UNIT AND DIMENSIONS NEED TO INCLUDE IN THIS DOCUMENT

TABLE OF CONTENTS

1 UNIT I: Thermodynamic Basics ..............................................................................................2

1.1 Thermodynamic system and control volume ....................................................................2
1.1.1 Thermodynamics System..........................................................................................2
1.1.2 Definitions of Thermodynamics System ...................................................................2
1.1.3 Pictorial Representation ...........................................................................................2
1.1.4 Types of systems.......................................................................................................3
1.1.5 Boundary ..................................................................................................................6
1.1.6 Macroscopic and microscopic approach ..................................................................7
1.2 Properties & state .............................................................................................................8
1.3 Process & cycle ................................................................................................................8
1.4 Zeroth law...................................................................................................................... 10
1.5 Temperature scales ........................................................................................................ 11
1.6 Phase equilibrium .......................................................................................................... 11
1.7 Independent properties .................................................................................................. 11
1.8 Equations of state .......................................................................................................... 12
1.9 Compressibility factor ................................................................................................... 13
1.10 Tables of thermodynamic properties & there use .......................................................... 14
1.11 Definition of work and its identification ....................................................................... 14
1.12 Work done at the moving boundary .............................................................................. 15
1.12.1 Constant volume process ...................................................................................... 15
1.12.2 Constant Pressure process .................................................................................... 16
1.12.3 PV=Constant (constant Temperature)................................................................... 16
1.12.4 PVn =Constant (Polytrophic Process) ..................................................................... 17
1.13 Concept of heat and heat transfer modes ....................................................................... 17
1.14 Comparison of heat and work........................................................................................ 18
1 UNIT I: Thermodynamic Basics
1.1 Thermodynamic system and control volume

1.1.1 Thermodynamics System

A system is a finite quantity of matter or a prescribed region of space.

1.1.2 Definitions of Thermodynamics System

The thermodynamics system may be defined as below:

Thermodynamics is an axiomatic science which deals with the relations among heat,
work and properties of system which are in equilibrium. It describes state and changes in
state of physical systems.
Or
Thermodynamics is the science of the regularities governing processes of energy
conversion.
Or
Thermodynamics is the science that deals with the interaction between energy and
material systems.

The block diagram illustrated below shows a typical thermodynamics system where heat
energy is converted to mechanical energy.

1.1.3 Pictorial Representation

The thermodynamics system is represented pictorial for below.

A thermodynamics system consists of three different parts as follows:
a) Systems
b) Boundary
c) Surroundings

1.1.4 Types of systems

The thermodynamics system can be classified as below,
i. Open system
ii. Closed system
iii. Isolated system
iv. Adiabatic System
v. Homogeneous System
vi. Heterogeneous System

1.1.4.1 Characteristics of Open system

An open system is one in which matter flows into or out of the system. Most of the
engineering systems are open. Mass and heat transferred across the system.

1.1.4.2 Example of Open System

i. IC Engine
ii. Boiling of water in open pan
1.1.4.3 Characteristics of Close system
If the boundary of the system is impervious to the flow of matter, it is called a closed
system. In this system mass transfer does not takes place, but heat transfer takes place.

1.1.4.4 Example of close System

An example of this system is mass of gas or vapour contained in an engine cylinder, the
boundary of which is drawn by the cylinder walls, the cylinder head and piston crown.
Here the boundary is continuous and no matter may enter or leave.

1.1.4.5 Characteristics of isolated system

An isolated system is that system which exchanges neither energy nor matter with any
other system or with environment. Heat exchange and mass transfer do not takes place in
the system.
1.1.4.6 Example of isolated System

1.1.4.7 Characteristics of adiabatic system

An adiabatic system is one which is thermally insulated from its surroundings. It can,
however, exchange work with its surroundings. If it does not, it becomes an isolated
system.

1.1.4.8 Example of adiabatic System

Student will be taught later

1.1.4.9 Characteristics of homogeneous system

A system which consists of a single phase is termed as homogeneous system.

1.1.4.10 Example of homogeneous System

Mixture of air and water vapour, water plus nitric acid and octane plus heptane.

1.1.4.11 Characteristics of heterogeneous system

A system which consists of two or more phases is called a heterogeneous system.
Example of heterogeneous System:

1.1.5 Boundary
The actual or hypothetical envelope enclosing the system is the boundary of the system.
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. It is not difficult to
envisage a real boundary but an example of imaginary boundary would be one drawn
around a system consisting of the fresh mixture about to enter the cylinder of an I.C.
engine together with the remanants of the last cylinder charge after the exhaust process

1.1.5.1 Fixed boundary

Definitions:
A thermodynamic system is a quantity of matter of fixed identity, around which we can
draw a boundary (Figure below). The boundaries may be fixed or moveable. Work or
heat can be transferred across the system boundary. Everything outside the boundary is
the surroundings.

