LECTURE NOTES

ON
THERMODYNAMICS

II YEAR B.TECH MECH - I Sem

UNIT – I Introduction: Basic Concepts:
System, Control Volume, Surrounding, Boundaries, Universe, Types of Systems, Macroscopic and
Microscopic viewpoints, Thermodynamic Equilibrium, State, Property, Process, Exact & Inexact
Differentials, Cycle – Reversibility – Quasi – static Process,
Irreversible Process– Energy in State and in Transition, Types, Displacement & Other forms of Work,
Heat, Point and Path functions, Zeroth Law of Thermodynamics – Concept of Temperature –
Principles of Thermometry – Reference Points – Const. Volume gas Thermometer – Scales of
Temperature, Ideal Gas Scale

Thermodynamics can be defined as the science of energy. The name thermodynamics stems
from the Greek words therme (heat) and dynamis (power), which is most descriptive of the early
efforts to convert heat into power. So the field of thermodynamics is concerned with the science of
energy focusing on energy storage and energy conversion processes.
 The most of general sense of thermodynamics is the study of energy and its relationship to the
properties of matter. All activities in nature involve some interaction between energy and matter.
Thermodynamics is a science that governs the following:
Energy and its transformation
Feasibility of a process involving transformation of energy
Feasibility of a process involving transfer of energy
Equilibrium processes
More specifically, thermodynamics deals with energy conversion, energy exchange and the direction
of exchange.
APPLICATION AREAS OF THERMODYNAMICS
All activities in nature involve some interaction between energy and matter; thus, it is hard to
imagine an area that does not relate to thermodynamics in some manner.
The heart is constantly pumping blood to all parts of the human body, various energy conversions
occur in trillions of body cells, and the body heat generated is constantly rejected to the environment.
The human comfort is closely tied to the rate of this metabolic heat rejection.
Also, the following engineering devices are typically designed based on the principles of
thermodynamics.
Automotive engines, Turbines, Compressors, Pumps, Fossil and Nuclear Power Plants, Propulsion
systems for the Aircrafts, Separation and Liquefication Plant, Refrigeration, Air-conditioning and
Heating Devices.

The principles of thermodynamics are summarized in the form of a set of axioms. These
axioms are known as four thermodynamic laws:
The zeroth law, the first law, the second law and the third law.

The Zeroth Law deals with thermal equilibrium and provides a means for measuring temperatures.
The First Law deals with the conservation of energy and introduces the concept of internal energy.
The Second Law of thermodynamics provides with the guidelines on the conversion of internal
energy of matter into work. It also introduces the concept of entropy.
The Third Law of thermodynamics defines the absolute zero of entropy. The entropy of a pure
crystalline substance at absolute zero temperature is zero.
SYSTEMS AND CONTROL VOLUMES

FIGURE 1 System, surroundings, and boundary

A system is defined as a quantity of matter or a region in space chosen for study. To study a
quantity of matter contained within a closed rigid walled chambers, or to consider something such as
gas pipeline through which the matter flows can be considered as a system. The composition of the
matter inside the system may be fixed or may change through chemical and nuclear reactions. A
system may be arbitrarily defined. It becomes important when exchange of energy between the system
and the everything else outside the system is considered. The mass or region outside the system is
called the surroundings. The real or imaginary surface that separates the system from its
surroundings is called the boundary (Fig. 1). The boundary of a system can be fixed or movable.
Note that the boundary is the contact surface shared by both the system and the surroundings.
Mathematically speaking, the boundary has zero thickness, and thus it can neither contain any mass
nor occupy any volume in space. System and surroundings when put together result in universe.
Universe = System + Surroundings
The system is also sometimes defined as the control system and the boundary defined for separating it
from surroundings is called control boundary, the volume enclosed within the boundary is control
volume and the space enclosed within the boundary is called control space.
On the basis of mass and energy transfer the thermodynamic system is divided into three types.
1. Closed system
2. Open system
3. Isolated system
Closed system: A system in which the transfer of energy but not mass can take place across the
boundary is called closed system. The mass inside the closed system remains constant.

(a) (b)
FIGURE 2. (a) Closed system with Mass cannot cross the boundaries of a
closed system, but energy can. (b) A closed system with a moving
boundary
For example: Boiling of water in a closed vessel. Since the water is boiled in closed vessel so the
mass of water cannot escape out of the boundary of the system but heat energy continuously entering
and leaving the boundary of the vessel. It is an example of closed system.
Open system: A system in which the transfer of both mass and energy takes place is called an open
system. This system is also known as control volume.
For example: Boiling of water in an open vessel is an example of open system because the water and
heat energy both enters and leaves the boundary of the vessel.
A large number of engineering problems involve mass flow in and out of a system and,
therefore, are modelled as control volumes. 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).

(a) (b)
FIGURE 3. (a) A control volume (CV) with real and
imaginary boundaries (b) A control volume (CV) with fixed and
moving boundaries as well as real and imaginary boundaries
The boundaries of a control volume are called a control surface, and they can be real or imaginary. In
the case of a nozzle, the inner surface of the nozzle forms the real part of the boundary, and the
entrance and exit areas form the imaginary part, since there are no physical surfaces there (Fig. 3a). A
control volume can be fixed in size and shape, as in the case of a nozzle, or it may involve a moving
boundary, as shown in Fig. 3b. Most control volumes, however, have fixed boundaries and thus do not
involve any moving boundaries. A control volume can also involve heat and work interactions just as
a closed system, in addition to mass interaction.
Isolated system: A system in which the transfer of mass and energy cannot takes place is called an
isolated system.

FIGURE 4. Isolated system

For example: Tea present in a thermos flask. In this the heat and the mass of the tea cannot cross the
boundary of the thermos flask. Hence the thermos flak is an isolated system.

Definition Work Heat Mass

Isolated system
No No No
 Also called
Closed system Yes Yes No
Control Mass
Also called
Open system Yes Yes Yes
Control Volume
MACROSCOPIC AND MICROSCOPIC POINTS OF VIEW
Microscopic Approach:
The approach considers that the system is made up of a very large number of discrete particles
known as molecules. These molecules have different velocities are energies. The values of these
energies are constantly changing with time. This approach to thermodynamics, which is concerned
directly with the structure of the matter, is known as statistical thermodynamics.
The behaviour of the system is found by using statistical methods, as the number of molecules
is very large. So advanced statistical and mathematical methods are needed to explain the changes in
the system. The properties like velocity, momentum, impulse, kinetic energy and instruments cannot
easily measure force of impact etc. that describe the molecule. Large numbers of variables are needed
to describe a system. So the approach is complicated.
Macroscopic Approach:
In this approach a certain quantity of matter is considered without taking into account the
events occurring at molecular level. In other words this approach to thermodynamics is concerned
with gross or overall behaviour. This is known as classical thermodynamics. The analysis of
macroscopic system requires simple mathematical formula.
The value of the properties of the system are their average values. For examples consider a
sample of gas in a closed container. The pressure of the gas is the average value of the pressure
exerted by millions of individual molecules. In order to describe a system only a few properties are
needed.
S.No Macroscopic Approach Microscopic Approach
1 In this approach a certain quantity of The matter is considered to be comprised of
matter is considered without taking a large number of tiny particles known as
into account the events occurring at molecules, which moves randomly in
molecular level. chaotic fashion. The effect of molecular
motion is considered.
2 Analysis is concerned with overall The Knowledge of the structure of
behaviour of the system. matter is essential in analyzing the
behaviour of the system.
3 This approach is used in the study of This approach is used in the study of
classical thermodynamics. statistical thermodynamics.
4 A few properties are required to Large numbers of variables are required to
describe the system. describe the system.
5 The properties like pressure, The properties like velocity, momentum,
temperature, etc. needed to describe kinetic energy, etc. needed to describe the
the system, can be easily measured. system, cannot be measured easily.
6 The properties of the system are their The properties are defined for each molecule
average values. individually.
7 This approach requires simple No. of molecules are very large so it
mathematical formulas for analyzing requires advanced statistical and
the system. mathematical method to explain any
change in the system.
THERMODYNAMIC EQUILIBRIUM
 Thermodynamics deals with equilibrium states. The word equilibrium implies a state of
balance. In an equilibrium state there are no unbalanced potentials (or driving forces) within the
system. A system in equilibrium experiences no changes when it is isolated from its surroundings.
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. Thus, for attaining a state of
thermodynamic equilibrium. the following three types of equilibrium states must be achieved:
Thermal equilibrium. The temperature of the system does not change with time and has same value
at all points of the system.
Mechanical equilibrium. There are no unbalanced forces within the system or between the
surroundings. The pressure in the system is same at all points and does not change with respect to
time.
Chemical equilibrium. No chemical reaction takes place in the system and the chemical composition
which is same throughout the system does not vary with time.
PROPERTIES OF SYSTEMS
Any observable characteristic of a system is called a property. Thermodynamic properties are
observable characteristics of the thermodynamic system. Some familiar properties are pressure P,
temperature T, volume V, and mass m etc.
Properties are considered to be either intensive or extensive. Intensive properties are those
that are independent of the 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. Extensive properties per unit
mass are called specific properties. Extensive properties are often divided by mass associated with
them to obtain the intensive properties. Example specific volume (v = V/m) and specific total energy
(e = E/m).
STATE
State is the condition of the system at an instant of time as described or measured by its
properties. Or each unique condition of a system is called a State. State of a system indicates the
specific condition of the system. To know the characteristics of the system quantitatively refers to
knowing the state of system. Thus, when the properties of system are quantitatively defined then it
refers to the state.
PROCESS
Whenever one or more of the properties of a system change, we say that a change in state has
occurred. The path of the succession of states through which the system passes is called the process.
A process is said be done if a system changes from one equilibrium state to another.

