THERMODYNAMICS

Thermodynamics is the science of energy transfer and its effect on the physical properties of
the substances.
 Thermodynamics is defined as science of energy transfer.
 It deals with Energy and its transformation, including heat, work and physical
properties of the substances.
 Thermodynamics deals with three E’s, namely Energy, Equilibrium and Entropy.
 Thermodynamics laws are based on experimental observations and have no
mathematical proof. Like all physical laws, these laws are based on logical reasoning.
 Every engineering activity involves an interaction between energy and matter.
 The Zeroth law deals with thermal equilibrium and establishes a concept of
temperature.
Zeroth law of thermodynamics states that when two systems are separately
in thermal equilibrium with a third system, then they themselves is in
thermal equilibrium with each other.
 The First law throws light on concept of internal energy.
First law of thermodynamics states that when system undergoes a cyclic
process the net heat transfer is equal to work transfer.
 The Second law indicates the limit of converting heat into work and introduces the
principle of increase of entropy.
Kelvin – Plank statement of second law of thermodynamics
Kelvin – Plank states that it is impossible to construct a heat engine working on
cyclic process, whose only purpose is to convert all the heat energy given to it into
an equal amount of work.
Clausius statement of second law of thermodynamics.
It states that heat can flow from hot body to cold without any external aid but heat
cannot flow from cold body to hot body without any external aid.
 The Third law defines the absolute zero of entropy.
The Third Law of Thermodynamics is concerned with the limiting behavior of systems as
the temperature approaches absolute zero. Most thermodynamics calculations use only
entropy differences, so the zero point of the entropy scale is often not important.
However, we discuss the Third Law for purposes of completeness because it describes
the condition of zero entropy.

Third Law states, “The entropy of a perfect crystal is zero when the temperature of the
crystal is equal to absolute zero (0 K).”

Selected Areas of Application of Engineering Thermodynamics

 Automobile engines
 Turbines
 Compressors, pumps
 Fossil- and nuclear-fueled power stations
 Propulsion systems for aircraft and rockets
 Combustion systems
 Cryogenic systems, gas separation, and liquefaction
 Heating, ventilating, and air-conditioning systems
 Vapor compression and absorption refrigeration
 Heat pumps
 Cooling of electronic equipment
 Alternative energy systems
 Fuel cells
 Thermoelectric and thermionic devices
 Magnetohydrodynamic (MHD) converters
 Solar-activated heating, cooling, and power generation

[Type text]
  Geothermal systems
 Ocean thermal, wave, and tidal power generation
 Wind power
 Biomedical applications
Life-support systems
Artificial organs
MACROSCOPIC AND MICROSCOPIC POINTS OF VIEW
Systems can be studied from a macroscopic or a microscopic point of view
Thermodynamic studies are undertaken by the following two different approaches.
1. Macroscopic approach—(Macro mean big or total)
2. Microscopic approach—(Micro means small)
Thermodynamics

Macroscopic and Microscopic Point of view:

The study of thermodynamics begins with the study of restricted region in space or a finite portion of a
matter called the system. Once the system is chosen the next step is to describe in terms of quantities
that will be helpful for discussing the behavior of the system or its interaction with the surroundings or
both.

There are 2 general views adopted for description of the system.

Macroscopic Point of view:

Let us take a system, the contents of a cylinder of an automobile engine. The chemical analysis mixture
of petrol and air before ignition and after the mixture is ignited there would be combustion describable
in terms of certain chemical composition. The system occupies a certain volume and exists at certain
pressure and temperature, All these quantities can be measured in the lab. The contents of the cylinder
now being describable by means of and quantities namely composition, volume, pressure and
temperature. These quantities refers to the gross characteristics of the system is a specification of a few
fundamental measurable quantities.

Characteristics:

They involve no assumption regarding the structure of an atom.

They are few in number

They are suggested more or less by the sense perception

They can be measured directly Eg: Pressure by pressure gauge.

[Type text]
Microscopic Point of view:

If a gas consists of ‘n’ no. of molecules at having same mass of each moving with a velocity independent
of other. The position of any molecule is specified by 3 cartesian coordinates X,Y,Z. The velocity of 3
components be VX, VY,VZ. Therefore to describe the position of velocity of molecule 6 no.s are
required.This equivalent to a imaginary 6- ‘D’ space called phase space whose co-ordinates are XYZ+ V X
VY VZ.

Characteristics:

Assumptions are made regarding the structure of matter that exist in molecular form.

Many quantities must be specified.

The quantities Specified are not suggested by our sense perception.

These quantities cannot be measured.

This type of description is used for statistical thermodynamics. The study from macroscopic point of
view is subject to classical thermodynamics.

Macroscopic v/s Microscopic:

Although the point of view seems different view and incomparative there is a relation between them
where both the points of view are applied to the same system at the end of the relation lies in the fact
that few measurable properties which deals with the macroscopic description are partly the average
over the period of a large no. of microscopic characters. Ex: Pressure is average rate of change of
momentum due to all molecular collision/ unit sec.

Macroscopic approach Microscopic approach

 The macroscopic approach to  The approach considers that the
thermodynamics is concerned with the system is made up of a very large
gross or overall behavior. number of discrete particles
 In this approach a certain quantity of known as molecules. These
matter is considered without taking into molecules have different velocities
account the events occurring at molecular and energies. The values of these

[Type text]
 level. energies are constantly changing
 In other words this approach to with time.
thermodynamics is concerned with gross or  This approach to thermodynamics
overall behaviour. This is known as classical which is concerned directly with
thermodynamics. the structure of the matter is
 The analysis of macroscopic system known as statistical
requires simple mathematical formulae thermodynamics.
 The values of the properties of the system  The behaviour of the system is
are their average values. For example, found by using statistical methods
consider a sample of a gas in a closed as the number of molecules is
container. The pressure of the gas is the very large. So advanced statistical
average value of the pressure exerted by and mathematical methods are
millions of individual molecules. Similarly needed to explain the changes in
the temperature of this gas is the average the system.
value of translational kinetic energies of  The properties like velocity,
millions of individual molecules. These momentum, impulse, kinetic
properties like pressure and temperature energy, force of impact etc. which
can be measured very easily. The changes describe the molecule cannot be
in properties can be felt by our senses. easily measured by instruments.
 In order to describe a system only a few Our senses cannot feel them.
properties are needed.  Large numbers of variables are
needed to describe a system. So
the approach is complicated.

Although the macroscopic approach seems to be different from microscopic one, there exists
a relation between them. Hence when both the methods are applied to a particular system,
they give the same result.

THERMODYNAMIC SYSTEMS
System:
A thermodynamic system is defined as a certain quantity of matter or prescribed
region in space considered for thermodynamic study.

Boundary: System and surroundings are separated by an imaginary line is called boundary.
The boundary may be fixed or it may move, as and when a system containing a gas is
compressed or expanded. The boundary may be real or imaginary.
Universe: The system + the surroundings.
In a general sense, the universe consists of everything that exists anywhere. From a
thermodynamic standpoint, the universe usually consists of whatever the system we’re
referring to is as well as whatever is putting energy into or taking energy away from it.

[Type text]
Example: If we’re studying a space heater, the heater will be our system, the house will be
our surroundings, and the universe will be the heater and the house together (we ignore the
irrelevant rest of the world, since it doesn’t really play a part in anything).
Closed System:
The system in which the transfer of energy takes place across its boundary with the
surrounding, but no transfer of mass takes place is called as closed system.
The closed system is fixed mass system.
 Gas trapped within piston-cylinder device: The fluid like air or gas being
compressed in the piston and cylinder arrangement is an example of the closed
system. In this case the mass of the gas remains constant but it can get heated or
cooled.
 Food items in pressure cooker
 Refrigerator
 Ice-cream Freezer
 Thermal power plant
 Electrolytic Battery
 Bulbs and lamps
 Water being heated in the closed vessel: where water will get heated but its
mass will remain same.

Open System: The system in which the transfer of mass as well as energy can take place
across its boundary is called as an open system. 
Example: Most of the engineering systems are open.
 Flow through tubes and nozzles
 Water boiler
 Air compressor
 IC engine
 Gas turbine
Control Volume: For an open system analysis such as air compressor, attention is focused
on certain volume in space surrounding the compressor known as control volume.
Control Surface: The surface that completely surrounds the control volume is called
control surface.

Isolated System:  

[Type text]
The system in which neither the transfer of mass nor that of energy takes place across its
boundary with the surroundings is called as isolated system.
 For example if the piston and cylinder arrangement in which the fluid like air or gas
is being compressed or expanded is insulated it becomes isolated system. Here there
will neither transfer of mass nor that of energy.
 Similarly hot water, coffee or tea kept in the thermos flask is closed system.
However, if we pour this fluid in a cup, it becomes an open system.
Isolated system is not affected by surroundings. There is no heat, work and mass
transfer take place. In this system total energy remains constant.

Example: Entire Universe

The processes undergone in a closed system ⇒ non-flow process.
The processes undergone in an open system ⇒ flow process.

Properties: Every system has certain characteristics by which its physical condition may be
described, e.g. volume, temperature, pressure etc. Such characteristics are called
properties of the system. These are all macroscopic in nature.
Thermodynamic property:
Thermodynamic property is any characteristic of a substance which is used to identify the
state of the system and can be measured, when the system remains in an equilibrium state.
Example: Volume, temperature, pressure etc.
The salient features of thermodynamic property are:
 Measurable characteristic describing the state of a system.
 It has definite value when system is in a particular state.
 It helps to distinguish one system from other.
 The magnitude of a property depends upon the sate of system and it is independent
of the path or route followed by a system during a process.
 A property is an exact differential.
The differential quantity of a property P is designated as dP, and its integral between the
2
states 1 and 2 of the system is ∫ dP=P2−P1 .
1
For a given expression of a property,
dP=Mdx+Ndy
a simple check can be a useful tool to recognize whether a quantity is a property or not.

( dMdy ) =( dNdx )
x y
Thermodynamic property can be classified into two types.
1. Intensive or Intrinsic and
2. Extensive and Extrinsic property.
An easy way to distinguish whether a property is intensive or extensive is to divide the
system into two equal parts with a partition. After partition, each part will have the same
value for the intensive properties as of the original system, but half the value for extensive
properties.

Intensive properties:

[Type text]
The properties which are independent on the mass of the system are called intensive
properties. E.g., Pressure, Temperature, Specific Volume etc.,

Extensive properties:
The properties which are dependent on the mass of the system is called extensive
properties. E.g., Total energy, Total volume, weight etc.

State: When all the properties of a system have definite values, the system is said to exist
at a definite state. Properties are the coordinates to describe the state of a system. They
are the state variables of the system.

Change of state: Any operation in which one or more properties of a system change is
called a
change of state.

Path: The succession of states passed through during a change of state is called the path
of the change of state.
Process: When the path is completely specified, the change of state is called a process,
e.g. a constant pressure process.

Thermodynamic Cycle: A thermodynamic cycle is defined as a series of state changes

such that the final state is identical with initial state.

.
Thermodynamic Cycle
Adiabatic System: An adiabatic system is one which is thermally insulated from its
surroundings. No heat transfer. It can, however, exchange work with its surroundings. If it
does not, it becomes an isolated system.
Phase:A phase is a quantity of matter which is homogeneous throughout in chemical
composition and physical structure.
Homogeneous System: A system which consists of a single phase is termed as
homogeneous system. Examples: Mixture of air and water vapour, water plus nitric acid and
octane plus heptane.
Heterogeneous System: A system which consists of two or more phases is called a
heterogeneous system. Examples: Water plus steam, ice plus water and water plus oil.

