NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

By
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 01: Introduction, Definition of System,

Properties and State of a System

This is the introductory lecture to the course, Laws of Thermodynamics. Thermodynamics is

the branch of science that describes the basic laws and principles governing the processes of
transfer and transformation of energy. The laws are formulated from the observations in nature,
while the basic principles as the corollaries of the laws are established through logical
deductions following the laws.

The science of thermodynamics provides also the relationships between the thermodynamic
properties of a system of substance, these helps us in determining the changes in property of a
system executing a process.

You can just think of the classical thermodynamics today as a tabletop rested on four legs
which are the four laws of thermodynamics. They are namely the zeroth law of
thermodynamics which provides the concept of temperature, another one is the first law of
thermodynamics which puts a quantitative constraint on the conservation of energy, or simply it
is the law of conservation of energy.

The third one is the second law of thermodynamics which imposes a directional constraint on a
physical process whether it occurs spontaneously or is manmade. The third law makes us aware
of the unattainability of a state by any system executing any process. Thus, the four basic laws
make the foundation pillar of the classical thermodynamics.

Now as a whole if we look, we see what actually we gain from the science of thermodynamics.
In fact, the science of thermodynamics provides us the information regarding the feasibility of a
process under a given condition, the direction of a process in which it should occur. Just for an
example, let us consider a chemical reaction taking place from reactants to products, at some
conditions. Whether the reaction will take place at all or it will be an equilibrium, a mixture of
reactants and products, will be given or will be known from thermodynamics, or at given
condition whether the net reaction will be from reactants to products or from products to
reactants, that is, in which direction the reaction will take place, or it will take place
simultaneously in both directions with the net effect in one direction, will be told by
thermodynamics.

Another thing that will be discussed afterwards is that a process cannot be made in both the
directions or cannot be made to occur in both the directions. For example, let us consider that a
flywheel is rotating with certain RPM, it has a kinetic energy. If you stop the wheel by applying
a brake, it comes to rest, and we will observe that the temperature of the wheel and the brake
shoe (if you apply the mechanical brake) has increased. From the conservation of energy, that
means kinetic energy is converted into intermolecular energy which raises its temperature, but
there are no means by which we can utilize this intermolecular energy or convert intermolecular
energy into kinetic energy to set the flywheel in motion. It's not possible, that means this
process of converting the kinetic energy into intermolecular energy of a substance or system is
unidirectional.

But there are a number of processes which can take place in both the directions but we have to
pay something for it, all these things will be discussed afterwards while discussing the second
law of thermodynamics. So, this way, thermodynamics states the direction of the process,
feasibility of a process, and these are extremely important. This is because when we intend to
work, to execute a process or a process occurs in nature, our main aim is to get some useful
desired output, for example useful work. Then our objective will be to make the process as
efficient as possible so that we can get the maximum desired output out of a given energy with
minimum energy dissipation. This is in the perspective of both energy conservation and energy
dissipation, and this is extremely important to design a process, any physical process, and this
analysis of the processes occurring in any engineering device or engineering plant is extremely
important, and of primary requirement from the viewpoint of the design of the plant or device.
This is known as thermodynamic design, under which condition the plant or the device will
work at its maximum efficiency with minimum dissipation of energy and maximum conversion
of the energy from one form to other. So, this way we see thermodynamics is a very important
subject and plays the role of foundation pillar to all branches of engineering science and
technology.

And this motivates us to read thermodynamics well. This is a conceptual subject with less
mathematics involved, but we have to understand the concept very clearly so that we can solve
problems on thermodynamics applied to real cases.

Now with this introduction regarding the importance of thermodynamics and our motivation to
read thermodynamics, now we will start the course with definitions of certain basic
terminologies which you have probably known by this time or you have read already but this
will be a recapitulation in that case. For instance, system, what is the definition of a system? For
the analysis of any problem whether in thermodynamics, fluid mechanics, heat transfer, any
engineering science or physical science, we always deal with system, therefore, we must first
start with the definition of system.

Let us see that a system is basically defined as a quantity of matter or substance, a definite
quantity of matter and substance bounded by some boundaries at the instant of our investigation
or analysis. So therefore, we can write about system by its basic definition, its two characteristic
features. One is the definite quantity of mass or definite quantity of matter or substance, and
secondly it will have boundaries or boundary whatever you call, and this is known as system
boundary. It will have definite quantity of matter or substance; the definite quantity means
mass. I am not using the word ‘mass’ at the present moment. Definite quantity of matter or
substance (you can call also mass) should be defined with a boundary which will distinguish the
system from external things which are known as surroundings.

So, whenever the definition of system comes, surrounding is that which is external to the
system, but not the vast external. This is that external to the system with which the system
interacts, that means in its close vicinity. In fact, when two systems interact with each other and
with nothing else, then one system is the surrounding of the other. That means, the definition of
surrounding and system is not that very clear; a system can also be called as a surrounding to
other system(s) with which it interacts. So this way, we define system and surrounding.
(Refer Slide Time: 09:58)

Now this system is of usually three types. One is known as control mass system, or closed
system or simply system. These three are synonymous terms for one class of system. Another
one is the control volume system or sometimes we call simply control volume. These are both
synonymous terms of a class of system, open system. Usually in thermodynamics, people use
the terminology open system, while in the analysis of fluid mechanics control volume system or
control volume is used.

Another one is isolated system. (Refer Slide Time: 11:52)

It is defined in this manner that there is a definite quantity of mass or definite quantity of matter
or substances which interacts with surrounding in terms of energy, but there is no interaction of
mass across the system boundary. First, I tell this there is no interaction of mass across the
system boundary for this control mass or closed system but there may be interaction of energy.

While defining the system boundaries one thing should be remembered, these boundaries
maybe real or imaginary. Usually we have real boundaries in practical system; sometimes for
analysis we can have a real imaginary boundary, but it should obey all the restrictions or
definition imposed for the system. Like, for a closed system, the boundary should not allow any
(Refer Slide Time: 13:03)
mass interactions between the system and the surrounding. The system can interact with its
surrounding in terms of energy and you will know afterwards that this energy interaction is in
two forms, one is heat and another is work. Both in the form of heat and work the system can
interact, so therefore what happens in this system the mass remains fixed with the fixed
identity, that means no mass is allowed to go out or allowed to come in, so therefore the mass
remains same and with the same identity. This is a very important feature of a closed system or
control mass system. But it can interact with the surrounding in terms of energy and heat, these
arrows in two directions means the energy can go from the system, energy can come to the
system from the surrounding either in the form of heat or in the form of work.

While in a control volume system or simply the control volume, there will be mass transfer in
any direction, that means mass can come in can go out, and also energy transfer in both
direction in the form of heat and work. So therefore control volume boundary allows the mass
transfer from the system to the surrounding or from the surrounding to the system, and it also
allows at the same time the energy interactions between the system and the surrounding in
terms of heat and work, so this is the control volume system or simply the control volume or
open system, so one difference is that here the mass may not remain same if the inflow and
outflow of mass if both takes place and they are not in balance. But under some special
conditions if the inflow and outflow of mass is balanced, that means the rate of inflow into the
control volume or open system equals to the rate of outflow, then the mass remain same, so it
one way resembles the characteristics of the closed system or the control mass system where
the mass remain same, but still there is a difference here; though the mass remains same, their
identity changes because of the mass transfer across the system boundary.

Isolated system is a system which does not allow any mass transfer in any direction, that means
no mass can come in, no mass can go out, and also there is no energy transfer. Energy transfer
can take place only (as I told earlier) in the form of heat and work. So, energy interactions and
mass interactions both are not permissible by the system boundary, that means system remains
isolated, it cannot interact with its surroundings or with any other system close to. In that case,
what happens is that the mass of the system remains same with its identity, so that way it is
same as the control mass system or the closed system, and at the same time all other properties
remains unchanged because the system doesn't interact in terms of energy also with the
surrounding. So this is known as isolated system.
(Refer Slide Time: 17:48)

Now I will give you example of the two systems. The most popular example or which we come
across in practice is a gas in a piston-cylinder. Let us have a piston like this, a definite quantity
of gas, a gas in a piston, this is a closed system or control mass system. The system boundaries
are the face of the piston, the walls of the cylinder. There may be both heat and work transfer,
for example the piston may go up, come down, that means boundary has no restriction,
boundary may be flexible, boundary may expand, boundary may contract, but the mass within
the system will remain same with the same identity. When piston goes out because of high
pressure in the gas the system delivers work to the surrounding, when the piston is pushed by
the external cause then the gas will be compressed, this boundary will go inside, and the work
will be done into the system. Similarly, the heat may come out and go in, depending upon the
temperature difference between the gas in the cylinder and the surrounding. (Refer Slide Time:
19:43)
Now one example of control volume system I give you is that of an air compressor. Probably
from your popular knowledge you know that in an air compressor, air is taken in and it flows
through the compressor and comes out at high pressure. Its job is to compress air from a low
pressure to a high pressure and automatically its temperature is also increased, and to do so,
work has to be put into the compressor this is put in the form of the shaft work. A shaft is
allowed to rotate at some speed, high speed, or the desired speed so that the work is made input
to the air compressor, and this way the compressor works. This gives an example of an open
system. If we define a system with this boundary, enveloping this compressor and this entry and
exit line or the pipe, this is an example of a control volume system or control volume. Why?
Because across this boundary
(Refer Slide Time: 21:22)
there is a mass inflow, this is air coming in, across this boundary there is a mass outflow that is
air going out. In all practical situations the steady-state inflow and outflow remains the same.
The system boundary permits the mass transfer across the system boundary, which is known as
control surface.
And at the same time in this case, in this example of air compressor the work comes in, and if
the air compressor is made insulated which is usually done there is no heat transfer between the
system and the surrounding, so therefore work input is there to the compressor.
(Refer Slide Time: 22:25)
Another example you can have for this system is a pipeline, where there is a continuous flow
into the pipe and going out, a section of the pipeline. We consider some short section of the
pipeline as the control volume; the pipe surfaces are the control surface, and so are the
imaginary boundaries at the inlet and outlet. I told you there may not be any rigid or there may
not be any real boundary. So, as a whole this is a control volume or control volume system.
What happens here? It allows the mass to come in and to go out, whether there will be energy
transfer that depends upon the situation. In this case there will be no work transfer but there
may be heat transfer, if the fluid flowing through the pipe is hot or at higher temperature than
the surroundings then heat will come out or in the other way that means if this is at lower
temperature than this surrounding, the heat will come in, so that way it can have heat transfer
without any restriction.

Here, for example, the energy transfer is there, but the characteristic feature is that continuous
flow of mass through the system, some part of the boundary mass comes in, some part of the
boundary mass goes out. But not necessarily always there will be inflow and outflow both,
there may be only outflow, that means if there is a tank, and you just drain the fluid from the
tank, there is only outflow, or you charge a tank, there is only in flow, so either inflow or
outflow or both have to be there. That means there will be mass transfer across
(Refer Slide Time: 24:27)

the system boundary for a control volume system so therefore you should be clear that the
system should be divided into three categories one is control mass system, closed system which
is usually used or which is generally used in thermodynamics or simply system, another one is
control volume system or simply we can tell control volume or open system. This terminology
is used in thermodynamics, while in fluid mechanics we use the terminology control volume, it
is control volume system.
And another one is isolated system, we really come across the isolated system which does not
interact with the surrounding. Its boundary is such that it does not allow to interact and it
remains in the same state forever.

Now after this, I will tell you two very important terminologies associated with the definition of
the system. One is property and the other is state. These two are very closely related and
sometimes we confuse one for the other. This is the typical chicken-egg problem type of thing
which one will come first, but I think we should start first with property. What is the definition
of the property? Property of a system can be defined as its characteristic features which
describe or define the, for example if you tell that this is a system that means you have to tell
the system contents, type of substance, mass, etc. For instance, it contains this amount of
quantity at some characteristic features like its pressure, temperature, volume, we tell that so
much kg of gas is there in a piston cylinder at this temperature and pressure. That means we
require certain characteristic features to describe or specify a system. This is obvious today and
this is nothing great, so we know what a property is.

So, properties are the characteristic features describing or specifying a system, for example
pressure, temperature, volume, mass. We will see the infinite number of properties that we will
discuss afterwards but you should know at this moment that the property must have certain
characteristic features, it should be not necessarily all together sensible, it may be observable,
measurable, directly or indirectly, not that it should have all the characteristics together. For
example a body temperature is a
(Refer Slide Time: 28:25)

property which we can sense by its hotness or coldness. If you touch the system or touch the
body, body itself is a system, then we feel hot, some sensation is there, or we feel cold. That
means some properties are sensible, some properties are observable, For example if body is
moving with some velocity it has the kinetic energy which is the energy which is contained
within this system by virtue of which it can move it with the velocity V, that is, we can see the
movement of the particles.

If you have some solid particles moving within the liquid, or liquid itself is moving, you can
observe the motion of the liquid which is also a property, the kinetic energy contained within
the system that will be explained further in details while discussing the first law. So therefore, it
may be sensible, may be observable, but not necessarily. Pressure can be sensible; you can put
your hand in gas pressure and you will feel the pressure. But there will be number of properties
which may not be sensed, which may not be observed, they may not be sensible, for example
entropy, enthalpy, that we will see afterwards, that properties cannot be always sensible and
observable, but property should be measurable, so that we can know the property from its
measurement, and that measurement may be direct or indirect. Some properties cannot be
measured directly but can be determined indirectly from the measurements of properties which
can be directly measured, for example entropy. Entropy cannot be directly measured but it can
be determined from the measurement of other properties from experiment, so this has to be
measured. These are the basic characteristic features of properties, they can be sensible,
observable, and measurable directly or indirectly.

Now we come to the definition of state. The state is described by the fixed values of the
property, that means, if we say a system is at a given state, all its properties say X1, X2, X3, X4
will be fixed to determine the state. (Refer Slide Time: 30:52)

So fixed values of properties of a system determines its state, a system will be at a given state
where you will tell, that means it is specified by fixed values of property. But here two very
important concepts come into picture, what is that? That when you define a state of a system
with giving a definite quantity of matter or substance with fixed values of properties that means
for example the property X1, it should be same throughout the system. Here another thing you
must know from the property definition that property is of two types, one is extensive property,
another is intensive property. Extensive properties are those properties which depend on the
mass of the system, for example here I write total energy of the system, total entropy, total
enthalpy, all these things will be discussed afterwards you may not know at this time, these are
defined for the system as a whole, and this depends on the mass, so extensive properties are
those property which depends on the mass. Whereas,
(Refer Slide Time: 32:14)

intensive properties are those properties which do not depend upon mass, which do not vary
with the mass, but at the same time these can be defined at a point. For example, pressure and
temperature, these are intensive properties, and can be defined at a point. Pressure can be
defined at a point, temperature can be defined at a point, and they do not depend on mass.

For example, two gases at same pressure or same temperature are there in a container divided
by a partition. If you remove the partition the temperature and pressure of the gas will get
mixed and remain the same, does not depend upon the mass. Whereas if the energy contained in
one part of the container is E1, another part is E2, if you remove the partition the total energy
will be E1+ E2. It will be of additive type, it depends upon the mass. If the masses are different
that will be proportional to the mass, the total energy plus the total energy of the another part
will be added together and give the total energy, so therefore extensive property depends upon
mass, whereas intensive property doesn’t depend upon mass, but the specific values of these
extensive properties, for example specific energy E/M, or specific entropy ‘s’ is entropy by m,
or the specific enthalpy is ‘H’ by M, the specific values are also now intensive properties which
can be defined at a point, and do not depend upon mass.
(Refer Slide Time: 33:51)
For example, the volume is an extensive property, but specific volume, volume per unit mass, is
an intensive property, so therefore this makes the difference between extensive and intensive
property.

Now here when you say the state of a system will be defined by fixed values of its property,
fixed value means it is invariant with time and at the same time this should be same for the
whole system. For example, if we tell that the system is at say some pressure that means this
pressure should be uniform throughout the system, that is system can be specified or expressed
by the single value of the property, that means the property should be uniform throughout the
system if this is an intensive property, like pressure and temperature. There should not be any
gradient of pressure and temperature, this state is the state of thermodynamic equilibrium of the
system which will be again discussed afterwards where internally there will be no variation in
the intensive properties like pressure and temperature, that will be uniform so that the system
can be described by single value of these intensive properties along with the extensive
properties, and at the same time they do not vary with time. This is a very essential requirement
and it comes when the system is in equilibrium with the surrounding, and this can come under
two occasions, the system boundary is such that they do not allow the system to interact further
with the surrounding, makes the system as isolated system, in that case system properties will
not change with time, and if any variation is there for the intensive properties within the system,
that will be evened out and made uniform to a single fixed value.

Another option is that the boundary allows all type of energy interaction or mass interaction but
the system properties become same as those of the surroundings, that means with the interacting
systems or the local surroundings. In that case whatever maybe the system boundary, system
properties will remain invariant, it cannot interact with the surrounding. There is no difference
between the properties which will give the driving force to interact and that
(Refer Slide Time: 36:20)
state is known as dead state, so therefore at the very beginning we should have some primary
concept like this which I have told about the properties of this system and its state, how the
state is defined, and to define the state the system should be in thermodynamic equilibrium, so
that system can be expressed by single value of the properties, mainly the intensive properties
along with the extensive property, and that should not vary with time. In that way, we can
define the state of a system. Thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

By
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 02: Properties of Pure Substances

Today's agenda is to discuss one very important topic which helps in understanding various
facets, basic aspects of thermodynamics and that is, properties of pure substances. If you look
into the keywords, on one side you have a terminology called as property, on another side you
have a terminology called as pure substances.

We will discuss what a property is, what a pure substance is, and then we will connect these
two together. When we discuss about properties, we will concentrate on some concept called as
microscopic and macroscopic point of view.
(Refer Slide Time: 02:12)
It's a way in which you can describe a system. In the previous lecture, it has been discussed that
what is meant by a thermodynamic system, and today we will discuss how you characterize a
thermodynamic system.

When we characterize a thermodynamic system, one obvious way is to look into the
microscopic constituents like atoms, molecules and try to analyze the system in terms of their
either individual characteristics or statistically average behavior of many molecules or atoms,
then later this statistically averaged behavior of many molecules is also covered under the
purview of kinetic theory of substances, or kinetic theory of gases if they are referring to gases.

On the other hand, by macroscopic point of view what we essentially mean is that we are not
considering individual entities as atoms or molecules, but a significant number of atoms or
molecules as a whole. We are not considering their discreteness rather we are considering the
medium as a continuous medium disregarding the discontinuities in the atomic level or the
molecular level, so that is also called as continuum approach.
(Refer Slide Time: 04:10)

And the corresponding point of view is called as macroscopic point of view.

So, the thermodynamics that we are going to study in this particular course is essentially
studying the subject in macroscopic point of view. This is also known as classical
thermodynamics. There are other facets of thermodynamics, like statistical thermodynamics
where one can give due consideration to microscopic point of view. However, it needs to be
understood that not for all scenarios microscopic point of view will work, neither for all
scenarios macroscopic point of view will work. Like let us say that you have a system where
you have only a few molecules, for example a rarefied gas. How rarified the gas is, is described
by a non-dimensional number called as Knudsen number.
(Refer Slide Time: 05:22)
It is the ratio of the mean free path. It is the average distance traversed by a molecule before
encountering a collision, so this is the mean free path and this is the characteristic length scale
of the system. If there are only a few molecules, this mean free path is quite large because one
molecule will traverse a large distance before encountering another one, so then this Knudsen
number is large and that will indicate that it is a rarified system. So there, macroscopic point of
view will not work.

Why macroscopic point of view will not work is because in such a case, you have to consider
the discreteness of the molecular entities, so you can no more consider this as a continuous
medium. Another example could be high-speed gas flows which is as good as rarefied gas
flows in this particular perspective and many applications involving lasers or cryogenic
applications, it is important that one looks for microscopic viewpoint. Not only that, even in
classical thermodynamics, microscopic viewpoint is important. It is because if you want to
assess or estimate certain properties which are not directly measurable, like entropy for
example, you have to take into account certain microscopic considerations to assess or to
estimate properties which cannot be directly measured. So, these are certain considerations
based on which one has to decide whether to go for microscopic or macroscopic point of view.

Let me give you one concrete example to distinguish the difference between microscopic and
macroscopic point of view. Let us discuss about the quantity pressure.
(Refer Slide Time: 07:47)
I am not going for a formal definition of pressure because all of you know what pressure is, so
when you say pressure, it is defined in the microscopic point of view in terms of the rate of
change of linear momentum as a molecule, say for example a gas molecule encapsulated in a
container interacts with the wall of the container. When the gas molecule interacts with the
wall, there is a change in molecular momentum and that collision history is used to calculate the
pressure in terms of a microscopic point of view.

On the other hand, from a macroscopic point of view pressure is nothing but time average force
on a given area, and that force is something which is directly measurable by measuring devices.
So, there are two different viewpoints of looking into the same quantity.

When we understand macroscopic point of view so then we come to the understanding of

something which is called as properties. Property is a macroscopic characteristic of a system,
for example we say pressure is a property, temperature is a property. We will learn properties
one after another when we go through the basic laws of thermodynamics, so when we say
properties so by properties we essentially mean macroscopic characteristics of a system.
(Refer Slide Time: 09:55)
When we say macroscopic characteristics of a system, the question is how do you specify a
system? To specify a system, you define something which is called as state.
(Refer Slide Time: 10:31)

State is condition of a system as designated by its thermodynamic properties.

(Refer Slide Time: 11:05)
We essentially mean that a property will be defined or a property will be fixed up or rather a
state will be fixed up by describing it in terms of certain properties.

How many properties will be required to describe a thermodynamic state, we will discuss about
that in significant details, but right now when we say that we define something as state, we
define a state by using thermodynamic properties.

When there is a change in state, that should be defined by something which is a thermodynamic
process, like in high school physics you have learnt about certain processes like adiabatic
process, isothermal process. These are certain processes which will lead to the change in some
of the thermodynamic properties or may be change in all the thermodynamic properties. Now
we will discuss about pure substances. So, what is a pure substance?

Pure substance is something which is chemically homogeneous,

(Refer Slide Time: 13:24)
that means if you take various samples from the substance you will find the chemical
composition same everywhere.

On the other hand, there is a related terminology which is called as phase.

(Refer Slide Time: 13:52)

Phase is not only chemically homogeneous but also physically distinct,

(Refer Slide Time: 14:16)
this means that a pure substance can exist in various phases. Let us consider two common
examples air and water. Air and water are two very classical fluids which we commonly deal
with in thermodynamics, so question is, is water a pure substance? The answer is yes, because it
has the same chemical composition, and it is defined by H₂O and that chemical composition
doesn’t change no matter in what physical state the water is, but the water can exist in different
phases like it can be liquid water, it can be solid water, it can be water vapour. So, the
understanding is that a pure substance can exist in different phases like water has its different
phases.

On the other hand, let us think about air. Is air a pure substance? Normally if you think of
gaseous air, it is having a chemical composition which is approximately homogeneous,
however if air is being condensed or liquefied then a mixture of liquid and gaseous air will not
be treated or should not be treated as a pure substance. The reason is that the liquid-air has a
certain chemical composition which is different from that of gaseous air, and the reason again
for this is that the different constituents of air have different condensation characteristics,
condensation temperatures and so on. So, we cannot treat a mixture of liquid air and gaseous air
as a pure substance.

Even mixture of two liquids may or may not be treatable as a single phase, for example if you
mix alcohol and water, the resultant mixture will have a distinct physical appearance so it will
act like a distinct phase. However, if you try to mix oil and water there will be two
distinguishable liquid phases, so the moral of the story is that depending on the physical
distinction, sometimes depending on the micro structural characteristics, and so on, the same
apparent physical state or the same apparent physical characteristics might be attributed with
distinct phases. There are many examples in metallurgy where you have distinct types of solid
phases which are defined as alpha phase, beta phase, gamma phase.
Similarly liquid also can exist in different phases, so phase is a very important terminology and
the summary of this discussion is that a pure substance can exist in different phases. When we
discuss about properties of pure substances we will then try to understand that how many of
these properties will be required to specify the state, and that is something which is very
important for something called as thermodynamic equilibrium.

