 22.4lits.(STP)

1gmol of a gas has a volume of 22.4 x 103cm3 and 1 kg mol of gas has a volume of 22.4m3
at Normal temperature and pressure.(NTP)

5.2 Enthalpy and Internal energy of an Ideal gas:

Enthalpy and Internal energy for Ideal gas are functions of temperature alone.
dh  Tds  vdp
 V 
From Second Tds Equation, Tds  c p dt  T   dp
 T  p

 V    V  
dh  c p dt  T   dp  vdp  dh  c dt   v  T    dp ---------- (1)
 T  p
p   T p 

Let h=h(T,p)

 h   h 
dh    dt    dp ------------------------- (2)
 T  p  p T
Compare the coefficients of eq. (1) and (2)

 h    V  
We get     v  T    For Ideal Gas pv  RT
 p T   T  p 
  V  R v   V    h 
     v  T     0    0
 T  p P T   T p   p T


So dh  c p dT .

It proves that, for Ideal gas enthalpy is not changing with pressure. Similarly we can
prove enthalpy is not changing with volume either.

So Enthalpy of an Ideal gas is a function of temperature only.

 Internal Energy of an Ideal gas is also function of temperature alone.

du  Tds  pdv
 p 
From 1st Tds Equation Tds  cv dT  T   dv
 T v
  p  
du  cv dT   T    p  dv
  T v 
Let u = u(T,v)
 u   u 
du    dT    dv
 T v  v T
Comparing the coefficients
 u    p  
  dv =  T    p  dv
 v t   T v 
From Ideal gas Equation, pv  RT
 p  R p
   
 T v v T
 p 
T   p0
 T v
 u 
  =0, similarly we can show that internal energy is not a function of Pressure either.
 v t

 du  cv dT . Therefore Internal energy is a function of Temperature alone.

u = u (T) only. Now
Enthalpy H= sum of internal energy U + Flow energy (PV)
H h  u  pv
Specific enthalpy = h    
m

For an Ideal gas pv  RT

 dh  du  RdT du  cv dT for Ideal gas.

dh   cv  R  dT
Since h is also a function of temperature alone for ideal gas
 dh 
c p     dh  c p dT
 dt  p
From the above Two equations

cv  R  c p
c p  cv  R

cp
 The ratio of is of importance in Ideal gas computations
cv
 It is designated by the symbol γ(gama)
cp
   c p   cv  (  1)cv  R
cv
R R
cv  cp 
(  1) (  1)
 Variation of specific heat with temperature
The specific heat of a real gas varies with temperature. The functional relationships denoting
this variation are determined from experimental tests. Table 4.1 lists several formulas hat
predict the specific heat of a gas at a given temperature. Figure 4.2 shows a diagram of the
specific heat variation with temperature for a few gases.
Entropy change of an Ideal Gas
 From the general property relations
Tds  du  pdv
Tds  dh  vdp
du pdv
ds  
T T
c dT R
ds  v  dv ( du  cv dT )
T v

2
c dT
2
R
2
 T   v 
1 ds  1 vT  1 v dv  s2  s1  cv  ln 2   R  ln 2 
 T1   v1 
Also

dh vdp
ds  
T T  dh  c p dT

c p dT R
ds   dp
T p

 T   p 
2 2 2
c p dT R
 ds   T

p
dp =
s2  s1  c p ln 2   R  ln 2 
 T1   p1 
1 1 1
  v   p 
Since R  c p  cv  s2  s1  c p ln 2   cv ln 2 
 v1   p1 

Reversible Adiabatic Process

 The general property relation for an ideal gas may be written as

Tds  du  pdv  cv dT  pdv
Tds  dh  vdp  c p dT  vdp
For a reversible adiabatic change, ds=0
cv dT   pdv
c p dT  vdp
And by division
cp vdp
 
cv pdv
dp dv
 0
p v
Or
ln p   ln v  ln c = pv   C

For an Ideal gas

pv  RT

From the equation, pv  C
p  C.v 
RT
p = C.v  = RT  Cv1
v

Tv  1  C
 1
Between states 1 and 2 T2  v1 
Similarly  
T1  v2 
1
 c   1

v  T2  p  
 p   2 
T1  p1 
  1 
Tp    C 

 

The Internal energy change of an Ideal gas for a reversible adiabatic process is given by

Tds  du  pdv

 
 1
2 2 2
c
1 du  1 pdv  1 v dv  R T1   p 2   
u 2  u1      1
  1  p1 
 
The change in enthalpy of an ideal gas for a reversible adiabatic process is 

Tds  dh  vdp

 
1  1

c  RT1   p 2 
2 2 2  

1 dh  1 vdp  1  p  dv  h2  h1  
  1   p1 
  1
 

The work done by an ideal gas in a reversible adiabatic process is given by

 w  du
i.e. the work is done at the expense of Internal energy.