Thermodynamic equilibrium:
When a system is in thermodynamic equilibrium, it should satisfy the following three
conditions.
(a) Mechanical Equilibrium :- Pressure remains constant
(b) Thermal equilibrium :- Temperature remains constant
(c) Chemical equilibrium:- There is no chemical reaction.

[Type text]
Equilibrium:

A system is said to exist in a state of thermodynamic equilibrium when there is no change in any
macroscopic property of the system, if the system is isolated from the surrounding.

The system is said to be in thermodynamic equilibrium if the condition for the following types of
equilibrium are satisfied.

1. Mechanical equilibrium: If there are no unbalanced forces in the interior of the system and
between the system and the surrounding, the system is said to be in state of mechanical
equilibrium.
2. Chemical equilibrium: If there is no chemical reaction or transfer of matter from one part of the
system to another, the system is said to exist in a state of chemical equilibrium.
3. Thermal equilibrium: For a system which is in chemical and mechanical equally if there is no
change in the property of the system, the system is said to be in thermal equilibrium. Ex. co
ordinates of system do not change.
When the condition of any one of the three types of equilibrium is not satisfied the system is said
to be in Non equilibrium state.

Thermodynamic system is defined as a quantity of matter of fixed mass upon which attention is focused
on thermodynamic study.

Any prescription and identifiable collection of matter across the boundary of which there is a transfer of
mass and energy is called System.

Everything external to the system is called Surrounding.The system and surrounding is separated by
means ofa system Boundary.It may be real or imaginary, movable or fixed body. The combined system
and surrounding is commonly known as Universe.

System is divided into three types –

1. Closed System: If mass within the system remains constant and if there is only transfer of energy
across the boundary of the system, then it is called a closed system.

[Type text]
 Ex: consider a system consisting of a gas as shown, if the heat is added to the gas

it will expand and work will be done by the gas on the piston. Thus heat and work will cross the
boundary of the system and volume of system will change due to expansion of gas but no mass
crossesthe boundary of the system, such a system is called Closed system.

2. Open System: If both mass and energy are allowed to cross the boundary of the system, then it
is called an Open System.

Ex: An air compressor in which air enters atlow pressure and leaves at high pressure,

there is a transfer of energy across the boundary of a system.

E.g. Gas turbine and air compressor.

3. Isolated System: In this system neither mass nor energy crosses the boundary of the system.
Here there is no interaction between the system and the surrounding.
Ex: Thermo flask filled with hot coffee.

Boundary:

[Type text]
The hypothetical envelope enclosing a system.

State:

When all the properties of a system have definite values the system is said to exist in a definite state
properties are co ordinates to represent state of a system.

Any operation in which one or more of the properties of a system changes is called change of state.

Process:

When a system changes from one equilibrium state to another equilibrium state a process is said to
have taken place.

Cycle:

If the initial and final state of a system are identical, the system is said to have undergone a cycle i.e. the
system in a given state goes through a number of processes and finally returns to its initial state. System
is said to have undergone a cycle.

Ex: H2O in a stem power plant.

Properties:

Any observable characteristics such as pressure, volume and temperature by which the physical
condition of a system can be described is called property of a system.

Thermodynamic properties can be divided into two groups –

[Type text]
 1. Intensive property: If the value of a property is independent of mass of the system it is called
the Intensive property. Ex. Velocity, weight, viscosity, temperature, pressure.
2. Extensive property: If the value of a property is directly proportional to the mass of the system it
is called Extensive property. Ex. volume, area, density, energies of all kind, electric charge,
magnetization.
The ratio of extensive property to the mass is called specific value of that property and it is an
intensive property. Ex. Volume/ mass = specific volume

Quasi static process:

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

A quasi static process can be viewed as a slow process which allows the system to adjust itself
internally so that properties in one part of the system do not change any faster than those at the other
part.

Pure substance: A pure substance is one that has homogeneous & invariable chemical composition. It may exist in
more than one phase but chemical composition is same in all phases. Every substance exists in any one of the 3
phases i.e. solid, liquid & gaseous state.

Eg: Pure substance like H 2O may exist in solid phase as ice, liquid phase as H 2O & gaseous phase as steam. H 2O, N2
& He are all pure substance. It has uniform chemical composition.

Classify the following as intensive & extensive properties: Temperature, pressure, mass, elevation, length, specific
weight, specific volume, surface tension, enthalpy, volume, force

Intensive properties Extensive properties

Temperature, pressure, elevation, length, surface tension, mass, volume

Specific weight enthalpy, entropy, force

[Type text]
Classify the following into closed, open and isolated system

Closed System:

1. Mixture of ice and water in conducting cylinder.

2. Pressure cooker
3. Storage battery producing electricity.
Open System:

1. Automobile engine
2. wind mill
3. Reciprocating air compressor
4. Steam turbine
5. Water wheel
6. Boiler
Isolated System:

1. Thermos flask with hot coffee.

Quasi – Static process:

The process is said to be quasi – static, it should proceed infinitesimally slow and follows
continuous series of equilibrium states. Therefore, the quasi static, it should proceed
infinitesimally slowly and follows continuous series of equilibrium states. Therefore, the
quasi static process may be a reversible process.

[Type text]
PMM of first kind.
PMM of first kind delivers work continuously without any input. It violates first law of
thermodynamics, it is impossible to construct an engine working with this principle.

Reversible and Irreversible process:

A process is said to be reversible, it should trace the same path in the reverse direction
when the process is reversed. It is possible only when the system passes through a
continuous series of equilibrium state.
If a system does not pass through continuous equilibrium state, then the process is said to
be irreversible.

ZEROTH LAW OF THERMODYNAMICS

When a body A is in thermal equilibrium with a body B, and also separately with a
body C, then B and C will be in thermal equilibrium with each other. This is the zeroth law
of thermodynamics.

Importance of zeroth law of thermodynamics:

It is the basis of temperature measurement. In order to obtain a quantitative measure

of temperature, a reference body is used, and a certain physical characteristic of this body
which changes with temperature is selected. The change in the selected characteristic may
be taken as an indication of change in temperature. The selected characteristic is called the
thermometric property, and the reference body which is used in the determination of
temperature is called the thermometer. A very common thermometer consists of a small
amount of mercury in an evacuated capillary tube. In this case, the extension of the
mercury in the tube is used as the thermometric property.

Reference Points

Temperature scales enable us to use a common basis for temperature measurements.

All temperature scales are based on some easily reproducible states such as the freezing

[Type text]
and boiling points of water, which are also called the ice point and the steam point,
respectively. A mixture of ice and water that is in equilibrium with air saturated
with vapor at 1 atm pressure is said to be at the ice point, and a mixture of liquid
water and water vapor (with no air) in equilibrium at 1 atm pressure is said to be
at the steam point. These points are also called as the reference points.

A temperature scale may of two reference points (steam and ice point) like the Celsius
scale or of a single reference point (273K, i.e, the ice point) like the Kelvin scale.

The ice point and steam points have the following disadvantages:

(a) The difficulty of achieving equilibrium between the pure ice and air-saturated water
(since when ice melts, it surrounds itself only with pure water and prevents intimate
contact with air-saturated water), and
(b) Extreme sensitiveness of the steam point to the change in pressure.
To overcome this difficulty, triple point of water is chosen as the reference point,
at which ice, liquid water and water vapour coexist. Triple point of water is also
known as the standard fixed point of thermometry.

PATH & POINT FUNCTIONS

 Path functions - their magnitudes depend on the path followed during a process.
Eg: Heat and Work.
 Point functions - they depend on the state only, and not on how a system reaches
that state. Eg: Properties

WORK AND HEAT TRANSFER

A closed system can interact with its surroundings in two ways:

a. Work Transfer
b. Heat Transfer
A. Work Transfer
The work is done by a force as it acts upon a body moving in the direction of the force.

Therefore, from definition Work Done = Force x Distance

[Type text]
 B. Heat Transfer
 Heat is defined as the form of energy that is transferred between two systems (or a
system and its surroundings) by virtue of a temperature difference .
 That is, an energy interaction is heat only if it takes place because of a temperature
difference.
 Then it follows that there cannot be any heat transfer between two systems that are
at the same temperature.

PATH FUNCTION:

 Path function depends on history of the system (or path by which system arrived at a
given state). Examples for path functions are work and heat.

POINT FUNCTION:

 Point function does not depend on the history (or path) of the system. It only
depends on the state of the system. Examples of point functions are: temperature,
pressure, density, mass, volume, enthalpy, entropy, internal energy etc.


[Type text]
  Path functions are not properties of the system, while point functions are properties
of the system.
 Change in point function can be obtained by from the initial and final values of the
function, whereas path has to defined in order to evaluate path functions.


 Figure shows the difference between point and path functions. Processes A and B
have same initial and final states, hence, the change in volume (DVA and DVB) for
both these processes is same (3 m3 ), as volume is a point function, whereas the
work transferred (WA and WB) for the processes is different since work is a path
function.
 It should also be noted that the cyclic integrals of all point functions is zero, while
the cyclic integrals of path functions may be or may not be zero.

[Type text]
[Type text]
[Type text]
[Type text]
[Type text]
[Type text]
[Type text]
Concept of continuum:
The concept of continuum is used in macroscopic approach of thermodynamics and not in
microscopic approach.

Matter is supposed to be composed of molecules with intermolecular spacing in between. In

microscopic approach where effect of forces is to be observed on individual molecules and
this study at molecular level is put together statistically to observe it's effect on aggregate,
this discontinuity is of importance due to intermolecular spacing and thus the system under
consideration is not continuous.

In macroscopic approach, where gross effect is of importance, the system is taken to be

continuous. As this is an assumed state of continuum in substance so the order of analysis
or scale of analysis becomes very important. Thus, in case the scale of analysis is large
enough and the discontinuities are of the order of intermolecular spacing or mean free path
then due to relative order of discontinuity being negligible it may be treated continuous.
In Macroscopic approach of thermodynamics the substance is considered to be continuous
whereas every matter actually comprises of myriads of molecules with intermolecular
spacing amongst them. For analyzing a substance in aggregate it shall be desired to use
laws of motion for individual molecules and study at molecular level be put together
statistically to get the influence upon aggregate. In statistical thermodynamics this
microscopic approach is followed, although it is often too cumbersome for practical
calculations.
In engineering thermodynamics where focus lies upon the gross behaviour of the system
and substance in it, the statistical approach is to be kept aside and classical
thermodynamics approach be followed. In classical thermodynamics, for analysis the atomic
structure of substance is considered to be continuous. For facilitating the analysis this
concept of continuum is used in which the substance is treated free from any kind of
discontinuity. As this is an assumed state of continuum in substance so the order of analysis
or scale of analysis becomes very important. Thus, in case the scale of analysis is large
enough and the discontinuities are of the order of intermolecular spacing or mean free path
then due to relative order of discontinuity being negligible it may be treated continuous.
In the situations when scale of analysis is too small such that even the intermolecular
spacing or mean free path are not negligible i.e. the mean free path is of comparable size
with smallest significant dimension in analysis then it can not be considered continuous and
the microscopic approach for analysis should be followed. For example, whenever one deals
with highly rarefied gases such as in rocket flight at very high altitudes or electron tubes,
the concept of continuum of classical thermodynamics should be dropped and statistical
thermodynamics using microscopic approach should be followed.
Thus, in general it can be said that the assumption of continuum is well suited for
macroscopic approach where discontinuity at molecular level can be easily ignored as the
scale of analysis is quite large. The concept of continuum is thus a convenient fiction which
remains valid for most of engineering problems where only macroscopic or
phenomenological informations are desired.