FIGURE 5. A process between states 1 and 2 and

the process path.
 The series of states through which a system passes
during a process is called the path of the process (Fig. 5). 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.
Process diagrams plotted by employing
thermodynamic properties as coordinates are very useful in
visualizing the processes. Some common properties that are
used as coordinates are temperature T, pressure P, and volume V
(or specific volume v). Fig. 6 shows the P-V diagram of a
compression process of a gas.

FIGURE 6 The P-V diagram

of a compression process.
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. In simple
words, we can say that if system is going under a thermodynamic process through succession of
thermodynamic states and each state is equilibrium state then the process will be termed as quasi static
process.

FIGURE 7. System undergo a quasi-equilibrium

Process
In fig. 7 Weight placed over the piston is just balancing the force which is exerted in upward
direction by gas. If we remove the weight from the piston, system will have unbalanced force and
piston will move in upward direction due to force acting over the piston in upward direction by the
gas. If the weights on the piston in Fig. 5 are small and are taken off one by one, the process could be
considered quasi-equilibrium. However, if all the weights are removed at once, the piston will rise
rapidly until it hits the stops. This would be a nonequilibrium process, and the system would not be in
equilibrium at any time during this change of state.
CYCLE
When a system in a given initial state goes through a number of different changes of state or
processes and finally returns to its initial state, the system has undergone a cycle. Therefore, at the
conclusion of a cycle, all the properties have the same value they had at the beginning. Steam (water)
that circulates through a steam power plant undergoes a cycle. Thermodynamic path in a cycle is in
closed loop form
Thermodynamic processes, path and cycle are shown on p-v diagram in Fig. 8
 FIGURE 8. Thermodynamic process, path and cycle.
REVERSIBILITY AND IRREVERSIBILITY
Reversible process. A reversible process (also sometimes known as quasi-static process) is one which
can be stopped at any stage and reversed so that the system and surroundings are exactly restored to
their initial states.
This process has the following characteristics :
1. It must pass through the same states on the reversed path
as were initially visited on the forward path.
2. This process when undone will leave no history of events in
the surroundings.
3. It must pass through a continuous series of equilibrium
states.
No real process is truly reversible but some processes may approach
reversibility, to close approximation.
Examples. Some examples of nearly reversible processes are :
(i) Frictionless relative motion.
(ii) Expansion and compression of spring. (iii)
Frictionless adiabatic expansion or compression of fluid.
(iv) Polytropic expansion or compression of fluid.
(v) Isothermal expansion or compression.(vi) Electrolysis. FIGURE 9. Reversible process

Irreversible process. An irreversible process is one in which heat is transferred through a finite
temperature.
Examples.
(i) Relative motion with friction (ii) Combustion (iii) Diffusion (iv) Free expansion (v) Throttling (vi)
Electricity flow through a resistance (vii) Heat transfer (viii) Plastic deformation.
An irreversible process is usually represented by a dotted (or discontinuous) line joining the
end states to indicate that the intermediate states are indeterminate
Irreversibilities are of two types :
1. External irreversibilities. These are associated with dissipating effects outside the working fluid.
Example. Mechanical friction occurring during a process due to some external source.
2. Internal irreversibilities. These are associated with dissipating effects within the working fluid.
Example. Unrestricted expansion of gas, viscosity and inertia of the gas.
 FIGURE 10. Irreversible process
POINT FUNCTION
When two properties locate a point on the graph (co-ordinate axes) then those properties are
called as point function.
Examples. Pressure, temperature, volume etc.

PATH FUNCTION
There are certain quantities which cannot be located on a graph by a point but are given by the
area or so, on that graph. In that case, the area on the graph, pertaining to the particular process, is a
function of the path of the process. Such quantities are called path functions.
Examples. Heat, work etc.
Heat and work are inexact differentials. Their change cannot be written as difference between their
end states.

Thus and is shown as 1Q2 or Q1-2

similarly, and is shown as 1W2 or W1-2

Note. The operator δ is used to denote inexact differentials and operator d is used to denote exact
differentials.
ENERGY
Energy is usually defined as the ability to do mechanical work. Total energy at any moment
may be the algebraic summation of the different forms of energy. In thermodynamics we are primarily
interested in studying the change in total energy of a system. Thus, for analysis relative value of
energy is considered instead of absolute value.
Energy can be classified in the following general categories;
(a) Energy in transition: It refers to the energy that is in process of transition between substances or
regions because of some driving potential, such as difference or gradient of force, or of temperature,
or of electrical potential etc. For example heat, work etc.
(b) Energy stored in particular mass: It refers to the potential and kinetic energy associated with
masses that are elevated or moving with respect to the earth.
Some of the popular forms of energy are described below:
Potential energy: This type of energy is based on relative position of bodies in a system, i.e. elevation
in a gravitational field.
Potential energy for a mass m at elevation z is given as :
P.E. = m.g.z
Here g is the gravitational acceleration and elevation is measured from some reference point.
Kinetic energy: It is based on the relative movement of bodies. For a mass m moving with certain
velocity c it could be mathematically expressed as;
K.E. = (1/2) m.V2
Internal energy: Internal energy of a system is the energy associated with the molecular structure
at molecular level.
HEAT AND WORK
Heat and work are the forms of energy in transition. 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. Heat can be identified only as it crosses the boundary. Thus, heat is a transient
phenomenon. Heat is a form of energy transfer to or from a system.
Sign convention:
If the heat flows into a system from the surroundings, the quantity is said to be positive and,
conversely, if heat flows from the system to the surroundings it is said to be negative.
In other words :
Heat received by the system = + Q
Heat rejected or given up by the system = – Q.
Work, like heat, is an energy interaction between a system and its surroundings. Thus, Work is a
transient quantity which only appears at the boundary. If the energy crossing the boundary of a closed
system is not heat, it must be work. Work shall be done by the system if the total effect outside the
system is equivalent to the raising of weight and this work shall be positive work.
Units of Work
Our definition of work involves the product of a unit force (one newton) acting through a unit distance
(one meter). This unit for work in SI units is called the joule (J).
1 J = 1Nm
Sign convention:
If the work is done by the system on the surroundings, e.g., when a fluid expands pushing a piston
outwards, the work is said to be positive.
i.e., Work output of the system = + W
If the work is done on the system by the surroundings, e.g., when a force is applied to a rotating
handle, or to a piston to compress a fluid, the work is said to be negative.
i.e., Work input to system = – W
Comparison of Work and Heat
Similarities:
(i) Both are path functions and inexact differentials.
(ii) Both are boundary phenomenon i.e., both are recognized at the boundaries of the system
as they cross them.
(iii) Both are associated with a process, not a state. Unlike properties, work or heat has no
meaning at a state.
(iv) Systems possess energy, but not work or heat.
Dissimilarities:
(i) In heat transfer temperature difference is required.
(ii) In a stable system there cannot be work transfer, however, FIGURE 11. Use of pressure-volume
diagram to show work done at the
there is no restriction for the
moving boundary of a system
transfer of heat.
(iii) The sole effect external to the system could be reduced to rise of a weight but in the case
of a heat transfer other effects are also observed.
PdV- WORK OR DISPLACEMENT WORK
 Consider an example of piston and cylinder arrangement to find work done at the moving
boundary of a system. Say, the air in the cylinder undergoes change in state from 1 to 2 which is
represented by a quasi-static process 1-2 on the p-V diagram. To find the work done for small ‘dL’
movement of the piston. During this small movement the pressure ‘p’inside the cylinder is considered
constant. Then work done for small ‘dL’ is given by
δW = F.dL = p.A .dL
where, F is the force acting on the piston
A is the area of the piston face