 
 1

mRT1   p2   
 W  m (u 2  u1 ) = 1  
  1   p1  
 

In a Steady flow Process where both flow and external work are involved, we have from S.F.E.E

 
 1

   p2   
W  p1v1 1    
 1  p1 
 

Reversible Isothermal Process

When an ideal gas of mass m undergoes a reversible Isothermal process from state 1 to state 2,
the work done is given by
2 2

  =  mRT dV  mRT ln V2 = mRT ln p1

2
 W  pdv
1 1 1
V V1 p2

Polytropic Process

An equation of the form pvn=C, where n is a constant can be used approximately to describe
many processes which occur in practice. Such a process is called a polytropic process. It is not
adiabatic but it can be reversible.

It may be noted that γ is a property of a gas but n is not. The value of n depends on the process.

From the two states of the process,

p1v1n  p2 v2 n

log p1  log p2
n
log v2  log v1

Two other relations of a polytropic process are

n 1
n 1
T2  p2  n
T2  v1 
  and  
T1  p1  T1  v 2 

The entropy change in a polytropic process is given by 3 equations.

n  T 
s2  s1  R ln  2 
   1 n  1  T1 
n P 
s2  s1  R ln  2 
   1 n  P1 
n  v 
s2  s1   R ln  2 
  1  v1 
Heat and work in a polytropic process

Using the first law to unit mass of an ideal gas

R
Q  W  u2  u1  cv T2  T1   T2  T1 
 1
 p2 v2  p1v1
=
 1

For a steady flow of unit mass of an Ideal gas

 p2 v2  p1v1 
Q W =  
  1 

Integral Property Relations in a Polytropic process

In a pv n  c , process

 
n 1

p1v1   v1   p 1 v 1
n 1
 p2 
2 2 n
pv  n

 pdv   1 1
n
v
dv  1     =
n  1   v2   n  1  1  


p1  
1 1    

Similarly for   vdp

1

np1v1   v1  
n 1

= 1    
n  1   v2  
 
The integral of Tds is obtained from property relation

Tds  du  pdv
2 2 2

 Tds   du   pdv
1 1 1

= u2  u1  pdv 
1

 n
2

 Tds    1 n  1 R T  T 
1
1 2

 n
2

 Tds  c
1
v
1 n
T

 Tds  c T
1
n where cn is called polytropic specific heat.
For n > γ there will be positive heat transfer and gain in entropy. For n < γ, heat transfer will be
negative and entropy of the gas would decrease.

The polytropic process for various values of n is shown in fig.

Deviation from ideal gas behaviour:

 A gas which obeys the gas laws and the gas equation PV = nRT strictly at all temperatures
and pressures is said to be an ideal gas.
 The molecules of ideal gases are assumed to be volume less points with no attractive forces
between one another. But no real gas strictly obeys the gas equation at all temperatures and
pressures.
 Deviations from ideal behaviour are observed particularly at high pressures or low
temperatures.

The deviation from ideal behaviour is expressed by introducing a factor Z known

as compressibility factor in the ideal gas equation.

Z may be expressed as Z = PV / nRT

 In case of ideal gas, PV = nRT ∴ Z = 1

1. In case of real gas, PV ≠ nRt ∴ Z ≠ 1
Thus in case of real gases Z can be < 1 or > 1
 When Z < 1, it is a negative deviation.
 It shows that the gas is more compressible than expected from ideal behaviour.
1. When Z > 1, it is a positive deviation.
 It shows that the gas is less compressible than expected from ideal behaviour.
Causes of deviation from ideal behavior
The causes of deviations from ideal behavior may be due to the following two assumptions of
kinetic theory of gases.
 The volume occupied by gas molecules is negligibly small as compared to the volume
occupied by the gas.
 The forces of attraction between gas molecules are negligible.
 The first assumption is valid only at low pressures and high temperature, when the
volume occupied by the gas molecules is negligible as compared to the total volume of
the gas.
 But at low temperature or at high pressure, the molecules being in compressible the
volumes of molecules are no more negligible as compared to the total volume of the
gas.

The second assumption is not valid when the pressure is high and temperature is low. But at high
pressure or low temperature when the total volume of gas is small, the forces of attraction
become appreciable and cannot be ignored.