Example:
1.1.5.2 Imaginary Boundary
For closed systems, boundaries are real while for open system boundaries are often
imaginary. Figure below has shown the real and imaginary boundary.

Example:

Real and Imaginary Boundary

1.1.6 Macroscopic and microscopic approach

Thermodynamic studies are undertaken by the following two different approaches.

1. Macroscopic approach—(Macro mean big or total)

2. Microscopic approach—(Micro means small)

These approaches are discussed (in a comparative way) below

Sl Macroscopic approach Microscopic approach

no
1. In this approach a certain quantity of The approach considers that the system is
matter is considered without taking into
made up of a very large number of
account the events occurring at discrete particles known as molecules.
molecular level. In other words this These molecules have different velocities
approach to thermodynamics is and energies. The values of these energies
concerned with gross or overall are constantly changing with time. This
behaviour. This is known as classical approach to thermodynamics which is
thermodynamics. concerned directly with the structure of
the matter is known as statistical
thermodynamics.
2. The analysis of macroscopic system The behaviour of the system is found by
requires simple mathematical formulae. 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.
Sl Macroscopic approach Microscopic approach
no
3. The values of the properties of the The properties like velocity, momentum,
system are their average values. For impulse, kinetic energy, force of impact
example, consider a sample of a gas in a etc. which describe the molecule cannot
closed container. The pressure of the be easily measured by instruments. Our
gas is the average value of the pressure senses cannot feel them.
exerted by millions of individual
molecules. Similarly the temperature of
this gas is the average value of
translational kinetic energies of millions
of individual molecules. These
properties like pressure and
temperature can be measured very
easily. The changes in properties can be
felt by our senses.
4. In order to describe a system only a few Large number of variables are needed to
properties are needed. describe a system. So the approach is
complicated.

1.2 Properties & state

Thermodynamics Properties are classified into two groups
a) Intensive Property
b) Extensive Property

Intensive properties. These properties do not depend on the mass of the system.
Example: Temperature (T), pressure(p) and density (𝜌) are good examples.

Extensive properties. These properties depend on the mass of the system.

Examples of extensive properties include:
i. Amount of substance (mol)
ii. Energy (E)
iii. Enthalpy (H)
iv. Entropy (S)
v. Gibbs energy (G)
vi. Heat capacity (Cp)
vii. Internal energy (U)
viii. Mass (m)

1.3 Process & cycle

Process :
A process occurs when the system undergoes a change in a state or an energy transfer at a
steady state. A process may be non-flow in which a fixed mass within the defined
boundary is undergoing a change of state.
Example : A substance which is being heated in a closed cylinder undergoes a non-flow
process (A). Closed systems undergo non-flow processes. A process may be a flow
process in which mass is entering and leaving through the boundary of an open system.
In a steady flow process (B) mass is crossing the boundary from surroundings at entry,
and an equal mass is crossing the boundary at the exit so that the total mass of the system
remains constant. In an open system it is necessary to take account of the work delivered
from the surroundings to the system at entry to cause the mass to enter, and also of the
work delivered from the system at surroundings to cause the mass to leave, as well as any
heat or work crossing the boundary of the system.

Figure A Figure B

Quasi-static process. Quasi means ‘almost’. A quasi-static process is also called a

reversible process. This process is a succession of equilibrium states and infinite
slowness is its characteristic feature.

Cycle
Any process or series of processes whose end states are identical is termed a cycle. The
processes through which the system has passed can be shown on a state diagram, but a
complete section of the path requires in addition a statement of the heat and work
crossing the boundary of the system. Fig. C shows such a cycle in which a system
commencing at condition ‘1’ changes in pressure and volume through a path 123 and
returns to its initial condition ‘1’.
 Fig C
1.4 Zeroth law
The zeroth law of thermodynamics states that if two thermodynamic systems are each
in thermal equilibrium with a third, then they are in thermal equilibrium with each other.

Example. System ‘1’ may consist of a mass of gas enclosed in a rigid vessel fitted with a
pressure gauge. If there is no change of pressure when this system is brought into contact
with system ‘2’ a block of iron, then the two systems are equal in temperature (assuming
that the systems 1 and 2 do not react each other chemically or electrically). Experiment
reveals that if system ‘1’ is brought into contact with a third system ‘3’ again with no
change of properties then systems ‘2’ and ‘3’ will show no change in their properties
when brought into contact provided they do not react with each other chemically or
electrically. Therefore, ‘2’ and ‘3’ must be in equilibrium.