As A.dL = change in volume of the gas due to dL movement of piston, it is taken as dV.
δW = p.dV
To find work done during process 1-2, integrate
the above equation.

Other forms of work

Electrical work
When a current flows through a resistor taken as
a system, there is work transfer into the system.
This is because current drives the motor, the motor can drive a
pulley and the pulley can raise the weight. The current flow, I, in
amperes is given by

where C is the charge in coulombs and t is time in seconds. Thus dC is the charge crossing a boundary
during time dt. If E is the voltage potential, the work is
dW = E. dC = EI. dt

or
The electrical power will be
W =EI

Shaft work
If T is the torque applied to the shaft and dθ is the angular displacement, the shaft work is

and the shaft work is

FIGURE 12. paddle-wheel work, stirring work

Where ω is angular velocity

Paddle-Wheel Work or stirring work
As the weight is lowered, and the paddle wheel turns, there is work transfer into the fluid system
Which gets stirred. Though there is no change in volume of the system still work has been done on the
system.
If m is mass of weight lowered through a distance dz and T is the torque transmitted by the shaft in
rotating through an angle dθ, the differential work transfer to the fluid is given by

dW= mgdz=Tdθ
and the total work transfer is

Work done in changing the area of surface film

A film on the surface of a liquid has a surface tension, which is a property of the liquid and the
surroundings. The surface tension acts to make the surface area of the liquid a minimum. It has the
unit of force per unit length. The work done on a homogeneous liquid film in changing its surface area
by an infinitesimal amount dA is
dW= -σdA
where σ is the surface tension(N/m)

Free expansion process

Consider the arrangement in which gas and vacuum in a container are separated by a membrane as
shown in Fig. 5.7 (a). Gas in the container constitutes a system and it is at an initial state ‘1’. Now, let
the membrane be ruptured and gas fills the entire volume of the container and it is at final state ‘2’ as
shown in Fig. 5.7 (b).Neglect any work associated with the rupturing of the membrane.

Even there is moving boundary of a system still work done by the system is zero because there is no
resistance (no force) at the system boundary as the volume increases.

(a)

(b)
FIGURE 13 Example of a process involving a change of volume for which the work is zero.

Problem: A gas in the cylinder and piston arrangement comprises the system. It expands from 1.5 m3
to 2 m3 while receiving 200 kJ of work from a paddle wheel. The pressure on the gas remains
constant at 600 kPa. Determine the network done by the system.
Solution:
Given: V1 = 1.5 m3; V2 = 2 m3 ; Wpaddle= −200 kJ = 2 x 105 J;
P = 600 kPa = 6 x 105 N/m2
To determine network done by the system, Wnet :

Formula: Wnet = Wdisplcament + Wpaddle

Finding unknown, Wdisplacement :

Wdisplacement is the displacement work done by the system = ∫pdV

(because p is
constant)
= P (V2 − V1)
= 6 x 105 (2 − 1.5) = 3 x 105 Nm or J
Answer: Net work by the system is,
Wnet = Wdisplcament + Wpaddle
= 3 x 105 - 2 x 105 = 1 x 105 Nm or 100kJ

Problem: A piston and cylinder machine containing a fluid system has a stirring device as shown in
Fig. The piston is frictionless, and it is held down against the fluid due to atmospheric pressure of
101.3 kPa. The stirring device is turned 9500 revolutions with an average torque against the fluid of
1.25 Nm. Meanwhile the piston of 0.65 m diameter moves out 0.6 m. Find the net work transfer for
the system.

Work done by the stirring device upon the system,

W1 = 2πNT
where T = torque = 1.25 Nm
N = number of revolutions = 9500
W1 = 2π × 9500 × 1.25 = 74622 Nm = 74.622 kJ
This is negative work for the system.
Work done by the system upon the surroundings
W2 = (pA). L
where, p = Pressure = 101.3 kPa
A = Area of the piston = π/4 × (0.65)2 = 0.3318 m2, and
L = Distance moved by the piston = 0.6 m
 W2 = 101.3 × 0.3318 × 0.6 = 20.167 kJ
This is a positive work for the system.
Hence, the net work transfer for the system
Wnet = W1 + W2 = – 74.622 + 20.167 = – 54.455 kJ. (Ans.)
TEMPERATURE
The temperature is a thermal state of a body which distinguishes a hot body from a cold body. The
temperature of a body is proportional to the stored molecular energy i.e., the average molecular kinetic
energy of the molecules in a system.
EQUALITY OF TEMPERATURE OR THERMAL EQUILIBRIUM
Any two bodies are said to have ‘equality of temperature’ when no change in any observable property
occurs when they are brought in for thermal communication. The equality of temperature is also
termed 'thermal equilibrium'.
The following example is illustrated in order to understand the equality of temperature:
Consider two blocks of copper, one hot and the other cold. Each of blocks has a mercury thermometer
and an arrangement to measure electric resistance and length of block so that any change in length of
mercury column, resistance and length of block could be measured for each block due to temperature
change. Let these two blocks of copper are brought in contact for thermal communication. We would
then observe that:
Height of mercury column of thermometer in the hot block would drop and in cold body it would rise
at first and after sometime, no further change in height would be observed.
Electrical resistance of hot block decreases with time and for the cold block it increases with time and
after a period of time, no further changes in resistance would be observed.
Length of a hot block decreases and for the cold block it increases with time, and after a period of
time, no further change in length of either of the blocks would be observed.
So we may say that the two blocks of copper have equality of temperature after a period of time when
no change in observable properties like height of mercury column, electrical resistance and block
length would be observed.
ZEROTH LAW OF THERMODYNAMICS
The Zeroth law of thermodynamics states that when two bodies satisfy thermal equilibrium with a
third body individually, they in turn will be in thermal equilibrium with each other.
This law permits us to test the equality of temperature of two bodies without actually bringing them in
thermal communication.