Vander Waals’ Equation of State for a Real Gas

The deviations from ideal gas behaviour can be ascertained to the following faulty
assumptions by kinetic theory of gases.
 The real volume of the gas molecules is negligible when compared to the volume of the
Container.
  There are no forces of attraction or repulsion between the gas molecules.
Hence van der Waal suggested the following corrections:
 The gas molecules possess finite volume and hence should not be neglected. It is
especially true at high pressures and low temperatures and should be accounted for.
 In case of real gases, both the forces of attraction as well as repulsion operate
between gas molecules.
Note: If the gases obey the kinetic theory of gases, then they cannot be compressed since the
attractions between the gas molecules are negligible.
Also the following corrections are applied by vander Waals to the ideal gas equation:
Volume correction:
The volume available for the gas molecules is less than the volume of the container, V.
The available volume is obtained by subtracting excluded volume of ‘n’ moles of gas, nb
from the volume of the container.
Available volume = V - nb
where n = Number of moles of real gas
V = Volume of the gas
b = A constant whose value depends upon the nature of the gas
The ideal gas equation can be written after correcting for this as:
P(V-nb) = nRT
Pressure correction:
 Take a real gas of pressure P
 The molecular attraction between one molecule to another molecule the pressure generated ,at
that time is the pressure force considered as negligible( not considered)
 The pressure force generated in this container more in case of Ideal gas than the Real gas
 Suppose the pressure generated by molecular attraction in the real its molecules in the reverse
direction
 The pressure force in case of Ideal Gas =(P+p) (p is the pressure lost by the gas molecules due to
attractions).
p = This small pressure p would be directly proportional to the extent of attraction between the
molecules which are hitting the container wall and the molecules which are attracting these.
Therefore p ∝ n/v (concentration of molecules which are hitting the container's wall)
P ∝ n/v (concentration of molecules which are attracting these molecules) p ∝ n2/v2
P = an2/v2 where a is the constant of proportionality which depends on the nature of gas.
A higher value of 'a' reflects the increased attraction between gas molecules.
Hence ideal pressure
 Pi = (P + an2 / V2)
Here,
n = Number of moles of real gas
V = Volume of the gas
a = A constant whose value depends upon the nature of the gas
Substituting the values of ideal volume and ideal pressure in ideal gas equation i.e. pV=nRT,
the modified equation is obtained as
(P + an2 / V2) (V-nb) = nRT
(P + a(n / V)2) (V-nb) = nRT
(P + a(n / V)2) → Ideal pressure
(V-nb) → Ideal volume
P = measured pressure
a(n / V)2 = correction factor to account for intermolecular attractions
V = measured volume
nb = correction factor to account for the finite size of the molecules
a=Vander Waals attraction constant
b=volume for a given gas.
Some salient feature of a & b are:
 For a given gas Vander Waal’s constant of attraction ‘a’ is always greater than Vander
Waals constant of volume (b).
 The gas having higher value of ‘a’ can be liquefied easily and therefore H2 & He are not
liquefied easily.
 The units of a = litre2 atm mole–2 & that of b = litre mole –1
 The numerical values of a & b are in the order of 10–1 to 10–2 & 10–2 to 10–4 respectively.
Higher is the value of ‘a’ for a given gas, easier is the liquefaction.
Different forms of Van der Waal’s equation
 At low pressures:
‘V’ is large and ‘b’ is negligible in comparison with V.
The Vander Waals equation reduces to:
(P + a / V2) V = RT;
PV + a/ V = RT
PV = RT – a/V or PV < RT
This accounts for the dip in PV vs P isotherm at low pressures.
 For high pressures
2
a/V may be neglected in comparison with P.
The Vander Waals equation becomes
P (V – b) = RT
PV – Pb = RT
PV = RT + Pb or PV > RT
This accounts for the rising parts of the PV vs P isotherm at high pressures.

 At very low pressures:

V becomes so large that both b and a/V2 become negligible and the Vander Waals equation
reduces to PV = RT. This shows why gases approach ideal behaviour at very low pressures.

A GAS MIXTURE:
Mass and Mole Fractions
 To determine the properties of a mixture, we need to know the composition of the
mixture as well as the properties of the individual components.
 There are two ways to describe the composition of a mixture:
 Specifying the number of moles of each component, called molar analysis,
 Specifying the mass of each component, called gravimetric analysis.
Consider a gas mixture composed of k components.
The mass of the mixture mm is the sum of the masses of the individual components, and the
mole number of the mixture Nm is the sum of the mole numbers of the individual components
 k k
mm  m
i 1
i an d Nm  i 1
Ni

 The ratio of the mass of a component to the mass of the mixture is called the mass
fraction
mi Ni
It is donated by mf mfi  and yi 
mm Nm
 The ratio of the mole number of a component to the mole number of the mixture is called
the Mole fraction
mi Ni
mfi  and yi 
It is denoted bymy:
m Nm

Note that
k k

 mf
i 1
i =1 and y
i 1
i 1

The mass of a substance can be expressed in terms of the mole number N and molar mass M of
the substance as m =NM. Then the apparent (or average) molar mass and the gas constant of
a mixture can be expressed as
k k
mm Ni
Mm 
Nm
 
i 1 Nm
Mi   i 1
yi M i ( kg / km o l )

The apparent (or average) gas constant of a mixture is expressed as

Ru
Rm  ( kJ / kg  K )
Rm is given as Mm
k
Rm   i1
m fi Ri

To change from a mole fraction analysis to a mass fraction analysis,

yi M
m fi  k
i


i1
yi M i

To change from a mass fraction analysis to a mole fraction analysis,

m fi / M
yi  k
i

i1
m fi / M i

Gravimetric analysis
  Gravimetric analysis is a technique through which the amount of an analyte (the ion
being analyzed) can be determined through the measurement of mass.
 Gravimetric analyses depend on comparing the masses of two compounds containing the
analyte. The principle behind gravimetric analysis is that the mass of an ion in a pure
compound can be determined and then used to find the mass percent of the same ion in a
known quantity of an impure compound. In order for the analysis to be accurate, certain
conditions must be met:
1. The ion being analyzed must be completely precipitated.
2. The precipitate must be a pure compound.
3. The precipitate must be easily filtered.