(Refer Slide Time: 19:35)

A system is in thermodynamic equilibrium if it is in mechanical equilibrium, thermal

equilibrium, and phase and chemical equilibrium.
(Refer Slide Time: 20:23)
So mechanical equilibrium means equilibrium of forces. By equilibrium of forces what we
mean is that all forces are balanced. That means there cannot be any pressure difference
between one point in the system and another point. A system under equilibrium will get
deviated from equilibrium if you create a pressure differential, however a system can remain in
equilibrium with a pressure differential if the pressure differential is only due to hydrostatic
effect, that is due to fluid statics, the difference in pressure because of the difference in height.

So, a system in mechanical equilibrium must have same pressure throughout if hydrostatic
effects are not considered, this is very important because normally when we say that a system is
in mechanical equilibrium, we normally say that it means that the pressure is same throughout
the system. The general philosophy is it's not a question of whether pressure is same throughout
the system or not, the philosophy is that all the forces are balanced then as a consequence of
that pressure will remain same throughout the system if there are negligible hydrostatic pressure
variations within the system.

Thermal equilibrium means equilibrium with respect to temperature because if there is a

temperature difference across two different points in the system, there will be a tendency of
heat transfer. So, thermal equilibrium means the system has come to a state when there is no
internal heat transfer. Temperature can change but at a given instant it remains same throughout
the system, so it is called as a uniform temperature system, means there is no spatial gradient of
temperature within the system.

Similarly, phase and chemical equilibrium means that there is no further change of phase that is
occurring. There is equilibrium with respect to any chemical change or phase change. How do
you designate that? Like pressure is a property by which you designate mechanical equilibrium,
temperature is a property by which you designate thermal equilibrium, similarly chemical
potential is a property
(Refer Slide Time: 24:54)
 by which you designate chemical equilibrium. We do not have a scope of defining and
discussing chemical potential formally in this course, but I can tell you physically what it
means. It is the net driving force for a chemical change to take place. Let us say we have two
components A and B or let us say one component 1, another component 2.
(Refer Slide Time: 25:33)

Let us say that there is a system, this system has several phases, phase 1, phase 2, phase 3, in
this way up to phase P, capital P
(Refer Slide Time: 26:08)
and each phase has component 1, 2 up to C (C number of components).
(Refer Slide Time: 26:19)

When we say that there is chemical equilibrium that means chemical potential of component 1,
in phase 1 is same as chemical potential of component 1 in phase 2, and this is same as
chemical potential of component 1 in phase 3, and eventually chemical potential of component
1 in phase P.
(Refer Slide Time: 26:45)
So, just like pressure is same throughout in mechanical equilibrium, temperature is same
throughout in thermal equilibrium, chemical potential of particular components is same in all
phases. This is chemical equilibrium. When all these conditions are satisfied, the system is said
to be in thermodynamic equilibrium.

Now you have to understand that thermodynamic equilibrium is something which is basically a
hypothetical concept. It's a conceptual paradigm which in reality will not be existing so much
when there is a change in state. Why? Because if you are transferring heat to a system, a system
will take its own time to adjust in such a way that everywhere within the system that
temperature comes to a new state, and then we say that the system has come to thermal
equilibrium. So, you require some time for the system to adjust to the changing state so that it
comes to an equilibrium state. So, in reality if the processes are not very, very slow you are not
really allowing this time. Hence, you have a system in equilibrium when the process is very
slow. It is so slow that deviation from thermodynamic equilibrium is only infinitesimal.

Let me give you an example. Let us you have a piston cylinder arrangement, a classical
example seen in thermodynamics. In one case there is a load W and there is some gas which is
there in the system. Now, suddenly if this load is removed, what will happen?
(Refer Slide Time: 29:26)
This piston will go up, because the pressure will fall, its volume will increase. This is very
intuitive physics.

Let us take another example, where you have a piston of same weight W but divided into small
slices,
(Refer Slide Time: 30:02)

say divided into n number of slices technically, where n tends to infinity, so practically a large
number of slices.
When you take these slices one after the other, this piston will slowly go up. You take away the
first slice and piston will go up a little bit, you take away the second slice and the piston will go
up a little bit more.
(Refer Slide Time: 30:36)

In this way, you will find that the same load is being removed in one case gradually, and in
another, rapidly. Both describe a thermodynamic process, using the same external loading, but
one is a very slow process where all the intermediate states are getting enough time to achieve
thermodynamic equilibrium or almost thermodynamic equilibrium.

On the other hand, the 2nd process is so fast that the system is not getting enough time to
achieve thermodynamic equilibrium within itself. The 1 st one is a scenario where the system
may be deviated from thermodynamic equilibrium but only slightly, so for all practical
purposes we can consider the process to be a collection of thermodynamic equilibrium states,
and this is called as a Quasi-Equilibrium, or a Quasi-Static Process, or Quasi-static, both are
equivalent terminologies.
(Refer Slide Time: 32:00)
So you can describe a system, in terms of its equilibrium properties very nicely during a process
if the process is itself a quasi-equilibrium or a quasi-static process, otherwise you may be able
to describe the end properties but you may not be in a position to describe the changing state.

So how do you conceptually demonstrate it in a diagram? Let us say this is a pressure versus
volume diagram, so in this case you have the initial state, you have the final state, but you do
not know the thermodynamic path by which it went, so you may represent it by a dotted line.
(Refer Slide Time: 32:43)
In the other case you may have the thermodynamic path
(Refer Slide Time: 32:51)

exactly known as a collection of equilibrium states.

The next question comes that if there are equilibrium states how many properties do you
require, and this is the last question that we will address before ending up this module. So, let
us see how many equations we have, and how many number of unknowns we have. Mechanical
equilibrium means pressure in phase 1 is same as pressure in phase 2 is same as pressure in
phase 3 is same as pressure in phase number of capital P.
(Refer Slide Time: 33:41)
Thermal equilibrium means temperature in phase 1 is equal to temperature in phase 2 is equal to
temperature in phase 3, in this way temperature in phase P.
(Refer Slide Time: 33:56)

Similarly, for chemical equilibrium, chemical potential of 1 in 1 is equal to chemical potential

of 1 in 2 is equal to chemical potential of 1 in phase P, similarly chemical potential of 2 in 1 is
equal to chemical potential of 2 in phase 2 is equal to chemical potential of 2 in phase P, and
finally,
(Refer Slide Time: 34:47)
chemical potential of C in phase 1 is equal to chemical potential of C in phase 2, in this way
chemical potential of C in phase P.

(Refer Slide Time: 34:58)

So how many equations? This is P-1 independent equations,

(Refer Slide Time: 35:20)
in this way C number of P-1 equations, so C(P-1). Hence, total is (P-1) C +1 +1, so (P-1) (C+2).

(Refer Slide Time: 35:40)

How many unknowns are there? There are P unknowns for pressure, there are P unknowns
(Refer Slide Time: 36:14)
for temperature because there are P phases, each phase has an unknown temperature and each
phase has C-1 number of compositions, why not C?
(Refer Slide Time: 36:28)

Because total fraction is 1, so if you specify C-1 compositions the remaining fraction will be 1-
some of the other compositions, so that is why if you have C components basically you are
talking about C-1 composition, so for total phase P it is P (C-1), so we can say that total is P(C-
1) +1+1, so C+1
(Refer Slide Time: 37:06)
Number of unknowns - number of equations, is PC+P and number of equations is (P-1)x(C+2),
(Refer Slide Time: 37:39)

so PC+P -PC -2P+C+2, so PC gets canceled so this is C+2-P.

(Refer Slide Time: 38:07)
This is called as degree of freedom. If the number of equations were same as the number of
unknowns then you would have specified the system without any freedom of specifying any
property, because the equation themselves should be used to evaluate the property, but now you
have some more unknowns than the equation, so some of the properties you can independently
specify and that is called as degree of freedom F.
(Refer Slide Time: 38:40)

So what is F? This is the degree of freedom, this is the number of independent properties that
you can use to specify a system, so you can write this in another way, that is F+P = C+2. This is
known as Gibbs phase rule.
(Refer Slide Time: 39:06)

So, this rule can be used under some considerations. One important point is that it's a simple
compressible substance, so what is a simple compressible substance? In a system, in
(Refer Slide Time: 39:37)

addition to pressure, volume and temperature changes, you could have other effects like
electrical effect, magnetic effect, there could be other so called non thermal effects. If there is a
system where the pressure, volume and temperature changes are more important than the
electrical magnetic or other effects, then that is called as a simple compressible substance.
So here we have used pressure and temperature as two important parameters, we have not
considered any electrical property or magnetic property that means other effects we are not
implicitly considering, and we are considering that the same components are existing, that
means we are not considering any chemical reaction, so simple compressible substance and no
chemical reaction.
(Refer Slide Time: 40:39)

I will give you two examples before we conclude this lecture. One particular example of use of
Gibbs phase rule. Let us say P = 1, C = 1,
(Refer Slide Time: 41:01)
that is one phase and one component, then F = 2, that means

(Refer Slide Time: 41:16)

you require two independent properties to specify the state of the pure substance.

What these two properties are, will be seen in the next lecture, but important thing is these
properties must be intensive properties. Intensive property means a property that does not
depend on the extent or total size of the system, like pressure, temperature, specific volume that
is volume per unit mass.

So the moral of the story that we learnt from this example is that the state of the property or the
state of a simple compressible pure substance can be fixed up by two independent intensive
thermodynamic properties. This is known as state postulate. (Refer Slide Time: 42:36)
We will look into properties of water as an example in the next lecture to see that how we can
apply this state postulate to actually define properties and understand various thermodynamic
processes that we will take up in the next lecture. Thank you very much.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

By
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 03: Properties of Pure Substances

(Contd.)

In the previous module we were discussing about certain basic concepts which lead us to the
understanding of properties of pure substances.

Let us try to understand one particular scenario where we take an example of liquid to vapour
phase change of water. (Refer Slide Time: 00:55)

Let us say that we are thinking of a pressure of 0.1 Mega Pascal,

(Refer Slide Time: 01:18)
which is like typically close to 1 atmospheric pressure, and then let us say there is water at 20
℃, which is the system.
(Refer Slide Time: 01:43)

You heat this and you will find that, the temperature will tend to go up till this becomes 99.6
℃.
(Refer Slide Time: 02:17)
You will find that when the temperature has come close to 100 ℃, there will be no further
change till all the liquid water at 20 ℃ is converted to vapour water.

And then when all the liquid is converted into vapour, you will find that again the temperature
will shoot up. This is a common observation and we can plot this in a temperature versus
specific volume diagram.
(Refer Slide Time: 03:09)

We have not defined yet what is specific volume, it is basically volume per unit mass, so it is
inverse of density. In thermodynamics, instead of density, we commonly use specific volume
because we will see that you can very elegantly use the law of mixtures to calculate the specific
volume of a mixture of two phases, so it is just a matter of convenience otherwise there is no
preference of using either specific volume or density. One is just the inverse of the other.

If you draw the T-͘V

͘ ͘diagram you will find that from 20 ℃ it will become 99.6 ℃, then it will
come to this state and then
(Refer Slide Time: 04:21)

it will get vapourized, temperature will change. Let us give it some names, this state point
where the liquid has just started getting converted to vapour is called as saturated liquid state,
and this state where the vapourization is just complete is called as dry saturated vapour or
saturated vapour.
(Refer Slide Time: 05:06)
The question is, what is the temperature at which this process is taking place? This temperature
depends on the pressure so during phase change pressure and temperature are not two
independent properties, how do you know that? Let us use the Gibbs phase rule that we learnt
in the previous module, so you have F+P = C+2 where P is the number of phases, C is the
number of components.
(Refer Slide Time: 05:51)

When the liquid is getting converted to vapour, how many phases are there? There are two
phases, and one component, that is just water. That implies F =1, which means
(Refer Slide Time: 06:08)

you can specify only one of the properties. You cannot specify independently pressure and
temperature both. If one is specified the other is automatically specified as a function of the
other.

The pressure at which this change of phase is taking place is called as saturation pressure, the
temperature at which this liquid vapour phase change is taking place is called as saturation
temperature, and the saturation pressure is a single valued function of saturation temperature.
(Refer Slide Time: 06:56)
That means if you identify a particular state, say phase change temperature, you will get a
corresponding phase change pressure from this graph, or if you identify a phase change
pressure you will get a corresponding phase change temperature; you cannot vary them
independently.

So now let us try to make a plot of this phase change process in P-V and T-V diagram. (Refer
Slide Time: 08:02)

We can identify two distinct regimes in the diagram, one demarcating a boundary the left of
which is completely liquid, and another demarcating a boundary the right of which is
completely vapour.
(Refer Slide Time: 06:48)

Let us draw the P-V diagram for the process at 2 different temperatures, say T1 and T2, where T1
< T2.
The saturated liquid states are marked by pink color and designated by ‘f’, and the saturated
vapour states are marked in blue, which we designate with ‘g’.
(Refer Slide Time: 10:37)

So, let us draw the locus of all the pink colored points and all the blue-colored points.
Eventually, if you merge these two loci, you will get a dome shape like this.
(Refer Slide Time: 11:22)
On the left of this, there is complete liquid, on the right side is completely vapour, and in
between is liquid + vapour.

Now there is a very interesting thing that what happens here, this is a point which is a point of
inflection. It is called as critical point.
(Refer Slide Time: 11:56)

Every substance will have its own critical point and water has also a particular critical point
state, and this is specified by a particular pressure, particular specific volume and particular
temperature. Let me tell you what are the properties of water at the critical point. For water,
Pcritical is 22.09 Mega Pascal, Tcritical is 374.14 ℃ and Vcritical is 0.003155 m3/kg.
(Refer Slide Time: 13:13)

If you go beyond critical point, you cannot call it a vapour, so it is better to call it just a fluid
because then there will be no sharp or distinct phase transition that is taking place like a liquid
to vapour phase transition. If you draw this dome shape diagram in a T-V plane, you will get
the diagram like this for water, so this is P1, this is P2.
(Refer Slide Time: 14:14)
Can you tell out of P1 and P2 which one is more? If you look into this saturation diagram for
water, you see that if the saturation temperature is increasing the saturation pressure will also
increasing, so P2 is greater than P1.

Now a very important point comes that when the substance is in the two-phase region, you have
either pressure or temperature as an independent property. Now we introduce a property which
is called as dryness fraction or quality. Why do we require another property? Because it tells us
where we exactly are on the liquid-vapour saturation line.
(Refer Slide Time: 16:34)

This is defined as follows:

Mass of vapour
x
Mass of vapour + Mass of liquid
(Refer Slide Time: 16:48)
So how do you describe it in terms of properties? We know, total volume is volume of vapour +
volume of liquid.
(Refer Slide Time: 17:10)

So what is the volume of vapour? (Refer Slide Time: 17:19)

‘vg’ is the specific volume of vapour. We always denote specific property by small letters
(specific property means the extensive property per unit mass). So, volume of vapour per unit
mass multiplied by mass of vapour gives the total volume of vapour.
(Refer Slide Time: 17:59)

Similarly, vf is the specific volume of saturated liquid, so ml (mass of liquid) multiplied by vf is

the total volume of liquid.
(Refer Slide Time: 18:23)
So, what is the specific volume of the mixture?
(Refer Slide Time: 18:53)

V mv
v , and x  .
ml  mv mv  ml
 v  xvg  (1  x)v f

(Refer Slide Time: 19:12)

So as I told you, specific volume is very commonly used in thermodynamics as you can see that
simple rule of mixtures can be used to describe the property of the system. This is true for
specific volume and for several other properties that we will learn when we will discuss about
first law. We will learn about internal energy and enthalpy and when we will be discussing
about second law we will be learning about entropy, and for all these properties you can use this
rule of mixtures, provided it's in a two phase system.

If it's a two phase system, there are 2 limiting cases: x = 0, this is saturated liquid,
(Refer Slide Time: 20:08)
And x = 1, it is called as dry saturated vapour or saturated vapour.
(Refer Slide Time: 20:27)

On the other hand it is important to understand that if you are going out of these bounds you
cannot use this formula, so in that case the region to the left of the boundary is called as sub
cooled liquid or compressed liquid, and the region to the right is called as superheated vapour.
(Refer Slide Time: 21:18)
Sub cooled means the temperature at a given location for a given pressure is less than the
corresponding saturation pressure temperature. If the temperature is same as that of the
saturation pressure temperature, then it is changing its phase.

On the other viewpoint if the pressure is more than the saturation pressure at a given
temperature then it is called as compressed liquid, and all of us understand the reason of this
that it is there in a pure liquid region, it's compressibility is much less as compared to the
saturated region, so this is in a highly compressed state already, and is called as compressed
liquid.

So question is how do you know what are the values of these properties? There is no way that
you can remember this. From experiments and use of statistical measures, the values of
properties of a pure substance like water or several other engineering substances like say
refrigerants are given in various thermodynamic tables, and whatever thermodynamics book
that you are using contains these tables. If you are going from school level to college level you
have to keep in mind that in school level, for working out most of the properties you would
have used ideal gas properties, but most of the practical substances are not ideal gases, so you
have to use the property tables to describe the properties, and the property tables for describing
the water liquid or vapour or the phase change are very popular because these are commonly
used for running many practical engineering devices, like, for designing thermal power plants
you require to understand the properties of water, and these properties are tabulated in the form
of a table called as property table, loosely termed as steam table.

So, I will work out a very simple example first to let you understand that how to use these
tables so that you are not tempted to use the ideal gas equations. Of course, at very high
temperature or very low pressure the real substance can be modeled as an ideal gas but not for
all states, so let us start with an example. The steam table that I was telling you (Refer Slide
Time: 24:33)
 will look like this. First column is saturation temperature, second column is saturation pressure,
so each temperature is characterized by its corresponding saturation pressure, then vf and vg are
there. There is something which is vfg. vfg is vg - vf, so basically there are many tables where vfg is
separately not given or vg is separately not given, but if you know any one of vf & vfg you can
calculate vg, any two of these if you know the third you can calculate.

Then you have internal energy which is commonly used to calculate or to understand the
change of state from the viewpoint of the first law of thermodynamics, also you can tabulate
similar properties for enthalpy, entropy, etc, so when you have such a table you are meaning
that there is a change of phase that is why F, G all these properties are there.
(Refer Slide Time: 26:09)

If you have superheated table, you have a particular temperature, and a particular pressure that
will fix up the state. For example, if you have 10 KPa and if you specify the temperature which
is there in the left column then you can specify all properties, specific volume, internal energy,
enthalpy, entropy, etc., so the temperature and pressure are two independent properties here. So,
for each pressure, the table is given where different temperatures will specify different states, so
the state is specified by the combination of pressure and temperature, it may also be specified
by the combination of pressure and specific volume, it can also be specified by combination of
temperature and internal energy. Hence, two independent intensive properties are required, that
is important, it is not always pressure and temperature it doesn't have to be pressure and
temperature, it needs to be two independent properties.

(Refer Slide Time: 27:24)

Similarly, in compressed liquid zone also you will have similar philosophy but the pressure
ranges are very high because it's in a compressed liquid state.
(Refer Slide Time: 27:35)

The first example that I am going to discuss, is mainly there to help you understand how to read
steam tables. The problem description is given here: water vapour initially at 3 MPa and 300 ℃
that is state 1 is contained within a piston cylinder assembly, the water is cooled at constant
volume until its temperature reaches 200 ℃ which is state 2, the water is compressed
isothermally to a state when the pressure is 2.5 MPa which is state 3. Locate the state 1, 2 and 3
on a T-V and P-V diagram, determine the specific volume at state 1, 2, and 3 and the quality at
state 3, quality is the dryness fraction.

So how to identify the states? Water vapour is at 3 MPa, 300 ℃. The first question that will
come to your mind is, is it a two-phase region, is it a superheated vapour, or is it a compressed
liquid. Look into this table. For 3 MPA that is 3000 KPA, look at the saturation temperature in
this red colored row which is 233.9 ℃. What is the given temperature? Your temperature given
is 300 ℃, which is greater than the saturation temperature so it must be in a superheated state.
Let us draw the liquid vapour domes in the P-V and T-V diagrams.
(Refer Slide Time: 29:45)

So, state 1 is superheated vapour, how do you specify the state 1? You specify the state 1 by the
(Refer Slide Time: 29:57)
pressure and temperature, so your value of pressure is 3 MPA, value of temperature is 300 ℃.
So, you go to superheated table now, superheated water vapour table 3000 KPa, that is 3 MPA,
300 ℃. Again with a red color we have indicated the corresponding properties, so you can see
from the table that the specific volume
(Refer Slide Time: 30:26)

is 0.08114 m3/kg, so v1 is 0.08114 m3/kg. (Refer Slide Time: 30:46)

(Refer Slide Time: 30:58)
Then the water is compressed, the water is cooled at constant volume until its temperature
reaches 200 ℃, so from state 1 it is cooled at constant volume, total volume is constant and its
mass is constant, that means specific volume is also constant, so it comes to state 2.

So the question is how do you know that the state 2 is in the two-phase region or superheated
region? Now, you have V2 = V1,
(Refer Slide Time: 31:45)
and state 2 is at 200 ℃. If you look into the table this is between vf and vg at 200 ℃, that
(Refer Slide Time: 32:03)

means state 2 is in the two-phase region.

Then the next is the third process where the water is compressed isothermally to a state where
the pressure is 2.5 MPa, so, T3 = T2 = 200 ℃.
(Refer Slide Time: 33:09)
Look into the saturation temperature at saturation pressure 2.5 MPA. You will find that the
saturation temperature at 2.5 MPA is greater than T3, that means that T3 is less than the
saturation temperature at 2.5 MPA, that means it is in sub cooled or compressed liquid region.

(Refer Slide Time: 34:18)

Finally, these are the P-V and T-V diagrams. It is very important to identify the states and
processes in P-V and T-V diagram for solving almost all problems in thermodynamics.

And how do you find out the quality at state 2? You have
v2  xvg 2  (1  x )v f 2 .
Vf2 and vg2 are vf and vg at 200 ℃.
(Refer Slide Time: 35:06)

This you get from the table, and v2 = v1 is known, so from here you can find out what is x2.
(Refer Slide Time: 35:18)
Here, x2 is 0.633.
(Refer Slide Time: 35:32)

How do you define state 3? From compressed liquid table, you have to identify state 3 at T3 and
P3, and that will give you v3, which is 1.1555x10-3 m3/kg.
(Refer Slide Time: 36:17)
So, this is a simple example using which I tried to illustrate how to look into these properties,
but the question is that if instead of water other substances are used, can we go back to our good
old equation of ideal gas, that is PV = RT?
(Refer Slide Time: 37:03)

This R is gas specific constant. The universal constant is 8.314 kJ kmole-1 K-1. So, for different
substances R will come out to be different because the molecular weight will be different for
different gases.
(Refer Slide Time: 38:07)
 But in reality, the substances are not ideal gases, so in reality PV is not equal to RT, if it is not
an ideal gas. But you can convert this inequality to equality by writing PV = ZRT, where the Z
is called as compressibility factor.
(Refer Slide Time: 38:36)

Z is 1 at very low pressure or at very high temperature. Low pressure is defined by the non-
dimensional pressure which is P/Pcritical,
(Refer Slide Time: 38:57)
typically, less than 0.05 (also known as reduced pressure). TR = T/Tcritical, this is reduced
temperature.
(Refer Slide Time: 38:20)

If the reduced pressure is less than 1, 0.05 or the reduced temperature is greater than 15 that
means it can be treated as very low pressure or very high temperature, so under those conditions
you can neglect the intermolecular forces of attraction and you can consider a real gas to be an
ideal gas. Now, the question is that if you know Pr and Tr, do you know what is Z. To do that
people try to plot the properties of various substances and when they try to plot Z versus Pr they
found a remarkable thing that almost all substances show a universal type
(Refer Slide Time: 40:22)

of physical behavior, so this is called as generalized property chart where this compressibility
factor is almost a single valued function of Pr and Tr, not quantitatively but qualitatively. So, Z
as a function of Pr and Tr is something which merges the
(Refer Slide Time: 40:50)

properties of different substances to a universal characteristic, a behavior which is very similar

and common to all substances and this is known as the law of corresponding states.
So, what are the typical values of Z? Typically, Z is less than 1. That means V is less than V of
ideal gas, that means density is greater than density of ideal gas, real gas density will be more
than ideal gas density, the reason is real gas will have intermolecular forces of attraction that
will make it denser than ideal gas. However very interestingly it is also possible that Z is
slightly greater than 1, for highly compressed situation, so if Z is greater than 1, say 1.1, that
may be possible when the situation is such that the molecules are so close to each other that
instead of intermolecular attraction there is intermolecular repulsion. Hence, typically Z < 1, Z
= 1 for ideal gas but when intermolecular force of repulsion is dominating because the
molecules are highly compressed to be in very close proximity to each other, Z > 1.