FIGURE 13. Zeroth law of thermodynamics

Fig. 13 illustrates the zeroth law of thermodynamics. The bodies A and B are in thermal equilibrium
with a third body C separately then the two bodies A and B shall also be in thermal equilibrium with
each other. This is the principle of temperature measurement.
PRINCIPLES OF THERMOMETRY
Thermometry is the science and practice of temperature measurement. Any measurable change in a
thermometric probe (e.g. the dilatation of a liquid in a capillary tube, variation of electrical resistance
of a conductor, of refractive index of a transparent material, and so on) can be used to mark
temperature levels, that should later be calibrated against an internationally agreed unit if the measure
is to be related to other thermodynamic variables.
Thermometry is sometimes split in metrological studies in two subfields: contact thermometry and
noncontact thermometry. As there can never be complete thermal uniformity at large, thermometry is
always associated to a heat transfer problem with some space-time coordinates of measurement, given
rise to time-series plots and temperature maps.
TEMPERATURE SCALE
In order to measure the temperature of the system by thermometer, a temperature scale must be
provided on the thermometer. The Fahrenheit and the Centigrade are two common temperature scales
for measuring temperature. These temperature scales were based on some fixed points.
Ice point: The temperature of a mixture of ice and water which is in equilibrium with saturated air at
a pressure of 1 atmosphere. On the Fahrenheit scale and Centigrade scale this point is assigned the
numbers, 32 and 0, respectively.
Steam point: The temperature of water and steam which are in equilibrium at a pressure of 1
atmosphere. On the Fahrenheit scale and Centigrade scale this point is assigned the numbers, 212 and
100, respectively.
For simplicity, let us consider that the temperature ‘t’ be some linear function of asd thermometric
property, say height L of the mercury column.
Therefore, t = A .L + B -------------(1)
For Celsius scale

100 = A .Ls + B

0 = ALi + B
where, Li and Ls are the height of the mercury column at ice point and steam point respectively.
From these two equations we can obtain

By substituting the values of A and B in equation (1), we get

Similarly for Fahrenheit scale we can obtain

From equations (2) and (3) we can establish a relation between Fahrenheit and Centigrade scales.
toF = (9/5) toC + 32
So any two scales with different numerical values of temperature at two fixed points can be related
with each other.
Temperature scale based on one fixed point
The single fixed point is the triple point of water (The state in which solid, liquid, and vapor of a pure
substance can co-exist in equilibrium).The triple point of water is assigned the value of 0.01 °C.
The Ideal-gas temperature scale: The magnitude of the degree is defined in terms of the ideal-gas
temperature scale which is discussed below:
Both constant-pressure and constant-volume gas thermometers have been used for ideal-gas
temperature scale. But pressure measurement at constant volume is easier than the measurement of
volume at constant pressure. Hence, the constant volume gas thermometer is more commonly used.
CONSTANT-VOLUME GAS THERMOMETER
Fig. 14 shows a constant volume gas thermometer. It consists of a glass bulb with capillary
tube having a definite mass of gas. A mercury filled U-shaped transparent flexible rubber pipe is
connected to the capillary tube. The pressure on the gas (P gas) is due to the ‘L’ difference in height of
mercury column in U-tube together with atmospheric pressure acting on the open end of the flexible
pipe i.e. Pgas = ρ.g.L + patm. The open end of the flexible pipe can be raised or lowered to keep the
volume of the gas constant.
Let the gas bulb be placed in the system where the temperature ‘T’ is to be measured as shown
in Fig. 14 (b). Depending on the system temperature, the gas in the gas bulb will expand and this
results in increase in gas volume and change in mercury level in the right limb of U-tube from
reference mark ‘A’ to ‘A1’. Now, let the mercury column be so adjusted by raising the open end of the
flexible pipe that the level of mercury stands at the reference mark ‘A’ as shown in Fig 14 (c). Thus
the volume of gas in the gas bulb is maintained constant. At this point, let the pressure of the gas be P
which is calculated based on new difference in height of mercury column ‘L1’ of U-tube.
Let a similar measurement of pressure be made when the gas bulb is placed in the location
where the triple point of water (Tt.p. = 273.16 K) is maintained. For triple point, let the pressure of the
gas be Pt.p..

FIGURE 14. Schematic diagram of a constant-volume gas thermometer.

Since for an ideal gas T varies as p, we have

Or
By using the above relation, the unknown temperature T of a system could be determined from
pressure measurement, P. The temperature so measured is referred to as the ideal-gas temperature.
On this scale, when the gas bulb is placed in the system having steam point, the steam point is
experimentally found to be 100.0°C. Thus, there is an essential agreement between the old and new
temperature scales.

OBJECTIVE QUESTIONS
1. A definite area or space where some thermodynamic process takes place is known as
(a) thermodynamic system (b) thermodynamic cycle
(c) thermodynamic process (d) thermodynamic law.
2. An open system is one in which
(a) heat and work cross the boundary of the system, but the mass of the working substance does not
(b) mass of working substance crosses the boundary of the system but the heat and work do not
(c) both the heat and work as well as mass of the working substances cross the boundary of the system
(d) neither the heat and work nor the mass of the working substances cross the boundary of the
system.
3. An isolated system
(a) is a specified region where transfer of energy and/or mass take place
(b) is a region of constant mass and only energy is allowed to cross the boundaries
(c) cannot transfer either energy or mass to or from the surroundings
(d) is one in which mass within the system is not necessarily constant
(e) none of the above.
4. In an extensive property of a thermodynamic system
(a) extensive heat is transferred (b) extensive work is done
(c) extensive energy is utilised (d) none of the above.
5. Which of the following is an intensive property of a thermodynamic system?
(a) Volume (b) Temperature (c) Mass (d) Energy.
6. Which of the following is the extensive property of a thermodynamic system ?
(a) Pressure (b) Volume (c) Temperature (d) Density.
7. When two bodies are in thermal equilibrium with a third body they are also in thermal equilibrium
with each other. This statement is called
(a) Zeroth law of thermodynamics (b) First law of thermodynamics
(c) Second law of thermodynamics (d) Kelvin Planck’s law.
8. The temperature at which the volume of a gas becomes zero is called
(a) absolute scale of temperature (b) absolute zero temperature
(c) absolute temperature (d) none of the above.
9. The unit of energy in SI units is
(a) Joule (J) (b) Joule metre (Jm) (c) Watt (W) (d) Joule/metre (J/m)
10. One joule (J) is equal to
(a) 1 Nm (b) kNm (c) 10 Nm/s (d) 10 kNm/s.
11. The heating and expanding of a gas is called
(a) thermodynamic system (b) thermodynamic cycle
(c) thermodynamic process (d) thermodynamic law.
12. A series of operations, which take place in a certain order and restore the initial condition is
known as
(a) reversible cycle (b) irreversible cycle (c) thermodynamic cycle (d) none of the above.
13. The condition for the reversibility of a cycle is
(a) the pressure and temperature of the working substance must not differ, appreciably, from those of
the surroundings at any stage in the process
(b) all the processes, taking place in the cycle of operation, must be extremely slow
(c) the working parts of the engine must be friction free
(d) there should be no loss of energy during the cycle of operation
(e) all of the above (f) none of the above.
14. In an irreversible process, there is a
(a) loss of heat (b) no loss of heat (c) gain of heat (d) no gain of heat.
15. The main cause of the irreversibility is
(a) mechanical and fluid friction (b) unrestricted expansion
(c) heat transfer with a finite temperature difference (d) all of the above (e) none of the above.
16. A system comprising a single phase is called a
(a) closed system (b) open system
(c) isolated system (d) homogeneous system (e) heterogeneous system.
ANSWERS
1. (a) 2. (c) 3. (c) 4. (d) 5. (b) 6. (b) 7. (a) 8. (b) 9. (a) 10. (a) 11. (b) 12. (c) 13. (e) 14. (a) 15.
(d) 16. (d).
QUESTION BANK