Volume fraction :
Divide the container into k sub containers, such that each sub container has only one of the gases
in the mixture at the original mixture temperature and pressure.
 The prediction of the P-v-T behaviour of gas mixtures is usually based on two models: Dalton’s
law of additive pressures and Amagat’s law of additive volumes. Both models are described
and discussed below.
Amagat's law of additive volumes states that the volume of a gas mixture is equal to the sum of
the volumes each gas would occupy if it existed alone at the mixture temperature and pressure.
Amagat's law: k
V m   V i ( T m , Pm )
i1

Where, vi = v1 + v2+v3 +----------vi, Volume of number of constituent gases. vm = volume of

mixture; Tm = temperature of mixture & Pm = Pressure of mixture

The volume fraction of the vfi of any component is

V i ( T m , Pm )
vfi 
Vm
and k

i1
vfi = 1

For an ideal gas mixture

N i R u Tm N m R u Tm
Vi  and Vm 
Pm Pm
Taking the ratio of these two equations gives
V N
f i fractioni of a component
The volume fraction and thev mole i
in any ideal
i
gas mixture are the same.
Dalton’s Law of partial pressure: V m N m
 In a mixture of gases, which don’t react with each other, total pressure of the mixture is
equal to the sum of the partial pressures of the constituent/individual gases, at the same
temperature & volume as that of the mixture.
or
Partial pressure of an individual gas: It is the pressure exerted by an individual gas when it
alone occupies the mixture volume at the mixture temperature
i.e, p = p1 + p2 …….pn (because, partial pressure = mole fraction x total pressure p)Partial
pressure :
  The partial pressure of component i is defined as the product of the mole fraction and the
mixture pressure according to Dalton’s law. For the component i
Pi  y i P m

Dalton’s law: k
Pm  
i1
Pi ( T m , V m )

Dalton’s and Amagat’s laws hold exactly for ideal-gas mixtures, but only approximately for real-
gas mixtures. This is due to intermolecular forces that may be significant for real gases at high
densities. For ideal gases, these two laws are identical and give identical results.

Now, consider placing each of the k gases in a separate container having the volume of the
mixture at the temperature of the mixture. The pressure that results is called the component
pressure, Pi' .

Ideal-Gas Mixtures:
Ideal-Gas Mixtures For ideal gases, Pi’ and Vi can be related to yi by using the ideal-gas relation
for both the components and the gas mixture:

N i R u Tm N m R u Tm
Pi '  and Pm 
Vm Vm
Note that the ratio of Pi' to Pm is
Pi ' Vi Ni
   yi
Pm Vm Nm
 Here yiPm = is called the partial pressure (identical to the component pressure for ideal gases),
and the quantity
yiVm = is called the partial volume (identical to the component volume for ideal gases).
Note: An ideal-gas mixture, the mole fraction, the pressure fraction, and the volume fraction of
a component are identical.

Avogadro’s Hypothesis: Equal volumes of all gases measured at the same temperature &
pressure contain the same number of molecules or particles.
Avogadro’s Law:
 At constant temperature & pressure, the volume of a gas is directly proportional to the
number of moles of that gas.
i.e., V α n, numbers of moles at constant temperature and pressure.
V = a constant n.
Or
V/n = a constant

PROPERTIES OF GAS MIXTURES:

IDEAL AND REAL GASES:
The extensive properties of a non reacting ideal or real-gas mixture: Just add the contributions of
each component of the mixture. Then the total internal energy, enthalpy, and entropy of a gas
mixture can be expressed, respectively, as
k k k
U m  
i1
U i  
i1
miui  i1
N iui (k J )
k k k
Hm  
i1
Hi  
i1
m i hi  i1
N i hi (k J )
k k k
Sm  
i1
Si  
i1
m i si  
i1
N i si (k J / K )
The internal energy, enthalpy, and entropy of a mixture per unit mass or per unit mole of the
mixture can be determined by dividing the equations above by the mass or the mole number of
the mixture (mm or Nm). We obtain
k k
um   mf i ui and um   yi ui (kJ / kg or kJ / kmol)
i 1 i 1
k k
hm   mf i hi and hm   yi hi (kJ / kg or kJ / kmol)
i 1 i 1
k k
sm   mf i si and sm   yi si (kJ / kg  K or kJ / kmol  K)
i 1 i 1