So one can say that we can fix up properties of various substances by looking into the property
tables, the property tables can be generalized in form of generalized chart and these can be
formulated in terms of curve fitted equations known as various equations of state. I don't want
to bombard on you different equations of state. The Van Der Waals equation of state is one
classical equation that you have learnt in high school physics. There are similar other equations
of state which I don't want to discuss, but the whole philosophy that I wanted to give you
through this module is how you can specify the thermodynamic state using its requisite number
of independent thermodynamic properties.

In the tutorial examples I have given you certain problems which I hope you will attempt to
solve and get a complete insight on the problem-solving aspects related to properties of pure
substances. We will revisit with some of those examples through some tutorial sessions if we
get time later on, otherwise in the next lecture we will start learning the concept of energy
transfer in terms of heat transfer and work.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

By
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 04: Heat and Work

In this module we will discuss about important modes of energy transfer and thermodynamics as
such is very critically linked with these modes of energy transfer that is heat and work. There are
many classical definitions of these two terminologies, and we'll first start with work.

Work is done by a system if the sole effects on the surroundings could be that of raising of a weight.
This is a very classical statement, it says that ‘if there is a raising of a weight, that gives a flavor of
work done’. Raising of a weight is conceptually representing a situation when you are pulling up
something against gravity, that means you are creating a displacement against resistance. Raising of
a weight does not technically mean that literally it has to be raising of a weight, what it means is that
it is essentially the displacement against a resistance.
So, raising of a weight this should not be literally interpreted, but it should be interpreted as
displacement against a resistance.
(Refer Slide Time: 03:06)

That means if there is no resistance then there is no work done. See many of you are who are
attending this course are now undergraduate students in different engineering colleges, universities
and so on, when you are students in higher secondary level you expected that there will be a lot of
resistance for you to establish a carrier, in terms of getting an entrance in a good university or good
engineering college or good institute, so you were really fighting against a lot of resistance and
working in a very tough and competitive environment. But now that you have come to an
engineering college you believe that life is like a large cell so you may be attending class every day
but you are gaining no value. You are not doing any work because it is like no resistance against you,
you are just having a happy go life.

In terms of doing work, if you are having no resistance, you are doing no work. This is a very
important philosophical aspect of thermodynamics, if you have to succeed, if you have to do a net
work you have to overcome resistance, if there is no resistance there is no thermodynamic work
done.

To define this in more concrete terms, we will discuss about various types of work. The first example
is work done by a system comprising a simple compressible substance undergoing a quasi-
equilibrium process due to a moving boundary.

We will get back to the old example that we refer to in one of the previous modules, let us say, there
is a piston like this.
(Refer Slide Time: 06:57)

There are two important keywords that we are considering, one is simple compressible substance,
another is quasi-equilibrium process.

Let us recall what is the simple compressible substance, a simple compressible substance is such a
substance where the pressure, volume, temperature related effects are much more important than the
non-thermal effects like the electrical effect, magnetic effect, and so on, so in such a scenario there is
a system boundary like this.
(Refer Slide Time: 07:38)

This system boundary is moving in a quasi-equilibrium process, how it can move in a quasi-
equilibrium process? I have given you one such example earlier.
(Refer Slide Time: 07:57)
So, there are many such small loads you remove one of these loads and piston will displace slightly,
so let us say it comes to a new position like this, so there is a displacement of dx.
(Refer Slide Time: 08:17)

So, what is the elemental work done due to this displacement? Let us apply the definition,
We are calling this as delta W.

See it is very important that why you are using this delta not dW, and we will come to this in a
moment, so what is this? δW= Fresistance*dx this is the basic definition.
(Refer Slide Time: 09:22)

This definition is valid no matter whether the system is undergoing a quasi-equilibrium process or
not, but if we are able to describe this resistance force in terms of pressure of the system considering
that the system is in equilibrium then it is a quasi-equilibrium process, how? Let us draw the free
body diagram of the piston.
(Refer Slide Time: 10:25)

The resistance force is Fresistance = mp *g + W + Po *A, where W is the total load (blue colored), Po is
the atmospheric pressure.
(Refer Slide Time: 11:00)
For equilibrium the resultant force is zero, that means Fresistance = P*A.
(Refer Slide Time: 11:25)

Fresistance*dx the moment that you write this as P*A*dx.

(Refer Slide Time: 11:36)

You are assuming that it is in equilibrium, so F resistance*dx for any process, but when you replace
Fresistance by P*A that means you are committing that it is in mechanical equilibrium, so it must be a
quasi-equilibrium process.

Now A*dx = dV the change in volume, therefore this is P*dV.

(Refer Slide Time: 12:12)

So sometimes it is loosely called as P*dV work. Now the question is that there could also be other
forms of work like electrical work, magnetic work and so on, but we are not considering those
components here, because we are considering that it's a simple compressible substance.

Now the very important question why δW? It is δW because we are now trying to distinguish these
two symbols d and δ. When we write dx, we mean that this change only depends on the initial x and
the final x, not the thermodynamic path by which it has undergone the change. For example when we
write integral of dV from 1 to 2, this is V2-V1, doesn't matter whether the system has undergone a
change in state by an adiabatic process, isothermal process, whatever process, the change in volume
is final volume minus initial volume, this type of differential is called as exact differential, and the
function over which this exact differential is operated is called as point function.
(Refer Slide Time: 13:54)

Point function only depends on the end points, doesn't depend on the thermodynamic path by which
the change in state has taken place. For example, in the PV diagram, there could be a change in state
by various ways.
(Refer Slide Time: 14:27)

The work done will be ꭍPdV, that means area under this diagram, so, work done will be dependent
on how P varies with V. Even if you fix up the state points 1 and 2 the work done will depend on the
path that connects 1 and 2, not just the end state points, that is why this is called as path function, and
this is in exact differential.
(Refer Slide Time: 15:24)

Let me give you a couple of examples, so let us define as example one, PV = constant,
(Refer Slide Time: 15:47)
This is a thermodynamic path, typically this is the path for an isothermal process of an ideal gas. So,
work done will be:

Where, C is either P1V1 or P2V2.

(Refer Slide Time: 16:27)

Example 2, PVn=C
(Refer Slide Time: 16:34)
So, W12 is:

Instead of C you can write PVn.

(Refer Slide Time: 17:37)

These are examples of work done if you are thinking of that there is a moving boundary, moving
system boundary and the system is undergoing a quasi-equilibrium process. We have to keep in mind
that there are other forms of work.
The next example that we will talk about is called as flow energy or flow work, so let us say that
there is a pipe, and there is a fluid that is entering the pipe, because the fluid has pressure, the fluid
must do some work to maintain the flow. Let us say that, there is a displacement of the fluid by an
amount dx and A is the cross-sectional area of the pipe. The reason behind considering differentially
small region is that the pressure will not vary significantly over this region otherwise the pressure
may vary.
(Refer Slide Time: 20:04)

So now you can write this as the work done is, W= PAdx
(Refer Slide Time: 20:22)

What is the work done per unit mass? So, work done per unit mass to maintain flow in presence of
pressure is work divided by mass, mass is the density times the volume is

This is P/ρ = P*υ

(Refer Slide Time: 21:29)

Those of you who are familiar with fluid mechanics have learned the significance of P/ρ while
dealing with the Bernoulli's equation. P*υ is nothing but work done per unit mass to maintain flow in
presence of pressure, this is called as flow energy or flow work.

There can also be an example of something called shaft work. There is a shaft, it is undergoing
rotation it is also overcoming a resistance.
(Refer Slide Time: 22:50)

Here the rate of work done is normally expressed rather than the work itself that is the torque times
the angular velocity, so the rate of shaft work is:
There can also be some other forms of work. Like work due to stretching of a wire, work done
because of stretching of a wire and this is due to surface tension effect, then aligning of ions in a
paramagnetic salt due to magnetic field.
Third is electrical work, if you have an electrical potential E and there is a charge (dq) flowing in
presence of that, then the electrical work is -E dq.
(Refer Slide Time: 25:36)

Now question comes that when do we consider the work as positive and when do we consider the
work as negative. This is the sign convention that will be based on what we developed, what we
adopted. If we say that work done is positive when energy leaves from the system to the
surroundings, so if energy is leaving from the system to the surrounding, that is the system is getting
rid of energy by utilizing some of that to do work, then that is called as positive work.

So, energy transferred from the system, by our sign convention, to the surroundings this we call as
positive work, somebody else may take a different sign convention, but this is the sign convention
that is commonly taken in all almost all thermodynamic states.
(Refer Slide Time: 27:13)

There are certain important things about work, first of all, work is not a property. Pressure is a
property, volume is a property, but work is not a property. Mathematically, the differential of work is
not represented by an exact differential, it is not represented by dW but δW, that means the work
done doesn’t depend on only the end states but it also depends on the process that connects the two
end states. That shows that work differential of work is not exact differential it is inexact differential
and therefore work is not a property.

The second important point is work is an energy in transient, that means the system doesn’t possess
any work, it is a system boundary phenomenon that is taking place during a change of state.
There is an analogous quantity in thermodynamics which is also very important and that is heat. Heat
is defined as an energy in transient due to temperature difference. That means heat is an energy
which a system doesn’t possess. Sometimes very loosely we say that this bucket of water contains
one joule of heat or one kilo joule of heat, this is completely wrong because heat cannot be possessed
by a system, heat can only be transferred across a boundary either from a system to the surrounding
or from surrounding to the system based on the temperature difference and it stops when the
temperature difference is nullified when there is no temperature difference, so in that way, heat is
also not a property because heat transfer from state 1 to state 2 depends on what kind of process it is,
for example if it's an adiabatic process there is no heat transfer, if it's an isothermal process there is
heat transfer. So, if we call Q as heat then the differential of heat that is δQ, this is inexact
differential, so in this way there is a lot of similarity between heat and work.
(Refer Slide Time: 31:13)

Only dissimilarity is, as per the sign convention that we adopt, if there is a system like this if there is
heat transfer to it, this we call as positive that means energy supply to the system in terms of heat is
positive, energy leaving the system in form of work is positive work, that is our sign convention,
somebody else may adopt a sign convention that no matter whether it is heat or work if energy is
entering the system it is positive, if it is leaving it is negative or the other way that can also be a sign
convention, but we have to stick to a sign convention and write appropriate expressions using these
sign conventions when we write the mathematical forms of various laws of thermodynamics which is
the main agenda of this course, the first law we will discuss as a follow up of this.

Worked out example.

(Refer Slide Time: 32:12)
(Refer Slide Time: 35:32)

State 1 is given. In state 2 piston is at the stops, then V2 = V1/2.

Initial volume is 1+1= 2 meter times the cross-sectional area, the final volume if it comes down to
the stops it is 1 times cross-sectional area, therefore, V 2 = V1/2, and if you assume air as ideal gas
which is not a bad assumption, then P1 V1/T1 = P2 V2/T2, where V2 = V1/2,
(Refer Slide Time: 36:36)
T2 and T1 are given, T1 is 400°C that is 673.15 Kelvin, remember that for using this formula all
temperatures must be absolute temperature, and T2 is 293.15 kelvin. So, if you calculate all this you
will get P2 is 130.7 kilopascal which is less than P1.
(Refer Slide Time: 37:20)

P2 is less than P1, P1 was 150 kilopascal and T1 400°C, that means the resistance pressure is also 150
kilopascal, if the state 1 is in equilibrium. Here at state 2 the resistance pressure is still 150
kilopascal, but the inside pressure is 130.7 kilopascal, so the piston wants to come further down, the
stops are preventing it to come further down. The piston is at the stops now draw a PV. From state 1
constant pressure the volume has decreased, we are assuming that in all problems that we are
discussing in thermodynamics here the process is quasi-equilibrium, that means initial pressure is
150 kilopascal, so the resistance pressure is also 150 kilopascal, so if it is coming down, it is coming
down slowly so that at all intermediate states its pressure inside is also same as the resistance
pressure, which is 150 kilopascal. Then when it has come to the stops, this is not state 2, then at
constant volume (that is at the stops) the pressure is falling to 130.7 kilopascal, this is state 2.
(Refer Slide Time: 39:28)
Work done is ꭍPdV from state 1 to state 2a, because from 2a to 2 there is no change in volume, since
there is no change in volume there is no work done. So W12=P1(V2a-V1).
(Refer Slide Time: 40:20)

So, if you put the values then this is -96.6 kJ/kg. If you consider 1 kg of air. You can use PV = RT so
if you write it for let us say m = 1 kg as the system, you can use PV = RT, and replace PV by RT so
it is basically R(T2 – T1). So, you have T1 and T2 known, and then you can calculate the total work
done.

See one final remark that I want to make before closing today's session is that thermodynamics if you
think of the algebra involved actually it is much simpler as compared to the algebra involved in
many other subjects in engineering. But thermodynamics is often considered to be a tough subject
from the point of view of many students, because the problems are not stereotype problems, for each
and every other problem you have to use a different outlook and a very fundamental approach to
address the problem. So it is not that you have one stereotype formula and you plug in the value in
the formula to solve a problem, for different problems you may have to use different concepts and
different ideas based on the fundamentals that you have learnt and that is why thermodynamics may
become so interesting at the same time a little bit tricky.

So with this little bit of note we conclude today's session, in the next session we'll be having
tutorials, the tutorials will cover both properties of pure substances as well as heat and work, but we
have to keep in mind that we will try to balance the tutorial in such a way that maybe a couple of
problems we will solve from properties of pure substances and a couple of problems we will solve
based on heat and work, and regarding properties of pure substances I will start with a simple sort of
a short question through which I will discuss one very important concept which we did not discuss
during our earlier session of discussion of properties of pure substances because of constraints in
time and that is essentially the concept of triple point, so we have discussed about the concept of
critical point, but we have not discussed about the concept of triple point so far, and we will discuss a
short question through which we will introduce the concept of triple point, then we will work out
maybe a couple of problems on properties of pure substances, and maybe another couple of problems
related to either work or heat and that will complete the agenda for the next tutorial which will warm
us up for the subsequent discussions which is one important agenda of this particular course and that
is the first law of thermodynamics.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

By
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 05: Tutorial 1: Properties of Pure

Substances, Heat and Work

In today's session we will be discussing about some example problems and questions related to
the topics that we have learnt so far, and these topics are mainly associated with properties of
pure substances and the concept of heat and work.

So before starting with any problem let me start with a simple school level question. Let us say
that there is some ice which is heated at a constant pressure. What will happen to the ice? A
junior school child will say that if the ice is heated it will get converted into liquid water and
then eventually water vapour. The answer to this question is not so simple. It is not complex
either but it is not that obvious and to give an answer to this question it is important to draw the
phase diagram of water.
(Refer Slide Time: 02:20)
So, if you look at this diagram there are 3 zones – solid, liquid and vapour. (Refer Slide Time:
02:30)

Now you can see in this diagram that there is a very interesting state point which is called as
triple point.
(Refer Slide Time: 03:05)
This is the point where the solid, liquid and vapour states coexist. For water, this triple point
data corresponds to 0.6113 kPa, and 0.01 ℃.
(Refer Slide Time: 03:34)

If you are in the solid region and you heat it at constant pressure, that is, if you follow a
horizontal line, the outcome depends at which you are. If your pressure is greater than the triple
point pressure then the solid ice will get first converted to liquid water, and then eventually to
water vapour. This process is follows melting and vapourization.
On the other hand, if you are below the triple point pressure then if you heat the solid ice at
constant pressure it will get directly converted into vapour without going through the
intermediate liquid step. This is known as sublimation.

It is also possible that if you heat it at the triple point pressure then the solid ice will eventually
pass through a combination of states where all the three phases solid, liquid and vapour can
coexist, so it will pass through the triple point. Hence on heating the solid ice what will happen
at a constant pressure depends on where you are located in this phase diagram.

Let us now get into our tutorial problems. The first problem that we will discuss is problem
number 1.4,
(Refer Slide Time: 05:50)

This problem is from the chapter of properties of pure substances. It says, a steel tank
containing 6 kg of propane at 20 ℃ with a volume of 0.015 m³. The tank is now slowly heated.
Will the liquid level rise or eventually drop? What happens if the initial mass is 1 kg instead of
6 kg? So, the physical problem is there is a steel tank in which there is propane, so now if you
heat it what is the general intuition? The general intuition is the liquid level will go down as the
vapour content will be more.

Let us see whether this answer is correct. To understand this, let us draw the phase diagram of
propane (T-V diagram in this case) and identify what the critical point is.
(Refer Slide Time: 07:27)
The critical point specific volume is 0.004604 m³/kg.
(Refer Slide Time: 07:53)

Now I will tell you how to solve this problem instead of getting into numbers. You have to
figure out whether your initial specific volume given is in which side of the critical point data.
How do you show the heating in a TV diagram? See, because the total volume is constant and
the mass is constant, volume per unit mass or specific volume is constant, so at constant
specific volume because of heating the temperature is increasing, so it could be on either side of
the critical point. (Refer Slide Time: 09:00)
In the 1st case, the quality value, x is very small, almost close to 0. Once it is heated the x value
is decreasing, so this is a situation where you have the quality decreasing (the situation is
opposite for the other case).
(Refer Slide Time: 09:43)

The quality is decreasing as it is approaching saturated liquid state.

(Refer Slide Time: 10:42)
(Refer Slide Time: 11:03)

So now let us look into the problem data, your specific volume at state one which is given V₁ is
0.0025 m³/kg this is less than Vcritical .
(Refer Slide Time: 11:34)
So, if you heat it then it is approaching the saturated liquid line, that means actually the liquid
level is rising.

On the other hand, in the next case the initial mass is 1 kg, so this is 1 prime, so V1' is 0.015 m³/
kg, how will you calculate it? Its volume at this state divided by the mass is greater than Vcritical .
(Refer Slide Time: 12:18)

This means liquid level will fall.

The moral of the story is
(Refer Slide Time: 12:37)

whether liquid level will rise or fall will depend on whether the initial state is in the left of the
critical point or the right of the critical point. If it is in the left, on heating it will approach the
saturated liquid line, so the liquid level will rise. If it is on the right, then on heating it will
approach the saturated vapour line so the liquid level will fall and vapour will increase.

So, this problem again gives us a clue that on heating of a liquid, it is not necessary that liquid
level will fall, the liquid level may rise or fall depending upon the situation.

Let us get into the next problem, problem number 1.5.

(Refer Slide Time: 13:49)
This is actually the last tutorial problem of chapter 1, that is properties of pure substances. It
says that there is a piston cylinder arrangement loaded with a linear spring. (Refer Slide Time:
14:28)

It contains water at 5 MPa and 400℃, which is state 1. Normally when pressure and
temperature are both given
(Refer Slide Time: 15:03)
 you must understand that it is either superheated vapour or sub cooled liquid, so this is not too
high a pressure that means this state is expected to be in the superheated vapour region. You
can look into the table of superheated vapour to calculate its specific volume.

The specific volume corresponding to it is 0.05781 m³/kg

(Refer Slide Time: 15:33)

If the piston is at the bottom the spring exerts a force. The piston is at the bottom means the
volume is 0, which is a hypothetical state. Then Plift = 200 kPa.
(Refer Slide Time: 16:05)
It is a linear spring, that means the force is proportional to displacement, that means the
pressure is proportional to the volume for the spring. The system cools from state 1 until the
pressure reaches 1200 kPa. So, if you draw the P-V diagram,
(Refer Slide Time: 16:36)

because of the linearity of the spring, the pressure versus volume graph will be linear. (Refer
Slide Time: 17:09)
What we can say is that the state point 2 will be somewhere on this line, so for state point 2 you
know that the pressure is 1200 kPa.
(Refer Slide Time: 17:45)

The question is where is V₂? Let us say, the state point 2 is here, so we can write the equation
of the line as,
Y  Y1 X  X1

Y2  Y1 X 2  X 1
Here Y is like P, and X is like V, so our equation is
P  Plift V  Vlift

P1  Plift V1  Vlift
(Refer Slide Time: 18:54)

Now this equation will be satisfied by the data point 2, so you substitute P = P₂ you will get V =
V₂.
(Refer Slide Time: 19:16)
V₂ is 0.01204 m³/kg, thus V₂ is less than Vg at P₂, but it is greater than Vf at P₂.
(Refer Slide Time: 19:41)

That means it is in the two-phase region.

Now find out the final state and plot the process in the P-V diagram. Also find the initial mass
from the specific volume and the given volume. (Refer Slide Time: 20:35)

Although the volume changes, the specific volume also changes and it adjusts itself in such a
way that the mass of water within this remains the same. This is a control mass system.
From the steam table, the saturation temperature corresponding to 1200 kPa is the temperature
at state 2, which is 188 ℃ and the mass is 1.73 kg, so M is 1.73 kg, T ₂ is 188 ℃, and V₂ is
0.01204 m³/kg. This is the answer to this problem.
(Refer Slide Time: 21:53)

Next let us work out another problem this time from chapter 2 that is heat and work. Let us
work out problem 2.3. (Refer Slide Time: 22:47)

2 kg of water is contained in the piston cylinder arrangement with a massless piston loaded with
a linear spring and outside atmosphere. Initially the spring force is 0, and P₁ = P₀ = 100 kPa
with a volume of 0.2 m³.
If the piston just hits the upper stops, the volume is 0.8 m³ and temperature is 600 ℃. Heat is
now added until the pressure reaches 1.2 MPa. Find the final temperature, show the P-V
diagram and find the work done during the process.

So let us try to make a sketch of this. This is the linear spring, this is water, these are the stops,
this is our system. The specific volume at state 1 is 0.1 m³/kg (mass of the total system is 2 kg,
and the volume is 0.2 m³, so this is volume per unit mass).

At state 2 which is the stops, V₂ = 0.4 m³/kg, because it is given that the final volume at the
stops is 0.8 m³
(Refer Slide Time: 25:27)

and that divided by 2 kg is 0.4 m³/kg. Also, T₂ is 600 ℃ so this combination will give you P ₂
from table of water of course.
(Refer Slide Time: 26:05)
Now you can see that the final pressure at state 3 is 1.2 MPa. This is greater than P ₂, therefore
on heating the piston will move up it will reach the stops, after which the pressure will build up
inside at constant volume from 1 MPa to 1.2 MPa.
(Refer Slide Time: 26:27)

So if you draw the P-V diagram for the process, state 2 to state 3 is a vertical line.
(Refer Slide Time: 27:09)
The question is to find the final temperature at state 3. For state 3, we have P₃, and V₃ = V₂, this
will identify what is state 3, and T₃ comes out to be 770 ℃.
(Refer Slide Time: 27:54)

What is the work done? The work done is simply the area under the PV diagram, so this is the
1
work done, so W₁₂ is (V2  V1 )( P2  P1 ) , this is basically integral PdV.
2
(Refer Slide Time: 28:26)
So this is 330 kilojoule, that is the answer to this problem.
(Refer Slide Time: 28:36)

Let us work out problem number 2.5. One of the important challenges in thermodynamics is
that each problem has a unique way of addressing and it is very difficult to cast a formula for
that.
(Refer Slide Time: 29:30)

In the next problem 2.5, two springs with the same spring constant are installed in a massless
piston cylinder arrangement with the outside air at 100 kPa. If the piston is at the bottom both
the springs are relaxed, and the second spring comes in contact with the piston at V = 2 m³. The
cylinder initially contains ammonia at - 2 ℃ with quality = 0.13 and volume as 1 m³ which is
then heated until the pressure reaches 1200 kPa.