This law was enunciated by R.H. Fowler in the year 1931. However, since the first and
second laws already existed at that time, it was designated as zeroth law so that it
precedes the first and second laws to form a logical sequence.

Thermal equilibrium
Two physical systems are in thermal equilibrium if no heat flows between them when
they are connected by a path permeable to heat. Thermal equilibrium obeys the zeroth
law of thermodynamics. A system is said to be in thermal equilibrium with itself if the
temperature within the system is spatially and temporally uniform.
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

2
∫1 𝑑𝑉 = V2 - V1

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.
2
Thus ∫1 𝛿𝑄 ≠ Q2 – Q1
Note. The operator 𝛿 is used to denote inexact differentials and operator d is used to
denote exact differentials.

Control Volume :??

1.5 Temperature scales

Temperature Definitions: 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. (A particular molecule does not have a temperature, it has energy. The gas as a
system has temperature).

Measurements of Temperature: Instruments for measuring ordinary temperatures are

known as thermometers and those for measuring high temperatures are known as
pyrometers.

1.6 Phase equilibrium

1.7 Independent properties

There are other methods of temperature measurement which utilize various other
properties of materials, that are functions of temperature, as thermometric properties.

Six different kinds of thermometers, and the names of the corresponding thermometric
properties employed are given below :
Thermometer Thermometric property
1. Constant volumes gas Pressure (p)
2. Constant pressure gas Volume (V)
3. Alcohol or mercury-in-glass Length (L)
4. Electric resistance Resistance (R)
5. Thermocouple Electromotive force (E)
6. Radiation (pyrometer) Intensity of radiation (I or J)

1.8 Equations of state

The State of a System

We specify the state of a system - say, a sample of material - by specifying the

values of all the variables describing the system. If the system is a sample of a
pure substance this would mean specifying the values of the temperature, T, the
pressure, p, the volume, V, and the number of moles of the substance, n.

(We must assume that the system is at equilibrium. That is, none of the
variables is changing in time and they have the values they would have if we let
time go to infinity. We will give a thermodynamic definition of equilibrium
later, but this one will suffice for now.)

(If the system is a mixture you also have to specify the composition of the
mixture as well as T, p, and V. This could be done by specifying the number of
moles of each component, n1, n2, n3, . . . , or by specifying the total number of
moles of all the substances in the mixture and the mole fraction of each
component, X1, X2, X3, . . . . We will not deal with mixtures on this page.)

Equations of State

Let's consider a sample of a pure substance, say n moles of the substance. It is

an experimental fact that the variables, T, p, V, and n are not independent of
each other. That is, if we change one variable one (or more) of the other
variables will change too. This means that there must be an equation connecting
the variables. In other words, there is an equation that relates the variables to
each other. This equation is called the "equation of state." The most general
form for an equation of state is,

.
 Gas Law Formulas
Ptotal = P1 + P2 + P3 ... Dalton’s Law of Partial Pressure
X1 = n1/ntotal = P1/Ptotal Mole Fraction
P1V1 = P2V2 Boyle’s Law
V1 / T1 = V2 / T2 Charles’ Law
V1 / n1 = V2 / n2 Avogadro's Law
P1 / T1 = P2 / T2 Gay-Lussac’s Law

Combined Gas Law

P1V1 / T1 = P2V2 / T2

Graham's Law

PV = nRT
R = 8.3145 L kPa/mol K or Ideal Gas Law
R= 0.08206 L atm/mol K
(mm) P = dRT
mm = molar mass
Gas Density/Molar Mass
d = density
R= 0.08206 L atm/mol K
vrms = √(3RT / M)
M = molar mass in kg / mol Root Mean Square Velocity
R = 8.3145 J/mol K
[Pobs + a(n/V)2] x (V – nb) = nRT van der Waals Equation
Standard Atmospheric Pressure:
1 atm = 760 torr = 760 mm Hg = 101.3 kPa = 14.7 psi

1.9 Compressibility factor

The compressibility factor (Z) is a useful thermodynamic property for modifying the ideal gas
law to account for behavior of real gases. It may be thought of as the ratio of the actual volume of
a real gas to the volume predicted by the ideal gas at the same temperature and pressure as the
actual volume.

BASIC EQUATIONS OF COMPRESSIBLE FLUID FLOW

𝝆𝑨𝑽 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕.
The basic equations of compressible fluid flow are :
(i) Continuity equation,
(ii) Momentum equation,
(iii) Energy equation, and
(iv) Equation of state.
1.10 Tables of thermodynamic properties & there use
Energy:
Heat, like work, is a form of energy transfer. Consequently, it has the same dimensions as energy, i.e.
ML2T-2, and is measured in units of Joules (J).