Sl.No Questions Mark BTL Course

. (Select Questions from University question Bank and s level Outcome
mention year in bracket or you may give own standard (Please (Please
question with (new) in bracket) mention mention
L1 or CO1 or
L2 or CO2
etc...) etc…)
UNIT - I
PART-A

1 What is the difference between the work transfer and 2 L1 CO1

heat transfer? &L2
2 What is the difference between a closed system and 2 L1 CO1
open system? &L2
3 What is Quasi static process? 2 L1 CO1
&L2
4 Differentiate between point function and path function 2 L1 CO1
&L2
5 Differentiate the macroscopic and microscopic point of 2 L1 CO1
view of thermodynamics &L2
6 Define the terms – State, path, process and cyclic 3 L1 CO1
process &L2
7 State Zeroth law of Thermodynamics 3 L1 CO1
&L2
PART-B
1. a) Explain the concept of ideal gas temperature scale. 5 L2 CO1
Mark
s
b) A milk chilling unit can remove heat from the milk 5 L3 CO1
at a rate of 41.87 MJ/H. Heat leaking into milk from
surroundings at an average rate of 4.187 MJ/h. Find the
time required for cooling a batch of 500 kg of milk
from 450C to 50C. Take the C P of milk to be 4.187
kJ/kg K?
2. a. Explain what do you understand by concept of 5 L2 CO1
continuum? How will you define density and pressure
using this concept?
b) A balloon is filled with air (200kPa and 300K) such 5 L3 CO1
that it becomes as sphere of diameter 1m. It is then
gradually heated till the pressure rises to 500 kPa.
Determine the amount of work done during the
process, assuming that the pressure inside the balloon
is proportional to the diameter of the balloon
3. a). Why does free expansion has zero work transfer? 5 L2 CO1
4. a) Explain the working of constant volume gas 5 L2 CO1
thermometer.
b) 2kg of gas at a pressure of 1.5 bar, Occupies a 5 L3 CO1
volume of 2.5 m3. If this gas compresses isothermally
to 1/3 times the initial volume. Find initial, Final
temperature, work done, heat transfer.
5. a) The resistance of a platinum wire if found to be 6 L3 CO1
11000 ohms at the ice point,15.247 ohms at the steam
point and 28.887 at the sulpur point. Find the constants
A and B in the equations. R=R0(1+At+Bt2)
b) What is irreversibility and stat the causes of
irreversibility.
b) A turbine operates under steady flow conditions 4 L3 CO1
,receiving steam at the following
state:1.2mpa,1800C,2785 KJ/KG,33.3 m/sec and
elevation 3m.steam leaves the turbine at the following
state:20kpa,2512 KJ/KG,100 m/sec and elevation 0 m.
Heat is lost to the surround in at the rate of 0.29
KJ/sec. if the rate of steam flow through the turbine is
0.42 kg/sec. what is power output of turbine in KW
6 a) Explain the working of constant Volume gas 5 L3 CO1
thermometer with the help of a neat sketch. ?
b) Discuss in detail about quassi static process 5 L3 CO1
 UNIT II
PMM I - Joule’s Experiments – First law of Thermodynamics – Corollaries – First law applied to a
Process – applied to a flow system – Steady Flow Energy Equation. Limitations of the First Law –
Thermal Reservoir, Heat Engine, Heat pump , Parameters of performance, Second Law of
Thermodynamics, Kelvin-Planck and Clausius Statements and their Equivalence /Corollaries, PMM
of Second kind, Carnot’s principle, Carnot cycle and its specialties, Thermodynamic scale of
Temperature, Clausius Inequality, Entropy, Principle of Entropy Increase – Energy Equation,–
Thermodynamic Potentials, Gibbs and Helmholtz Functions, Maxwell Relations – Elementary
Treatment of the Third Law of Thermodynamics

JOULES EXPERIMENT

FIGURE 1. Adiabatic work

Let us consider a closed system which consists of a known mass of water contained in an adiabatic
vessel having a thermometer and a paddle wheel, as shown in Fig.1. Let a certain amount of work W 1-2
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. The system was initially at temperature T 1, the
same as that of atmosphere, and after work transfer let the temperature rise to T 2. The pressure is
always 1 atm. The process 1-2 undergone by the system is shown in fig. 2 in generalized
thermodynamic coordinates X, Y.

FIGURE 2. Cycle completed by a system with two energy interactions work transfer W1-2 followed
by heat transfer Q1-2

Let the insulation now be removed. The system and the surrounding interact by heat transfer till the
system return to initial temperature T1, attaining the condition of thermal equilibrium with the
atmosphere. The amount of heat transfer Q2-1 from the system during the process 2-1 shown in Fig. 2
can be estimated. The system thus executes a cycle which consists of a definite amount of work input
W1-2 to the system followed by transfer of an amount of heat Q 2-1 from the system. It has been found
that this W1-2 is always proportional to Q 2-1 and the constant of proportionality is called joule’s
equivalent or the mechanical equivalent of heat If the cycle involve many more heat and work
quantities the same result will be found and expressed algebraically as
(ΣW)cycle = J (ΣQ)cycle
This can also be expressed as

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
If both heat and work are expressed in the same unit of J or kJ, then it becomes

FIRST LAW OF THERMODYNAMICS FOR A CLOSED SYSTEM UDERGOING A CYCLE

For a closed system undergoing a cyclic process, first law of thermodynamics states that the net
heat supplied to the system from the surroundings is equal to net work done by the system on its
surroundings.

Where the symbol denotes the sum for complete cycle

The First Law of Thermodynamics may also be stated as follows:
“Heat and work are mutually convertible but since energy can neither be created nor destroyed,
the total energy associated with an energy conversion remains constant”.
FIRST LAW OF THERMODYNAMICS FOR A CLOSED SYSTEM UNDERGOING A
CHANGE OF STATE
The expression (ΣW)cycle = (ΣQ)cycle applies only to the systems undergoing cycles, and the algebraic
summation of all energy transfer across system boundaries is zero. But if a closed system which is
undergoing a change of state during which work energy and heat energy both are crossing the system
boundaries. Net energy will be stored or accumulated within the system and we must note it here that
energies stored within the system will be termed as internal energy of the system or also termed as
energy of the system.
Let us see the fig. 3, Q heat energy enters the system from surrounding and work energy W leave the
system or we can also say that system is doing work W on the surrounding by taking Q amount of
heat energy from the surrounding.
So, what will be the net amount of energy stored within the system during this process?
(Q-W) will be the net energy and it will be accumulated within the system and hence there will be
increment in internal energy of the system as (Q-W) amount of energy will be stored within the
system during this process. Therefore, according to the first law of
thermodynamics, we have following equation for above FIGURE 3. Heat and work
thermodynamic process where system is under a change of state. interactions of a system with its
surroundings in a process
Q-W = ∆E
Q= W+ ∆E------------(1)
Where, ∆E is increase in internal energy of the system during the process
Let we have one system where multiple energies are crossing the system boundary in a process as
shown in following fig. 4,
Now with the concept of “Sign convention used for heat and work energy transfer across the system
boundary “writing the equation of energy transfer across the system boundary according to the first
law of thermodynamics for this process as

FIGURE 4. System – surroundings interaction in a process involving many energy fluxes

Q1 + Q2-Q3-W1+W2+W3 = ∆E
Q1 + Q2-Q3 = ∆E+ W1 -W2-W3
Energy is thus conserved in the operation. The first law is particular formulation of the conservation
of energy. Equation (1) may also be considered as definition of energy. This definition does not give
an absolute value of energy E, but only the change of energy ∆E for the process. It can however, be
shown that the enery has a definite value at every state of a system and is, therefore, a property of the
system.
ENERGY- A PROPERTY OF THE SYSTEM
Let us assume that we have one system which is undergoing a change of state from initial state 1 to
another state 2 via following the path A as shown in following figure. System is returning to initial
state i.e. state 1 from state 2 via following the path B. Here, we can say that system is undergoing in a
cycle 1-2-1 as displayed in figure.