At what pressure will the piston touch the second spring? Find the final temperature and the
total work done by ammonia. This is a very interesting problem, so here there are two springs.
(Refer Slide Time: 30:57)
The initial volume is 1 m³, so let us say V₁ is 1 m³, and then at state 2 the volume is 2 m³.

(Refer Slide Time: 31:25)

(Refer Slide Time: 31:41)

State 2 is that situation when the second spring comes in contact with the piston, so after this,
both the springs are in contact with the piston. Because the spring is linear up to 1, between 1
and 2 the pressure versus volume variation will be a straight line. What will be the equation of
the straight line? It is given that when the volume is 0, you have P0 is 100 kPa.
(Refer Slide Time: 32:30)
You have to look into the table of ammonia, not water, so ammonia at -2 ℃ and quality = 0.13
means it is in the saturated state or the two-phase region, so P₁= Psat of ammonia at -2 ℃, which
is 396.775 kPa.

(Refer Slide Time: 33:19)

Ammonia is a very good refrigerant, so it is used as a refrigerant normally. (Refer Slide Time:
33:41)
Now how do you know where will be state? You simply join these two by a straight line and
extrapolate it, because it is a linear spring. Wherever it will cut the V=2 m³ line will be your
state 2, so again you can identify state 2 by noting that (P₂ - P₀)/(P₁-P₀) = (V₂-V₀)/(V₁-V₀).
(Refer Slide Time: 34:23)

From here, P₂ is 694.875 kPa.

(Refer Slide Time: 34:44)
At this stage, the second spring comes in contact with the piston, so that means both the springs
are now in contact, and both springs have same stiffness. Remember the slope of the P-V
diagram represents qualitatively the stiffness. If it was a force versus displacement diagram, F
versus X, then the slope would actually represent stiffness. But pressure is force per unit area,
and volume is the displacement times the cross-sectional area of the cylinder, therefore this
slope does not quantitatively represent stiffness but it qualitatively represents stiffness.

So, if there are two springs now coming together the stiffness will be doubled, and when the
stiffness will be doubled then what will happen is that from 2 onwards, the slope will get
doubled. (Refer Slide Time: 36:10)
The final pressure is 1200 kPa, (Refer Slide Time: 36:40)

so from the equation of the straight line you can get V₃. So state 3 is governed by P3 =1200 kPa,
and V₃ is known.
(Refer Slide Time: 37:10)
That will give you what is T₃, which is 51 ℃.

And what is the work done? 0 to 1 is not the actual state; it is the hypothetical situation given
just to know the equation of the straight line, so the actual physical process is from 1 to 3.
(Refer Slide Time: 38:00)

The work done is the shaded area between states 1 and 3, and this comes out to be 1342.6 kJ.
(Refer Slide Time: 38:08)
Let us work out another problem quickly before we conclude this tutorial session on the first 2
chapters. So the next problem is problem 2.6.
(Refer Slide Time: 38:40)

There is a cylinder with a cross-sectional area of 7.012 cm 2 . This has two pistons, the upper
one having mass of 100 kg is initially resting on the stops, the lower piston is almost mass less,
has 2 kg of water below it with a spring in vacuum. So between the two pistons there is vacuum
so there is no atmosphere. The spring force is 0 when the lower piston stands at the bottom, and
when the lower piston hits the stops the volume is 0.3 m³. The water initially at 500 kPa and
0.00206 m³ is heated to saturated vapour. You have to find out the initial temperature and
pressure that will lift the upper piston, the final temperature, pressure, volume and the work
done by water, so this is again is a very interesting problem.

Let me try to draw a schematic of this.

(Refer Slide Time: 40:24)

So in this situation, first the bottom piston will be lifted, after some time there will be a
situation when both the pistons move together. So, what is that pressure when both the pistons
move together? To understand that, we draw the free body diagram of the system when the both
the pistons are connected. The upper piston is piston 1, and the lower one is piston 2.
(Refer Slide Time: 41:09)
On the top there is atmosphere, so force is P₀*A. Inside, the pressure is, let us say Plift ,
(Refer Slide Time: 41:36)

and you have the weight of the pistons, so the forces are m p1 g and m p 2 g . One of the pistons is
given of negligible mass,
(Refer Slide Time: 41:48)
but I am solving the general problem no matter whatever is the mass given. So under
m  mp2
mechanical equilibrium, all forces are balanced, so Plift  P0  p1 g.
A
(Refer Slide Time: 42:24)

If you plug in all the values Plift will come out to be 1500 kPa.
(Refer Slide Time: 42:38)
So now let us try to draw a P-V diagram to visualize the process. (Refer Slide Time: 43:08)

When the bottom piston is only moving, how will the pressure versus volume diagram look
like? When the bottom piston is only moving the top piston is against the stops, so the force
versus displacement will be based on the linearity of the spring. The spring will be compressed
as this piston is going up and the pressure will increase linearly with the volume.

What will be the equation of the straight line? For that, one important data point is given that
the lower piston has mass 2 kg and with a spring in vacuum to connect the 2 pistons, so if the
volume is 0 the pressure is also 0. Why? When the volume is tending to 0 at that point what is
exerting pressure from the top is this atmosphere which is 0, and then the weight of this piston
which is also 0, therefore if the volume is 0 the pressure is 0. This is a very important data point
for the problem. It is given that for state 1, V₁ is 0.00103 m³/kg, P₁ = 50 kPa.
(Refer Slide Time: 44:52)

State 0 is hypothetical state but from 1 it is the real situation that is coming into the picture as
the process starts. From 1 it goes up to a state which is, let us say 1A where the pressure is
given, so the pressure at state 1A is Plift , which is 1500 kPa.
(Refer Slide Time: 46:20)
After this the PV diagram will be horizontal, because the spring force will not be coming into
the picture as the action reaction force are nullified within the system. So, it is a constant
pressure process after that. The water initially at the state 1 is now heated to saturated vapour.
The question is what is the volume of the stops. The volume at the stops is 0.3/2 = 0.15 m³/kg.
It is given that when the lower piston hit the stops the volume is 0.3 m³, so the specific volume
is 0.15 by this.

Now this, if you look into the table, is greater than V g at 1500 kPa, this means that before
hitting the stops this reaches the saturated vapour,
(Refer Slide Time: 47:55)

and then the process ends, because it is given that the water is heated to saturated vapour, so the
P-V diagram for this particular case is as shown.

Now if V stop is less than V g at 1500 kPa, then you would have stopped somewhere in between
and then the process would have been a vertical line till the saturated vapour is reached. That is
why I tell that thermodynamics is such a subject where through formula based learning you
cannot follow the subject, what you should do is you should interpret the situation based on the
data. So for this particular data given this is the P-V diagram. The initial temperature is
T₁=81.33 ℃,
(Refer Slide Time: 49:27)
then the P lift is 1500 kPa, the final specific volume is 0.15 m³ /kg, and the work done is the
area under this P-V diagram, which is 348.91 kJ.
(Refer Slide Time: 50:01)

So again I am telling you that for working out these types of problems it is always useful to
visualize the process by drawing the P-V diagram, because the process diagram is not given in
form of equation; you have to visualize it through the physical process and then find out the
work by constructing the area under the P-V diagram.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 06: Zeroth Law of Thermodynamics

Good morning and I welcome you all to this lecture of the course laws of thermodynamics, now
today I will introduce you with the zeroth law of thermodynamics that is the starting point of all
the laws.

(Refer Slide Time: 00:42)

That is zeroth law of thermodynamics. As I told you earlier the zeroth law provides the concept
of temperature, the zeroth law provides the concept of temperature through the concept of
thermal equilibrium, through the concept of thermal equilibrium through the concept of thermal
equilibrium, concept of thermal equilibrium, the concept of temperature. The zeroth law first
tells us what is thermal equilibrium, then through this concept of thermal equilibrium it provides
the concept of temperature. Now at this moment we know everything, the thermal equilibrium
we have already discussed, we have read it that concept of temperature.

Now temperature as we know but the very first definition is that by hotness or coldness of a body
temperature can be defined from various angles, for example in statistical thermodynamics from
viewpoint of kinetic theory of matter the microscopic approach the temperature is the
manifestation of kinetic energy of the molecules due to this random motion, so this way we
define temperature it is the sense of hotness or coldness or this is the manifestation of the kinetic
energy of the molecules from the molecular or microscopic approach.

But in classical physics how do you define temperature usually we tell temperature that it is a
property by virtue of the difference of which between the two systems an energy transfer takes
place that we call as heat or when we define heat energy we tell heat energy is that energy that is
transferred between one system to other system because of the temperature difference or from
one point to another point of a system by virtue of the temperature difference and temperature is
that property which allows the heat to flow or heat to be transferred.

This way we define temperature, thermal equilibrium also you know by this time because you
have already come to know the thermodynamic equilibrium of a system which requires three
criteria the mechanical equilibrium, thermal equilibrium and chemical equilibrium to be there
simultaneously and thermal equilibrium means there will be no change in temperature that means
if two bodies are kept into contact and there is no difference between the temperature between
the two bodies or two systems the temperature will remain unchanged.

If there is a difference in temperature the heat transfer will take place and the temperature will
change so long they come to a common value which will not be changed any further, so this way
we know that temperature is the property that allows the system to come into thermal
equilibrium and because of the difference of which the heat is being transported. This is known
to us but how at the beginning the zeroth law evolved to define the concept of temperature in
classical thermodynamics that I will tell you today through the concept of thermal equilibrium.

Now earlier class one of the classes I told and of course we have come to know by this time that
when we define the state of a system by a number of properties like X 1 X2 X3 like this the
question comes that all the properties cannot be independent cannot be independently varied
there maybe some number of properties which are independent, so that if they are fixed other
properties are automatically fixed by the relationship of thermodynamic properties which is very
important aspect of subject thermodynamics.

So therefore the number of independent properties to fix this state is fixed and you know by this
time this is given by this equation known as Gibbs phase rule that number of independent
intensive properties to fix the state of a system is given by
f=C-R+2
where C is the number of component, R is the number of phases +2 and for a single component
with single phase, for example a mass of gas in a tank or in a closed chamber in a piston
cylinder, this is one component, one single gas one phase.

So two independent intensive properties are required to fix the state and in that case the state of a
system, of course it has to be in equilibrium otherwise system cannot be prescribed it goes on
changing I told earlier then I cannot specify this system for the given values of the intensive
property, so that other properties will be automatically fixed, other intensive property. So
therefore this will be at thermodynamic equilibrium then we can, since in this particular case of
one component 1 phase 2 are the dependent properties.

Let the property be x and y instead of x 1 x2 or you can write x1 x2 does not matter x2 x1 two
independent properties, intensive properties for the special case we can fix or we can show the
state of the system in a two dimensional property plane given by x2 and x1 with the value of some
X2´ – Y2´ - some given value X2 Y2 show this. So therefore with this as the background I now
explain you what is zeroth law rather how the zeroth law, how the zeroth law evolved in which
way today we know everything what is thermal equilibrium, what is temperature all these things
you have learnt.
(Refer Slide Time: 06:57)

But now the concept temperature how did it evolve through the definition of thermal equilibrium
by Zeroth law. Now with this thing we consider a system 1 with single component single phase
so that two intensive properties are required to fix its State and let us consider -properties at x 1
and y1 and another system we consider here system 2 which is specified by x 2 y2, now in this
context I will tell that there are two boundaries defined or two walls are defined how now if we
consider that the two systems interact with each other through a common boundary which is
known as wall like this.

And with nothing else the two system interacts with each other and with nothing else and it
interacts through one common boundary or wall like this, wall then in this context there are two
types of wall, wall are of two types one is adiabatic wall another is known as diathermic wall
today immediately we will tell from our knowledge that adiabatic wall is the wall which does not
allow the heat to for heat to be transferred from one system to us and diathermic wall is the wall
which allows the heat to flow or heat to the transferred from one system to other system.
But if you do not know all these things, but if you do not want to define through that I do not
want to use all these things which you already know. The adiabatic wall, let this wall is adiabatic
and you have it, so adiabatic wall is defined in way so when zeroth law was first postulated by
Fowler then it was postulated like that then adiabatic wall is such an wall that if we make these
two systems in contact through this wall then the system can attain any value of x 1 y1 x2 y2. Any
attainable values of x1 y1 and x2 y2 we may have or we have through these adiabatic wall.

Provided the adiabatic wall is strong enough to withstand the stress develop due to the difference
in the sets of this XY between the two systems. For example if the pressure difference is there
one of the xx properties x1 is p1 pressure of the system one x2 pressure of the system two, now I
am defining terms of general quantities it can be any two properties for example pressure due to
that difference in pressure there will be a force acting on this net force and that will cause a
stress, so therefore provided the wall can withstand any stress develop due to the difference in
these sets of X values x1 y1 sets of that XY values.

Then we can attain any properties of x1 y1 x2 y2 with this wall that is known as adiabatic or an
practical example of the adiabatic wall is wood, asbestos these are insulating material Styrofoam
all these things are asbestos Styrofoam all these things are adiabatic wall so this is the way the
adiabatic wall is defined but if we make this system 1 and 2 x 1 y1 and the system x2 y2 system 2
and x2 y2 another set through another kind of wall which is diathermic wall this is diathermic wall
let this is represented like this is diathermic wall.

So another kind of wall which we call as diathermic wall if the two systems are in contact
through this wall and they interact only through this wall like this adiabatic wall then the system
properties XY will have a spontaneous change will go on changing and the equilibrium state will
come when this will attend let some property X1´ Y1´ and X 2´ and Y2´ and the value of this set
X1’ Y1’ and X’2 Y2’ will depend upon the initial value of x 1 y1 x2 y2 these are not very arbitrary or
some any in for any choice able values we can have.

That means the system at some initial state x 1 Y1 and system 2 at some initial x2 y2 if they come
into contact by a diathermic wall they will go to some X 1´ Y1´ X 2´ Y2´ value and this value this
sets depends upon the initial set of this XY by the 2 system so therefore we can say here that in
this case the system will come to equilibrium through some restricted sets of XY through some
restricted this is very important restricted sets of XY like this we cannot have any attainable
values of xy for the two systems if it is in contact with adiabatic or provided it can withstand the
stress associated with the difference in this sets xy.

But here the system will come to equilibrium with restricted sets of XY that depends upon the
initial state if it is through diathermic wall which is also sufficiently strong enough to withstand
the stress associated with this sets xy and this type of equilibrium through the restricted states of
xy okay the restricted states of xy due to interaction through a diathermic wall is known as
thermal equilibrium thermal equilibrium is known as thermal equilibrium, so this is the concept
of thermal equilibrium without defining the temperature how it evolved through the first step of
zeroth law okay.

Now with this as the background I come to another case, what is this let us consider, now let us
consider now two systems AB.

(Refer Slide Time: 14:32)

Now let us consider this way rather I tell you in a different way let us consider three systems one
is system A, another is system B another is system C, now let us consider system A and system
B, system A and system B are made in contact through diathermic wall, through a this is
diathermic wall sorry not the system B let us system C that will be better to understand system C
A and C and if it is found that with this state X AYA that again XY is the set of the property
independent property fixing the state and with this state X C YC for this system they are in
equilibrium.

Initial states I am not bothered with just I start with equilibrium state that diathermic wall they
interacted with each other and have come to equilibrium when the system is attained the state by
XA YA set and XC YC. Similar way if the system B this is diathermic wall system B and C are
made into contact through diathermic wall and with the values XC YC of this system if system B
attained a thermal equilibrium state that I have defined earlier with its value of XY as X B YB you
understand with the XB YB that system A comes into thermal equilibrium system C X C YC at XA
YA.

And similarly this system B comes into thermal equilibrium with this system C with X C YC when
its value will be XB YB under this situation if the two system A and B with this state of defined
by XA YA for system A and XB YB of system B through a diathermic wall through this is that
through a diathermic wall we will see that state will not change that means the sets X A YA and XB
YB will not change that means it will be thermal equilibrium that as I discussed earlier the first
step of the zeroth law defines the state of thermal equilibrium.

Then we see that how the thermal equilibrium is reached what is thermal equilibrium, to the
concept of diathermic wall that when two systems are made in contact with diathermic wall and
it interact only through this thermal wall interaction between the system and they do not interact
with nothing else then they come to an equilibrium state with the specific some values of the set
XY the two properties then we call it is a thermal equilibrium and that sets are restricted states
not any state they can appear then that set depends upon the final equilibrium set depend upon
the initial sets of XY for the two systems.
That we have already discussed that first step. Then the second step is that if system A and
system C comes into thermal equilibrium through the diathermic wall at this specified state X A
YA and XC YC and similarly the system B comes to that specified state X C YC of the system C at
thermal equilibrium that means obviously through diathermic contact through diathermic wall at
system A with the state XB YB then the two systems are kept into contact through a diathermic
wall.

Or they allowed they are allowed to interact with each other through the diathermic wall then
they will not interact that they will remain at the equilibrium that means there will be no change
in this sets and this is actually the zeroth law and this was postulated by the man R.H. Fowler, in
this fashion that I will not write in on the board but I will tell you slowly.

That this was postulated this phenomena was postulated like this if the two bodies are in thermal
equilibrium with a third body they are in thermal equilibrium with each other. If the two bodies
or two systems are in thermal equilibrium with a third body or third system then they are in
thermal equilibrium with each other and this precise this is precisely the statement of zeroth law
this is very obvious today.

So nobody will feel anything great to know these things but the most important thing is that how
did this evolve today we know what is thermal equilibrium we know what is the concept of
temperature either by classical physics or classical thermodynamics or by microscopic or
statistical thermodynamics or statistical physics. But how in classical thermodynamics or
classical physics the concept of temperature initially originated by the zeroth law is a very
important today for us to know.

When you run the subject thermodynamics you know, how the thermal equilibrium concepts
came to the zeroth law and how the definition of temperature came here through this law as
stated by Fowler that two are in thermal equilibrium two systems in thermal equilibrium system
A and B with a third system third system is C then they will be in thermal equilibrium with each
other at that given state.
The property which enables us which enables us which enables the system enables us to make
this is known as temperature that means the property which enables the two systems to come into
equilibrium that is the temperature that means one property definitely which allows this
spontaneous change when they come into contact through diathermic wall for system A and
system B.

It is probably the same so that when they are kept into contact with each other through
diathermic wall or nothing is happening that means there is some property common to them
some property common to them is same, so that when they come into thermal equilibrium with
the system C and that property in system C is also the same that means there is some property
which for system ABC are same for which this phenomena the entire phenomenon can occur.

At which the two systems are in thermal equilibrium with a third one are in thermal equilibrium
with each other. Okay, so this is the concept of thermal equilibrium and concept of temperature
this property is the temperature and this type of equilibrium as I have told earlier in the first step
of zeroth law is the thermal equilibrium. So this is the concept of thermal equilibrium and at the
same time this gives the concepts of temperature measuring instrument, a thermometer.

That means C with which the system A and B rather is calibrated what is thermal equilibrium is
gives the concept of temperature measuring instrument thermometer, that means system A and
system B has the same property so that they are in thermal equilibrium with each other that is
temperature which is same for system C that means system C gives the concept of measuring
instrument of temperature.

For example thermometer, so therefore zeroth law gives basically the concept of temperature
through the concept of thermal equilibrium and finally provides us also the concept of
temperature measuring instrument the third body C is actually the temperature measuring
instrument or thermometer so this way the definition of zeroth law originates and which is very
important in thermodynamics to know it way how the zeroth law is defined, okay.
I think today I will not discuss anything else so we will start the first law of thermodynamics in
the next class okay, thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 07: First Law of Thermodynamics

for Closed Systems (Part I)

Today’s agenda will be to discuss about the first law of thermodynamics for a control mass
system.

(Refer Slide Time: 00:31)

So the first law of thermodynamics has its classical inception long back when people where
arguing about the inter convertibility of heat and work. See this is a classical philosophical way
of looking into thermodynamics so the one quest in thermodynamics has always been that how to
convert heat to work that means convert thermal energy into a form of energy that could be
utilized to do work.

So to do that people came across various process and people were conceptualizing various
processes. So one such type of process is a cyclic process, so the first law for a cyclic process
was the first version of the first law that was classically introduced but we will see later on that
the first law although introduced through the concepts of heat and work is conceptually nothing
but a description or depiction of conservation of energy in it is generalized from.

So here in the conservation of for the conservation of energy we are considering heat and work
as two interaction mechanisms between the system and the surrounding but eventually it is not
just heat and work but other forms of energy transfer also that we are taking into account while
discussing about the first law in general, whereas for the classical statement we will be
concerning mainly with energy transfer associated with heat and work.

So for a cyclic process the first law states that,

∮ δQ ∝ ∮ δW

that means in the in a cyclic process whatever is the work done whatever is the heat transfer that
is proportional to the work done, so if we think of something which is very simple instead of
discussing the classical Joule's experiment which you have done which we have gone through in
the even in the high school level.

Let us think of a simple experiment without any instrument, so you just rub your palms. So if
you rub your palms you will see that what you are doing is your doing some work and if the
other way around this work is being converted into something which we will learn latter on as
the intermolecular form of energy and that eventually we will heat up the your palms.

So there is a relationship between heat and work that we understand and in a cyclic process
whatever is the work done and whatever is the heat transfer they are proportionate to each other
or in other words it is called as the cyclic integral of heat is proportional to the cyclic integral of

work, if you reduce this proportionality to a equality then you can write J ∮ δQ=∮ δW
this J is called as mechanical equivalent heat which was introduced in those days.

Because the heat and the work units where different just to patch up the difference in units
between of heat and work, so for example the heat unit was classically calorie and the work unit
was Joule. On the other hand in the SI system you have the heat and work units both are same
units that is both are Joule and therefore these mechanically equivalent of heat in that case is one.

So this J is nothing but a unit converter from one unit to the other but if the both the heat and
work are experienced in the same unit then it is

∮ δQ=∮ δW → SI
The next we will discuss first law of any process for a control mass system or close system so in
some books it will be written as control mass system in some little bit older books it is written as
closed system but they essentially mean the same that is the system, boundary across which there
is no mass flow. So now let us try to plot a process diagram I am not committing whether it is PV
TV whatever some process diagram where we have one cycle made of two processes. What is
the cyclic process or cyclic process is such that

You start with an initial state after going through a sequence of thermodynamic process you
come back to the same state then you say that, a thermodynamics cycle is completed. So for the
cycle one the individual process are A and B, let us consider another cycle where we have covers
the path 1 to 2 by A but the return from 2 to 1 you have by path C. Therefore we can say that for
cycle one if we apply the first law

∮ δQ=∮ δW
that means
2A 1B 2A 1B

∫ δQ+¿ ∫ δQ=∫ δW +∫ δW ¿
1A 2B 1A 2B

Similarly for cycle two

2A 1C 2A 1

∫ δQ +¿ ∫ δQ=∫ δW + ∫ δW ¿
1A 2C 1A 2C

Okay, so now what we can see from here is something as follows if you subtract these two one
from the other you will see that we subtract
1B 1C

∫ ( δQ−δW ) =∫ (δQ−δW )
2B 2C

Okay so what we can see here is something very interesting δQ is a path dependent function the
δW is also a path dependent but δQ – δW integral of that that is not path depended because if
you are fixing up the states one and two the difference between δQ and δW the integral of that
does not change from path B to C.