Similarly, the specific heats of a gas mixture can be expressed as

k k
Cv , m   mf i C v , i
i 1
and Cv , m  yC
i 1
i v,i

k k
C p, m   mf i C p , i
i 1
and C p, m  yC
i 1
i p, i

These relations are applicable to both ideal- and real-gas mixtures. The properties or property
changes of individual components can be determined by using ideal-gas or real-gas relations.
Ratio of specific heats k is given as
C p ,m C p ,m
km  
C v ,m C v ,m
Properties per unit mass involve mass fractions =mfi
Properties per unit mole involve mole fractions yi.
 The relations given above are exact for ideal-gas mixtures, and approximate for real-gas
mixtures. (In fact, they are also applicable to non reacting liquid and solid solutions
especially when they form an “ideal solution.”)
 The only major difficulty associated with these relations is the determination of
properties for each individual gas in the mixture.
Ideal-Gas Mixtures:
 The gases that comprise a mixture are often at a high temperature and low pressure
relative to the critical-point values of individual gases.
 At that case, the gas mixture and its components can be treated as ideal gases with
negligible error.
 Under the ideal-gas approximation, the properties of a gas are not influenced by the
presence of other gases, and each gas component in the mixture behaves as if it exists
alone at the mixture temperature Tm and mixture volume Vm.
 This principle is known as the Gibbs–Dalton law, which is an extension of Dalton’s law
of additive pressures. Also, the h, u, cv, and cp of an ideal gas depend on temperature only
and are independent of the pressure or the volume of the ideal-gas mixture.
 The partial pressure of a component in an ideal-gas mixture is simply Pi = yiPm,
  where Pm is the mixture pressure.
 ∆u or ∆h of the components of an ideal-gas mixture easily to calculate only
knowledge of the initial and final temperatures.
 ∆s is depends on the pressure or volume of the component as well as on its
temperature.
 The entropy change of individual gases in an ideal-gas mixture during a
process can be determined from

T  P 
si  C p ,i ln  2   Ri ln  i ,2 
P 
 T1   i ,1 
The entropy change of the mixture per mass of mixture is
sm 2 2  T   P 
sm    mfi si  mfi  C p ,i ln  2   Ri ln  i ,2  
  P 
mm i 1 i 1   T1   i ,1  
The entropy change of the mixture per mole of mixture is
_
sm 2 _ k  T   P 
 sm    iy  s i  yi  C p ,i ln  2   Ru ln  i ,2  
  P 
N m i 1 i 1   T1   i ,1  
In these last two equations,
Pi ,1  yi ,1 Pm ,1
Pi ,2  yi ,2 Pm ,2
ENGINEERING THERMODYNAMICS
 Unit – VI
Objectives:
 To introduce the students to gas power cycles, vapour power cycles and
refrigeration cycles

Syllabus:
Gas power cycles: Otto, diesel, dual combustion cycles, description and representation
on P-v and T-s diagram, thermal efficiency, mean effective pressure on air standard
basis- comparison of cycles, Brayton cycle
Vapour power cycles: Simple Rankine cycle, Refrigeration cycles: Bell Coleman
cycle, vapour compression refrigeration system- performance evaluation.

Outcomes:
Students will be able to
 Evaluate thermal efficiency of Otto, diesel, dual cycle and Brayton cycle and
they can represent on P-v and T-s diagrams
 Compare various gas power cycles
 Understand vapour power cycles
 Understand refrigeration cycles
 Evaluate performance of refrigeration cycles
 Air-Standard Assumptions

In our study of gas power cycles, we assume the working fluid is air, and the air undergoes a
thermodynamic cycle even though the working fluid in the actual power system does not
undergo a cycle.

To simplify the analysis, we approximate the cycles with the following assumptions:

• The air continuously circulates in a closed loop and always behaves as an ideal gas.

• All the processes that make up the cycle are internally reversible.

• The combustion process is replaced by a heat-addition process from an external

source.

• A heat rejection process that restores the working fluid to its initial state replaces the
exhaust process.

• The cold-air-standard assumptions apply when the working fluid is air and has
constant specific heat evaluated at room temperature (25oC or 77oF).

 Terminology for Reciprocating Devices

The following is some terminology we need to understand for reciprocating engines—

typically piston-cylinder devices. Let’s look at the following figures for the definitions of
top dead center (TDC), bottom dead center (BDC), stroke, bore, intake valve, exhaust
valve, clearance volume, displacement volume, compression ratio, and mean effective
pressure.

 The compression ratio r of an engine is the ratio of the maximum volume to the minimum
volume formed in the cylinder.
V max VBDC
r 
V min VTDC
 The mean effective pressure (MEP) is a fictitious pressure that, if it operated on the piston
during the entire power stroke, would produce the same amount of net work as that produced
during the actual cycle.

Wnet wnet
MEP  
Vmax Vmin vmax  vmin

 Otto Cycle (Constant Volume Cycle):

This ideal heat engine cycle was proposed in 1862 by Bean de Rochas. In 1876 Dr. Otto
designed an engine to operate on this cycle. The Otto engine immediately became so
successful from a commercial stand point, that its name was affixed to the cycle used by it.