FIGURE 5. Energy- a property of a system

Apply “first law of thermodynamics for a system undergoing a change of state” and apply for path A,
where system is changing its state from state 1 to state 2. We will have following equation
QA- WA= ∆EA
Similarly, we will have following equation when system is changing its state from state 2 to state 1 via
following the path B.
QB- WB= ∆EB
It was seen that system is undergoing in a cycle 1-2-1 as displayed in fig .5. Hence, applying concept
of “first law of thermodynamics for a system undergoing a cycle”. The following equation can be used
for system which constitutes a cycle 1-2-1.
(ΣW)cycle = (ΣQ)cycle
WA+WB= QA+QB
WB- QB = QA- WA
- (QB- WB) = QA- WA
- (∆EB) = ∆EA----------------------(2)
Let assume that system is returning to initial state 1 from state 2 via following the path C, in that case
using the similar procedure to get equation (2) the following equation can be obtained
- (∆EC) = ∆EA----------------(3)
Now it is observed that the end result for first case where system is returning to initial state by
following the path B and of second case where system is returning to initial state by following the path
C, the system energy in both cases is same and it will not depend over the path followed by the system
to return to its initial state.
Therefore, it can be concluded that system energy will have some definite magnitude for each state of
the system and it will not depend over the path followed by the system and hence energy will be
considered as a point function and also a property of the system.
PERPETUAL MOTION MACHINE OF THE FIRST KIND—PMM 1
The first law of thermodynamics states the general principle of the conservation of energy. Energy is
neither created nor destroyed, but only gets transformed from one form to another. There can be no
machine which would continuously supply mechanical work without some form of energy
disappearing simultaneously (Fig. 6). Such a fictitious machine is called a perpetual motion machine
of the first kind, or in brief, PMM 1. A PMM 1 is thus impossible.

FIGURE 6. A PPM 1. Figure 7. The converse of PMM 1.

An imaginary device which would produce work continuously without absorbing any energy from its
surroundings is called a Perpetual Motion Machine of the First kind. The converse of the above
statement is also true, i.e., there can be no machine which would continuously consume work without
some other form of energy appearing simultaneously (Fig. 7).
COROLLARIES OF FIRST LAW OF THERMODYNAMICS
Corollary 1:
There exists property of closed system; the change in value of this property during the process is given
by the difference between heat supplied and work done during any change of state.
If the property is denoted by U, the corollary can be expressed as
dU = δQ - δW
where Q and W are the net quantities of heat and work crossing the boundary during the change of
state. The property U is called the internal energy of the system and equation is called the non-flow
energy equation. Here E is property of system and is called as total energy that includes internal
energy, kinetic energy, potential energy, electrical energy, magnetic energy, chemical energy, etc.
Internal energy is a thermodynamic property and hence it is a State function and independent of
process. If two independent properties are given, U is uniquely determined.
Corollary 2:
The internal energy of a closed system remains unchanged if the system is isolated from its
surroundings.
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
The first law of thermodynamics gives
dE = 0
or E = constant
The energy of an isolated system is always constant. Corollary 2 is often called the Law of
Conservation of Energy.
Corollary 3:
A perpetual motion machine of first kind is almost impossible.
SPECIFIC HEATS
The specific heat of a solid or liquid is usually defined as the heat required to raise unit
mass through one degree temperature rise.
For small quantities, we have
dQ = mCdT
where m = mass, C = specific heat, and dT = temperature rise.
For a gas there are an infinite number of ways in which heat may be added between any two
temperatures, and hence a gas could have an infinite number of specific heats. However, only two
specific heats for gases are defined.
Specific heat at constant volume, Cv
and, Specific heat at constant pressure, Cp.
We have
dQ = m Cp dT For a reversible non-flow process at constant pressure -----(3)
and, dQ = m Cv dT For a reversible non-flow process at constant volume ------(4)
The values of Cp and Cv, for a perfect gas, are constant for any one gas at all pressures and
temperatures. Hence, integrating eqns. (3) and (4), we have
Flow of heat in a reversible constant pressure process
= mCp (T2 – T1) …..(5)
Flow of heat in a reversible constant volume process
= mCv (T2 – T1) ........(6)
In case of real gases, Cp and Cv vary with temperature, but a suitable average value may be
used for most practical purposes.
Joule’s Law
Joule’s law states as follows :
“The internal energy of a perfect gas is a function of the absolute temperature only.”
i.e., u = f(T)
To evaluate this function let 1 kg of a perfect gas be heated at constant volume.
According to non-flow energy equation,
dQ = du + dW
dW = 0, since volume remains constant
∴ dQ = du
At constant volume for a perfect gas, from eqn. (4), for 1 kg
dQ = CvdT
∴ dQ = du = CvdT
and integrating u = cv T + K, K being constant.
According to Joule’s law u = f(T), which means that internal energy varies linearly with absolute
temperature. Internal energy can be made zero at any arbitrary reference temperature. For a perfect
gas it can be assumed that u = 0 when T = 0, hence constant K is zero.
i.e., Internal energy, u = Cv T for a perfect gas ............(7)
or For mass m, of a perfect gas
Internal energy, U = mCv T ..............(8)
For a perfect gas, in any process between states 1 and 2, we have from Eqn. (8)
Gain in internal energy,
U2 – U1 = mCv (T2 – T1) ..................(9)
Eqn. (9) gives the gains of internal energy for a perfect gas between two states for any process,
reversible or irreversible.
Ratio of Specific heats
The ratio of specific heat at constant pressure to the specific heat at constant volume is given the
symbol γ
Enthalpy
Enthalpy (H) of a substance at any point is quantification of energy content in it, which could be
given
by summation of internal energy and flow energy. Enthalpy is very useful thermodynamic property
for
the analysis of engineering systems.
Mathematically, it is given as,
H = U + PV
On unit mass basis, the specific enthalpy could be given as,
h = u + pv
H = U + pV, where H = mh.
Referring equation
h = u + pv
= CvT + RT [⸪ pv = RT]
= (Cv + R)T
= CpT [⸪ Cp = cv + R]
i.e., h = CpT
and H = mCpT.
H= mh

APPLICATION OF FIRST LAW OF THERMODYNAMICS TO NON-FLOW OR CLOSED

SYSTEM
Reversible Constant Volume (or Isochoric) Process (v = constant) :
In a constant volume process the working substance is contained in a rigid vessel, hence the
boundaries of the system are immovable and no work can be done on or by the system, other than
paddle-wheel work input. It will be assumed that ‘constant volume’ implies zero work unless stated
otherwise.
Fig. 8 shows the system and states before and after the heat addition at constant volume.
 FIGURE 8. Arrangement for constant volume heat addition and its p-V diagram.
Considering mass of the working substance unity and applying first law of thermodynamics to the
process
Q = (u2 – u1) + W .....................(10)

The work done

∴ Q = (u2 – u1) = Cv(T2 – T1) ...........(11)
where Cv = Specific heat at constant volume.
For mass, m, of working substance
Q = U2 – U1 = mCv(T2 – T1)………(12)
Reversible Constant Pressure (or Isobaric) Process (p = constant).
Fig. 9 shows the system and states before and after the heat addition at constant pressure.