And these are any arbitrary paths that mean we can say that integral of δQ – δW is a path
independent function that means it is a point function so we can say that 𝛿Q – 𝛿W
(Refer Slide Time: 12:25)

This is a path independent differential or exact differential. So we can write

𝛿Q – 𝛿W = d( )
of something, d of a thermodynamic property, why? Because if you have two differentials or if
you have a differential such that the differential is operating on an operator where the change in
that particular parameter.

That does not depend on the path so 𝛿Q – 𝛿W its difference when integrated whether it is
through path B or path B it is just dependent on the end states 1 and 2 we can write that as
𝛿Q – 𝛿W = d(E)
the exact differential of a thermodynamic property that is the definition of a thermodynamic
property that the change in property a property is such a parameter where its change does not
depend on the path but it only depends on the end states.
So this E is called as the energy of the system this is a thermodynamic property, so we can write
δQ=dE+ δW

This is the first law for a closed system. Undergoing any process it need not be cyclic process so
certain things that we have to understand very carefully, so first of all what is the physical
interpretation of this let us say you transfer 10 kilo joule of heat towards this step so let us say
this is a system.

You transfer 10 kilo joule of heat and the system utilizes four kilo joule of heat to do some work
so it uses it takes up out of these 4 kilo joule of heat to do work, then the balance will increase
the energy of the system by an amount 10-4 = 6 kilo joules, so if you transfer some heat to a
system if a part of that is utilize to do work, the remaining part of the heat will be utilized to
increase the energy of the system. So this is grossly a statement of energy balance which follows
from intuition. The next question is, that when we say energy what kind of energy we are talking
about?

(Refer Slide Time: 16:23)

So when we say energy we say

 E= K.E. +P.E. +I.E.
we normally discuss about kinetic energy + potential energy these are mechanical forms of
energy +thermal energy which we call as internal energy, so if you say what is the definition of
internal energy in terms of classical or macroscopic thermodynamics it is a bit I should say tricky
or it is a bit on a very conservative side it is trying to address the situation without referring to
what are the physical implications of these.

What it is saying, it is saying that any form of energy rather than kinetic or potential energy is
internal energy, this is the classical way of looking into it but eventually the internal energy from
microscopic view pint will be dependent on the atomic structure chemical bonding and all these
things and it will include the vibrational, translational and rotational degrees of freedom of the
atomic or molecular entities.

But the gross manifestation of the mechanical energy will be the kinetic energy and the potential
energy so from a macroscopic view point again the internal energy will not get into the details of
the definition but what we can say is that it is just the form of energy which is other than kinetic
energy and potential energy, so it will include virtually everything other than kinetic and
potential energy many other things that we have possibly not listed when I was talking about the
atomic and inter atomic interactions. So kinetic energy typically is 1/2mv 2 potential energy is
mgz and internal we symbolize as U.
E=1/2mv2+mgz+U
So
δQ=d(1/2mv2)+d(mgz)+dU+δW
so this is essentially dE, now there are many thermodynamic processes for which the kinetic and
potential energy changes are negligible has compared to the changes in thermal energy. So we
can say that.

(Refer Slide Time: 19:26)

For many thermodynamic processes changes in kinetic energy and potential energy are
negligible as compared to changes in internal energy, so for such a scenario we can write
δQ=dU+δW
so this is the form of the first law which you are familiar with from your school level, only one
important differences is that in the school level possibly you would have written dQ and dW but
we have to understand that because these are dependent on thermodynamic path and not point
functions, it is customary to write these as δQ and δW instead of dQ and dW.

And when you write these

δQ=dU+δW
the assumption is that kinetic energy and potential changes are negligible this is not something
which is very obvious because some people would do not go through the derivations will
normally take this as the exact form of the first law no, ideally there should also come an
additional term which will include the changes in kinetic energy and potential energy. Again by
these we are emphasizing that we are not talking about any process where kinetic energy and
potential energy themselves are negligible; we are considering that their changes are negligible.

These energies may be important but their changes are not that important as compared to the
changes in the thermal form of energy that is what we are talking about here. So through this we
have introduced to a new property which is called as internal energy. This internal energy data is
given in the table as other properties like specific volume you will have specific internal energy,

So specific internal energy

u = U/m
Okay, so this is expressed in the unit of J/kg and for a two phase mixture, so the rule of mixture
is same as that of the rule of mixtures for the specific volume.
u = (1-x)uf + xug
Now we have learnt the first law we will then try to use the first law for an example which is the
constant pressure quasi equilibrium process.

(Refer Slide Time: 23:35)

Quasi equilibrium process undergone by a closed system of a closed system of a constant

pressure quasi equilibrium process of a closed system, let us say that you have the piston
cylinder arrangement and then heat is transferred slowly to the system so that this system
expands during the process it is expand slowly the pressure will remain the same why? See the
internal pressure for equilibrium will be same as that of the resistance pressure.
So what is the resistance pressure? The resistance pressure is the atmospheric pressure plus mass
of the piston in to g divided by a, so if this weight of the piston does not change and the
atmosphere equation does not change there is no reason to believe that the internal pressure will
also not change okay. So what we can conclude from here is that this is the model case where
under constant pressure the system volume will expand due to heating.

So we can write here

δQ=dU+δW
assuming negligible changes in kinetic energy and potential energy this form of the first law
again very important assumption neglecting changes in kinetic energy and potential energy.
Because it is a quasi equilibrium process we can write this as pdv, so this we can write
δQ=dU+ pdV
then we can also add vdp why? Because these as good as adding 0 because it is a constant
pressure process. So dp is 0 therefore vdp is as good as adding 0, so this is
δQ=dU+ pdV+Vdp
δQ=dU+ d(pV).

So we can write this as

δQ=d (U+ pV)
so we have got a new combination of properties where if u which is a property p is property and
v is a property this combination of property is also a property and this is called enthalpy. So h or
enthalpy by definition is
H=U + pV
so we have introduced this through this example of a constant pressure process but the enthalpy
is defined for any state no matter whether the state is arrived through a constant pressure process
or not it is just defined as a combination of properties.

So you can write the corresponding specific properties small

h = u + pv
so in the thermodynamic tables you will find that sometimes h is tabulated sometimes it is not
tabulated but you can calculate it by u + pv. So either way if it is not tabulated you can calculate
using this sometimes for helping your calculation this is already tabulated, and for a two phase
mixture again this is the rule of mixture that is given.
h = (1-x)hf + xhg

Next we will try to learn the concept of specific heat of matter and these definitions we will try
to learn in the light of the understanding of the first law that we have just discussed so far.

(Refer Slide Time: 29:52)

When we say concept of specific heat, heat there is a definition which is C p which is specific heat
at constant pressure so what is this so specific means per unit mass the rate of heat transfer
required for each degree for change in temperature so what we can say from here is that specific
heat will mean that heat transfer required to change the temperature of unit mass by one degree.
1 ∂Q
C p= ( )
m ∂T p

The heat transfer will depend on the process so specific heat at constant pressure means this
process is being executed at constant pressure and we have seen already that for a constant
pressure process if we have designing a constant pressure quasi equilibrium process this is
nothing but
 1 ∂Q 1 ∂H ∂h
C p= ( ) ( ) ( )
= =
m ∂T p m ∂T p ∂T p

Similarly Cv is specific heat at constant volume so at constant volume see

1 ∂Q
C v= ( )
m ∂T v

∂Q is equal to dU plus ∂W which is pdv for quasi equilibrium process of a simple compressible
substance so for constant volume process the work done is 0 so ∂Q is equal to dU
1 ∂Q 1 ∂U ∂u
C v= ( ) ( ) ( )
= =
m ∂T v m ∂ T v ∂T v

special cases number one is solid or incompressible fluid so if we have a solid have a
incompressible fluid there is no distinction between Cp and Cv why see for a incompressible fluid
δQ=dU+ pdV
this pdV is 0 or even you can add for a in compressible fluid the specific volume is small so for a
reasonable dp this Vdp is also 0.
δQ=dU+ pdV+ Vdp= dU= dH
Therefore for an incompressible fluid or a solid you can write du and dh to be same only for
incompressible fluid or solid because all this like dv= 0 or vdp is small all this we can conclude
only for incompressible fluid or solid so for therefore in this case C p and Cv are identical so we
can say Cp is equal to Cv equal to C which is also known as specific heat capacity
Next for an ideal gas u and h are functions of T only, so this is very important.
Normally for substances this u and h will be a function of two independent properties but for an
ideal gas it can be shown that the internal energy and enthalpy are functions of temperature only
and nothing else. Therefore we can write
dh
C p=
dT
because h is the function of T only, not a question of keeping pressure constant, volume constant
this does not matter because h is the function of T only.

So and then
 du
C v=
dT
so Cp we can now write in this way
d ( h−u ) d( pv)
C p−C v = =
dT dT
and for an ideal gas pv = RT,
d ( RT )
C p−C v =
dT
So the formula
C p−C v =R
this you can apply for ideal gases. So for an ideal gas the change in the enthalpy or change in the
internal energy, so for example if you are writing
2 2

∫ du=∫ C v dT
1 1

So the change in the internal energy, you can write by using this formula. Now a very important
situation is the situation is when Cp and Cv are constant, for those ideal gases where C p and Cv
constant these are called calorically perfect gas.

So there is a different between perfect gas and ideal gas. Ideal gas it obeys the ideal gas equation
of state but the perfect gas is something where the C p and Cv are not functions of temperature but
are constant these are called as calorically perfect gas.
2 2

∫ du=∫ C v dT =C v (T 2−T 1 )
1 1

So these you can take out of the integral if it is calorically perfect gas, if it is not calorically
perfect gas you cannot take it out of the integral, so you can take it out of the integral it is simply
Cv x T2 – T1 where the Cv is some constant Cv, similarly for Cp.

So what are the factors on which Cp and Cv depends, these depend on whether it is mono atomic
or diatomic or poly atomic gas. For mono atomic gas you have, because of the restricted degree
of freedom you will have the dependence of C p Cv with the temperature not very important. For
diatomic gas like hydrogen, oxygen all these for di atomic gas you will find that the depends C p
Cv with temperature is more that C p Cv will more strongly depend on temperature. However for
poly atomic gas where the number of atoms in the molecule is even more you will find that the
Cp Cv variation with temperature is even more because of the added degrees of freedom.

Therefore we can say that we can say that there are many situations where either because of large
number of the degrees of freedom or because of large temperature range over which Cp and Cv
may vary appreciably it may not be possible to treat C p Cv as constant, in that situation we will
have to use this Cp Cv as a function of temperature and integrate these two
2 2

∫ du=∫ C v dT
1 1

2 2

∫ dh=∫ C p dT
1 1

to get the changes in properties like internal energy and enthalpy. To summarize we have
discussed about the first law of system, undergoing a cyclic, undergoing any process.

We have introduced the concepts of internal energy and enthalpy and we have discussed about
the specific heats the concept of specific heat at constant pressure at constant volume and we
have discussed about the special case of ideal gas. Thank you very much, in the next session we
will be discussing or working out some example problems, illustrating the use first law
thermodynamics for a close system.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 08: First Law of Thermodynamics

For Closed Systems (Part II),
Some examples

In today’s section we will work some problems related to the use of first law thermodynamic for
a closed system, so these problems will be based on the tutorial problems that we have already
given to you and we will I will project this problems one after another in the screen.

(Refer Slide Time: 00:43)

And we will try to go through the solutions up to certain details that is possible within the time
limit.
(Refer Slide Time: 00:57)

So let us look into the first problem 3.1 a piston cylinder arrangement contains 1 kg of water as
shown in the figure below okay so you can see this figure that this kind of situation we have
discussed earlier and this is again a linear spring and operation of 300 kPa will just float the
piston and at a volume of 1.5m3 operation of 500 kPa will balance the piston, the initial state of
water is 100 KPa with volume of 0.5m 3 heat is now added until a pressure of 400 kPa is reached,
find the initial temperature and the final volume work done on heat transfer in the process and
plot the PV diagram.
(Refer Slide Time: 02:12)

So let us try to solve this problem, I am trying to draw this here in the board so this is the system
with m = 1 kg, so let us try to see what is state one P 1 is 100kPa and V1 is 0.5 m3 so you know
what is the specific volume this volume per unit mass so v 1 is specific volume at state one is
0.5m3 per kg so the pressure and specific volume combination fixed up the state one now what
happens is that heat is added until the pressure of 400kPa is reached.

So the pressure at which piston gets lifted its 300kPa so if you transfer the heat until and unless
the pressure goes up 100 to 300kPa this piston will not leave so if you try to draw this in PV
diagram from state one you go to state lift this is 300kPa and then from this state because of
linearity of the spring it will be like this but what is the slope of these line how will know so for
that there is additional data point which is given that a pressure of 500 at a volume of 1.5 m 3  a
pressure of 500 kPa will balance the piston that means 500 kPa and 1.5m3.

This combination 500kPa and 1.5m3 this particular combination will lie on the process diagram
that starts with this lift but that is not the end state what is the end state the end state is 400 kPa
so somewhere here, this is state 2 and of course you can find out what is the V 2 by considering
the equation of the straight line so at state 1 you have V1 is 0.5m3 so you can write
(500 – 300) / (400 – 300) = (1.5 – 0.5) / (V2 – 0.5)
so this will tell you what is V 2 this is the equation of this straight line essentially, so the entire
process is governed by this diagram up to 2 between 2 to these is hypothetical just to help you to
construct the process diagram so if you calculate in this way.

You will get the final volume as 1m3 so state 2 P2 = 400 kPa and V2 is 1m3 so state 1 v1 is 0.5m3/
kg state 2 similarly v2 is 1m3 / kg so identity given that you know we P1 and specific volume see
again I want to emphasis on one very important thing as per state postulate to identify the state
we you required two independent intensive properties for a simple compressible pure substance,
so to identify the state is not the total volume that is sufficient in addition to pressure in addition
to pressure.

You must know the specific volume in addition to pressure, so the specific volume is the total
volume per unit mass so these two are the properties not this that will be required to identify the
state so if you look it to the table of water so with this combination you will get what is T 1, T1 is
99.60C from table and also you will get what is u 1 this is also from table so you can so why you
require u1 for calculating the work done you would not required u1 or u2 but for calculating the
heat transfer you require that.

Why you required that for calculating the heat transfer the reason is that for calculating the heat
transfer we have to relate the heat transfer with the work through the first law of thermodynamics
and for that you require the change of internal energy neglecting the changes in kinetic energy
and potential energy that is why we required these. So similarly for state 2 you will get u 2 from
table so what is the work done. This is the shaded area this is 175 kJ okay and now if we apply
the first law for the system.

So the heat transfer is nothing but the change in internal energy this is
Q12 = m(u2 – u1) + W12
so if you substitute the values of the internal energy and the mass and the work done this will be
2435 kJ that is the answer to this problem so we have worked out the problem 3.1 next we will
go to the problem 3.2.
(Refer Slide Time: 12:14)

In the problem 3.2 you consider the system as shown in the figure below, the tank has a volume
of 100 liters and contains saturated vapor R-134a at 30 0 centigrade this R-134a see R is for
refrigerant so R-134a is a typical refrigerant which is used for refrigeration or air conditioning
purposes, so when the valve is crack open so you see there is a valve which connects the tank
with a cylinder when the valve is cracked open R-134a flows slowly into the cylinder B.

The piston must requires a pressure of 300 kilopascal in the cylinder B to raise the piston the
process ends when the pressure in the tank A has fallen to 300 kilopascal, during the process heat
is exchanged with the surroundings such that R-134 a always remains at 30 0 centigrade, calculate
the heat transfer for the process. So let me try to draw a schematic of the problem.
(Refer Slide Time: 14:11)

This is the direction of gravity given in the diagram and this is the valve. So state 1 first of all
before considering state 1 we have to identify a control mass system, so let me ask you
something, what is the control mass system here, the fluid in the tank A the fluid in the tank B
sorry cylinder B or the fluid in the tank A + the fluid in the cylinder B so I give you three
options, what is the appropriate control mass system to be chosen for solving this problem.

The fluid in the tank A option 1, the fluid in the cylinder B that is here option 2 and the fluid in
the tank A + within the cylinder B that is option three, so to answer this question let us try to
analyze this, by definition a control mass systems should be something which for which the mass
will be identified and that will not change with time, so if you consider the tank A when the
valve is open the mass within the tank A is decreasing.

Because the fluid is coming out from tank A through this valve and it is pressurizing and filling
up the cylinder B, so mass within A is varying, mass within B is varying but if you consider A +
B the total mass within this tank + cylinder with along with this pipeline that remains the same
therefore your control mass system, fluid in tank A+ cylinder B + pipeline. So for this the state 1
is given so for this system, what is the state 1? T 1 = 300 centigrade the fluid is R-134a and it is at
saturated vapor that means quality x1 =1, what is v1 at state 1 everything is there in the tank A so
volume of the tank A is divided by the mass, the mass is given so you have tank A has a volume
of 100 liters.

(Refer Slide Time: 19:05)

So if you look into the problem statement the tank A has a volume of 100 liters and contains
saturated vapor at R-134a at 30°C, so how do you know the mass, so you know the volume of
the tank A which is 100 liters.
(Refer Slide Time: 19:18)

And v1 is vg1 vg at T1 so this will give you what is m, state 2 it is given that during this process
heat is exchanged with the surroundings and the final pressure is the pressure in the tank A is 300
kPa because the system is in mechanical equilibrium the pressure B is also 300kPa so the final
pressure is 300kPa and temperature during this entire process remains at 30°C so this will tell
you what is specific volume at state 2.

So what is the work done, how do you calculate ∫pdv here, so this is nothing but ∫p res dV and pres
is 300 kPa it is a constant. So this is
W12 = ∫pdV = ∫presdV = (300kPa) (V2-V1) = (300kPa)m(v2-v1)
v2 how will you get from the table, so this is the work done but the question asked is not what is
the work done but what is the heat transfer, so for that you have to use the first law. So you
require u2 and u1 also so u1 is nothing but ug at T1 this is from table.
And u2 v2 and u2 both you get from the table, so this data you can substitute from the table m you
already know and work done you already calculated so this will give you what is Q 12, so the Q12
is 84.61kJ that is the answer to this problem, okay. Next we will consider the problem 3.3.

(Refer Slide Time: 23:29)

Which is projected in a screen you can see here, so problem 3.3 the statement is like this water
filled reactor with a volume of 1m3 is at 20 MPa and 360°C, so this small rectangular box with
the blue color inside this is the water filled reactor and the hemispherical dome is a room the
room is well insulated and initially evacuated due to a failure the reactor ruptures and the water
fills up the containment room, find the final question okay so let us work out this problem let me
draw the schematic of this.
(Refer Slide Time: 24:43)

So this system must be the water state one we have p 1= 20 MPa, T1 =3600 C, the volume of the
reactor is 1m3 so from the p1 and T1 you can use the table to get table means property table of
water that in short we are writing as table to get V 1. So V reactor is 1m3 so what is the mass of
the system
m= Vreactor / v1
say initially this is evacuated so whatever is the mass which is their inside that mass is the that
mass eventually does not change with time so this is the mass that you get.

Now you apply the first law for the system,

Q12 = m(u2 – u1) + W12
so how do you know what is the work done here so logically you will think that there is some
work done because when this one ruptures there is a change in volume of the water which
occupying this small space now it will occupy the big room but there is actually no work done,
why? Because this was initially evacuated and therefore this is water is expanding freely, free
expansion or unrestraint expansion will not involve any work as I told you in the chapter relating
to heat and work that there is no work done when there is free expansion because there is no
resistance.

So in this case the work done is 0, W 12 =0, this is very important concept what is the heat
transfer? The heat transfer is also 0, Q 12 =0, because it is insulated, insulated means there is no
heat transfer so that means you have u2 = u1 so how do you get the value of u2 you table to get v1
and also u1 and because u2 = u1 you know what is this. So state 2 how to identify state 2 you
require two independent intensive properties one is u 2 what is another property see another
property is you know what is the specific volume at state two what is this?

This is the final volume is the volume of the room and the mass you already know. So the
volume of the room is given the volume of the room is 100m 3, so you know what is v2, so u2 v2
combination will give you state two. This is very interesting, it is not always pressure volume
pressure temperature, temperature volume these combinations give a state, sometimes the other
property combination also if they are independent intensive like here internal energy and specific
volume that combination also give state two.

So by using these two from the table you should be able to identify the state two these days there
are interesting software so that by without looking in to the physical or the hard copy table you
can use you can enter these two data and using the software that is the digitized property table
you can get the corresponding other properties for state 2, but I always suggest that as a beginner
you should look in to the physical table.

So that you get a physical feel of where the property data lies, what is the corresponding state is
it saturated is it super heated and so on that kind of physical insight you will not get if you use
just a digitized table where you entered this property and get the other properties as an output.
(Refer Slide Time: 31:10)

So you can get what is the state two and the state two corresponds to the p 2 of 568.5 kilopascal.
okay this is the answer to this problem we will work out another problem before closing this
session that is problem number 3.4 so let me project the problem 3.4 in a screen you see this is
again the piston cylinder arrangement consider the piston cylinder arrangement shown in the
figure in which our friction less piston is free to move between two sets of stops when the piston
rests on the lower stop the volume is 400 liters when the piston is there in the upper stop the
volume is 600 litres.
The cylinder initially contains water at 100kPa with 20% quality it is heated until the water
comes saturated vapor and the mass of the piston is such that it requires at 300kPa to move again
the outside pressure determine the final pressure and the heat transfer and the work done so let us
try to draw the schematic of this problem.

(Refer Slide Time: 32:17)

So clearly the system is water control mass system let us try to draw a PV diagram of this process
state 1 is P1 is 100Kpa and quality x1 is 20% so this identifies state one the state final is the stops
so state one is two phase region let me draw it like this so just for a change let us try to draw TV
diagram so now the first step is from one to two during the process the heat is added so it will go
up like this.

At what pressure it will go up it will go up to the temperature corresponding to which the

saturation pressure is the Plift, Plift is 300 kPa so this is P 2, from at this state you will find the
corresponding volume is between Vf and Vg therefore it is in a two phase region then it will be
heated and until and unless the phase change process is complete a constant pressure heating will
ensure that it is a constant temperature heating also.

The question is what final state is, the final state is a it is the water eventually exists as saturated
vapor so will continue up to this we have to see what is the volume of the stops if the volume of
the stops is greater than this then it will continue up to this, but if the volume of stops is less than
this, so what is the specific volume at this stops, specific volume at the stops is what? That is
vupper stops = 600 litre /m,
so how do you what is the mass? So initial volume is you know the initial state when the piston
on the lower stops the enclosed volume is 400 litre. So you know the specific volume at state 1
you know the total volume, so you know the mass.

So you divide this by the mass you will get the specific volume at the upper stops and you will
see that this specific volume at the upper stop is such that this is less than vg at 300 kPa therefore
the stops will be encountered somewhere, let us say this is state three and then so this is v upper stop
and this is vlower stop. Then from 3 if it wants to go to the saturated vapor only way at state 3
physically what has happened.

This piston has reached here, so once this piston has reached here only way when the heat is
transferred it is temperature will increase but will increase at constant volume. So from 3 to 4 it
will be a constant volume process. So state 4, state 2 is v 2= v1 and p2 = 300 kPa, state 3 v3 =
vupper stop and p3 is 300 kPa and what is state 4, v4 = v3 and x4 = 1, this is the saturated, so how do
you find what is the pressure at state 4?