This approach is used in macroscopic approach . when:

a)  the dimension of individual particles  constituting the system is negligible w.r.t overall
dimensions of system
b) when the numbers of individual particles is very large

When both the above stated points are satisfied ,we can apply macroscopic approach.

This concept is used only for macroscopic analysis.

[Type text]
  Properties of any substance is the function of time and space.
 For any substance at each and every point there is a molecule so matters are
composed of molecules. And if you want to define the property only the property as
a continuous function of space in the matter there should not be any discontinuity.
 But there will be always a gap between the molecules, but you always assume while
defining this way the properties that the gap between the molecule is almost zero.
 This is highly true for solids and liquids where the molecules are closely packed and
we can consider this as an assemblance of a single substance but this is not so true
for gases at low pressure as distance between molecules are more.
 But according to avocrado hypothesis it 6.22×10^23 molecules at STP per 22.4 liters
of gas. From this molecular density of approximately 2.7×10^25 molecules per
meter cube which is very high. So we can define the properties of gases as
continuous function of space. This is concept of continuum.
 We can check the whether concept of continuum is valid or not from the Knudsen
Knudsen Number which is the ratio of mean free path to the characteristics lenght.
 If Knudsen Number is less than 0.01 then concept of continuum is valid.

The concept of continuum is the criteria to apply the macroscopic viewpoint

of thermodynamics. In macroscopic approach, our attention is focused on
the small volume which is huge as compare to molecular dimension. So the
concept of continuum gives the minimum volume which must be considered
so that matter can be considered as continous and macroscopic approach
can be applied.

HEAT AND WORK

Work: In mechanics “Work is said to be done when the point of application of force moves in the
direction of force”.

[Type text]
 Work is the form of interaction between a system and surrounding. In thermodynamics work is
identified only when it crosses the boundary of the system “work is said to be done by a system if the
sole effect on things external to the system can be deduced to the rising of a weight”. Here rising of
weight is effect of force acting through a distance.

Let us consider battery and motor as a system as shown in fig.1. The motor is driving a fan the system is
doing work upon the surrounding. When the fan is replaced by a pulley and weight as shown in fig.2.
The weight may be raised by the pulley driven by motor. The sole effect of thing external to system is
raising of weight.

Work: When work is done by a system, it is taken to be positive and when work is done on the system, it
is taken to be negative.

Eg: A gas expanded against a piston is positive work. Piston compressing a gas is negative work. Positive
work means energy leaves the system and negative work means energy is added to system.
Heat: It’s a form of energy that is transferred across the boundary by virtue of temperature difference.
The direction of heat transfer is taken from the high temperature system to low temperature system.

Heat flow into a system is taken to be positive and heat flow out of a system is taken to be
negative. A process in which no heat crosses the boundary of the system is called adiabatic process
(Q=0). A heat is a transient quantity which can be identified only as it crosses the boundary of the
system.

Displacement work or pdv work or work done at the moving boundary of a simple compressible
system in a quasi static process.

Consider a gas in a cylinder as a system having initially pressure and volume of P1 & V1. As it occupies a
new position the pressure and volume are P 2 & V2

[Type text]
respectively. Consider the movement of piston through an infinitesimal distance ‘dl’ and if ‘A’ is area of
c-s of piston.

Then force acting on the piston

F= Pressure×area=P×A

The amount of work done by the gas on the piston W.d.=Force ×dl

∂w= p×A×∂l ∂w= pdv Therefore dv=A×dl

When the piston moves from position 1 to 2 the total work done by the system will be ∂w

2 v2 v2

∫ δW = ∫ pδv W = ∫pdv
1-2

1 v1 v1

The magnitude of work is given by area under the path 1-2 as shown in pv-diagram. The integration pdv
can be performed only on a quasi static path.

2 3
1. A non-flow reversible process occurs for which p=3v +1/v ; P→ bar, v→m What will be the w.d.
3
when v changes from 0.5 to 1.5 m .

2
Sol: 1 bar = 1× 105 N/m2 ; V =0.5; V2=1.5; p=3v +1/v
1

w= ∫2pdv
1

1.5 1.5

W= ∫ ( 3V2 + 1/V1) dV = [ V3 + logV] W= 4.348× 105N-m

0.5 0.5

2. A fluid system undergoes a non flow frictionless process from V = 6m3

1

[Type text]
V2= 2 m3 . The process is given by P = 15/V + 2. Determine workdone ?

v2 2 2

W = v1∫ pdv = ∫ ( 15/V + 2) dV = [ 15logV + 2V] W=-24.479×105 N-m

6 6

-‘ ve sign indicates work is done on the system.

3. A non flow Quasistatic process, occurs for p = -3V + 16. What is the workdone when V changes from 2
to 6m3?

v2 6 6

W = ∫ pdv = ∫ (-3V + 16) dV = [-3 V2 + 16 V] W = 16×105 N-m

2 2
v1

+ve indicates workdone is done by the system

4. When the valve of a evacuated bottle is opened atmospheric air rushes into it. If the atmospheric air is
95 KPa & 1.5m3 of air enters into the bottle calculate the work done by air.

Sol: Total work done = ∫ work done by bottle + ∫work done by air = 0 + ∫pδv.

W =P V = -955×1.5 = -142.5 KJ
air air air

Work is done by the air on the system. Since free air boundary is contracting, the work is done on the bottle & it is
–ve.

3
5. A gas in the cylinder and piston arrangement compressed the system. It expands from 1.5 -2 m by receiving
4
20×10 N-m of work from a pedal wheel. The pressure of gas remains constant at 6 bar. Determine the workdone.

[Type text]
 v2

5 4
Sol: W.d. gas = ∫ pδv = 6 × 10 [2-1.5] = 30 × 10 N-m
v1

+ W.d
Net W.d = W.dgas pedal

= 30 × 104 4
- 20× 10

4
= 10× 10 N-m

6. A piston and a cylinder machine contains fluid has a stirring device in the cylinder. The piston is frictionless and
it is held down against the fluid to atmospheric pressure of 101.325 KPa. The stirring device is turned 10000 rev
with an average torque against a fluid of 1.275 N-m. Meanwhile the pistonof 0.6m dia moves out of a distance of
0.8 m. Find the net work transfer for the system.

Sol: Dia of piston – 0.6m l = 0.8m P= 101.325 KPa

W. d by the stirring device = 2πNT = 80.11 KJ or N-m

W.d. by the gas on the piston = P. A. L

2
= 101.325 × π/4 (0.6) × 0.8 = 22.92 KJ

W.d. on the system by the stirring device = -80.11 KJ

The workdone is positive by the pressure of air acting on the system

Net W.d. = -80.11 + 22.92 = -57.19 KJ

[Type text]
Equality in temperature:

Consider 2 bodies one hot and other cold are placed in contact in an isolated system. After sometimes the hot
body loses heat and becomes cold. The cold body becomes hot. This process continues till the exchange of heat
attains a state of thermal equilibrium..

When two bodies have equal temperature then there is no change in any observable property when they are
in thermal equilibrium.

Zeroth Law of Thermodynamics:

“If two systems are in thermal equilibrium with the third system, then the two are themselves in equilibrium with
each other”

Ex: Let us apply the concept of equality of temperature to 3 system, 1, 2 & 3 . Let 1 be a container fitted with a
pressure gauge.The system 2 & 3 are metallic spheres.Let system 1 be brought in contact with 2 if thereis no
change in pressure of system 1. Then system 1& 2 are equal in temperature, similarly if the system 1 is brought in
contact with 3 again there is no change in property of system1 then system 1 & 3 are in thermal equilibrium. The
experiment shows that if system 2 is in contact with 3, if there is no change in property of system, then the system
2 & 3 are at equal temperatures. When two system are in thermal equilibrium, according to Zeroth law of
thermodynamics.

Ice point: it is defined as a temperature of a mix of ice and H 20 which is

inEquilibrium with saturated air at atmospheric pressure.

Steam point: It is defined as temperature of steam and H20 at atmospheric pressure.

[Type text]
Temperature scale: On a centigrade scale ice point is numbered as zero and steam
point as 100 on the Fahrenheit scale.

o o
The respective points are32 F & 212 F.

If solid ice liquid H20 and water vapour exist at equilibrium condition, the state of equilibrium is
called triple point of water.

Toc = ToK – 273 T oF

= ToR – 460

ToF = 1.8oc + 32 T oR
= 1.8 ToK

International Temperature scale: The procedure for measuring temperature was adopted to
provide a scale that could be used to calibrate scientific instruments. They specified certain fixed
points at which instruments like thermometers, thermocouples, pyrometers, resistant
thermometers etc... can be calibrated.

Temperature
o
Sl.no Fixed point c

     

1 Triple point of H2 -259.34

Normal boiling point

2 of 02 -182.962

3 Triple point of H20 0.01

4 Ice point 0

5 Steam point 100

6 Sulphur point 444.6

7 Silver point 960.8

8 Gold point 1064.44

[Type text]
Problems:

1. The equation Rt= Ro(1+αT) is applicable to a resistant thermometers. Rt & Ro are the
o o
values of resistance, at temperature t c and t k. The thermometer is calibrated by
o o
immersing in boiling H20 273 k + boiling sulphur 718 k. The instrument indicates the
resistance values at these two temperatures to be 14.7 Ω & 29.2 Ω respectively.
Determine the temperature of fluid for which the corresponding thermometer
resistance is 23.64 Ω

Sol: Rt1=14.7 Rt2=29.2 t1= 273 K t2= 718K

Rt= Ro(1+αt) 14.7=Ro(1+α

(273))-----1 29.2= Ro(1+α(718))------2

Equatingthe equations eq1/eq2 =

14.7/29.2=1+α273

1+α 718 α =5.6*10-3

Rt=Ro(1+αt)====>14.7=Ro(1+5.6*10-3*273) Ro=5.8

o
At 23.54 Ro=5.8 23.54= 5.8(1+5.6*10-3*T) T=543.7 K

Problem2. The temperature on a thermometric scale is defined in terms of a property

‘p’ by the relation t = a log p+b where a & b are constant. The temperature of ice point
& steam point are assigned 32 + 212. Experiment gives the values of ‘p’ 1.86 + 6.81 at
ice point + steam point respectively. Evaluate‘t’ corresponding to p= 2.50.

Sol: t = a logep + b a =138.69

32= a log 1.86 + b b = -54.06

e

[Type text]
212 = a log 6.81+b
e

-180 = a (log 1.86 -log 6.81)

t = 138.69 loge 2.5 + (-54.06)

t=73.02

3. A constant volume gas thermometer containing He gives the reading of gas pressure at 1000 +
1366 mm of Hg at ice point and steam point respectively. Assuming the linear relationship of the
form t = a+b. Express the gas thermometer / Celsius temperature ‘t’ in terms of gas pressure ‘p’.
What is the temperature recorded by the thermometer.

Sol: t = a + bp 0 = a + bp → 0 = a+b(1000) a = -1000b

b = 0.2732

100= a + b(1366) = -1000b + 1360b = 366b a = -273.2

T = -273.2 + (0.2732) (1074) t = 20.2168

First-Law—of-Thermodynamics:

[Type text]
Joule’s Experiment: Take a quantity of H20 in a rigid vessel,which-was isolated
adiabatic, from its environment as shownin the vessel was fitted with a peddle
wheel. The initial state ofthe system was determined by measuring the pressure-
and temperature.