The ideal p - v and T-s diagrams of this cycle are shown in fig. In working out the air-
standard efficiency of the cycle, the following assumptions are made:

(i) The working fluid (working substance) in the engine cylinder is air, and it behaves as
a perfect gas, i.e., it obeys the gas laws and has constant specific heats.
(ii) The air is compressed adiabatically (without friction) according to law pvγ = C
(iii)The heat is supplied to the air at constant volume by bringing a hot body in contact
with the end of the engine cylinder.
(iv)The air expands in the engine cylinder adiabatically (without friction) during the
expansion stroke.
(v) The heat is rejected from the air at constant volume by bringing a cold body in contact
with the end of the engine cylinder.
 Process 1 2 Isentropic compression
Process 2  3 Constant volume heat addition
Process 3  4 Isentropic expansion
Process 4  1 Constant volume heat rejection

Consider one kilogram of air in the engine cylinder at point (1). This air is compressed
adiabatically to point (2), at which condition the hot body is placed in contact with the end of
the cylinder. Heat is now supplied at constant volume, and temperature and pressure rise; this
operation is represented by (2-3). The hot body is then removed and the air expands
adiabatically to point (4). During this process, work is done on the piston. At point (4), the
cold body is placed at the end of the cylinder. Heat is now rejected at constant volume,
resulting in drop of temperature and pressure. This operation is represented by (4-1). The cold
body is then removed after the air is brought to its original state (condition). The cycle is thus
completed. The cycle consists of two constant volume processes and two reversible adiabatic
processes. The heat is supplied during constant volume process (2-3) and rejected during
constant volume process (4-1). There is no exchange of heat during the two reversible
adiabatic processes (1-2) and (3-4).

The performance is often measured in terms of the cycle efficiency.

W
th  net
Qin
Thermal Efficiency of the Otto cycle

Wnet Qnet Qin  Qout Q

 th     1  out
Qin Qin Qin Qin

Now to find Qin and Qout.

Apply first law closed system, V = constant.

Heat supplied during constant volume operation (2-3), Heat rejected during constant volume
operation (4-1) is
qin  u3  u2  cv (T3  T2 )
qout  u4  u1  cv (T4  T1 )

Q net , 23   U 23
Q net , 23  Q in  m C v (T3  T 2 )

Q net , 41   U 41
Q n e t , 4 1   Q o u t  m C v ( T1  T 4 )
Q o u t   m C v ( T1  T 4 )  m C v ( T 4  T1 )

The thermal efficiency becomes

Q out
 th , O tto  1 
Q in
m C v (T4  T1 )
 1
m C v ( T3  T 2 )

( T 4  T1 )
 th , O tto  1 
(T 3  T 2 )
T1 ( T 4 / T1  1)
1
T 2 ( T 3 / T 2  1)

Recall processes 1-2 and 3-4 are isentropic, so

 1  1
T1  v2  v  T4
   3  
T2  v1   v4  T3

Since V3 = V2 and V4 = V1
T2 T
 3
T1 T4
or
T4 T
 3
T1 T2
The Otto cycle efficiency becomes

T1
 th , Otto  1 
T2

Since process 1-2 is isentropic,

 1  1
T2  v1  1
   
T1  v2  r

Where the compression ratio is

 vmax v1
r 
vmin v2
1
 th , O tto  1 
r k 1
 Air-Standard Diesel Cycle (or constant pressure cycle):

The air-standard Diesel cycle is the ideal cycle that approximates the Diesel combustion
engine

Process Description

1-2 isentropic compression

2-3 Constant pressure heat addition

3-4 isentropic expansion

4-1 Constant volume heat rejection

The P-v and T-s diagrams are

Heat supplied  Q1  Q23  mc p (T3  T2 )
Heat Rejected = Q 2  Q41  mcv (T4  T1 )
Q2 mc (T  T ) (T  T )
Effieciency    1   1 v 4 1  1 4 1
Q1 mc p (T3  T2 )  (T3  T2 )

The efficiency may be expressed terms of any two of the following.

v1
Compression Ratio  rk 
v2
v4
Expansion Ratio  re 
v3
v3
Cut  off ratio  rc 
v2
rk  re .rc

Process 3-4
 1
T4  v3  1
    1
T3  v4  re
 1
v  re 1
T4  T3  3   T3
 v4  rk  1

Process 2-3

T2 p2 v2 v2 1
  
T3 p3v3 v3 re
1
T2  T3
re
Process 1-2

 1
T1  v2  1
     1
T2  v1  rk
1 T 1
T1  T2  1  3  1
rk rc rk

By subsisting T1,T2 and T4 in the expression of efficiency

rc 1 T3 1
T3  1 
rk rc rk  1
  1
 1
  T3  T3 
 rc 
1 1 rc 1
 diesel  1  .
 rc 1 rc  1

 Dual Cycle (mixed cycle/ limited pressure cycle):

Process 1  2 Isentropic compression

Process 2  3Constant volume heat addition

Process 3  4 Constant pressure heat addition

Process 4  5 Isentropic expansion

Process 5 1 Constant volume heat rejection

Thermal Efficiency:

v3 P3
where rc  and  
v2.5 P2

Note, the Otto cycle (rc=1) and the Diesel cycle (a=1) are special cases:

 Otto  1 
1
 Diesel  1 
 
1  1 rck  1 
 
r k 1
const cV   
r k 1  k rc  1 

The use of the Dual cycle requires information about either:

i) The fractions of constant volume and constant pressure heat addition (common
assumption is to equally split the heat addition), or

ii) Maximum pressure P3.