Pressure at state 4 is the pressure corresponding to which v g is this one v4, so p4 is the saturation
pressure or p4 is the pressure let us write in the another way at which v g = v4. So the process
diagram is something like this and what is the work done? So the work done is only between 2 to
3, other process 1 to 2 and 3 to 4 are constant volume process. So this is
W14 = ∫pdV = p2(V3 – V2) = p2 m (v3 – v2)
this is the work done and
 W14 = W 12 + W23 + W34
so W 12 =0, W34=0, its only W23.

So now the first law if you apply,

Q14 = m (u4 – u1) + W14
so u4 is ug at p4, u1 you already know from state 1, from table and W14 is calculated here. So if you
substitute all these you will get the expression the value for the heat transfer which is 2080 kJ, if
you want to check the answer for the work done as an intermediate calculation this is 60 kJ okay.
So interestingly although we have plotted the T-v diagram the P-v diagram will also look
essentially similar.

For this case and you can visualize the work done if you replace the T with p in this kind of
scenario, so to summarize we have worked out few problems typically 4 problems in this
particular session we will continue with discussions on some questions and problems related to
first law of thermodynamics for a closed system in the next session when we meet for the
tutorial, thank you very much.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 09: Tutorial 2: First law of

Thermodynamics for
Closed Systems

In the previous session we discussed about some problems related to the first of
thermodynamics for closed system and today we will continue with that. So we worked out
problems now problem numbers 3.1 to 3.4 and today we will continue with more problems.

(Refer Slide Time: 00:45)

So the first problem that we are going to address today is a projected in a screen you can see that
there is a copper block of volume 1 liter that is heat treated at 500 0 C and now cooled in a 100
liter oil bath initially at 200 C, assuming no heat transfer with the surroundings what is the final
temperature? Given the density of water and the density of oil. So this particular problem refers
to metallurgical process which we call as quenching, so I just want to give you a little bit if
perspective or background to this because that will create more interest on you on this particular
application.

So quenching means that basically you are heat treating a particular material typically metal and
then you are putting it in a fluid bath to freeze or to cool it down, so when you cool it down what
you see is that there is a change in microstructure because of the temperature gradients created
and that will eventually dictate what will be the properties of the material, therefore it is very
important to study the thermal characteristics of this kind of a system, so let us try to work out
this problem in the board.

(Refer Slide Time: 02: 43)

So we will draw a schematic, of this problem first, so there is a oil bath in which you have
copper so this copper block has a volume of 1 liter is heat treated at 500 0 C so T1, copper is 5000 C,
and the oil bath is initially at 200 C, the volume of the oil bath is given it is 100 liter, assume that
this is sufficiently insulated so that there is no heat transfer with the surroundings, what is the
final temperature?

So to solve this problem we have to first describe a system, so here can you tell what is the
convenient way of choosing the system, is it copper, is it oil or copper + oil, see technically there
is no harm if you choose just copper as a system, there is technically no harm if choose just oil as
a system, but if you choose copper + oil as a system then you know it is easier for you to analyse
the problem because why, the reason is that there is heat transfer between copper and oil, the
copper is hot and it is transferring heat to the oil.

So if you are considering copper and oil separately you have to consider the heat transfer but if
you consider copper + oil together then as a total system there is no net heat transfer because it is
insulated from the surroundings therefore let us identify the system as copper + oil so with this
copper + oil as a system let us apply the first law.
Q12 = U2-U1 + W12
This copper + oil as a system is insulated so there is no heat transfer the work done there is no
work done with this system so that means U 2 – U1= 0, so copper and oil these are typically
incompressible phases so that you can write du = C x dt this we discussed in the one of our
lectures related to the first law of thermodynamics, where this C is the specific heat capacity so
basically so this is du so dU is mCdT, so you can write these as
0 = mcopper Ccopper (T2 – T1)copper + moil Coil (T2 – T1)oil okay.

So you will get the mass of copper and mass of oil as the density of copper into volume of
copper and mass of oil as density of oil into volume of oil and these are given in the problem
statement. Given the density of water as 8900 this is 8900 kg/m3 and density of oil as 910 kg/m3,
so the let us see what are given the specific heats are also known so you have to look into the
table of specific heats to get the specific heat data, I mean unfortunately I do not have the data
right now which means so I cannot share the data with you.

But you have to look into the specific heat data to I mean there are tables of specific heat or
property data for copper and different types of oils and if you calculate this you will get the final
temperature, so depending on what oil you take you will get you have to use the corresponding
specific heat and that will give you a corresponding temperature so I am not giving you any
specific answer to this although in the tutorial sheet, we will be providing you with the specific
answer and based on a specific.

A particular value of the specific heat but because today I am not using any particular data for
the specific heat of oil and specific heat of copper, so I am just keeping it in this generic form so
that depending on the values that we substitute you will get the final value of T 2, now I want to
discuss something on this problem. See this kind of problem is a very simple problem which you
might have addressed in the high school level and for that there is something that you use which
is known as the principle of calorimetry.

And the principle of calorimetry is like the loose statement heat gained equal to heat lost so there
is something this copper is heated so it is losing some heat to the oil and oil is gaining some heat,
so here this statement like this expression is as good as heat loss by copper is equal to heat gain
by oil. So you can see that the intuitive statement of heat gained equal to heat lost can be
recovered from the first law of thermodynamics provided there is no net external heat transfer
and work done between the resultant system and its surroundings.

So if there is if this Q12 is not equal to 0 and W 12 is not = 0 or either of these two is not equal to 0
then you cannot use this calorimetric principle here, so there are some assumptions that go
behind the calorimetric principles that we have learned in the high school level okay.
(Refer Slide Time: 11:58)

So we will consider the next problem which is problem number 3.6 the problem number 3.6 is a
computer in a close room of volume 150 m3 dissipates energy at the rate of 10 kilowatt so that is
a closed room in which a computer dissipates energy, the air in the room was initially at 300
Kelvin 100 kPa when the air conditioner suddenly stops, what is the air temperature after 15
minutes? So this is a very classical situation there is AC room in which computer is working.

And suddenly because of some reason because of some problem in power supply or whatever,
the AC suddenly stops but the UPS is running so the computer is still working, so the computer
when it is running it is dissipating heat because of the power generation and that will heat the air
in the room, so we have to figure out that what is the final temperature after 15 minutes, what is
the final temperature? So let us write the problem data here in the board.
(Refer Slide Time: 13:36)

So for working out this problem let us try to, so the system is air. See we have to be careful what
is the system here, the system is not computer, computer is dissipating heat so there is some heat
transfer from the computer to the air but the system where we are considering the change of
temperature is the air in within the room and not the computer, so system is air within the room,
then what we will do is, we will try to apply the first law.

Now in this kind of a situation let us try to learn how to write the first law as a rate equation, so
we can write if you divide these by so this is essentially 𝛿Q is the change in internal energy +
𝛿W
𝛿Q = dU + 𝛿W
you divide both by the 𝛿t that small time interval and take the limit as the time 𝛿t  0, so if you
do that this will become
dU
Q̇= + Ẇ
dt
okay, so in this problem there is no work done and you can therefore write this as
dU =Q̇ dt
So if you consider the change from T 1 to T2, this ̇ is given as a constant what is this Q̇ . The
computer dissipates energy at a rate of 10 kilowatt this is the rate at which heat is transferred to
air, so if you draw a schematic, so there is a computer table, there is a computer and this is your
system. So system is something which excludes the, so let us draw the air boundary but
excluding the computer.
So in this particular system to this particular system there is a heat transfer at a rate of Q̇ . So
these Q̇ is given as 10 kilowatt so
U2 t2

∫ dU =∫ Q̇ dt =Q̇ ( t 2−t 1 )
U1 t1

(t2 – t1) is 15 minutes, so 15 x 60 seconds and dU is how do you calculate what is dU, dU is
basically mCv dt okay. So now we have to make an assumption that here the range of temperature
the heating is not over such a large range for which CV is a strong function of temperature, so we
may take CV approximately as a constant so this will this integral will eventually be
U2 T2

∫ dU =∫ mC v dT =mC v (T 2−T 1 )
U1 T1

so this is based on the assumption that C V is not a strong function of temperature otherwise you
have to write CV as a function of temperature and integrated from T1 to T2.

So now there are other problem data which are given using which you can solve these problems
so the pressure is 100 kPa initially T1 is 300K, so you can write m=(P 1V)/(RT1), R of air that is
universal constant divided by molecular weight of air, so typically 0.287 kJ/kgK. So (P1V)/(RT1),
so P1 is known, T1 is known, volume of air in the room it is given I think, the closed room of
volume 150m3, so from this equation, you can calculate by equation these two, you can calculate
what is T2 and T2 is 372K.

So you can see that it is really a very bad condition that if the AC suddenly stops and the
computer is running and there is not enough mechanism of dissipation of thermal energy, then
you like dissipation of thermal energy from the room so that the room gets cooled, if you do not
have that kind of a dissipation mechanism that is the room effectively remains insulated under
that condition you can see that there is a significant rise in temperature possible because of a
computer working in a room which cannot shed heat to the outside ambient, okay. So let us look
into the next problem.

(Refer Slide Time: 20:51)

Problem number 3.7, so a piston cylinder contains 2 kg of air at 27°C, 200 kPa as shown in the
figure. The piston is loaded with the linear spring mass and atmosphere. Stops are mounted so
that Vstop is 3m3 at which point pressure is 600 kPa which is required to balance the piston forces.
The air is now heated at to 1500 K, find the final pressure volume and work done and heat
transfer and find the work done on the spring.
So let us draw the schematic in the board and try to solve this problem. Here we have
encountered similar problems previously so I am trying to like work out more and more
problems of typical natures so that you get familiar with these types of situations if you need to
address this for your problem solving purpose.

(Refer Slide Time: 22:10)

So this is air, the system is this air so I am drawing the system boundary with a mass of 2 kg so
you can calculate the volume V1, so T1 is 273.15+27 K and P1 is 200kPa so assuming the air to
be an ideal gas. See this is very important whenever you are working out a problem you need to
see what is the substance then you need to make a judgment. This is the judgment based on your
practical considerations whether you can treat it as an ideal gas or you need to look into the
property tables to get the property data.
So suddenly do not start using the equation of state of ideal gas or whatever, first look in to the
substance what is the substance? And then accordingly use your judgment. So
mR T 1
V 1=
p1
so you get the state one so this state one you can plot in the PV diagram. By the way just as an
offshoot I want to ask you a question see from the very early days in school we draw pv diagram
with v in the horizontal axis and p in the vertical axis.

Never we draw a PV diagram with P in the horizontal axis and V in the vertical axis although
scientifically or mathematically there is nothing wrong with that because P is a function V or V
is the inverse function of P so we could plot V as function of P also, but we never do that do you
know why? See the answer to this is very simple when you are doing an experiment in the
experiment what you are independently able to vary is the volume and not the pressure.

So this remain the independent variable which in the experiment you are able to tune that is why
because this is something which you are independently varying this we are keeping in the
horizontal axis that is the convention that we always follow. So now we have got the state one
now what is that let us look in to the problem the air is heated so if the air is heated this will
move and because it is linear spring the pressure versus volume will be linear.

Now we have to get at least another data point on this straight line to fix up the straight line of
straight line requires two points to be fixed up, so the other data point is that at the stops the
volume is 3 m3 at which point pressure is 600 kilopascal. So this is Vstop = 3m3, this pressure =
600 kPa, but this is not the actual data point this is just a possible points so that you can construct
this straight line.

The actual data point is that the air is now heated to 1500 Kelvin. So what is the temperature here
is it greater than 1500 Kelvin or less than 1500 Kelvin. So let us see so if the temperature here is
pstop V stop
T stop =
mR
this is if you substitute the values this is 3136 Kelvin, therefore see this is greater than the T 2
which is 1500 Kelvin that means state 2 is not at such a high pressure but it is lower than this.

So see why we are calculating this? Our objective is to figure out whether the state 2 is at a
location extrapolated from this or not, if it is located at a location extrapolated from this then
that will not be correct because then it has already hit the stops so the volume cannot change
right. So if it is not within this then that means it should be at the stops and then at a constant
volume the pressure will raise.

So you cannot really you have the point 2 extrapolated on this straight line, at the most it has to
be within this, if not then it will be at a location where at these stop you will have pressure
building of at constant volume because the piston has already reach the stops. The volume cannot
increase anymore but here the situation is not like that T 2 is 1500 K which is less than the
temperature at the stop, so two will be somewhere in between, if not then 2 will be at a location
which is of vertical line from here that you have to understand.

So that is what I am repeating depending on the problem data the solution may change all
together, that is why do not try to prepare a formula base stereotype understanding of problem
solving in thermo dynamics. Depending on the problem data same problem might lead to
different types of PV diagram different types of solutions etc, so this is now the state 2 so the
state now you do not know what is V2 but you know p2V2 = mRT2, so if you substitute the values
here you know everything except p2 and V2 so you know p2 = 861/V2 if you substitute all the
values.

So this is, this 861 is 861 KJ so p and v have to be there in the adjusted units and then you can
write the equation of the straight line one to two in this way so
pstop −p1 V stop−V 1
=
p2− p1 V 2−V 1
this is the equation of the straight line (Y-Y 1) / (Y2-Y1)= (X-X1)/( X2-X1). So simultaneously
solving this equations see the two unknowns are p2 and V2 and there are two equations.
So you can solve for P2 and V2 so if you solve you will get P2 is 421.2 kPa. So then W12 that is
the shaded area this is
1
W 12 = ( p1 + p2 )( V 2−V 1 ) =367.3 kJ
2
if you apply the first law now
Q12=U2-U1+W12
See here the temperature range is large and because of the temperature range is large it is not
legitimate to keep Cp and CV as constant.

So depending on the temperature you can get the internal energy of air from something called as
air table which is there in the appendix of any thermodynamics text book, so instead of taking C p
Cv as constants you can consult the air table to calculate U 2-U1 and work done is already there.
So the answer to the heat transfer is 2350 kilojoule.

And there is a interesting tricky part which is last part of the question what is the work done on
the spring. So work done on the spring is not the total work done, so the total work done is
W12 = Wspring+ Watmosphere
right so what is Watmosphere,
Watmosphere = P0(V2-V1)
this is the work that is done to overcome the atmospheric resistance and create a change in
volume where P0 is an atmospheric pressure.

(Refer Slide Time: 33:51)

So Wspring will be not the total work but the total work - P0(V2-V1), this is
Wspring = W12 - P0(V2-V1) = 249 kJ.
You can very easily see that this is less than the total work done, okay. So we will work out
another problem before we close this tutorial session and the other problem is the final problem
in this assignment for first law for closed systems and that is problem number 3.8.

So this problem says that there is a cylinder with the cross sectional area of 0.1 m 2 which has a
massless piston with water at 20o centigrade on the top. Air at 300 Kelvin and 0.3 m 3 volume is
there under the piston and it is heated so that piston moves up spilling the water out. Find the
total heat transfer when all the water has been pushed out okay.

(Refer Slide Time: 34:28)

So let us try to draw a schematic of this problem, I will try to give you a guideline or an outline
of solving this problem and give you the final answer. So here you have air and here you have
water. So let us say that h is the height of the water which is varying with time. So what is the
system here, thermodynamics system, control mass system? Water, air or water plus air, see out
of all these three option only air is the mass which is remaining invariant, so for doing a control
mass system based analysis the air has to be the identified controlled mass system. So this is our
system.

So the pressure on the air for equilibrium. See if you draw the free body diagram of the piston
you will have on this side atmospheric pressure plus water pressure and on this side you have air
pressure. So what is the water pressure?

The height of the water x ρ x g,

pw=hρwg
So you can write sorry,
p A = p0 A + pw A,
so
p = p0 + hρwg,
ρw is 1/ specific volume of the water and this you can approximate as v f at 20 0 centigrade from
the table because the water is given at 20 0 centigrade and, so initial h at state 1, you have h =
what? How do you calculate h at state 1, you know the total volume, total height 10 m right, out
of that you subtract the air height.
You subtract the air height, neglect this piston height, see this is a practical considerations 10 m
is a long height out of that it is not that important, so you subtract the air height, you will get the
water height, so this is state 1, so if you know that you will get what is p 1 from here, so once you
get p1 then what is state 2? What is p2? State 2 is all water has spilled, so state 2 p 2 is only
patmosphere and V2 is this one, so V2 is 10m height x 0.1 m2 , this total 10m will be occupied by air
only.

All water has spilled out, so you can plot the process in a PV diagram how it will look
physically, because the water is spilling the pressure is falling, so because the water pressure
varies linearly with the height this is like a linear spring. See there is no spring here but the effect
is like the spring because the water pressure on the top is varying linearly with the height. So this
is 1 to 2, so once you know the PV diagram you can calculate the heat transfer and you can
calculate the work done.

This is the area under the curve and

Q12 = U2 – U1 + W12
so W12 is this, for this particular problem because the temperature range is not that large it is not
the significant amount of heating or cooling, so you can use constant Cv for calculating this and
if you substitute all these you will get the answer of the total heat transfer as 220.7 kJ.

Okay so we have worked out a significant number of problems concerning this first law of
thermodynamics for a closed system, in fact we worked out 8 number of problems and I believe
these are sufficient enough to give insight on problem solving, so thank you very much for this.
So subsequent to these there will be discussion on first law for a slow process and then problems
on for first law for a slow process and then there will be discussion on second law and we will
continue with that subsequently, thank you very much.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 10: First Law of Thermodynamics for

Open Systems

Good morning I welcome you all to this lecture section of the course law of thermodynamics
now today we will discuss the application of first law of thermodynamics to an open system or c
control volume the application of 1st law to a close system as already been discussed and you
have already come to know that 1st law is nothing but the law of conservation or energy and we
have come to know this thing that the energy in transit or we transfer between a system and the
surrounding or between two interacting systems are in the form of heat and work.

While energy in another form is stored in the system which bears the characteristics of a property
this we have learnt from 1st law now today we discuss the application of same conservation of
energy principle or 1st law to a close to an open system or a control volume before that we will
recapitulate a theorem know as Reynolds transport theorem many of you may have read this
thing earlier in fluid mechanics.

(Refer Slide Time: 01:23)

Now we will discuss this Reynolds transport theorem, what is Reynolds transport theorem no we
know that this statement of the law related to classical mechanics and thermodynamics have
usually been made on a control mass system approach or a Lagrangian particle approach all laws
area started in terms of control mass system or two system but in engineering applications we
have seen that since the control mass system is continuously deformable the it is easier to
analyses the process or a system with respect to control volume on an open system approach.

So therefore some kind of mathematical transformation is require to relate this laws to the
control mass system to that prior control volume or roping system and the this mathematical
transformation or theorem that does this is known as Reynolds transport theorem which relates
the change of a property with respect to a control mass system to that with respect to a control
volume system.

For an expel I tell you when we define this second law of motion by Newton second law of
motion that the rate of change of mass of a system that is a control mass system rate of change of
mass of a substance or body is equal to the force acting on the body so therefore you see that this
way the for example the conservation of mass we know the mass of a system control mass
system or a body remains constant, so therefore the physical laws are postulated always on the
approach of control mass system or close system.

Now the relationship between these applied prior control mass system to that of a control volume
system is given by Reynolds transport theorem so I will state the Reynolds transport theorem
without proving it what does it tell in this class, so Reynolds transport theorem tell that if we
have an extensive property then rate of change of property let N is the extensive property rate of
change of property N is a control mass system rate of change of property of control mass system
I am writing CMS = Rate of change of N in a control volume system or simply we use control
volume.

That is the open system + net rate of effects of N from the control volume that means across the
control surface the rate of effects of N this can be this can be written methodically if we defined
η as the corresponding intensive property for N that is this specific value of N that is N any
extensive property whose corresponding intensive property as I have told you in earlier class is
this specific value of the N that means N / unit mass then we can write the right hand side as
dNdt for the control mass system.

Now this can be written as consider a control volume system like this control volume system if
you consider at any point an elemental volume dv and the local density there is ρ we can write is
η ρ dv over the control volume the integration is done over the control volume that is rate of
change sorry ∂ ∂ t of this that ∂ ∂ t of the energy within the condole volume that N that means
this is the N within the control volume/ unit mass ∂Dv.

And it is integrated over the entire control volume plus the main rate of mass a flux which can be
written as ∂ η, η∂ this η is the mass the n per unit mass and this is the mass flash across the
control surface, this control surface so V.n, n is an this to understand if you take for example this
is the flash that means this is the velocity vector for example this is the velocity vector if you
consider and elementally area on the surface control surface dA.

This is represented by a vector or like this we can consider that you need vector l is an unit
vector which is directed normal outward, outward direction is positive direction and normal is
the direction normal to the area, so V.d and this dot product V.n represent the component of the
velocity, velocity vector is this the components of the velocity along the normal direction that
means this is the velocity component normal to the surface area dA V.n, n is an unit vector
normal to the elemental surface dA.

So therefore this as you know earlier from your fluid mechanism knowledge that this replace that
∂V.n, dA is the mass flow rate and this is be integrated over the control surface so therefore this
is the rate of change of CB and this is the rate net rate of effects of n from the see this one so this
is this and this one is this, now this can be written as this dt of this is the energy within the
control volume dt of these Ecv dt of Ecv that is the change rate of change of energy within the
control work.

dt or you can write δt does not matter now this can be written if you consider this η here we are
writing η actually we are considered this is the sorry I am extremely sorry this is the control this
is the general theory for any extensive property, now if we take this extensive property N as the
energy and η as energy by m1 sorry E e is the specific energy that is energy per unit mass now
before that I tell you one thing that this Reynolds transport theory with respective general
property N can be written that any general extensive property N.

And here this N cam be replace by any property if we replace then as m that is mass then this
will give you the conservation of mass with respective of control volume, if you written N as the
momentum then it will give the momentum theory, has we have already rate for the control
volume, and if we use the N as the energy it will give energy equation and apply to the control
volume or open system here it should be very much remember that this theorem that the net rate
of for the rate of change of property N, within the control volume plus net rate of reflects of N
from the control volume equal to the rate of change of property N of its control mass system
which coincides the control volume at that each time.

Okay now after this I come to the conservation of energy equation you please remember the
equation so that it will be easier for you to follow these things this board is small enough space
and you cannot accommodate everything now if you write this for.

(Refer Slide Time: 10:25)

N = energy and obviously η will be energy per unit mass that is specific energy then this can be
retained as these dE this Reynolds transpose theorem control mass system = δt of what will be
their η is small e that is specific energy within the control volume into ∂dV + ∫e ∂ that is the
velocity component perpendicular to the area dA over the control surface where n is unit vector
like this here I write, where n is the unit again I am drawing this think this is the velocity weight
that this is the out flow.

Velocity vector and we have an area dA here and let x normal is in this direction outward normal
so this is the velocity of vector component along the normal direction, so this is the size of the
mass flow rate across the control surface now this can be written as this dt for a control mass
system is this can be again written as this is the total energy of the control volume the δt of δE δt
of Ecv δEcv δt that means this is the rate of change of the energy within the control world time rate
of change, now if we consider.
This specific energy associated with from mass flask or the flow is constant across the control
surface over the entire control surface both in case of influx and afflux this can be written as e 0 –
where this is the o suffix o represent the outflow this is the rate of mass outflow from the control
surface f(x).

Into this specific energy across the control surface outflow surface which is constant across the
surface where the afflux is there, similarly ei represent this specific energy associated with the
flow across the inflow surface and this is the mass flow rate of the inflow surface if this is
constant and we can write this as dm0/dt – dm0 minus sign comes because of the fact that this V.
end or n- bar (V. n) is positive for outflow direction.

You see that the velocity vector and the outward normal vector to the area is in the same
direction means this is positive whereas in case of an inflow area the normal is in this direction
which is in the opposite direction, so this will be negative for inflow area and this will be
positive for the outflow area, you can take an example like this in a simple example you can
understand this afflux thing that.