As work was done on the system, by a peddle wheel which was

actuated by a falling weight ‘W’. Its temperature is increased.

The system was then placed on a constant temperature bath to restore to its initial
state.

Thus the system had undergone one complete cycle. The net work input to the system
was always α to the heat transferred out of the system. In other words, when a closed
system undergoes any cyclic process then cyclic integral of work is α to cyclic integral of
heat. Φ δW α φ δQ

Therefore φ δW = J φδQ where J → Joules constant

Statement of First Law of Thermodynamics:

The first law states that “ During any cycle a closed system undergoes, cyclic integral of
heat is directly proportional to cyclic integral of work.

Φ δQ α φ δW Φ δW α J φ δQ

where J→ proportionality constant→ Joule’ constant

Whenever a system executes a cyclic process the algebraic sum of heat transfer is equal
to algebraic sum of work transfer. i.e. Q1 + Q2 + Q3 + Q4 + …………= W1 + W2 + W3 +
W4 + ………..

∑ δQ = ∑ δW

[Type text]
To show that internal energy is a property of a

system consider a system, that undergoes a cycle

changing its state from 1- 2 along path A &returns

to its original state from state 2 to

state 1 along two paths B or C.

From First law of thermodynamics,

φ δQ = φ δW φ δQ - φ δW = 0 → 1

Now applying first law for cyclic process consisting of path A & B

2 1
Φ (δQ-δW) + Φ (δQ-δW) = 0 → 2

1 path A 2 path B

Consider another cycle in which the system changes its state from 1 to 2 along path A
but returns from state 2 to 1 along path C

2 1
Φ (δQ-δW) + Φ (δQ-δW) = 0 → 3

1 path A 2 path C

1 1
Equating 2 & 3 Φ (δQ-δW) = Φ (δQ-δW)

[Type text]
 2 path B 2 path C

The quantity (δQ-δW) is same for processes B & C but process B & C are two arbitrary
process between 1 & 2 .Therefore The quantity (δQ-δW) does not depend on the path
function between 1 & 2 but depends only on initial and final states. Hence it is a point
function and represents a change in property of the system and is denoted by E.

δQ-δW = δE δQ = δE+ δW

If this is integrated between 1 & 2

2 2 2

δQ = ∫ δE + ∫ δw Q = (E2-E1) + W
∫1 1 1 1-2 1-2

Q1-2 → Heat transferred between 1 & 2

E2→ Final value of energy

W → Work transferred between 1 & 2

1-2

E1→ Initial value of energy

The energy includes internal energy, potential energy and kinetic energy.

ie.. δE = δU + δ(KE + δ(PE)

δE = δU + δ(½mv2) + δ(mgh)

δ(KE) + δ(PE) = 0 When δE=δU δQ = δU+ δW

[Type text]
Since δQ-δW is the property of the system. Internal energy is also a property of a
system.

If an Isolated system is considered the heat + work cannot cross the boundary of the
system

Q=W=0 → E2=E1

ie.. the energy of an isolated system always remains constant.

Perpetual motion machine of 1st kind [ PMM- I]

A machine that creates its own energy or continuously produces work out of nothing is
called PMM- I. The machine violates first law of thermodynamics PMM- I is
thusimpossible.

Problems

1. In a cyclic process the heat transfers are 14.7KJ, -3.56KJ, & 31.5KJ, What is the net work done.

∑δQ = ∑W Q1+Q2+Q3+Q4 = W

14.7-25.2+31.54-3.56 = W

+ve === work is done by the system.

2. In a cyclic process the heat transfers are 10J,-24J,-3J & 31J determine the nett work done.

∑Q = ∑W 10-24-3+31 = W

W = 14 N-M

Work is done by the system.

[Type text]
 3. Closed system undergoes a process in which heat transfer from the system is 40 KJ & w.d on the
system is 18 KJ. Calculate the change in internal energy. The system is brought back to its initial
stage 20 KJ of work is done by the system heat transfer also takes place. Calculate magnitude &
direction of heat transfer.

From law of thermodynamics

δQ = δE + δW Q1-δE + W1

-40 =δE-18 δE = -40+18

δE = -22 KJ

i.e. The energy is increased by an amount of22 KJ

∑Q = ∑W Q1 + Q2 = W1 + W2

-40 + Q2 = -18 + 20

Q2 = 42 KJ

Heat is transferred into the system

4. A stationary mass of gas is compressed without friction from an initial state of 0.3 m3 & 0.105
mpa to a final state of 0.15m3 & 0.105mpa. the pressure remaining constant during process . how
much does the internal energy of the gas changes.
When there is a heat transfer of 37.6 KJ of heat from the gas during the process.

v2
δW = ∫ pdv = p(v2-v1) = 0.105(0.15-0.3) = 0.105(-0.15)

[Type text]
 v1

3
w = -15.75x10 J w = -15.75 kj

δQ = δu + δw δu = E2 – E1

δu = -37.6-(-15.75) = -37.6+15.75

δu = -21.85 KJ

Steady flow energy Equation :

Consider a steady flow system in which there is a mass m1 entering at section 1 & m2 leaving at section
2. There is no accumulation of mass or energy within the controlled volume & the properties at any
location within the controlled volume are steady with time. Section 1 & 2 are at an elevation of Z1 & Z2
respectively w.r.t datum line of the controlled volume undergoes process there will be heat & work
transfer applying 1st law of thermodynamics Q-W=∆E W includes all types of external work and the flow
work due to mass entering and leaveing the controlled volume

The following assumption are made for the analysis of the system:

1. the mass flow through the system remains constant m1=m2=m

[Type text]
2. There is no chemical composition of fluid

3. The state fluid at any point remains constant with the time

4. The rate of heat & work passing through the boundary of a system remains

5. The fluid or gas is uniform in composition

By the law of conservation of energy m 1e1+m1p1v1+Q=m2e2+m2p2v2+w-----1

e = ∆u+∆KE+∆PE e = u+v2/2+Zg substituting value of ‘e’ in 1

m1(u1+v12/2+gZ1)+m1p1v1+Q = m2(u2+v22/2+Z2g)+m2p2v2+W

The enthalpy is given by h = u+pv

m1(h1+v12/2+gZ1)+Q = (h2+v22/2+gZ2)m2+W

Mass remains constant therefore m1=m2=m

Q-W = m(h2-h1) + v22-v12 + (Z2-Z1)g

Q-W = m∆(h+v22/2+gZ)

Where A1 & A2 are area of c.s in m2.

m1 & m2 are mass flow rates in kg/sec

P1 & p2 are pressure9rates) in Pascal,

V1 & v2 are velocity in m/sec,

Z1 & Z2 are elevation above datum,

Q = heat in joule, w = work in joule

Application of steady flow energy equation

1 . Work developing system Ex-: Engine, steam gas & H2O Turbines.

[Type text]
 2 . Work absorbing System Ex-: Pump, Compressor & refrigerator

3 . Non work developing & absorbing system Ex-: Nozzles & Heat exchangers

Application of steady flow an equation for Throttling devices:

When fluid flow through a restricted passage like a partially opened valve or orifice or a porous plug
there is an appreciable drop in pressure & flow is said to be throttled. Fig shows process of throttling by
a partially opened valve fluid flowing in a insulated pipe from SFEE/

Q-W = (h2-h1 + v22-v12 + (Z2-Z1)g)m …….eq1

Q = 0 & W = 0 & potential energy is negligible. Than the equation becomes

0 = m((h2-h1) + ( v22-v12))………..eq2

velocity inlet isequalto-outlet than h2=h1 therefore itbecomes V2=V1

The enthalpy of fluid before & after throttling is equal.

Nozzle & diffuses

[Type text]
Nozzle is a device which increases the volume or KE of the fluid at the expense of the pressure drop
where as diffuser increases the pressure of a fluid at the expense of the KE. The nozzle is insulated. Than
the SFEE

Q-W = m((h2-h1) + v22-v12 + (Z2-Z1)g)

The W.d is zero, Q = 0, PE = Negligible

Than 0 = h2-h1 + v22-v12

v2 = √(2(h1-h2) + v12)

The inlet volume is negligible therefore v1 = 0

V2 = √(2(h1-h2))

Go to 15

8. 135KJ of work is done by each kg of fluid. The specific volume , pressure and velocity at the inlet are
0.37 m3/kg 600Kpa at 16 m/s. The inlet is 32m above the flow and the discharge is at float level. The
discharge conditions are 0.62m 3/kg ,100Kpa and 270 m/s. Total heat loss between inlet and discharge is

[Type text]
9KJ/Kg of fluid. It is flowing through this apparatus. Thus the speci mter ener increase, or decrease
and by how much?

Sol: V1 = 0.37 m3/kg P1 = 600Kpa V1 = 16m/s (V2= 0.62m3/kg) W= 135 KJ

V2 = 0.62 m3/kg P2 = 100Kpa V2= 270m/s Q= -9KJ

2
Q-W = m [(h2-h1) + V2 -V1 + g(Z2-Z1)]

2×1000 1000

U2-U1 + -20.53KJ -ve since internal energy is increased

9. A steam turbine receives steam blow of 5000Kg/hr and delivers 550Kw. The heat loss from the basin
and turbine is ~0 (i) Find change in enthalpy across the turbine if velocity at the entrance and difference
in elevation at entrance+ exit are negligible. Take the velocity at the exit as 360 m/s. (ii) Find change in
enthalpy across the turbine if velocity at entrance is 66 m/s and the inlet pipe is 3m above exhaust.

(i) Q=0 h2-h1=? W= 550Kw Z2-Z1= 0 m= 5000KG/hr = 5000 Kg/s = 5000 Kg/min

3600 60

1Kw = 60KJ/min

V1 = 0 V2 = 360 m/s W= 550 KJ/min

60

2
Q-W = m [(h2-h1) + V2 -V1 + g(Z2-Z1)] h2-h1= -64.8

2×1000 1000

0- 550×60 = 5000 [(h2-h1) + (360)2-0 + g(0) ]

60 2×1000 1000

1Kw-hr = 3.6×106 N-m 1Kw-min = 3.6×106 N-m/min

[Type text]
 60

Diameter ratio d1/d2 = √1000x10x4/√230.24x10 -4x4 = 2.08 d1/d2 = 2.08

7 Air expands from 3bar to 1bar in a nozzle in velocity is 90 m/s & in temperature = 150 oc,
final velocity from SFEE k = 1.4 T1 = (150+273)

from enthalpy equation ∆H = h1-h2 = cp(T1-T2)

When pressure p1 & p2 the temperature are known

k k
P1v1 = p2v2 -----1 for a polytrophic process

K
P1/p2 = (v2/v1) K—index constant for air

T k-1 k-1 k-1 k/k-1

1v1 = T2V2 ----2 v2/v1 = (T1/T2) p1/p2 =(T1/T2)

1.4/0.4
3 = (423/T2) T2 = 309k Cp of air 1.005 KJ/kg

∆H = 1.005(423.309) h 1-h2 = ∆H = 114.5

2
v2 = √(2(h1-h2) + v1 = 487 m/s v2 = 487 m/s

[Type text]
 8 Steam having specific enthalpy of 2930 KJ/kg flows through a turbine nozzle after expansion it
leaves the nozzle with an enthalpy of 2255 kj/kg in adiabatic determine exit volume. If the inlet
volume is 3600m/min.