Q1  mcv (T3  T2 )  mc p T4  T3 

Q 2  mcv (T5  T1 )

Here Q1 -= heat input

Q2 =Out put

Q2 mcv (T5  T1 ) T5  T1
  1  1  1
Q1 mcv (T3  T2 )  mc p T4  T3  (T3  T2 )   T4  T3 
 v1
Compression Ratio  rk 
v2
v4
Expansion Ratio  re 
v3
p3
cons tan t  volume  pressure  ratio  rp 
p2

rk  rc .re
rk
re 
re

process3  4
v T p T
rc  4  4 3  4
v3 p4T3 T3
T4
T3 
rc

Pr ocess 2  3
p2 v2 p3v3

T2 T3
p2 T4
T2  T3 
p3 rp rc

process  1  2
 1
T1  v2  1
  
T2  v1  rk  1

T4
T1 
rp .rc .rk  1

Process 4-5

T4
T1 
rp .rc .rk  1
 1
T5  v4  1
     1
T4  v5  re
r  1
T5  T4 c  1
rk

SubtitlingT1, T2,T3 and T4values

 rc 1 T4
T4  1 
rk rp .rc .rk  1 1 rp rc 1
dual  1   1
 T4 T4   T  rk  1 rp  1   rp  rc  1
      T4  4 
 rc rp rc   rc 

 Comparison of cycles:
 For the same inlet conditions P1, V1 and the same compression ratio P2/P1:

For the same initial conditions P1, V1 and the same compression ratio:

Otto   Dual   Diesel

 For the same inlet conditions P1, V1 and the same peak pressure P3:

For the same initial conditions P1, V1 and the same peak pressure P3

(Actual design limitation in engines):

 Diesel   Dual   otto
 Brayton Cycle (or Joule cycle)

The Brayton cycle is the air-standard ideal cycle approximation for the gas-turbine engine.
This cycle differs from the Otto and Diesel cycles in that the processes making the cycle
occur in open systems or control volumes. Therefore, an open system, steady-flow analysis
is used to determine the heat transfer and work for the cycle.

We assume the working fluid is air and the specific heats are constant and will consider the
cold-air-standard cycle.

The closed cycle gas-turbine engine

The T-s and P-v diagrams for the

Closed Brayton Cycle

Process Description

1-2 Isentropic compression (in a compressor)

2-3 Constant pressure heat addition

3-4 Isentropic expansion (in a turbine)

4-1 Constant pressure heat rejection

Thermal efficiency of the Brayton cycle

W n et Q
 th , B ra yto n   1  out
Q in Q in

Now to find Qin and Qout.

Apply the conservation of energy to process 2-3 for P = constant (no work), steady-flow, and
neglect changes in kinetic and potential energies.

E in  E out
m 2 h2  Q in  m 3 h3
The conservation of mass gives
m in  m o u t
m 2  m 3  m
For constant specific heats, the heat added per unit mass flow is

Q in  m ( h3  h2 )
Q in  mC
 p (T3  T2 )
Q in
q in   C p (T3  T2 )
m

The conservation of energy for process 4-1 yields for constant specific heats

Q out  m ( h 4  h1 )
Q out  m C p (T 4  T1 )
Q out
q out   C p (T 4  T1 )
m
The thermal efficiency becomes

Q out q
 th , Brayton  1   1  out
Q in q in
C p (T4  T1 )
 1
C p (T3  T2 )

(T 4  T1 )
 th , B rayton  1 
( T3  T 2 )
T1 (T 4 / T1  1)
 1
T 2 (T3 / T 2  1)

Recall processes 1-2 and 3-4 are isentropic, so

 1
T2  p2  
 
T1  p1 
 1
T3  p3  
 
T4  p4 

Since P3 = P2 and P4 = P1, T2 T3


T1 T4
or
T4 T3

T1 T2

The Brayton cycle efficiency becomes

T1
 th , B ra yto n  1 
T2
Since process 1-2 is isentropic,
 1
 1
T2  p2  
   rp 

T1  p1  1
Where the pressure ratio is rp = P2/P1 and th , Brayton  1  (  1)/ 
T1 1 rp
  1
T2
rp 
SIMPLE RANKINE CYCLE

Rankine Cycle: The simplest way of overcoming the inherent practical difficulties of the
Carnot cycle without deviating too much from it is to keep the processes 1-2 and 2-3 of the
latter unchanged and to continue the process 3-4 in the condenser until all the vapour has
been converted into liquid water. Water is then pumped into the boiler upto the pressure
corresponding to the state 1 and the cycle is completed. Such a cycle is known as the Rankine
cycle. This theoretical cycle is free of all the practical limitations of the Carnot cycle.