FIGURE 9. Arrangement for constant pressure heat addition and its p-V diagram.
Considering unit mass of working substance and applying first law of thermodynamics to the process
Q = (u2 – u1) + W

The work done,

∴ Q = (u2 – u1) +P(v2 – v1) = u2 – u1 + Pv2 – Pv1
= (u2 + Pv2) – (u1 + Pv1) = h2 – h1 [⸪ h = u + Pv]
or Q = h2 – h1 = Cp (T2 – T1) ..................(13)
where h = Enthalpy (specific), and
Cp = Specific heat at constant pressure.
For mass, m, of working substance
Q = H2 – H1 = mCp (T2 – T1) ............(14) [⸪ mh = H]
Reversible Temperature (or Isothermal) Process (pv = constant, T = constant) :
A process at a constant temperature is called an isothermal process. When a working substance in a
cylinder behind a piston expands from a high pressure to a low pressure there is a tendency for the
temperature to fall. In an isothermal expansion heat must be added continuously in order to keep the
temperature at the initial value. Similarly in an isothermal compression heat must be removed from
the working substance continuously during the process.
Fig. 10 shows the system and states before and after the heat addition at constant temperature.

FIGURE 10. Reversible isothermal process.

Considering unit mass of working substance and applying first law to the process
Q = (u2 – u1) + W
= Cv (T2 – T1) + W
= 0 + W [⸪ T2 = T1]

The work done,

In this case Pv = constant or (where C = constant)

The constant C can either be written as P1v1 or as P2v2, since

P1v1 = P2v2 = constant, C

or

∴ …...(15)
For mass, m, of the working substance

………..(16)
 or ……(17)
Reversible Adiabatic Process ( pvγ = constant) :
An adiabatic process is one in which no heat is transferred to or from the fluid during the process.
Such a process can be reversible or irreversible. The reversible adiabatic non-flow process will be
considered in this section.
Considering unit mass of working substance and applying first law to the process
Q = (u2 – u1) + W
O = (u2 – u1) + W
or W = (u1 – u2) for any adiabatic process ...(18)
Eqn. (18) is true for an adiabatic process whether the process is reversible or not. In an adiabatic
expansion, the work done W by the fluid is at the expense of a reduction in the internal energy of the
fluid. Similarly in an adiabatic compression process all the work done on the fluid goes to increase the
internal energy of the fluid.
For an adiabatic process to take place, perfect thermal insulation for the system must be available.

FIGURE 11. Arrangement for adiabatic process and its p-V diagram.
Adiabatic process is mathematically expressed as
Pvγ = C or
Expression for work W :
A reversible adiabatic process for a perfect gas is shown on a p-v diagram in Fig. 11.
The work done is given by the shaded area, and this area can be evaluated by integration.

Therefore since Pvγ = constant, C, then

 ……..(19)

……..(20)
Relationship between T and v, and T and p:

Now    = c   and

  Pv = m RT   
or      P1v1 = mRT1     &       P2v2 = mRT2

……….(21)
Polytrophic Reversible Process (pvn = constant) :
It is found that many processes in practice approximate to a reversible law of form pvn = constant,
where n is a constant. Both vapours and perfect gases obey this type of law closely in many non-flow
processes. Such processes are internally reversible.
We know that for any reversible process,

For a process in pvn = constant, we have

 where C is a constant

Since C can be written as

Heat transfer during polytropic process (for perfect gas pv = RT) :

Using non-flow energy equation, the heat flow/transfer during the process can be found, by applying
the first law of thermodynamics for a change of state, we get
        Q = (U 2 – U 1) +  W

From equation (23) using the value of W

Also

On substituting
In a polytropic process, the index n depends only on the heat and work quantities during the process.
The slope of the p-V curve increases in negative direction with increase in 'n' (polytropic index). This
is shown in Fig. 12.
From equation pvn = constant, it can concluded that
If n = 1, then the process is isothermal (temperature constant);
If n = γ, then the process is adiabatic (No heat transfer);
If n = 0, then the process is isobaric (pressure is constant);
If n = ± ∞, then the process is isochoric (volume is constant).
All these processes are shown in Fig. 12.
It may be noted that, since γ is always greater than unity, than adiabatic process must lie between
isothermal and constant volume processes

FIGURE 12. Various thermodynamic processes

EQUAL-INTERNAL ENERGY (FREE EXPANSION) PROCESS:
To analyze this process, consider a system having insulated vessel in which there are two
compartments separated by a membrane as shown in Fig. 13 (a). There is a gas in one compartment
while the other compartment is in a state of complete vacuum. Let the membrane be ruptured and gas
fills the entire volume of the compartment (Fig. 13 (b)). Neglect any work associated with the
rupturing of the membrane.  The free expansion process on U-V diagram is shown in Fig. 14   
Since the tank is insulated there is no heat transfer for change of state from state 1 to state 2 in the
vessel i.e.  Q = 0.
Since the expansion is free from any resistance, no work is done by the system for change of state in
the vessel. i.e.  W = 0.

Figure 13. Example of a process involving a change of volume for which the work is zero.

Applying the first law of thermodynamics for a change in state, we get

Q = (U2 – U1) +  W             

      

      0 = (U2 – U1) + 0              

Therefore, (U2 – U1) = 0;               
U1 = U2
       It is constant internal energy process.

       For perfect gas   (U2 – U1)  = m Cv (T2 – T1)

              Therefore, T1 = T2     

               
Process Index Heat added Work done = P v T relation Specific heat C
n

Constant
n=0 Cp(T2 – T1) P(v2 – v1) Cp
pressure
Constant
n=∞ Cv(T2 – T1) 0 Cv
volume
Constant
n =1 P1v1 = P2v2 ∞
Temperature

Reversible
n=γ 0 0
adiabatic

Polytropic n=n
Problem 1: A tank containing a fluid is stirred by a paddle wheel. The power input to the paddle
wheel is 1500 W. Heat is transferred from the tank at the rate of 450 W. Considering the tank and the
fluid as the system, determine the change in the internal energy of the system during 1 sec.
Solution:
Given: W = - 1500 W;    Q= - 450 W
To determine change in the internal energy of the system during 1 sec:
         Formula: Apply the first law of thermodynamics for a change in state
             Q = (U2 – U1 ) + W2   or     (U2 – U1 ) = Q – W

Answer:   The change in the internal energy of the system during 1 sec
(U2 – U1 ) = Q  –  W
(U2 – U1) = - 450 – (–1500)
(U2 – U1) = 1050 W
or    U2 – U1 (in one sec.) = 1050 J

Problem 2: A system undergoes a cycle that comprises the four processes 1-2, 2-3, 3-4 and 4-1. The
energy transfers are tabulated below. Determine the unknown kJ and complete the table.
Process i-f iQf (kJ) iWf (kJ) ΔU =Uf - Ui (kJ)
1-2 40 --- 25
2-3 20 – 10 ---
3-4 – 20 ---- ---
4-1 0 8 ---
where,  f- final   and i – initial
Solution:
Given:   1Q2= 40 kJ;   (U2 – U1) = 25 kJ;   2Q3= 20 kJ;   2W3= - 10 kJ; 3Q4= - 20kJ;  4Q1= 0 kJ;   4W1=  8
kJ.
(a) Process 1-2:
     To determine work, 1W2
         Formula: Apply the first law of thermodynamics.
2 2
                                      1Q2 = (U2 – U1) + ½ m(V2 – V1 )+ mg(Z2 – Z1) + 1W2

                      Or 1W2 = 1Q2 – (U2 – U1)

     Answer:            1W2 = 1Q2 – (U2 – U1)= 40 – 25 = 15 kJ

(b) Process 2-3:

     To determine work, U3 – U2
 Formula: Apply the first law of thermodynamics.
2 2
                        2Q3 = (U3 – U2) + ½ m(V3 – V2 )+ mg(Z3 – Z2) + 2W3

              or  (U3 – U2) = 2Q3 – 2W3

     Answer:    (U3 – U2 ) = 2Q3 - 2W3 =20 -(-10) = 30 kJ

(c) Process 4-1: 

    To determine work, U1 – U4
    Formula: Apply the first law of thermodynamics.
2 2
                              4Q1 = (U1 – U4) + ½ m(V1 – V4 )+ mg(Z1 – Z4) + 4W1