3 2 3
v2 = √(2(h1-h2)10 +(3600/60)) = √(2(2930-2255) 10 + 3600) = 1163.4 m/s

Reversible Process: The process said to be reversible if the system and all the elements of its
surroundings can be restored to the respective initial stage after the process has occurred.

Ex: Frictionless motion of solid, gradual extension of spring, slow frictionless adiabatic expansion of a
gas, electrolysis of water.

This process actually donot occur in nature. They are nearly idealization of actual process.

Irreversible Process: The change in the equilibrium of aa system and surrounding then the process that
doesn’t come back to its initial state is called irreversible process.

Ex: Combustion in an IC engine, diffusion of 2 unlike fluids into each other, electric current flows thru a
resistor , flow of river water over a waterfall, plastic deformation of materials, magnetization of material
exhibiting hystensis.

Turbine:-

Turbines & engines give power output whereas compressors & pump reg power for turbine which is
well insulated the flow velocities input are small & KE is neglected SFEE == Q-w=MA(h+v 2/2+gz) Q = 0,
v2/2=0, gz=0

[Type text]
 m(h2-h1)+w=0 w/m= h1-h2

In case of turbine h1>h2 i.e. the work is done by the fluid or gas at the expense of the enthalpy.

.
Compressor:- for a compressor work is done on the fluid & w is ‘-ve’ . . SFEE

w/m = h2-h1 the enthalpy of fluid m1 by an amt of work input.

Boiler:- is used to raise steam by supplying heat from an ext source the change in

KE+PE is negligible. The work done is zero, than SFEE Q = (h2-h1)m.

Condenser:- is a device used for condensing the exhaust steam from turbine into water

KE+PE & work done is zero therefore SFEE becomes Q = (h1-h2)m

1. A mix of gases expands at constant pressure from 1 mpa , 0.03m 3 to 0.06 m3 with
84KJ +ve heat transfer. There is no work other than that is done on heat system, Find the energy for
gaseous mixture.

V1 = 0.03m3 v2 = 0.06 m3 Q= +84KJ from 1st law of TD we have

v2
Q-δw=∆E Q-W=∆E work done = ∫ pdv = 1x106(0.06-0.03)

V1 = 3 x 10 4 KJ

W.D = 30KJ ∆E = 54KJ

2. A turbine operating under steady flow condition receives 5000kg of steam per hour.

[Type text]
 Steam enters the turbine at a velocity of 3000m/min in elevation of 5m & specific enthalpy of
2787KJ/kg. it leaves the turbine at a velocity of 6000m/min at an elevation of

1m & specific enthalpy of 2259 KJ/kg what losses from the turbine to the surrounding

amounts to 16,736KJ/hr. determine the power output of the turbine in kw.

m=5000kg/hr h1=2787KJ/kg h2=2259KJ/kg v1=3000m/min v2=6000 m/min z1=5m, z2=1m

Q= -16,736KJ/hr.

from SFEE Q-W = m{(h2-h1) +v22- v11/2x1000 + g(Z2-Z1)}/1000

W=723.4849KW

-16736/60x60-w =5000/60x50{-528 + 27x10 3/60x2000 – 9.81(4)/1000}

-4.468-W = 1.39{-528 + 36x106 – 0.039} = 723.485 Kw

3. In a steady flow system 1kg of fluid per/sec enters the container at a pr. Of 1bar & leaves the
system at a pr. of 10bar. The inlet & exit velocity are 40m/s & 20m/s respectively during the
process 36000KJ of heat is transferred /hr to the control volume .The rise in enthalpy is 15KJ/kg.
calculate the power dev. By the system neglect change in PE.
m=1kg/sec v1= 40 m/s v2= 20m/s Q = 36000x5/18 = 10,000 h2-h1 15 KJ

Ans W = 4.4 KW

4. A turbine operating under steady flow condition receives steam at 4500kg/hr. the steam enters the
turbine at a velocity of 2500m/min at an elevation of 4m with specific enthalpy of 665 KJ/kg. it
leaves the turbine at a velocity of 560 m/min at a elevation of 1m & specific enthalpy of 54KJ/min.
The heat losses from the turbine to the surroundings amount to 4000 KJ/hr. determine the power
o/p of machine in KW
m=4500 kg/hr v1=2500 m/min v2 = 560 m/min z1 = 4m Z2 = 1m, h1= 665 KJ/kg,

h2=540KJ/kg, Q = 4000KJ/hr

[Type text]
Second Law of thermodynamics:

Limitations of first law of thermodynamics:

The 1st law states that” When a closed system undergoes any cyclic process, the cyclic integral of work=
cyclic integral of heat ie energy from one transforms into another by an equivalent amount. The 1at law
doesnot impose any restriction on direction of flow of heat and work. However complete conversion of
heat into work is not possible as it is known from our experience. This kind of experimental evidence has
led to the formation of second law of thermodynamics. A hot cup of coffee can by virtue of heat transfer
to the surrounding but heat will not flow vice versa.

1. Heat engine and heat power:

A heat engine is a thermodynamic cycle in which there is a net heat transfer to the system and net work
transfer from the system without mass transfer across its boundary.

The mass transfer across its boundary is called as heat engine.

Ex: A steam power plant consists of a boiler, turbine, condenser and a pump in a steam engine but
petrol and diesel engines are not heat engines since the mass flows in the form of air- fuel mixture and
the exhaust gases crosses the boundary of the system.

The H2o flows from pump to boiler in which an amount of heat Q h is transferred to H2o from a high
temperature reservoir like a furnace. The steam formed is expanded in the turbine delivering the net
amount of work ‘W’. The steam then passes on the condenser where an amount of heat Q l is rejected
from the steam. The condensed H2o in a condenser is again pumped by pump to the boiler and the cycle
repeats such a device is called a heat engine.The substance to which and from which heat was
transferred is called the working substance.
st
From the 1 law of thermodynamics the netheat transfer = net workdone ie.. Q h- Ql =W

The efficiency of heat engine is defined as ratio of work output of cycle to heat input to the cycle.
Thermal efficiency is given by :

[Type text]
η = work done Qh- Ql ηHE = 1- Ql
=W =

Heat supplied Qh Qh
Qh

Heat pump: If the cycle is performed in the opposite direction so that absorption of heat is at lower
temperature and reference of large amount of heat at ahigher temperature where net amount of
workdone is on the system. Such a device is called a heat pump or refrigerator of a reversed heat
engine.

Example:-Vapour compressed refrigeration:

In this the working fluid NH4 or Freon 12is compressed in a compressor to

a higher temperature and pressure.It is passed into condenser where heat is rejected at constant
pressure and vapour becomes saturated liquid. This is expanded to a low pressure compressor in a
throttle valve. The temperature of liquid is reduced. This low temperature pressurized liquid is passed
onto the evaporator where it absorbs heat from a lower temperature body. Such a device is known as
reversed heat engine. If the purpose are utilized to deliver heat at high temperature a .Then it is called
H
as a heat pump whose purpose is to abstract heat at lower temperature Q l then the device is called as a

refrigerator.

The η of a refrigerator or heat pump is expressed by COP ( coefficient of performance).

[Type text]
COP of refrigerator: When the system works as a refrigerator then the main interest is refrigerating
effect Ql+ energy input will be the work which is required for the plant.

Therefore COP = Heat absorbed at low temperature = Ql

Work supplied Qh- Ql

COPref = Ql

Qh- Ql

COP of heat pump: When a system works as a heat pump is Qh the system will transfer to the
surrounding and energy input will be work.

Heat pump=heat delivered at high temperature =QH

Work supplied QH- QL

COPHp= QH

QH- QL

Representation of heat engine and heat pump:

[Type text]
State of II nd law of thermodynamics: there are two statements and are as follows,

1. Kelvin Planck's statement &

2. Clausius statement.

Kelvin Planck's statement: “it is impossible to construct a device which operates in cycle and
produces no effect other then the rising of a weight and exchange of heat with a single reservoir“
It means that it is impossible to construct a HE which operates in a cycle and
extracts a given amount of heat from the WTR and delivers an actual amount of work or “it is
impossible to construct a W.E of 100% efficiency or its impossible to construct all heat into
work.

Clausius statement: “ it is impossible to construct a device that operates in cycle and produces no effect
other then transfer of heat from a colder body to hotter body”.

This means it is impossible to construct a refrigerator that operates without an input of

work.

To show the violation of clausius statement implies violation of Kelvin Planck’s statement:

Consider a HP and HE operates between the same 2 reservoirs i.e. HTR and LTR. The HP required no
work to operate thus violating the clausius statement.

The HP extract an amount of heat from the LTR rejects the same amount of heat Q L to the
HTR. Now the H.E extracts an amount of heat Qh>QL from the HTR and rejects an amount of heat to QL
to LTR.

[Type text]
The net amount of W.D W=Qh-Ql. Since there is no change in heat transfer in LTR the heat pump, the
HTR and the HE together can be considered as a device which absorbs an amount of heat from the HTR
and produces an equal amount of work W without produces any change in LTR which infact violates the
Kelvin Planck’s statement. Hence the above statement is proved.

To show the violation of Kelvin Planck’s statement implies violation of clausius statement:

Consider a HE and HP working between HTR and LTR. The HE operates in cyclic process takes an amount
of heat from HTR and converts it completely into work W violates K.P statement let this work= be
utilized to drive a HP as shown. Let HP takes Ql amount of heat from LTR and pumps Qh+Ql amount of
heat to HTR on analysis of a part of heat i.e. pumped to the high from LTR to HTR is delivered to HE
while there remains a heat flow from LTR to HTR which infact violates clausius statement of second law
of thermodynamics. Hence the above statement is proved.

Carnot cycle:

[Type text]
Process 1-2 isothermal expansion at constant temperature T H. Heat is transferred isothermally and
reversibly from HTR at temperature T H. to the working fluid (steam organ) the heat observed is Q H.

Process 2-3 reservoir adiabatic expansion of a gas. The process is processed by thermodynamic
insulated system carrying out expansion reversibly and the temperature of working fluid falls from
temperature.

Process 3-4 reversible isotherm, compression of a gas at constant temperature T L with this prog system,
is brought in contact with LTR at temperature T L and heat is transfer, reversibly and isothermally from
the working fluid to LTR.Heat rejected during the process is Q L.

Process 4-1 reverse adiabatic compression prog. The prog is performed by thermally regulating the
system a carrying out compression prog, until working fluid is returned to its initial state. During this
process the temperature of working fluid risen from lower temperature T L to higher temperature T H as
shown in P-V and T-S diagram.

Since an amount of heat Q H is transfer to the system to HTR and an amount of heat QL is rejected from
system to LTR. The net amount of heat transfer Q W- QL will be numerically equal to the work done by
the system, I.e. W= QN- QL

Thermal efficiency of the Carnot engine is given by,

Carnot= WD = QH - QL in terms of temperature Carnot= TH - TL

QH QH TH

Carnot cycle for a heat pump:

[Type text]
The Carnot cycle is carried out in a reversed manner. The Carnot engine will work as a heat pump.

Process 1-4 reverse adiabatic expansion process. It is carried out by thermally insulate of the system and
carrying out the expansion process, until temperature of the working fluid form the T H to TL.

Process 4-3 reverse isothermal expansion. During the process, heat is transferred from LTR to working
fluid.

Process 3-2 reverse adiabatic compression process. During the process the system is thermally insulated
and work is done on the system. The compression process is carried out until the temperature of
working fluid, from TH to TL.