Figure (a) shows the schematic diagram for a simple steam power cycle which works on the
principle of a Rankine cycle.
The Rankine cycle comprises the following processes.
Process 1-2: Constant pressure heat transfer process in the boiler
Process 2-3: Reversible adiabatic expansion process in the steam turbine
Process 3-4: Constant pressure heat transfer process in the condenser and
Process 4-1: Reversible adiabatic compression process in the pump.
Figure (b) represents the T-S diagram of the cycle.
The numbers on the plots correspond to the numbers on the schematic diagram. For any given
pressure, the steam approaching the turbine may be dry saturated (state 2), wet (state 2 1) or
superheated (state 211), but the fluid approaching the pump is, in each case, saturated liquid
(state 4). Steam expands reversibly and adiabatically in the turbine from state 2 to state 3 (or
21 to 31 or 211 to 311), the steam leaving the turbine condenses to water in the condenser
reversibly at constant pressure from state 3 (or 31, or 311) to state 4. Also, the water is heated
in the boiler to form steam reversibly at constant pressure from state 1 to state 2 (or 21 or 211)

Applying SFEE to each of the processes on the basis of unit mass of fluid and neglecting
changes in KE & PE, the work and heat quantities can be evaluated

For 1kg of fluid, the SFEE for the boiler as the CV, gives,

h4+ Q1 = h1 i.e., Q1 = h1 – h4 --- (1)

SFEE to turbine, h1 = WT + h2 i.e., WT = h1 – h2 --- (2)

SFEE to condenser, h2 = Q2 + h3 i.e., QL = h2 – h3 --- (3)

SFEE to pump, h3 + WP = h4 i.e., WP = h4 – h3 --- (4)
 Wnet
The efficiency of Rankine cycle is  
Q1

Wnet WT  W p  h1  h2    h4  h3 
The efficiency of Rankine cycle is   
Q1 Q1 h1  h4

VAPOUR COMPRESSION REFRIGERATION SYSTEM

In vapour compression system, the refrigerants used are ammonia, carbon dioxide, freons etc.
the refrigerants alternately undergoes condensation and evaporation during the cycle. When
refrigerant enters the evaporator it will be in liquid state and by absorbing latent heat it
become vapours. Thus the C.O.P of this system is always much higher that air refrigeration
systems.
VAPOUR COMPRESSION REFRIGERATION SYSTEM

P-V Diagramv T-S Diagram

The various processes are

Process 1-2 .
The vapour refrigerant entering the compressor is compressed to high pressure and
temperature in a isentropic manner.
Process 2-3.
This high pressure and high temperature vapour then enters a condenser where the
temperature of the vapour first drops to saturation temperature and subsequently the vapour
refrigerants condenses to liquid state.
• Process 3-4.
This liquid refrigerant is collected in the liquid storage tank and later on it is expanded to low
pressure and temperature by passing it through the
throttle valve. At point d we have low temperature liquid refrigerant wuitn small
amount of vapour.
• Process 4-1.
This low temperature liquid then enters the evaporator where it absorbs heat from the space
to be cooled namely the refrigerator and become vapour.
Compressor work Wc = h2-h1 kJ/kg

Condenser work = h2-h3 kJ/kg

Expansion value = h3=h4 kJ/kg

hf2= hf1+(x4 hfg4)

x4 
 hf 2  hf1 
hfg 4

Evaporator Q2 = h4-h1 kJ/kg

Refrigerant effect is amount of heat removed from the surrounding per unit mass flow rate of
refrigerant

Q2 h1  h4
Coefficient of performance cop  
wc h2  h1

Air Refrigeration System And Bell-Coleman Cycle Or Reversed Brayton Cycle

The components of the air refrigeration system are shown in Fig.(a). In this system, air is
taken into the compressor from atmosphere and compressed. The hot compressed air is
cooled in heat exchanger upto the atmospheric temperature (in ideal conditions). The cooled
air is then expanded in an expander. The temperature of the air coming out from the expander
is below the atmospheric temperature due to isentropic expansion. The low temperature air
coming out from the expander enters into the evaporator and absorbs the heat. The cycle is
repeated again. The working of air refrigeration cycle is represented on p-v and T-s diagrams
in Fig.(b) and (c).
Process 1-2 represents the suction of air into the compressor.
Process 2-3 represents the isentropic compression of air by the compressor.
Process 3-5 represents the discharge of high pressure air from the compressor into the heat
exchanger. The reduction in volume of air from v3 to v5 is due to the cooling of air in the
heat exchanger. Process 5-6 represents the isentropic expansion of air in the expander.
Process 6-2 represents the absorption of heat from the evaporator at constant pressure
Assumptions:
1) The compression and expansion processes are reversible adiabatic
processes.
2) There is a perfect inter-cooling in the heat exchanger.
3) There are no pressure losses in the system.
Net refrigeration effect
cop 
Net work supplied
Net refrigeration effect
Net work supplied
Work done per kg of air for the isentropic compression process 2-3 is given by,
Wc= Cp(T3-T2) kJ/kg K
Work developed per kg of air for the isentropic expansion process 5-6 is given by,
WE= Cp(T5-T6) kJ/kg K
Net work required Wnet = (WC - WE ) =( Cp(T3-T2))- (Cp(T5-T6)) kJ/kg K
Net refrigerating effect per kg of air is given by,
Rnet = Cp (T2 - T6 ) kJ/kg K
c p T 2 T6 
cop 
c p (T3  T2 )  T5  T6 

For perfect inter-cooling, the required condition is T5 = T2

c p T 2 T6 
cop 
c p (T3  T2 )  T2  T6 
 1  1
 
T3 p1 T5 p2 T3 T5 T6 T2
    
T2 p2 T6 p1 T2 T6 T5 T3
or T5=T2
T2
Performance of The system cop 
T3  T2