If we consider a control volume like this where we already as a as recognized and inflow area
like this which is this inflow area okay and we have an outflow area like this where this is the
velocity flow out, now if we define this inflow area by suffix I and outflow area by suffix o and
if we consider Ei the energy specific energy associated with the inflow that is the mass inflow is
constant over this surface.

And similarly eo is constant and across this surface e o is constant across this surface and here also
we consider VI is the velocity that is the inflow velocity and Vo is the outflow velocity and this
two are the only recognized area through which the mass coming in and going out that is the
influx and afflux in the control volume we will get that you can get this things from here then if
you write this term the second term this term on the right hand side.

You get CS over the inflow area ei if the inflow area ei row now here we define a unit vector I in
this direction unit vector I, so here V is V – Vi because V is in the opposite direction to that of I
you understand this, this is I this is for the direction so therefore sorry then N is vi rather V x I, I
am sorry dot the normal to this surface is in the opposite direction, the normal vector N in this
case –I, the normal to this area inflow area this is inflow area the inflow area is –I.

So this ρV.N dD inflow similarly if we write the outflow area outflow area what happens ρ x e of
first e0 ρ x (V. I’ I bar) and this into here the normal to this area that is normal outward it is, is
equal to I so therefore this is I dA o it is dAi, it is dAo that means any elemental area in the inflow
any elemental area at the outflow section so therefore you see if E i is constant across this inflow
area E incomes out then Ei comes out and this I. –I -1.

So therefore –ρ V. dA so let us consider this V as Vi so I will give this as Vi this is the inflow
area Vi inflow area so Vi dA, similarly here if you do that it will be if e0 is constant across the
area it will come out and it will be simply ρ it will be 0 sorry it will be 0, dρ V0 dA o over the it is
this inflow this is the outflow, now this becomes mes the mass flow rate ρvidA over an area
integrated over an area if vi is constant vi and ρ these values are constant in all cases we assume
that they will come simply into be integration of dAi that means it will total Ai that means ρAv
that is the mass flow rate or simply these integration is the mass flow rate that is dmi/dt+ this one
will be e0dmo/dt.

So therefore we see that this integral which represents the net rate of energy +1 the control
volume can be retain that [Link]/dt –eidmi/dt where dmo/dt and dmi/dt are mass flux out of the
control volume mass flux into the control volume and eo and ei are the energy specific energy
associated with the mass flow. So this is the mathematically expression by which I tell you that
we can write this thing, so therefore the equation finally becomes like this, dm/dt control I can
rub this thing and then I can write again so you just recall it.

(Refer Slide Time: 19:33)

That dm/dt sorry dE/dt for the control mass system is equal to ∂ECv/∂t+ okay, e0dmo/dt-ei
dmi/dt that means in terms of outflow and inflow area e0dmo/dt if there are number of outflows
areas then this will be added all together this will be added all together okay, so this for a single
inflow area single outflow area of course here in this equation it does not matter it takes the
entire mass flow rate from the outflow area where 0 is constant over the entire control surface at
ei constant over the entire inflow control surface and dmi/dt is the total mass inflow rate of mass
inflow.

Now comes to this, what is dE/dt for control mass system that is you know that for a control
mass system already by the application of first law the ∂Q is dE+∂what is this, that means in a
control mass system or a close system if you add ∂Q among of heat small heat, small amount of
heat it required to the changing internal energy of the control mass system that means the energy
stored in the control mass system plus the work done and our conventional sign is that ∂Q is
positive when it is added to the control mass system and W the work is positive when it is comes
out of the control mass system.

And dE is the change of internal energy that means the energy stored in the system it is the
internal energy. Now what has done in internal energy can we stored in the system it will be
either inter molecular it will be inter molecular energy, kinetic energy and potential energy which
have been already discussed, so if we consider this thing that this is given for a time interval of δt
then this d I write this as d because E is a property and it is a prefect differential so that we write
this as dE whereas Q and W are the path functions.

So therefore it is written like this on the rate basis if I write this will be this, dE/dt is nothing but
small amount of energy ∂E added over a time δt limit, δt tends to 0 becomes dE/dt you can think
this way also that means it is the exact differential so it is the derivate with respect to time, but
this is not so this is path function that is δQ/δt represents the rate of heat transfer to the system in
this fashion and rate of work transfer from this system.

So therefore the rate of δQ/δt is dE/dt+δW/δt so therefore dE/dt for a control mass system equals
to δQ/dt- δW/δt this is clear. So for a control mass system we recall the first law applied to a
control mass system like this that is for a close system and we can derive from there that is the
rate of change of internal energy within the system recalls to the rate of heat transfer to the
system minus the rate at which the work comes out from the system.
(Refer Slide Time: 23:19)

So if now we substitute these here, that dE/dt control mass system is δQ/δdt now I told you when
I apply this law the control mass system and the control volume system coincides that distance
that means this is also with respect to the control volume system that means this is the rate at
which control heat is added to the control volume system and the rate at which the work done by
the control mass system this way we deal it try to understand this we substitute for the control
mass system law, but since the control mass system and control volume coincides that distance.

So then everything is now with respect to the control volume system that means these now states
that this is for the control volume system heat and working direction this is for the control
volume system that is the date of change up in a juie the control volume and this is the rate of
reflex this is the rate influx this becomes the nitrate of flux. So now if we write this in a different
fashion then you write ∂Ecj /∂t = just I write in a little different doing that is ei dmi dt little
rearrangement + ∂q ∂t – eg ρ dm0 / dt - ∂w/ ∂t.
Now you can better understand this equation is much more convenient that is the rate of change
your being internal energy within the control volume request to the amount of energy coming in
to the control volume on the form of the flow energy that is coming associated with the slow that
is influx rate must flowed in to this specific energy that means this is the total energy coming to
the control volume with the flow plus the heat that control volume receives the rate at which the
control volume receives energy Interviewer: he form a minus the total energy going out one is
going out with this flow that is the flow energy that is the energy going with the flow out flow
this is the mass flow rate out flow mass flow rate in to this specific energy at the out flow surface
minus the work that is going out that the energy that is going out in terms of work.

And this comes from the simple physical intuition form the conservation of energy clear, now if
there is no flow this two terms will be 0 and this two terms will be 0 this term and this term so
this will simply convert to the law that is ∂Ecv /∂t = ∂q/ ∂t - ∂w/ ∂t that is same to the close
system because in a close system there is no mass influx. Now mass influx or mass efflux now
∂q/∂t and ∂w/ ∂t will be opposite heat may be taken from this system or may be done to the
system in that case the sign will be change.

That means this clearly shows that the total energy of the control volume changes depending up
on its net gain in the energy, so control volume transfers energy or interrex energy with the
surrounding in two forms one associated with this mass flow another in terms of work in heat
transfer. So therefore we will account what energy a control volume has taken or gain from the
surroundings or another interacting system in the form of flow energy coming with flow and
either heat and work transfer and similar way the energy heat leaves in the form of flow
associated with the flow and also in terms of work and heart and if we make a balance this will
give the change of internal energy within the control volume.

Now here after this we have to know one thing after this I have be told allow is that the specific
energy associated with the mass flow at inlet or outlet in flow or out but what are those specific
energy is that a flow or a stream of flow contains when a stream of flow comes in to a control
volume for example in this room if stream of air comes in to it carry some mass similarly it
carries some energy for example you have very much familiar with the kinetic energy it comes
with some velocity v so it also brings a kinetic energy that is the rate of kinetic energy rate of
mass flowing to v2/ 2.
Similarly other forms of energy are there that is inter molecule energy u that is e is in terms of
specific value I am telling the specific inter molecule of energy by what should apply
temperature so any substance at any temperature has got some inter molecule energy which is the
result of the kinetic energy of the molecule from the molecular theory. So this is the inter
molecular energy plus the flow work already you are come across this term the flow work that
means a stream coming has got some energy by what should does work on the neighboring layer
one layer of this stream of flow does work on the neighboring layer and that work is known as
flow work and that is in some form of energy is inherent to within the stream at a particular cross
section by what should ands which it can do work on the neighboring cross section to make its
flow through.

This has been already discussed and sometimes this we tell as pressure energy then it will lose
term in fluid mechanic where p is the pressure of this stream of flow and v is he specific volume
plus the kinetic energy v2 / 2 and the potential energy all are per unit mass. So therefore this
specific energy carried by a flow of stream is given by this specific internal energy specific flow
work specific kinetic energy that is per unit mass plus specific potential energy. With this thing in
mind we can replace this in terms of this and quick and write that.

(Refer Slide Time: 29:41)

∂Ecv /∂t = ei is ui + corresponding quantity at the inlet plus Vi 2 / 2 + gzi okay + δ q /∂ t –u0 + e0
+p0v0+ v02/2 + gz0 okay into dm0 dt this is this -+∂Q/∂t so this is the general form of the
conservation of energy equation and apply to the volume or a open system so this is the general
equation applied to a control volume the general energy equation that law upon the energy apply
to a control volume or open systems.

Now this is the dm/dt+∂Q/∂t so this part is the inflow energy rte of inflow energy rate of heat
coming into the control volume rate of outflow energy okay and the work out from the control
volume that means this is the control volume that means this is the control volume if you got this
is the inflow energy coming in so this is the outflow energy going out and we consider that
+∂Q/∂t is the rate at which heat is given and rate at which one so it is general energy equation.

Now at some condition study state of the control volume now before that I write that dm/dt that
inflow rate- the outflow rate this is the conservation of mass this also will be like this dm cv/dt that
means that the rate of mass inflow- rte of mass outflow will be the rate of change will be the
mass control system so this is the typical continue equation the conservation of within the control
systems.

Now in case when dmi/dt is equal to that means this is 0 that means there is no mass
accumulation in the control volume in fact when the control volume operates in a steady state the
all property remains same that means the net energy outflow will be 0 energy inflow and energy
outflow not only inflow outflow the total energy taken by the control volume and the total energy
giving by the control volume will be same the energy will be same.

And also if the mass trucks at inflow and outflow remains same there will be no mass struck
increase in the control volume if in this case this equation can be written as in that case there will
be no change of energy within the control volume if we consider that is the operation of the
control volume when there will be no change of energy with the respective time of control
volume.

And no change of mss with that respective time in the control volume then this equation can be
written in simple way like this then we can write U i+Pi Vi+V12/2+gz1*dmi/dt +∂Q/∂t=U+Po
Vo+02/2+gz0*dmi/dt +-+∂Q/∂t which means that the total energy taken by the control volume
consisting of the flow energy coming in plus the heat coming in, in the rate basis equal to the rate
of energy living the control volume.
This is energy leaving as a suitable mass flow out and the work out so therefore this gives the
clear concept that the study states the total energy gain by the control volume or rate of total
energy gain by the control volume equals to that rate of total energy leaving the control volume
so this si the special case when study state is the all property remains constant that energy and
the mass.

And in this case it is usual to write everything in the form of unit mass in a sense that if we
divided by dmi/dmo this re the equal dmi/dt and let this is dmi/dt then if we divide again the
entire equation by dm/dt then you can get this expression Ui+Pi Vi+Vi 2/2 +gzi then this will be
the heat transfer per unit mass is equal to U0+P0 V0+P02/2+gz0 okay+∂Q/∂m this is per unit it
is use well to write per unit mass based in steady flow process. Then now you recall this U+Pv is
the enthalpy age so this will be enthalpy at inflow condition and this is the enthalpy at out flow
condition

So therefore we can write in short that we can write in short that now we can write in short this
hi + Vi2/2 + gzi + δq/δm = here ho + V o2 / gz0 + δw/ δm, so this the version of the general energy
equation for a control volume system or open system at steady state. From the general energy
equation at steady state that means it is the energy equation or the conservation of energy applied
to control volume system or open system at steady state.

(Refer Slide Time: 36:51)

This is known as steady flow energy equation, okay this is steady flow energy equation, now
usually in many cases this change in kinetic energy are neglected, this is not much with respect
to the change in enthalpy and the heat and work transfer and change in the collusion energy is
obvious is neglected because change in pollution is energy is very small because one cannot have
an engineering apparatus which is huge height.

So there is the substantial change in the energy between the inflow and out flow, so this will
never happen so that the change of kinetic energy and potential energy in many cases are
negligible compared to the enthalpy changes and work and heat interaction. Of course there are
certain cases where kinetic energy will not be neglected, that are the case of nusselt where the
thermal energy which is the enthalpy rather you can tell being is converted to the thermal energy
is converted to the kinetic energy.

So the outflow kinetic energy much more than the inflow but except those cases we can write for
a special case therefore δq/δm - δw/δm is h0 – hi, so where the kinetic energy changes and
potential energy changes and neglected this energy equations can be simplified to this. Then you
see that this enthalpy whose difference from outlet surface, outflow surface and inflow surface
give the work and heat interaction. The difference between the heat added and the work done.
In many devices there is only work interactions for example turbine and compressor which are
insulated so that the heat transfer is negligible, so either it gives work in case of turbine or it
takes work, so therefore it is the only the work interaction in that case which is equal to h0 – hi.
Similarly there are certain devices like heat exchanger δq/δm is there. Therefore we can get the
heat expression for heat added as this h0 – hi, so understand.

So therefore we see that this give a physically interpretation and how much useful the
significance of enthalpy that means in the open system it is the difference of the enthalpy which
gives us the value the work and heat interaction for the control, with the surrounding it is simply
the difference of the enthalpy, provided the kinetic energy changes and potential energy is
neglected only the enthalpy differs.

Otherwise we have to take care where there is the substantial change of kinetic energy this and
this but potential energy changes are always neglected, this does not come into the picture okay,
so today upto this, that means we have considered the application of the principle of the
conservation of energy to an open system or a control volume by evoking the Renaults transport
theorem. And finally we arrived at this steady flow energy equation which is the application
conservation of energy to the control volume steady.

This is the special case from the general energy equation which I have written earlier and in a
very simple case where the kinetic energy and potential energy changes neglected, this gives us
the heat and work interaction are given by the δq/δm - δw/δm simply by the enthalpy difference
from the outflow surface and that in the inflow surface okay. So one thing to be remembered that
potential energy changes are always neglected but kinetic energy are usually neglected except for
a special cases of nusselt and diffusers, where kinetic energy is been converted in diffusers to
thermal energy and nusselt thermal energy into kinetic energy okay, thank you for today, thank
you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 11: Tutorial 3: First Law of

Thermodynamics for
Open systems

Good morning and welcome you all to this lecture session of the course laws on thermodynamics
laws of thermodynamics earlier class we discussed the application of first law to an open system
or a control volume and we derived the equation in general form when the control volume is
around steady state and from there the special case for a steady state control volume and the
equation is referred to a steady flow energy equation in this class we will solve some problems
which are the applications of the energy equation that means energy equation applied to a control
volume an open system.

(Refer Slide Time: 01:02)

So let us first start with the first problem, problem one which state that two airflows are
combined to a single flow one flow is 1m 3/s that is the volume flow rate at 20 0 C and the other is
2m3/s at 2000 C the degree is not is emitted inadvertent mistake by both at 100 kPa they mix
without any heat transfer to produce and exit flow at 100kPa neglect kinetic energies and find the
exit temperature and volume flow rate.

(Refer Slide Time: 01:44)

So problem is like this two flows are combined to a single this is a pipeline this is one flow this
is another flow coming and this is going out one flow is coming here this is one flow this is
another flow coming through this and this is going out let us this is the inlet section of one flow
this is the inlet section of one flow let us define a control volume like this is the control volume
and there is no heat transfer with the surrounding of this pipeline that means the entire pipeline is
insulated.

That means no heat transfer no heat transfer that means ΔQ is 0 or Q is 0 now let this section is
designated by one let this section where this constriction of the surface of the control volume at
this stream cutis section 2 and this is section 3 combined stream now the quantity given is that P 1
is 100kPa now let me see the problem P1 is 100 kPa and T1 is 293 T1 is to 200C it is given P1 is
293 K and the volume flow rate Q 1. is 1m 3 /s for the section 2 P2 is also 100 kPa T2 is 2000C
that means 473K and Q2. = that is the volume flow rate 2 m 3 /s now at 3 the condition let us
consider the m3 now sorry m3 note Q3. is unknown is not known not known we have to find out
this we have to find out the volume flow rate and the temperature the exit temperature but exist
pressure is same because both the pressures at the inlet is same.

So there is an isobaric mixing at the same pressure but exit temperature is not known it is to be
found out so what we will do we will just apply the first law of thermodynamics to this now if
we consider this m1. as the mass flow rate at Inlet and m2. as the another inflow mass stream
then this is =m3. now m1. can again be written as Q1. by specific volume at Inlet similarly m2.
can be written as specific the flow rate divided by specific volume at the inlet 2

Now the specific volume can be found out from the condition of p1 t1 how can I write you know
that the relation PV is equal to RT for any ideal gas for any ideal gas, okay where P is the
pressure V is the specific volume R is the characteristic gas constant and T is the temperature
okay. So therefore we can find out from here v1 is r T1 / P1we know T1 293 K we know P
100kiloPascals and we have to substitute the value of R in the corresponding unit.

If you put it in kilo Pascal's so R will be in kilo Joule per kg K and for R the value of R is 0.28 7
kilo Joule easily you have to remember this part kg k this is the value of kilo joule per kg K, so if
you put R this key 1 you know and P1 you know you find out V1 and in a similar way you find
out V / R T2 P2 and where P2 is for 73 and P2 is same 100 kilo Pascal’s and you can find out
V2 so therefore if you find out V1 and V 2 you can find out m1 and m1. and m2. so therefore
you can find out m1. and m2.

And you can find out the mass flow rate at the section 3 this is found out I am not solving the
problem in details but you have to solve it I will give you the answer of the rod but I am giving
the answer now m1. will come out to be 1.m1 . will come out to be 1. m1 . is coming out to be
1.4733 1.4 7 3 3 kg/ s m2. will come out to be m1. if sorry 1.189 1.1892 and m1 m2. is 1.4733,
1. 4733 kg/ps 1.47 there may be little variations because they have taken the volumes where the
specific volume from the air table no they are found out by R T1 pure.

So you will get this exact value m1dot and m2 dot you get the value of m3 dot, now to find out
the temperature, because you cannot find out the Q2. until like Q3 until and unless you know the
temperature, so m3. is known now, now m1. m2. m3. m1.m [Link] now you have to find
out the temperature t3 now you write the energy equation steady flow energy equation this is a
steady flow and therefore there is nothing is changing within the control volume.
So therefore we can write m1 doth1 neglect kinetic energies it has been told in the problem and
potential energy also always neglected this is not to be told you always neglect so that becomes
the energy in flow and that equal to the energy outflow and here energy receiving and going
assuming by the control volume and leaving the control volume is only in terms of the mass flow
rate because there is no work and heat interactions working Direction is 0, in this case there is no
our interaction and it has been told that entire thing is insulated.
There is no heat transfer to the surrounding so therefore even if the temperature is greater than
the surrounding it may be or may not be I do not know but we do not put our brain into that
because it is told there is no heat interaction, so therefore this will be the specific form of the
energy equation you may not have to remember that you can just simply by your fundamental
principle you can write this is the energy coming in with a [Link] the kinetic and potential
energy this is with the incident and this is going out and steady flow case this has to be same so
therefore now we can write for an ideal gas.

(Refer Slide Time: 09:54)

This you have to use it is given by CP into T that is CP is the specific heat at constant pressure and
T is the absolute temperature so if you write this then you can write m1. CPT1 + m2. CPT2 = m3 is
(m1. + m2.) Cp and for an ideal gas CP is constant and it is not also vary with temperature so
therefore CP-CP will cancel out so it does not matter whether CP values we do not we know or
not so simply T3 is found out to be m1. T1 + m2 T2 /m1 + m2.

And you know m1. You know m 2. and you know T1,T2 you can find out the value of T3, when
you find out the value of T3 you can find out the value of T3 as RT3/P3, P3 is 100 kilopascals R
is the same point 287 kilo Joule per kg then when you know T3 from this energy equation then
you can find out the value of P3 and you can find out Q3. is a sorry M3 . M [Link] Q3/V3, okay. So
this is the first problem okay. Now we come to the second problem, now we come to this second
problem.

(Refer Slide Time: 11:52)

Now a 25 liter tank that is initially evacuated is connected by a valve to an air supply line
following flowing air at 20 degree Celsius 800 kilo Pascal, the valve is open until air flows into
the tank and the air flows into the tank until the pressure reaches 600 kilo Pascal's, determine the
final temperature and mass inside the tank assuming the process is adiabatic, develop an
expression for the relation between the line temperature and the final temperature using constant
specific heats, try to understand the problem there is an initially evacuated tank connected by a
bulb to an air supply line.

And air is supplied at 20 degree Celsius and 800 kilo Pascal's the valve is opened air flows until
the pressure reaches 600 kilo Pascal's when the valve is closed, determine the final temperature
and mass inside the tank assuming the process is adiabatic. Now develop an expression for the
relation between the line temperature and the final temperature using constant specification. Now
this problem is also very interesting problem, now let us see the problem what the problem tells.

(Refer Slide Time: 13:22)

This problem tells that there is a line which connects to a tank which connects to a closed tank
this is tank and the tank is insulated it is adiabatic condition there is no heat transfer from the
tank, this air is flowing for example in this there is a bulb, now first the valve is open so that the
air goes into the tank we take a control volume like this, surrounding the tank and cuts the
control surface here where the mass coming in.

Now try to understand problem physically dull there is a line where the air flows and the line
pressure is what the line pressure is line pressure is or evacuated tank line the following line
flowing air at 20 degree Celsius 800 kilo Pascal's that means if this is the condition I in the line
Pi = 800 kilo Pascal 800 kilo Pascal's kilo Pascal's and Ti = 20 degree valve a near supply line
following a at 20 degree means 293K this is the condition okay.

So now this air goes into this the tank is initially evacuated there is nothing any no air at all so
here comes into the tank is initially evacuated there is nothing any no air at all so air comes into
the tank and it is pressure and temperature increases, there is no heat flow because of the mask
introduction both pressure and temperature increases this is the physical problem. Let us consider
that tank state initial state is 1 it goes to the final state 2, now initial state 1final state 2 so final
state is giving P2 initially it is evacuated so everything is 0.

So final state is P2 600kPa and we have to find out what is T2 they will have an expression for
the relation between the line temperature and the final temperature using constant specific, this is
a very interesting problem this is known as charging a tank at an adiabatic condition. Now here if
you draw a control volume like this, now this is an unsteady problem because there is an inflow
there is no outflow and the mass in that tank is changing, okay.

So why write this a mass and energy everything is changing temperature is changing if I write
the continuity equation you do not have to recall any equation unsteady term equal the flow
unsteady flow energy question and all this thing you just simply see that if you write the energy
equation now and if we consider that in a finite time the mass which is coming which has come
in to this is mi this must be equal to m2-m1 that means if I integrate simply that earlier equation
dmcv/dt is dmo/dt is simply the integration –dmi/dt.

If you integrate it with dt over a time dt then simply it is ∂m say that is the change in the mass of
this is ∂mo that means the mass which is sorry, it is i not in it is i it is all the mass which are
coming minus mass which has gone out, simply this is integrated and it comes like this, so
therefore you do not have to remember any equation and integrate it is simply by your principle
of conservation of mass continuity that if over that time when this valve is stopped when P2
600kPa has reached.

Then I consider mi amount of mass as cross or has come from the line to the tank and that must
be equal to m2 that is the final mass-m1 and m1is 0 evacuated time, so therefore mi is equal to
final mass. Now if we recall or you do not have to recall if you recall you will get the same thing
that the change in the internal energy within the control volume that means Ecv2-Ecv1 that
means we integrate the ∂Ecv/∂t terms that means Ecv2-ecv1 is exactly equal to what there is no
heat working direction that will be equal to the inflow energy with this mask, that means it is by
that finite time [Link] simply [Link] that means this is the change of energy in the control volume it
is equal to the mass which has entered into the control volume across this section and this energy
is hi because we neglect kinetic energy and potential energy.