Process 2-1 reverse isothermal compression process. During this process, heat is transferred reversibly
and isothermally, from the working fluid to HTR. The process is continued until initial state is reached,

COP heat pump= QH = QH in terms of temperature COP = TH

W Q H - QL T H - TL

It works as a refrigerator COPrefrig= QL = TL

QH -QL Th-TL

Carnot cycle is not practicable due to the following reasons:

1. Heat transfer at constant temperature is virtually impossible.

2. Reversible adiabatic expansion and compression without heat transfer requires a large displacement
and the process must take place slowly. This is also not practicable. Therefore carnot cycle is only Ideal
cycle or theoretical cycle.

[Type text]
1. A heat engine performs many cycles while doing work – 21.5×10 5 N-m and receiving a heat transfer of
90×105 N-m. Evaluate the efficiency of the engine and heat tranfer from working fluid.

W= 21.5×105 N-m ηHE = W = 23.8% W= QH-QL

QH=90×105 N-m QH QL= 68.5×105J

2. A heat engine working at a rate of 100Kw has an Efficiency of 20%. Evaluate the magnitude of heat
transferred rate to and from the working fluid.

η=20% W= 100Kw 0.20= W/ QH QH= 500Kw

3. In a reversed heat engine the workdone on the engine is 75×10 3 N-m and heat transfer to the engine
from LTR is 220×103 J. Evaluate the heat transferred to the HTR and the COP of refrigerator and if it also
works as a heat pump. Calculate its COP?

3 3
QH= W+ QL= (75+220)10 295×10 J COPHE= QH = 295 = 3.93

W 75

COPrefrig= QL = 220×103 = 2.93

[Type text]
 W 75×10 3

4. A heat engine is supplied with a heat of 1800 KJ\min and gives an output of 9.5 KW . Determine the
thermal efficiency and the rate of heat rejection.

Q1=1800 KJ\sec W= 9.5 KJ\sec η = W= 31.6%

60 Q1

W = Q1- Q2 Q2= Q1-W = 30 -9.5 = 20.5 KJ \sec

5. A cyclic heat engine operates between a source temperature of 800 oc and a sink temperature of 30 oc
. What is the rate of heat rejection Kw + nett O/p of energy.

T1 = 800 + 273

T2 = 30 + 273

ηHE =W/ QH = QH-QL ηHE = T1- T2 = 71.76%

QH T1

ηHE =W/ QH W= 0.7176 QH W = QH-QL QH = 3.54

QL

QL= 1.393 Q2= 0.303 1 KW= QH-QL QL = 0.393 Kw QH= 1.393 kw

[Type text]
6. A domestic food freezer maintains a temperature of -15 oc. The ambient temperature is 30 oc. If heat
leaks in the freezer at a continuous rate of 1.75 KJ/s. What is least power necessary to pump this heat
continuously.

COPrefrig= T2 = -15 = -1/3 COPrefrig= 258/45 = 5.733

T1- T2 30 +15

COPrefrig= QL Qh = 2.05 KJ/s W= 0.305 Kw

Qh-QL

Perceptual motion machine II-Kind:-

A machine, which extracts heat from an infinite and readily available source (thermal reservoir) and
delivers equal amount of work container, to the surrounding such a device is PMM-II. The efficiency of
such a machine would be 100%.

Carnot theorems:

Corollary 1: “ It is impossible to construct an engine that operates between two given reservoirs and is
more efficient then a reversible engine operating between the same two reservoirs”.

[Type text]
Construct that there is an reversible engine operating between two given reservoirs that has a greater
efficiency than a reversible engine operating between same two reservoirs. Let the heat T R to the IR,
engine the QH. The heat rejected is QL the work WI= QH-QL.

Let the R, engine operates as a refrigerator or heat pump. The heat TR from LTR is Q L. The heat TR to the
HTR is QH than the work required by the engine is W R = QH - QL.

nJ>nR => WI>WR=> QH -QL > QH - QL.

The engine can run as a HP or a refrigerator delivers an amount of positive work, then neet work done
WN= WI - WR

WN= QH - QL- QH + QL = QL - QL. WN= QL - QL.

Now the HTR, IR and R, engine constitutes a PMM-II which operates in a cycle an extracts an amount of
heat QL - QLand delivers an equal amount of work WNeet = Q L - QL. Hence the theorem is
proved that it is impossible according to 2 nd law of TD, therefore efficiency of I R, engine cannot be >
efficiency of R engine.

Corollary 2:

“AD R engine have the same when operate between two given reservoirs”.

[Type text]
Consider 2 R, engines R 1+R2 working between 2 given reservoir. Let us assume nR1>nR2. Now R2 is
reserved to run as HP using some amount of work o/p of WR 1 of the engine R1results in PMM-II from
the Carnot theorem. nR1>/nR2. Similarly assuming n R 2>n R1 then reversing the engine R1 to work as a
HP and R2 as a HE. This also results in PMM-II therefore n R 2>nR1.

Therefore, nR2>nR1.

Corollary 3: TD temperature scale or Abs temperature or Kelvin temperature scale: -

The zeroth law of TD provides a basis for temperature means, but the temperature depends on the
thermometric property, of a particular substance and the mode of work of a thermometer.

The efficiency of Carnot is independent of working fluid and depends only the temperature of 2
reservoirs. This provides a basis for develop of an absolute scale of temperature which is independent of
nature of any thermometric substance.

Consider 3 reservoirs and 3 engines that operate on carnot cycle T1→ highest temperature , T3→ lowest

temperature, T2→ intermediate. Engine marked R1-2

receives heat Q1 at temperature T1 and reject heat Q2 at T2. Engine R2-3

receives heat Q2 at temperature T2 and rejects heat Q3 at T3. The engine R1-3

receives heat Q1 at T1 and rejects Q3 at T3. When it is working betweent he same 2 reservoirs.

Since η of carnot cycle, is a function of only the temperature. = 1- Q L/QH =1- TL/ TH

η= Ψ (TL, TH)

[Type text]
If the engine R η = 1- Q2/Q1 = 1- T2/T1 = Ψ (T2,T1)
1-2 12

η = 1- Q3/Q2 = 1- T3/T2 = Ψ (T3,T2)

2-3

η = 1- Q3/Q1 = 1- T3/T1 = Ψ (T3,T1)

1-3

where Ψ→ designate functional relations and is given by

Ψ (T3,T1) = Ψ (T2,T1) * Ψ (T3,T2)→1

The efficiency of engine R &R must be same together as the efficiency of the engine R Since
1-2 2-3 1-3.
they operate between the same 2 reservoirs, at temperature T1, T3. This functional expression is
expressed as Ψ (T1,T2) = f (T1)/f(T2)→2

Ψ (T2,T3) = f (T2)/f(T3)→3 Ψ (T1,T3) = f (T1)/f(T3)→4

Substituting the values of the functions in the expression →1

f (T3)/f(T1) = f (T2)/f(T1) * f (T3)/f(T2) ie the temperature quantities is expressed in terms of heat

quantity then Q3/Q1 = f (T3)/f(T1) OR QH/QL = TH/TL (general form)

Therefore η of carnot engine η= 1- TL/TH

o o
Relationship between c & k :

If the heat engine is operating as on a carnot cycle the heat received at the temperature of steam point
and heat rejected at a temperature of ice point is 100

ie. T steam point – T ice point = 100 →2

Tok = Toc + 273.16

Corollary 4: Clausius inequality theorem:

“ When a system executes a complete cyclic process than ∫ δQ/T

[Type text]
Around the cycle less than 0 or in the limit equal to 0”

Ie. Φ δq/T < 0

1. Proof for a reversible process: Φ δq/T = 0

Faraday’s Principle of increase of entropy:

“The entropy of an isolated system increases or the limit remains constant.”

Consider a system, undergoing a

cyclic process changing its state from

1 → 2along a reversible path R &

returning to its original state 2 → 1

along two possible paths one irreversible

& other reversible.

Consider for the path R + R

2R 1R 2R 1I

∫ δQ/T = ∫δQ/T =0→1 For path R+I ∫δQ/T + ∫ δQ/T = 0→2

1R 2R 1R 2I

From Clausius inequality theorem subtracting 2 from 1we get

1R 1I 1I 1R

∫ δQ/T = ∫δQ/T ∫δQ/T - ∫ δQ/T < 0

2R 2I 2I 2R

[Type text]
 1R 1I 1

The equating ∫ δQ/T = ds ∫δQ/T ≤ ∫ds ds ≥ ∫(δQ/T) I

2R 2I 2

If a system is isolated both heat to and from a system is o.

Therefore δs ≥ 0

Combination of 1st and 2nd Law of thermodynamics:

Consider a system in a equilibrium state at temperature T suppose the system absorbs heat δQ & does
work δW & its internal energy increases by δu then from 1 st law of thermodynamics δq = δu + δW→1

From 2nd law of thermodynamics the entropy relation ds = (δQ/T) Rev δQ= T ds→2

Substituting 2 in 1 Tds= δu+δw Tds = δu+pdv→3

The enthalpy h = u + pv diff. dh = du +pdv + vdp

dh= Tds+ vdp from 3

o
1. A carnot engine operates between T1 & T2 K. The output of engine is 0.6 times heat rejected. Given
the temperature difference between source & sink is 200 k. Find the source & sink temperature. Find
the thermal efficiency of the engine.

o
Sol: T1-T2 = 200 K W=0.6 Q2

W= Q1-Q2 0.6 Q2 = Q1- Q2 Q1 = 1.6 Q2

η= 1- Q2/Q1 = W/Q1 η = 37.55%

[Type text]
 o
η= 1-T2/T1 37.55/100 = 1- 200/T1 T1= 533 K

o
T2= 333.3 K

o o
2. A reversible engine works between 200 c & 60 c . Would the η be improved by raising the source
o o
temperature to 300 c OR by lowering the sink temperature to 30 c.

Sol: ηHE = W/Q1 = (Q1-Q2)/Q1 = (T1-T2)/T1 = (260+273)-(60+273)

260+273

ηHE = 37.5%

T1 = 300oc T2 = 60oc ηHE = T1-T2 = 41.85%

T1

T1 = 260oc T2 = 30oc η = 43.15%

T2 T2 T2

δQ/dT = 1KJ/K ∫ ds = ∫δQ/dT = ∫ 1 dT/T = log T 2 – logT1 =1.87 KJ/K

T1 T1 T1

S2-S1 = 0.177 KJ/Kg K

[Type text]
 Thermodynamic Process

Constant volume process: (Isochoric Process (CVP):

The movement of piston is prevented from moving so that the system volume remains unchanged. The
process is carried out by either by heating or by cooling . For a ConstantVolumeProcess P/T = C.

The workdone during the process :

V2

δW= ∫ pdv = 0 W=0

V1 1-2

The heat transferred from the 1st law of thermodynamics

δQ = δu + δW δW = 0 Therefore δQ = δu

The change in internal energy δu = Cv dT u2-uT = Cv(T2-T1)

Change in enthalpy δh = Cp dt h2-h1 = Cp (T2-T1)

2 2 2

Change in entropy ∫δs = ∫ δQ/T = ∫ Cv dT/T S2-S1 = Cv ln T2/T1

1 1 1

Constant pressure Process: (Isobaric process)

[Type text]
Consider a gas or fluid inside a cylinder as a system. The cylinder is closed by means of piston carrying
weight. If heat is transferred the gases expand lifting the piston in upward direction. If process is carried
out slowly pressure remains constant. The process is plotted in P-V diagram as shown.