                        (U1 – U4) = 4Q1 – 4W1

     Answer:     (U1 – U4 ) = 4Q1 - 4W1 =0 – 8 = – 8 kJ

(d ) Process 3-4:
      To determine work, U4 – U3
            Formula: As cyclic ;   

                         (U2 – U1) + (U3 – U2)+ (U4 – U3) + (U1 – U4) = 0

or    U4 – U3 = 0 – [(U2 – U1) + (U3 – U2) + (U1 – U4)]
     Answer:         U4 – U3 = 0 – [(U2 – U1) + (U3 – U2) + (U1 – U4)]
= 0 – [25 + 30+(-8)] = – 47 kJ
     To determine work, 3W4
    Formula: Apply the first law of thermodynamics.
2 2
                               3Q4 = (U4 – U3) + ½ m(V4 – V3 )+ mg(Z4 – Z3) + 3W4

                  or   3W4 = 3Q4 – (U4 – U3)

     Answer:        3W4 = 3Q4 – (U4 – U3) = - 20 – (–47) = 27 kJ

Answer: The complete table is:

Process Q (kJ) W (kJ) ΔU = Uf - Ui (kJ)
1-2 40   15   25
2-3 20 - 10  30
3-4 - 20   27 - 47
4-1 0 8 -  8

Problem 3: A stationary mass of gas is compressed without friction from an initial state of 0.3 m 3 and
0.105 MPa to a final state of 0.15 m3 and 0.105 MPa, the pressure remaining constant during the
process. There is a transfer of 37.6 kJ of heat from the gas during the process. How much does the
internal energy of the gas change?
Solution:
Initial volume V1 = 0.3 m3 , Final volume V2 = 0.15 m3 , initial pressure P1 = 0.105MPa
Final pressure P2 = 0.105MPa heat transfer Q = 37.6 kJ
First law for a stationary system in a process gives
Q=ΔU+W
Or Q1-2 = U2 -U1+W1-2
Here

0.1015(0.15-0.3) MJ
-15.75 kJ
Q1-2 = -37.6 kJ
-37.6= U2 -U1 -15.75
 U2 -U1 = -21.85kJ
Internal energy of gas is decreased by 21.85 kJ in the process
Problem 4: When a system is taken from state a to state b, in fig. along the path acb, 84 kJ of heat
flow into the system, and the system does 32 kJ of work. (a) How much will the heat that flows into
the system along path adb be, if the work done is 10.5 kJ? (b) When the system is returned from b to a
along

FIGURE
the curved path, the work done on the system is 21 kJ. Does the system absorb or liberate heat, and
how much of the heat is absorbed or liberated? (c) If U a = 0 and Ud =42 kJ, find the heat absorbed in
the processes ad and db
Solution:
Qacb = 84 kJ, Wacb= 32kJ, Wadb = 10.5 kJ Wb-a = -21kJ
Ua = 0, Ud =42 kJ
We have
Qacb = Ub – Ua +Wacb
Ub – Ua = 84-32 = 52 kJ
(a)
Qadb = Ub – Ua +Wadb
52+10.5= 62.5 kJ
(b)
Qb-a = Ua – Ub +Wb-a
=-52-21= -73 kJ
The system liberates 73 kJ of heat
(c)
Wadb = Wad + Wdb
Wad = 10.5 kJ
Qad = Ud – Ua + Wad
= 42-0 + 10.5 = 52.5 kJ
Now
Qadb = 62.5 kJ = Qad + Qdb
 Qdb = 62.5-52.5 = 10 kJ
Problem 5. Considering system composed of a stone having a mass of 10 kg and a bucket containing
100kg of water. Initially the stone is 10 m above the water and the stone and water are at the same
temperature. The stone then falls into the water.
Determine ΔU, ΔKE, ΔPE, δQ and δW for the cases:
(a)  At the instant the stone is about to enter the water. Assuming no heat transfer to or from the stone
as it falls
(b)  Just after the stone come to the rest in the bucket
(c)  After enough heat has been transferred so that the stone and water are at the same temperature
they
were initially
Solution: Consider stone and water as a system.
Given: Mass of stone = 10 kg;  Mass of water = 10 kg
(a)   Change of state from stone 10 m above the water to stone is about to enter the water
Given: 1 Q2 = 0;        ΔU=0 ;        1W2 =0;    
            Initial position of stone = 10 m above water

Determine change in kinetic energy ΔKE and potential energy ΔPE:

                 Formula: Apply the first law of thermodynamics for the closed systems.
Q2 = (U2 – U1) + ½ m(V22 – V12)+ mg(Z2 – Z1) + 1W2
                                 1

                         The above equation reduces to

                            − ΔKE = ΔPE = mg(Z2 – Z1)
Answer:   − ΔKE = ΔPE = mg(Z2 – Z1) =10 x 9.8 x (−10) = − 980 J
(b) Change of state from stone 10 m above the water to stone come to the rest in the bucket:
Given:   1Q2 = 0;        1W2 = 0;        ΔKE = 0;
Determine change in potential energy ΔPE and internal energyΔU:
             Formula: Apply the first law of thermodynamics for the closed systems.
                         1Q2 = (U2 – U1) + ½ m(V22 – V12) + mg(Z2 – Z1) + 1W2
                      The above equation reduces to
                          − ΔU = ΔPE =  mg(Z2 – Z1)
 Answer:  - ΔU = ΔPE = mg(Z2 – Z1)
                            =10 × 9.8 × (−10) = −980 J
             or    ΔU = 980 J;              ΔPE = − 980 J
  (c) Change of state from stone 10 m above the water to water are at the same temperature it
was initially due to heat transfer:
       Given: ΔU = 0;   ΔKE = 0 ;  1W2 =0;
       Determine heat transfer 1Q2:
               Formula: Apply the first law of thermodynamics for the closed systems.
                            1Q2 = (U2 – U1) + ½ m(V22 – V12)+ mg(Z2 – Z1) + 1W2
                            The above equation reduces to
                                           1Q2 = mg(Z2 – Z1)
       Answer:              1Q2 =   mg(Z2 – Z1) =10 * 9.8 * (−10) = − 980 J
Problem 6 : A gas of mass 1.5 kg undergoes a quasi-static expansion which follows a relationship p =
a + bV, where a and b are constants. The initial and final pressures are 1000 kPa and 200 kPa
respectively and the corresponding volumes are 0.20 m 3 and 1.20 m3. The specific internal energy of
the gas is given by the relation, u = l.5 pv – 85 kJ/kg, Where p is the kPa and v is in m3/kg. Calculate
the net heat transfer and the maximum internal energy of the gas attained during expansion.
Solution:

Mass m = 1.5 kg, initial pressure P1 = 1000kPa, final pressure P2 = 200kPa

Initial volume V1 = 0.2 m3 final volume V2 = 1.2 m3

Given equation p= a + bV u= 1.5pv-85

Substitute P1 V1 and P2 V2 in the equation of p to find a and b

1000 = a + 0.2b……..(1)

200 = a + 1.2b……(2)

Solving (1) & (2) for constants a & b

b = 800

substitute value of b in equation(1)

1000 = a + 0.2 b

a = 1160

the equation of p becomes

p =1160 – 800 v

work done
Change in internal energy

u1 = 1.5P1v1 – 85

u1 = 1.5 ×1000×(0.2) – 85 = 215 kJ/kg

u2 = 1.5p2v2 – 85 = 1.5 × 200 × 1.2 – 85 = 155 kJ/kg

Δu = m (u1 - u2 ) = 1.5(215-155)

Δu = 60kJ

i) The net heat transfer

Q = Δu + W = 60 + 600
Q = 660kJ
ii) The maximum internal energy
u= 1.5pv-85
u = 1.5(1160-800v) v – 85
u= 1.5(1160v - 800v2 ) – 85

Umax = 503.25 kJ