1.11 Definition of work and its identification

1.12 Work done at the moving boundary
What do you understand by work done by a thermodynamic system?

1.12.1 Constant volume process

1.12.2 Constant Pressure process

1.12.3 PV=Constant (constant Temperature)

1.12.4 PVn =Constant (Polytrophic Process)

1.13 Concept of heat and heat transfer modes

Specific heat
The specific heat of a material is the amount of heat necessary to raise the temperature of unit mass of
the material by one degree. Thus it has the dimensions L2T-2𝜃 −1 and is measured in units of J kg-1 0C-1
or J kg-1K-1.
With a gas there are two distinct ways in which the heating operation may be performed: at constant
volume and at constant pressure; and in turn these define important thermodynamic properties.
Specific heat at constant volume If unit mass of the gas is enclosed in a cylinder sealed by a piston,
and the piston is locked in position, the volume of the gas cannot change, and any heat added is used
solely to raise the temperature of the gas, i.e. the head added goes to increase the internal energy of
the gas. It is assumed that the cylinder and piston do not receive any of the heat. The specific heat of
the gas under these conditions is the specific heat at constant volume, cy. For dry air at normal
temperatures, cy = 718 J kg-1K-1.

Internal energy (E) is a measure of the kinetic energy of the molecules comprising the gas.
Thus internal energy per unit mass E = cvT

𝜕𝐸
or, more generally, 𝑐𝑣 = [𝜕𝑇]
𝑣

Specific heat at constant pressure Assume that the piston referred to above is now freed and acted on
by a constant force. The pressure of the gas is that necessary to resist the force and is therefore
constant. The application of heat to the gas causes its temperature to rise, which leads to an increase in
the volume of the gas, in order to maintain the constant pressure. Thus the gas does mechanical work
against the force. It is therefore necessary to supply the heat required to increase the temperature of
the gas (as in the case at constant volume) and in addition the amount of heat equivalent to the
mechanical work done against the force. This total amount of heat is called the specific heat at
constant pressure, cp, and is defined as that amount of heat required to raise the temperature of unit
mass of the gas by one degree, the pressure of the gas being kept constant while heating. Therefore, cp
is always greater than cy. For dry air at normal temperatures, cp = 1005 J kg-1 K-1.

Now the sum of the internal energy and pressure energy is known as the enthalpy (h per unit mass)
(see below). Thus
h = cpT

or, more generally,

𝜕ℎ
𝑐𝑝 = [ ]
𝜕𝑇 𝑝

1.14 Comparison of heat and work

Open system: An open system is a system that freely exchanges energy and matter with
its surroundings. For instance, when you are boiling soup in an open saucepan on a stove,
energy and matter are being transferred to the surroundings through steam.
Close system: no mass can be added ( pr cooker,

Isolated System: no energy or mass transfer (thermos flask, Universe)

Problem 1:
Gas from a cylinder of compressed helium is used to inflate an inelastic flexible balloon,
originally folded completely flat, to a volume 0.6 m3. If the barometric reads 760 mm of
Hg, what is the amount of work done upon the atmosphere by the balloon? Sketch the
system before and after the process.

Problem 2:
A piston and cylinder machine containing a fluid system has a string device as shown on
figure below. The piston is frictionless and it is held down against the fluid due to
atmospheric pressure of 101.325kpa. the string device is turned 9500 revolutions with an
average torque against the fluid of 1.25 Nm. Meanwhile the piston of 0.65 diameter
moves out 0.6 m. find the net work transferred for the system.

FAQ: (Subjective Questions)

1. Explain thermodynamics system with suitable diagram.
2. What do you understand by thermodynamics process, explain with neat diagram?
3. What do you understand by thermodynamics cycle, explain with suitable
diagram?
4. What do you understand by homogeneous and heterogeneous system? Explain
with suitable example and diagram.
5. Derive a standard work-done expression in thermodynamics system?
6. What is thermal equilibrium? Explain Zeroth law of thermodynamics.
7. What do you understand by path function and point function? Explain with
suitable diagram and properties.
8. Derive the work-done expression for i) constant volume, ii) Constant pressure, iii)
Constant temperature and iv) Polytrophic process.
9. What do you understand by specific heat?
10. Why Cp has higher value than Cv?
11. Write short notes on Macroscopic and microscopic properties.
12. Solve the problems given in this note.
FAQ (Objective Questions)
1. Temperature is path function. (True/false).
2. Define point function?
3. Illustrate few properties of point function.
4. Illustrate few properties of path function.
5. What value of n produce the constant pressure process in polytrophic process
(pvn = constant).
6. In close system mass and energy transfer occurs. (true / false)
7. Correct the wrong statement. ( Temperature measures in mm of Hg.)
8. At NTP the atmospheric pressure reads ______mm of Hg.
9. 1 atm = ______kPa.