Ex: in boiler and condenser.

For CPP, PV/T = C P = C V/T = Constant V1 /T1 = V2/T2 = C→1

Workdone = W1-2 = ∫ pdv = P2(V2-V1)

2 2 2

Heat transferred ∫δQ = ∫δu + ∫δW = u2- u1 + P(V2-V1)

1 1 1

= u2- u1 + PV2-PV1 = u2 + PV2 - u1 – PV1 = h2-h1 Q1-2 = h2-h1

Entropy δs = δQ/T we know δh = CpdT

Since heat transferred δQ = δH where δh = Cp dT S2-S1 = Cp ln T2/ T1

2 2

∫δs =∫CpdT/T = Cp log T2/T1

1 1

[Type text]
 S2 -S1 = Cp ln V2/ V1

Constant temperature process: (Hyperbolic Process):

Many substance carry out such process when expanding in a fully resistant manner at constant
temperature. For A CTP PV= C

P1 V 1 = P 2 V 2 = C

2 2

P1/P2 = V2/ V1 = C Workdone W1-2 = ∫ pdv = ∫ K/V dv From 1

PV = K P = K/V→1 1 1

W1-2 = K ln V2/ V1= P1V1 ln V2/ V1 = P2V2 ln V2/ V1

Heat transferred δQ = δu + δW δu = Cv dT (T is constant)

= 0 u2 = u1

Therefore δh = CpdT = 0 (T is const) h2= h1

Therefore δQ = δu + δW = δW (since δu=0) δQ = δW

Change in Entropy δs = δQ/T = PdV/T (since δQ = δW)

2 2

We know PV = RT P/T = R/V ∫ δs = ∫ R/V dV ( R = Cp-Cv)

1 1 Universal Gas constant

[Type text]
 S2-S1 = R ln V2/ V1 = (Cp-Cv) ln V2/ V1 S2-S1 = (Cp-Cv) ln V2/ V1

Isentropic process OR Reversible Adiabatic process:

An Adiabatic process is one in which no heat is transferred to or from the fluid or gas during the process.
Such a process can be reversible or irreversible. A reversible adiabatic nonflow process is considered.

γ
The general expression is PV = C→1 γ = K = 1.4 for air

2 2 2

Workdone W1-2 γ -γ 1-γ 1-γ

= ∫ pdv = ∫ C/V dV = C ∫ V dV = C [V2 – V1 ]

1 1 1 1-γ

γ 1-γ γ 1-γ

W1-2 = P2 V2 V2 - P1 V1 V1 = P2V2 – P1V1 (From 1) W = P2 V2 - P1 V1

1-γ 1-γ 1-γ

Heat transferred δQ = δu+δW For an Adiabaric process, δQ=0

Therefore Q = δu+δW δu =-δW δu = Cv dT dh = Cp dT

Change in Entropy δs = δQ/T δQ = 0 .Therefore δs = 0 S2-S1=0 S2= S1

[Type text]
 n
Polytropic Process PV = C:

It is found that many process in practice approximate to a reversible law of the form

n
PV = C. When n is a constant value. Both vapour and perfect gas obey this type of law in many non flow
processes. Such processes are internally reversible for a polytropic process.

1 1 1

n -n 1-n 1-n
Workdone = ∫ pdv = ∫ C/V dV = C ∫ V dV = C [V2 – V1 ]

2 2 2 1-n

n 1-n n 1-n

W1-2 = P2 V2 V2 - P1 V1 V1 W1-2 = P2 V2 - P1 V1

1-n 1-n

Heat transferred δQ = u2 – u1 + R(T2 – T1) [ from PV = RT P1 V1 = R T1

1-n P1 V1 = R T2 ]

δu = Cv dT = Cv (T2– T1) u2 – u1 = Cv (T2– T1)

δu = Cp dT = Cp (T2– T1) h2 – h1 = Cp (T2– T1)

[Type text]
 Change in Entropy δs = δQ/ T = [ Cv dT + R(T2 – T1) ] / T Since Cv dT= u2 – u1

1-n

δs/δt = ds = Cv dT/T + pdV/T δu+δW = Cv dT/T + R/V dV

S2-S1 = Cv ln T2/ T1 + R ln V2/ V1

1. The pressure exerted by the air inside a vessel of volume 0.14 m3 was 10 6 N/m2. When temperature
was 250oc due to cooling at constant volume the pressure falls to 3.5 * 10 5 N/m2. Determine the final
temperature heat exchange & change in entropy if Cp value = 1.005 KJ/Kgk & Cv = 0.718 KJ/Kgk

Constant Constant Reversible Constant

Process pressure volume adiabatic temperature Polytrophic

Index 'n' n=0 n=∞ n=r=k n=1 n=n

r r n n
PVT T2/T1 = V1/V2 P1V1 = P2V2 P1V1 = P2V2 P1V1 = P2V2 P1V1 = P2V2

T2/T1 = (V1/V2)r-
1 T2/T1 = (V1/V2)n-1

T2/T1 = (P2/P1)r-
1/r T2/T1 = (P2/P1)n-1/n

δQ = CvdT+ R(T2-
T1)
Heat
added Cp(T2-T1) Cv(T2-T1) δQ = 0 P1V1 lnV2/V1 1-n

P1V1-P2V2 P1V1-P2V2
W.D
∫Pdv P(V2-V1) 0 r-1 P1V1 lnV2/V1 n-1

Cv lnT2/T1 + R ln
δs Cp ln T2/T1 Cv ln T2/T1 0 R ln P1/P2 V2/V1

[Type text]
V1 = 0.14m3 ; P1V1 = mRT1 m= P1V1/RT1

T1 = (250+273) =523k ; R = 8314.3 = 287.6 J/kg k

m = 106*0.14 = 0.931 ; 28.9

287.6*523 m = 0.931 kg

P1V1/T1 = P2V2/T2 since (V1=V2) ; P1/P2 = T1/T2 T2 = 183.05k

Heat transferred δQ = mCv (T2-T1) ; δQ = -227kJ -ve sign indicates heat

Entropy s = Cv ln T2/T1 (m) s = -0.701 kJ/k transferred out of System

o
2) 1kg of air initially at a temperature of 165 c , pressure of 7bar is heated at constant pressure till
volume is doubled. Determine work done, heat exchange, δs , Cp = 1.005KJ/kgk , Cv = 0.715KJ/kgk.

m = 1kg, T1 = 165+273 = 438K, V1 = V, V2 = 2V, P1 = 7bar

P1 V 1 = P2 V 2 V/438 = 2V/T2--- (1), T2 = 876K

T1 T2

Heat transferred δQ = m.Cp (T2-T1) = 1*1.005(438) δQ = 440.49KJ

[Type text]
Entropy = s = Cp ln T2/T1 (m) s = 0.697

W1-2 = P (V2-V1) V1 = 0.18m 3 V2 = 0.36m3 from (1)

W1-2 = 7(0.18) = 126KJ (since 1bar = 1*105 N/m2)

3) Air at a pressure of 15bar & a temperature of 250 oc expands according to law PV 1.25 to a pressure of
1.5bar determined, w.d, δQ, and s. If it contains 0.9kg of air.

PVn = c PV1.25= C.

P1 = 15bar, P2 = 1.5bar, T1 = 523K, m = 0.9kg

n-1 1.25-1

n 1.25

T2/T1 = (P2/P1) T2/523 = (1.5/15)

T2 = 523(1.5/15)1/5 T2 = 329.9 K

W1-2 = P1V1 – P2V2 = RT1 – RT2 = R (T1-T2) * m

n-1 n-1 n-1

= 287.6(523-329.9)*0.9 W1-2 = 199.83KJ

0.25

δQ = m Cv (T2-T1) + W1-2 Q1-2 = 75.11KJ

S2- S1 = mCv ln T2/T1 + mR ln V2/V1 S2- S1 = 0.178 KJ/KgK

[Type text]
 1/n
S2- S1 = m (Cv ln T2/T1 + R ln (P1/P2) )

o
4. 0.9 Kg of steam at a pressure of 15 bar and 250 c is expanded adiabatically & reversible tp a pressure
of 1.5 bar γ= 1.4

γ-1

W= P2V2- P1V1 T2/T1 = (P2/P1)

γ -1

= mR(T2-T1) T2= 270.82 K

-γ+1 W= 163.19 KJ

o
5. 1Kg of air initially at 1 bar and 156 c is compressed isothermally till the volume is reduced to 0.28 m 3.
Determine W, Q, δs, δu?

[Type text]
 2 3
m = 1kg T = 429 K V = 0.28m m = P1V1/RT1

V1 = 1.234 m3

W = P1V1ln V2/V1= -183.03 KJ -ve’ sign indicates Wd on the system

δQ = δW = -183.03

δs = R ln V2/V1 = -426.57 KJ/K δu = 0

1000

6. A certain gas has Cp = 1.968 KJ/KgK & Cv = 1.507 KJ/KgK. Find its molecular weight & gas constant. A
Constant volume chamber of 0.3 m 3 capacity contains 2 Kg of this gas at 5 oc. Heat is transferred to the
gas until temperature is 100 oc. Find W, δQ, δs, δu, δh?

R = Cp- Cv = 0.461 MR= R = 8.314 M = 8.314 = 18.03

0.461

Wd = ∫PdV = 0 ( CVP ) δQ = δu = Cv (T2 – T1) * m δQ = 286.33

δh = mCp( T2- T1) = 373.92 KJ δh = 373.92

S2- S1 = mCv ln T2/T1 δs = 0.88 KJ/KgK

7. 0.5 Kg of air compressed reversible & adiabatic from 80 KPa of 60 oc to 400 Kpa & then expanded
under constant pressure, to original volume . Sketch this process in PV diagram. Calculate δQ, δW, for
the whole path.

[Type text]
P1V1 = mR T1 P 1 = 80 Kpa P2= 400 Kpa

V1 = 0.598 m3 T1 = 333K m = 0.5

γ = 1.4

T2= 527.412 K

γ-1

T2/T1 = (P2/P1)

W1-2= P1V1- P2V2

γ-1

W1-2 = mR (T2- T1) = -69.89 KJ W1-2= -69.89KJ

-γ+1

Q 1-2= 0

γ γ γ γ γ

P1V1 = P2V2 P2 = P1(V1/ V2) V2 = P1V1 V2 = 0.819 m3

P2

CPP 2-3 W2-3 = ∫PdV = P (V3- V2) W2-3 = -163.6KJ V2/ T2 = V3/ T3 T3= 1668.7 K

Q2-3 = mCp(T3- T2) = 573.5 KJ

[Type text]
Total Wnett = W1-2 + W2-3 = 93.71 KJ Qnett = Q1-2 + Q2-3 = 573.5 KJ

Ideal Gases

A Thermodynamic system has a no of thermo static properties such as temperature,

pressure,

specific volume, electricalresistance, δu etc... Any equation that relates P, T and specific

volume the substance, is called equation of state. (P, V, T)=0, if two of these parameters

of property are known then the other one can be easily calculated by using

equation of state.

By Charles law P=R (T/V). PV=RT

R= proportionality constant or Gas constant.

Ideal gas: the hypothetical gas which obeys the law PV=RT at all temperature and

pressure is ideal gas. There is no ideal or perfect gas in nature. At a very slow

pressureand hightemperature real property like N 2, H2, O2, HC etc (remain)

behave nearly as the same way of ideal property. These property can change

into liquid phase only if they are subjected to a great decrease in temperature and

increase in pressure.

Vanderwaal’s Equation: the Vanderwaal’s equation by apply of laws of

mechanics for in divide,

molecules introduced two corrected terms in ideal gas equation and it is given

by (P+a/V2) (V-b)=RT.

[Type text]
The coefficient ‘a’ was introduced for the existence if mutual attraction between

the molecules. The term O/V2= force of cohesion. The coefficient ‘b’ was

introduced to account for the volume of molecules and is known as

‘co-volume’ real propertyhaveinter-molecular forces. The molecules which are

close enough to a wall of container exerts an attractive force which prevents

the partic, molecule to exert full pressure, on container wall as an ideal gas

which is present in the container. This reducedcordinates

In pressure, is internal pressure, vanderwaal suggested that internal pressure is

propositional to square of density and is =a/V2

i.e. pressure =kinetic pressure –internal pressure= (RT/V-a/V 2),

P= (RT/V-a/V2).

a= constant accounts for reduction in total pressure, due to long range of

attractive force.

In real property the free volume is equal to total volume minus volume

of molecules themselves.

Hence total volume =V-b, where V= accounts for reduction in volume due to

finite size of molecules of a real gas. This reduction in volume causes more

molecular collision and hence on increase in pressure, contents a and b can

be alter from the critical proper,

Pc= (a/27)*b2.

VC=3b Tc= (8a)/ (27Rb)

Compressibility chart:

[Type text]
Real gases are those that deviate form the relation PV=RT, so this relation

has to be modified in order to describe behavior of real gas. This is done by

compressibility factor

Z=function of P and T and it is not constant for all the property.

For an ideal gas Z=1.

Since Z is a function of P and T.

The plot is drawn Z v/s P with constant temperature.

Lines on it as shown the values of Z for any gas can be determined, this

is done by gasesin terms of reduced property.

The reduced property is the ratio of exist of pressure, to critical

pressure of a substance

similarly for volume and temperature,

Pr= (P/Pc) Vr= (V/Vc) Tr= (T/Tc).

r = denotes reduced property,

c = denotes property at critical state.

The relation among reduced property , Pr,Vr, Tr is known as

law of corresponding states.

[Type text]
Ideal gas: it is a substance which has a equation of state PV=RT

Where P= pressure in pascals,

V= specific volume in m3/kg,

T= temparature in degree kelvin,

& R= universal gas constant in kj/kg ok and it has different values for different property,

multiple by ‘m’ we get PVm=mRT, but V=mv=total volume,

therefore PV=mRT.--------------1

If an ie=ideal gas undergoes a process from state 1 to 2 i,e. P1 ,V1,T1 and P2,V2,T2

with mass as constant, P1V1=mRT1 amd P2V2=mRT2,

therefore ( P1V1/ T1) = (P2V2/ T2)= mR=conatant.

One mole has a mass which is nearly equal to the molecular weight i,e mole of O 2 =32kg,

one mole of N2=28kg if ‘n’ is the number of moles and ‘m’ is molecular weight of

gas then mass =m*n,substituing for mass then,

PV=nMRT--------------2.

Avagadro’s law: it status that “Equal volumes of different gases at same temparature

and pressure have same number of moles”.

If they are two property occupaing the same volume and existing at same temparature

and pressure then,

PAVA=nAMARATA and PBVB=nBMBRBTB,

(PAVA/RATA)=(nAMA) and (PBVB)/( RBTB)=(nBMB) i,e nAMA= nBMB at constant P&T

Applying Avagadro’s law (PAVA/ nATA)=( RAMA) and (PBVB)/( nBTB)=( RBMB)

_ _

I,e RAMA= RBMB=MR. Where MR=R and R=8314.3Nm/KJ mol k.

[Type text]
Mixture charecteristics: Total mass of the mixture consider a mixture of property

a,b,c, etc., existing in equillibrium at presssure P, temparature T having the volume V.

The total mass of the mixture = sum of the masses of the indivisual property ,

mt = ma+mb+mc+md +----------

Mass function: it is defined as the ratio of mass of each component to the total mass

of the mixture,

ma/ mt=mfa, mb/ mT= mfb, and mc/ mT=mfc.

mfa+mfb+mfc+------------ =1

Mass fraction: it is the ratio of number of moles of each component to the total

number of moles of the mixture.

nt = na+nb+nc+--------

(na/ nt)=xfa (nb/ nt)=xfb (nc/ nt)=xfc (nd/ nt)=xfd

(xfa )+ (xfb )+ (xfc )+ (xfd )+------------- =1

Volume fraction: it is the ratio of volume of each component to the total volume of

the mixture, i.e,

va/vt =vfa vb/vT = vfb Vc/VT = vfc vfa+vfb+vfc+...... =1

Dalton’s law: total pressure of the mixture of a gas is equal to the sum of the

pressure of the each component if it alone occupaies the volume of mixture of that temparature, i.e,

pt = pa+pb+pc+-------- at constant temparature.

Gibb’s Dalton’s law: It states that “Entropy,enthalpy and internal energy of a

[Type text]
mixture of gases is = Sum of Entropy,enthalpy and internal energy of individual

component if it alone occupies the volume of mixture at that temparature”

Ut =Ua+Ub+Uc H = Ha+Hb+Hc S = Sa+Sb+Sc at constant temparature

Relations involving pressure, volume & temparatures:

For a mixture of gases ABC,

PV = mRT = nMRT = nRT

_ _ _ _

PVT = nT RT – (1), PVa = naRT – (2), PVb = nbRT – (3), PVc = nc RT – (4)

Dividing equation (2),(3)&(4) by (1) Va/VT = na/nT, Vb/VT = nb/nT, Vc/VT = nc/nT

Va/VT = xfa, Vb/VT = xfb, Vc/VT = xfc since: na/nT = xfa etc.

We know that xfa + xfb + xfc + .............. = 1 i.e, Va/V + Vb/V + Vc/V = 1

There fore Va + Vb + Vc = V at constant temparature.

Amagat’s Ludel’s law : It states that the total volume of a mixture of gases is equal

to the sum of the volume of individual components at the same pressure and temparature”

For a mixture of gases Abc

PV = nRT -- (5)

_ _ _

PaV = naRT PbV = nbRT PcV = ncRT –(6),(7) & (8)

Dividing equation (6),(7)&(8) by (5), Pa/P = na/nT = x/a, Pb/P = nb/nT = x/b, Pc/P = nc/nT = x/c

We know that xfa+xfb+xfc+...........= 1 = Pa/P + Pb/P + Pc/P = 1

There fore Pa + Pb + Pc = P at constant temparature.

For a mixrure of gases PV = mTRT mT  total mass, R Gas constant.

[Type text]
For a mixrure of gases Abc PaV = maRaT, PbV = mbRbT, PcV = mcRcT

P = Pa+Pb+Pc  mTRT/V = maRaT/V+ mbRbT/V + mcRcT/V

mTR = maRa+ mbRb+ mcRc R = 1/mT[maRa+mbRb+mcRc]—(A)

Molecular weight of mixture : From the relation Me = R for gases a,b,c

_ _

Ra = R/Ma, Rb = R/Mb,

Rc = R/Mc substitute in (a)

_ _ _

R = 1/mT [maRa+mbR/Mb+mcR/Mc =1/mT [maRa/ Ma +mbR/Mb+mcR/Mc]

_ _ _ _ _

mTR/M = ma R/Ma+mbR/Mb +mcR/Mc = R[ma/ Ma + mb/Mb +mc/Mc]

1/M = [ma/mT Ma +mb/mT Mb+mc/mT Mc]

1/M = [mfa/Ma + mfb/Mb +Mfc/Mc]

M= 1____________

mfa/Ma + mfb/Mb +Mfc/Mc

3. Specific Weight of a mixture: mass basis:

1. Specific weight at constant volume: Consider the internal energy of a gas mixture

Utotal = Ua + Ub . U = mu mT UT = maua + mbub + mcuc

UT = maua/mT + mbub/mT + mcuc/mT

[Type text]
UT = mfaua + mfbub + mfcuc→1 dUT = mfadua+ mfbdub+ mfcduc

du= CvdT → CvdT = mfa Cva dT + mfb Cvb dT+ mfc Cvc dT

If it is on mole basis Cv dT= xfa Cva dT + xfb Cvb dT+ xfc Cvc dT

2. Specific heat at constant pressure on mass basis:

HT= Ha+Hb+Hc H = mh mThT= maha+ mbhb+ mchc

Similiarly dh= mfadha+ mfbdhb+ mfcdhc We know that dh= CpdT

Therefore CpTdT= mfa Cpa dT + mfb Cpb dT+ mfc Cpc dT

1. Determine a. Pressure in the vessel. b. Mole fraction of each constituent.

C. Gas constant of the mixture from the given data.

mCo2= 2Kg mN2= 1.5Kg T =300K V= 0.2m3 mT= 2+1.5 Kg =3.5Kg

Mass fraction: mf Co2= mCo2 = 2/3.5 = 0.571 mf N2 = 1.5/3.5 = 0.4285

mT
_ _

MR=R PV=MRT PCo2V = mCo2 RCo2 T MCo2 RCo2 = R

RCo2 = 8314.3/44 RCo2 = 188.96 RN2= 8314.3/28 = 296.94 N-m/KJK mol

PCo2= mCo2 RCo2 T = 2 ×188.96×300 = 566.88 KPa PCo2= 566.8 KPa

V 0.2

PN2= mN2 RN2 T = 1.5×296.94×300 = 668.11 Kpa PN2=668.11 KPa

V 0.2

PT= PCo2 +PN2 = 566.88 KPa + 668.11 Kpa PT=1234.99 Kpa

[Type text]
Mole Fraction: m=nM nCo2= mCo2/ MCo2= 0.2/44 = 0.045 nCo2=0.045

n N2 =mN2/ MN2= 1.5/28 = 0.05357 nN2=0.05357 nT =0.099

xf Co2= nCo2 = 0.045/0.099 = 0.4589 xf N2= nN2 = 0.05357/ 0.099 = 0.5409

nT nT

Gas Constant: PV = mTRT 103×1234.98×0.2 = 3.5×R×300 R = 235.23 N-m/KJ molK

3
2. A vessel having a volume of 0.115 m is filled with a mix of 1.5 Kg Co2 & 1Kg 0f N2

At 25oc. Determine Mole fraction, mass fraction, gas constant.

mCo2= 1.5Kg mN2= 1Kg V= 0.115m3 T =273+25= 298 mT=1.5+1=2.5Kg

Mass fraction: mf Co2= 1.5/2.5 =0.6 mf N2 1/2.5=0.4

MR=R R Co2=83143/44 = 189.96 N-m/KJ molK

MN2 RN2= R RN2= 8314.3/28 = 296.94 N-m/KJ molK

P Co2V= mCo2 RCo2T Therefore PCo2= 1.5×189.96×298 PCo2=738.36 KPa

0.115

P N2V= mN2 RN2 T Therefore PN2= 1×296.94×298 PN2= 769.46 KPa

0.115

PT=1507.82KPa m=nM PT=1507.82KPa

nN2 =mN2/M = 1/28 =0.03571 nCo2= mCo2/M = 1.5/44 = 0.03409

nT= nN2/ nCo2 =0.0698 xf N2 = 0.03571/0.0698 xf N2 = 0.51159

xf Co2 = 0.03409/ 0.0698 xf Co2 = 0.4883

[Type text]
[Type text]