So only energy is Q+Pv that is enthalpy ,enthalpy at the conditioned line condition hi, this Ecv2
is what m2.e2 and this is Ecv is 0 specific energy this is 0, m 1 is 0 there is no mass, so there is
no energy so this is equal to mihi. Now this e2 that is the energy contained in the tank is only in
the form of intermolecular energy, because there is no motion it is a closed tank or even if there
is some motion we just neglect motion of the gas.
So therefore the energy contained in the control volume is only in the form of intermolecular
energy that means we can write as m2u2 is mihi since m2 and mi is same u 2 is hi that means u2
is hi, now for any perfect gas I told earlier that h is Cp.T similarly U is Cv.T where Cp is the
specific heat at constant pressure and U is the specific heat at constant volume. So therefore for
any ideal gas H can be expressed as CP x T and u can be expressed as CV x T this comes from the
genesis which may be beyond the scope of your course here that enthalpy and internal energy of
an ideal gas is a function of temperature okay is a function of temperature only and specific heats
are constant over the range of temperature.

And therefore we can write H is CP T and U is CV T this you just take it at the present moment
for any ideal gas we can express enthalpy and internal energy is like that. Now this u2 is H I care
for we can write CV t2 is CPTI, so therefore t2 becomes is equal to CP/ CV x T I. So this is the
general expression, so this is the general expression that the final temperature will be always the
ratio of specific heat times the line temperature.

So therefore with the numerical data you can solve the problem that is why a part of the problem
is develop so t2 is CP so simply you multiply 8 and 293 with the ratio CP / CV for air it is 1.4 so
t2 will be 1.4 times this 293 this is the answer, so this is the expression t2 is CP / CV x TI okay.
Now we will come to the next problem. Now we will write the next problem go to the next
problem see the next problem.

(Refer Slide Time: 22:11)

In nitrogen line at 300k and 0.5 mega Pascal is connected to a turbine that exhaust to a closed
initially empty tank of 50 meter cube okay the turbine operates to a tank pressure of 0.5 mega
Pascal's at which point the temperature is 250 K okay, assuming the entire process is adiabatic
determine the turbine work. So nitrogen is connected to a turbine line turbine exhaust to a tank
and ultimately it stops so in the tank reaches the point 5 mega Pascal's and the temperature is 250
K assuming the entire process is adiabatic determines the turbine work. Let us come to this
problem this problem is like this come to the board for this problem.

(Refer Slide Time: 23:05)

The problem is like this a very simple problem only a turbine is there it is same as the earlier one
this is the line, and now this exhaust to a tank the only difference is that here the turbine develops
and work W the sub is rotating this is the turbine this is the line which we denote that I the tank
which is initially evacuated however we take the initial state at two and final state at initial state
at one final state at two.

Here according to the problem let me see what are the values pi ti given so PI is now 0.5 mega
Pascal's VI is 0.5mega Pascal's Vi is 0.5mega Pascal what is Ti given the line temperature 300k,
300k is connected now the tank is closely initially empty, empty tank of 50 meter cube that
means tank volume is 50 meter cube that is the volume of the tank always I write volume as v-
cut to differentiate it from the velocity V now the final pressure of the tank is 0.5 mega Pascal's
and final temperature of the tank is T2 is what final temperature of the tank to 50k.

So you have to find out the turbine work and we enter system is adiabatic entire system is added
now we take a control volume like this surrounding this in circumscribing or enveloping this
entire system control volume like this where a part of the control surface cuts this inflow line
with where it enters to the turbine that is the line of nitrogen and it comes to this it is also an
unsteady problem because there is only one inflow to the tank but there is no outflow and at the
same time.

The temperature and temperature pressure mass everything changes in the tank so here also it is a
steady flow energy equation and the same mass flows to the turbine and the tank and we consider
that the mass which has been introduced during the operation of the turbine when the tank
reaches this condition is in then we write the energy equation energy equation is what this m 2 e2
that means the energy in the tank.

That is the control volume at to – energy in that tank at the initial state that is the change in the
energy in the control volume but here you can ask me a question very interesting and this is the
concept of the problem everything is routine this is the concept that the control volume consists
of both turbine and the tank but I am considering the mass and the internal energy of the tank this
is because the turbine is operating at a steady state that is the clue of the problem that means it is
so that during the operations the turbine operates and ultimately at some point it stopped during
its operation the internal energy within the turbine does not change.

So therefore if you take also as a part of the control volume both tank and the turbine so
changing the internal energy of the turbine is zero so therefore in with regard to the change in
internal energy of the control volume it is the internal energy changing the tank only and that is
because - what it has come that is the mass so this mass is nothing but the m - m 1 is zero the
same mass M2 has come from the line and it is hi that means you see here only difference that
this is the mass change in the internal energy control volume is equal to the energy which is
received.
And another thing will come what is that what is the difference between the earlier one here
work is done so work is done out by this control volume that means - W that means the control
volume is received this energy that is the energy inflow with the mass M 2 and the enthalpy of the
line hi minus the work done equals to the change in the internal energy of the control volume
okay, this m 2 and this m 2 is same because m 1 is 0 final m 2 is m 2 that means the change in the
mass is m 2 change in the mass of the control volume is m 2 and this m 2, has come from that
under steady state through the turbine.

So therefore this m2 s carat and influence energy m 2 x hi, we neglect the kinetic and potential
energy – the work done work developed by the turbine, so that is the only difference that what?
So therefore here you know the m2 how to know the m2? you know P2 you will know T2 okay, so
you can find out the specific volume or you can find out this way that P V = R this you tell that
mRT now P2 V tan that is the v2 = m 2 r.

So you know t2 you know R here nitrogen is there, so R for nitrogen is 28. So you know V tank
50 meter cube, you know p2 T2 you find out in, so when you find out game then e2 is what again
I write this equation m 2 sorry m 2 u2 = m 2 h i- W, so u2 it m 2 Cv t2 = m 2 Cpt you and I told CPT i h
is CPT + t- w here you know everything if you know the value of C P and CV you note P 2 and P I
also, so therefore you can find out what?

You can find out the earth okay you can find out the work output, so you know m 2 you know t2
and t1 you can find out the work output. Now C P values are like this CP = 4 nitrogen 1.04KJ/kgk
you take this value and Cv is equal to some point 785 per kg k and you get the work out. The
answer is like this they have taken the values of this UNH from the table so there will be little bit
of difference the value will be the final answer, we final answer will be W is equal to the final
answer will be 41.00 for MJ

You will get something close to that 40.01 for MJ, that is the answer so therefore you understand
how you can apply these you do not have to recall any unsteady flow energy question just simply
you apply your brain, the conservation of energy how you can write the difference with the
earlier problem is that that work is developed by this so therefore the amount received with the
inflow energy minus V was developed accounts for the energy change in the control volume and
initially it is evacuated.
So this part is 0, so into and by continue to your conservation of mass the amount of mass which
has come to the control volume during the operation is equal to the mass which is flowing to the
line so line mass flow is same this is the amount of mass enters the control volume. So finally we
get with this application of this equation and the concept that h is C PT and we get the value of W
everything is given only the workout has to be found out okay today up to this thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 12: Second Law and its Corollaries (Part I)

Good afternoon and I welcome you all to this lecture session of the course laws of
thermodynamics last class we discussed few problems in relation to the application of first law
that is the conservation of energy to an open system, so today we will discuss another problem
another interesting problem and then after that we will start the second law of thermodynamics.

(Refer Slide Time: 00:59)

So let us now concentrate on the problem which we will discuss today this problem 4, 3
problems were solved last class a mass loaded piston cylinder containing air is at 300 kPa and 17
0
C with a volume of 0.25m3 while at the stops v is equal to 1 m3an airline 500 kPa 600 K is
connected by a valve that is then opened until a final inside pressure of 400 kilo Pascal is reached
at which point t = 350 K find the air mass that enters the work and the heat transfer.

(Refer Slide Time: 01:55)

Now let us say this in the boat now the problem is like this there is a piston and air whose initial
state 1which is given by P1 = in the problem which is given by P 1 = 300 kPa T1 is 170 C that
means 290K and the volume V1 is 0.25m 3 okay this is the state on now what is the problem is
this air flows through this when the valve is open the air in the line this is the line flows through
this cylinder.

So line pressure PI that is the line pressure this is the I state I the line pressure PI is 500kPa the
line temperature is given by PI 600 Kelvin it is given now the problem is that as soon as the air
enters the pistol the mass loaded pistol goes up and it hits the stop, now the question tells that at
state 2 that final state let us consider the piston hits the top before the final state this is the final
state of the before the final state is reached that means here the condition the state point is two
this is the final state we consider the piston reaches the stop before the final state is achieved I
will tell how do you know.

It but at this final state P2 = that P2 is given by 400kPa 400 kPa t2 is given by T 2 is given as 350
K and the volume that is at stop it is written the volume at stops is 1m 3 when the piston reaches
the stops the volume is 1m 3 now this type of problem is like this you have to understand when
the air goes in this mass loaded piston it pushes the piston and piston goes up there is a
displacement of the piston and as it goes up the work is done by the system, now this case this
type of problems when mass loaded piston is there then it is pushed by air it is always going with
or expanding with constant pressure.

We have to assume that this process is such that this is a constant pressure process we have
already you have already come to know what is meant by quasi-static process that means it is
almost a very slow process quasi-static process which passes through number of equilibrium
state expands in such a way that the width of the piston is always balanced by the pressure within
the gas or within the air that pressure force within the air.

So pressure is balanced by view it so at every instant pressure is same until analyst it hits the stop
that is the pivotal concept of this problem, so piston expands under a constant pressure then
when it hits the stop if then air still flows then the pressure increases, so therefore we need just
detach the stop pressure is same as the initial pressure 300 kPa when we know the final state
pressure is 400 kPa that means the piston has reached the stop after that air still flows, so that the
pressure increases and that case we pressure is balanced by the piston weight plus the reaction at
the storms.

So that is the problem, so therefore this problem is very simple now when you understand the
problem this way and we can write the mass conservation from the mass conservation we can
write that m2-m1 that is initial final mass – initial mass is the mass that has entered through the
line.

Now m2 is found out by what m2 is P 2 V2 / RT2 and m 1 is P1 V 1 / RT1 so P1 P2 V2 T2 is given P2

V2 T2, similarly P1 V1 P1 is given so m2 and m1 can be found out, so therefore we can find out
the value of mi. now this value if you calculate use R for aR 0.287kj/ kg k, so it is there so you
get the value of mi. which comes out to be if you calculate the answer I am giving 3.082 to
3.082kg.

Now I write the energy equation for this finite process energy equation is also very simple that
changing the internal energy of the control volume, we have considered this as the control
volume we have considered this as the control volume and here the control volume does work so
control volume does work W and also heat transfer is there because in the problem it is told the
mass of air that enters work and heat transfer and ill-considered first the heat added to the control
volume Q and this is the positive.

If the result comes negative then heat will come out let us see how you will do now the change of
energy e2 is the specific energy m2 e2 the change of energy in this the control volume equals to
what m2 e2- m1 e1 or rather you can do this search okay, this is the change in energy in the
control volume equals to the inflow of energy that means mi into the energy which is coming
through this with the flow which is the flow energy which is nothing but the h enthalpy this we
have told that Q + PV so this is enthalpies there's flow work is added.

So in that case we can from the beginning write this is the within this cylinder air is at rest so
therefore this is only the intermolecular energy, so that you can understand so this is the energy
which is coming and at the same time it has received heat and it has delivered one so this is
simply the conservation of energy which you can get by integrating the as I told earlier the
general energy equation in the rate form, integrating with respect to time but it is not required all
the time to remember that equation.

You can state right from the concept of conservation of energy this is the rise in the internal
energy of the control volume, that means the internal energy of the tank then this equals to the
mass which has entered mi associated with its energy which is enthalpy because internal energy
plus the flow up and we neglect the kinetic energy and potential energy plus the heat required
heat received and the work done. Now here you see we know m – now U 2 is CV which we have
told CV T2 and E1 is CV T1, so therefore if we substitute this we know you to anyone with value of
CV for air = 0.717kj/ kg k, okay so therefore left hand side everything is known for an ideal gas
U2 is CV T2 e1 is CV T1 now here mi is known m2 - m1 already we have found that and hi you
substitute as CPT1.

And the value of CP for air is 1.00k4 you take this value kg key so to unknown is there Q and W
so to find out any one of them from this equation you have to know other one from an
independent equation what is that, that is the work done. This work I have told the piston is
moving slowly that at all stage stages is mass is balanced by the pressure and since this mass or
weight is balanced by the pressure force of the pressure means that the pressure remains constant
at 300 kilo Pascal's.
So this does PDB 1 and this PDB 1 get constant pressure amongst to be pressure p1 that is the
constant into v2 – v1 because PDB 1 W is integral this PDB 1 because the piston is moving very
slowly and always there is a balance between piston weight and the pressure of the air so if
pressure is constant it comes out v x(v2 – v1) we know V2 we know V1we know P1 so therefore
independently we can find the work done that is the PBR 1 at constant pressure.

So we can find out Q and the value of work and Q comes out to be I tell you the value of work is
mine 225 kilo joule 225 this is positive means this is done by the system and Q comes out to be -
819 kilo joule this minus sign indicates that heat has come out of the system that means heat
finally is not going in which we have taken and written this equation but finally it has come out
so this is the problem, clear? Okay.

So here we see the difference between the with the earlier problem is that where there was a
turbine work instead that there is a piston expansion that PDB1 here more important concept
through this problem is there that even in an open system we have PDB 1 that PDB work is not
only for a closed system this is an open system where there is a inflow but this is an unsteady
open system there is no outflow but this air pushes the piston to go up.

So therefore we can have PDB work even in a in an open system but this one requires a quasi-
static process or a reversible process which we will discuss afterwards very slow process that
always there will be thermodynamic equilibrium of the system okay . Then this is the problem.
Now we will discuss the second law of thermodynamics, the second law of thermodynamics is
very conceptual regime or rather we can tell is a very conceptual area.

Now first law we have seen it is a conservation of energy principle or law of conservation of
energy, second law as I told earlier in the introductory class is an independent law which puts the
directional constraint on all natural processes or a unidirectional characteristics of natural
processes, it apparently means that all natural processes takes place in one direction but it is not
like that it is not so rather we can understand it better in this way that yes there are natural
processes which always takes place in one direction.

For example the fluid flows from high energy level to low energy level the water runs down it
there is a statement like that that means if water is there at the top of the hill it spontaneously
comes down because the potential energy is high at the top and low at the bottom, similarly the
heat is always transferred from high temperature to low temperature not from low temperature to
high temperature.

Similarly the electric current flows from high voltage to low voltage the mass transfer of a
species takes place from high concentration to low concentration okay, so these are the examples
of natural processes which takes place spontaneously takes occurs in one direction there are
another class of problems which are not spontaneous process but which can be made by man
they also in take place in one direction, what are those process some example I am giving you.

That consider a rotating wheel now we stop it by applying a brake then what happens is that
mechanical break for example then what happens that will comes to rest and the breakthrough
and the will gets heated that means its temperature rises and let us consider the entire system is
insulated no heat transfer is the surrounding this process from first law of thermodynamics we
can tell that the kinetic energy is converted into intermolecular energy, so total energy within this
system remain same but the kinetic energy is transferred in the form of the energy is transferred
from the, in the form of from the form of kinetic energy to the intermolecular energy for which
this has become hot that means temperature is increased.

But there is no way by decreasing the temperature of the will and the break to set the wheel in
motion, so this is the one directional process. Similar is the case if you take liquid in a container
and if we start the liquid then you will see the liquid temperature increases and in that case also
we tell that the stirring for stirring the liquid some mechanical work is done on the system if we
consider liquid as a system the mass of the liquid the mechanical work which is transferred into
this liquid has increased this intermolecular energy for which there is an increasing temperature.

But there is no process by which temperature is brought down and we get back the motion of this
star this is not possible, these are known as adiabatic transformation of kinetic energy into
intermolecular energy or mechanical energy into intermolecular energy afterwards we will see
these are known as dissipation of energy and this type of processes are one directional or
unidirectional.

But there are number of processes which are not unidirectional, for example you can heat a body
from a lower temperature of T1 to a higher temperature of T2, but at the same time you can pull
the body from this higher temperature T2 to the lower temperature T1, so in that case the process
can be reversed what is the directional constraint. For example you can compress a gas from a
lower pressure and temperature to a higher pressure and temperature in a piston cylinder
arrangement and you can expand the gas from the same lower, higher pressure and temperature
to the lower pressure and temperature so the process can be reversed back.

So many such processes in nature can be made to occur in both the direction, but these processes
when they occur in both the direction they make some permanent changes in the surrounding
which I will come later on and they have to follow a particular principle because of the change in
the surrounding so when they go in one direction and they come back in other direction we make
the process to occur in both direction there is some permanent change in the surrounding for all
natural processes and that change in the surrounding is expressed in the form of some principle
okay, and that principle has to be followed by any natural processes.

And that principle or that law that is basically the second law is expressed in various forms in it
will working indifferent a different area they use for example people in material science, people
in mechanical engineering, people in electrical engineering, people of physics so they people in
chemical engineering working in different area this directional constant which is imposed
because of the occurrence of the process in both the directions as a permanent change in the
surrounding is expressed in different forms but the genesis is same that this imposes a directional
constraint.

Now this will be explained further afterwards but now from the viewpoint of mechanical
engineering there are two classical statements for the second law of thermodynamics one is
Kelvin-Planck statement another is known as Clausius statement, but before coming to this
statement I will tell you that certain definition.

(Refer Slide Time: 20:10)

So definition of first I will tell you the definitions of thermal reservoir thermal reservoir, thermal
reservoir is considered to be a body with very high capacity heat capacity so that if it supplies
heat or receives it supplies heat to somebody some system or receives heat from some system its
temperature does not change this thermal capacity is very high compared to this it transfer this is
known as thermal reservoir when it supplies it then it is known as source the reservoir is known
as source when it receives it the reservoir is known as sink, so this is known as thermal reservoir
this is the concept of thermal reservoir. Now with this concept we now go to the concept of heat
engine.

What is the heat engine? Now heat engine is defined like this basic definition of heat engine is
like that it is a device let us write this heat engine afterwards I will use H e only heat engine where
a working system operates on a thermodynamic cycle you know what is the thermodynamic
cycle that means thermodynamic cycle consists of a number of processes executed by the system
such that the system.

Come back to its initial state after the last process the final state and initial state becomes in the
final state is the initial state it operates heat engine on a thermodynamic cycle the working
system operates in thermodynamic cycle and it receives some heat that means it as a heat input
from a thermal reservoir let us consider a temperature T1 and it has an work out put W so this is
the basic definition of heat engine that which has an heat input q1 and to gave an heat input it has
to have a thermal source t1 and come that it has a work output that means it converts heat into
work.

Now in this respect we have to know that for a continuous conversion of heat to work the cyclic
operation is required a cyclic operation is required for continuous conversion of heat to work and
that is why the system has to operate on a thermodynamic cycle. So this is the basic definition of
heat engine takes a heat input and delivers or now from thermodynamics first law we can write
that this work equals to Q1.

So as far as the basic definitions of heat engine and first law of thermodynamic the conservation
of energy I am write up to this point but the second law which is formulated again I tell you from
the basic observations in nature tells no this is never possible you can never convert the entire
heat into work continuously in a cyclic process, so what then you can do? Thermodynamic
second law tells first know this you cannot do so what you have to do if you want to convert
work from heat q1 then you have to reject some amount of heat for which you require another
thermal reservoir that is sink this is source t2which is less than Q1 and in that case W will be q1 -
q2.
So which means W is always less than Q so the entire Q heat which you receive from the source
cannot be converted into what continuously in acyclic operation by a heat engine, so this is the
concept now in this context we define thermal efficiency thermal efficiency of a heat engine as
the desired output W divided by heat input q1, this is given by η. So therefore η is w / q 1or one
can write q1 - q2 / q1 that is equal to 1 - Q by second law W is always less than G 1 that means q2
can never become zero q2 has to be greater than 0 and W has to be less than q 1 which means each
other is less than100%.

That means a heat engine can never reach a hundred percent efficiency but here one very
important point is there that this heat engine can never reach100% efficiency that is even the heat
engine is an ideal one and it consists of all ideal processes that means reversible processes which
I will come afterwards even in the most ideal case that in absence of all dissipative effects and
everything then also this cannot achieve 100% efficiency here is a very strong concept that
sometimes we tell a generator cannot attain 100% efficiency electrical motor cannot attain 100%
efficiency and the mechanical transmission system cannot attain 100%t efficiency this is because
of practical things dissipative effects friction hysteresis all these things come into picture
electrical hysteresis magnetic hysteresis.

But in an ideal case we can conceive of such systems with 100% efficiency but yes we cannot
conceive of an ideal heat engine in absence of all frictional and all dissipative effects to attain the
100% then this imposition by the second law is imposition even on the ideal system so this is the
this is the heat engine definition okay.

(Refer Slide Time: 26:35)

Now I will tell you the Kelvin plank statement and the this is the Kelvin-plank statement which
says it is impossible for any device that operates on a cycle to exchange heat with single
reservoir and produce a net amount of water that I have described and Clausius statement tells it
is impossible to construct a device that operates in a cycle and produces no effect other than the
transfer of heat from a lower temperature body to a higher temperature body that fountain
spontaneously heat cannot be transferred from lower temperature body to higher temperature
body.
(Refer Slide Time: 27:24)

These are two statements so now these two statements are equivalent that means if Clausius
statement is invalid then Kelvin statement is invalid if Kelvin statement is invalid Clausius
statement is invalid now let me prove that let us consider the Kelvin-plank statement is invalid
that means there is a temperature t 1 and let us consider a sheet engine operating violating the
Kelvin-plank statement by exchanging heat let this is Q1 with this t1 temperature and develop
water.

And let us consider that a system that X so this is the Kelvin that is the violation of Kelvin-plank
statement t1 and we consider that this there is a heat pump of course we have to tell the heat
pump before that you have to know the heat pump otherwise it will be difficult for you to know
let us see that we'll go back to the definition of hit pump then we will put this sorry otherwise.
(Refer Slide Time: 28:36)

It is very difficult to understand Racal equality of the two a heat pump or a refrigerator heat
pump or a refrigerators just the reverse of the heat engine that means what it does it takes heat
from a low temperature body and pumps heat to a high temperature body but it is not possible
according to cross via statement but it takes work from outside so giving work from outside one
can take heat from a low temperature t 2 is less than t1 or t1 is greater than t2 to a high temperature
body in this case it is possible it takes 1 not spontaneously without any effect in the surrounding
in this respect if you write the conservation of energy Q1 becomes is equal to Q2+W.

So t1 is equal to this t1 giving equal to Q2 +W so this W taken this is just the reverse of heat
engine in this context two things are define coefficient of performance just like thermal
efficiency of a heat engine we define coefficient of performance COP now when our desired
objective is to pump heat to higher temperature then we call it as a heat pump when a desired
objective is to take heat from a lower temperature you call it as a refrigerator, a refrigerator and
heat pump is the same devices.

We will see in your house that if you stand the size of the refrigerator it will be hot it is
exchanging heat to the surrounding so if you think in that terms I get shipped from the
refrigerator outside that is a heat pump and if the inside of the refrigerator what is the evaporator
box that is the deep freeze so they are the cold space is there where the heat is being taken so if
the desired objective is Q2 that taken heat from the low temperatures refrigerator and the desire
then it is equal.

So therefore COP of a heat pump is given by the desire of the Q 1/W & COP of a refrigerator is
Q2/W and from the first law we can write that W is nothing but Q 1- Q2 so therefore Q2/Q1 so with
this definition of heat pump or refrigerator now we can prove the equivalence of cross here
statement and the Kelvin plank statement okay Kelvin-plank statement.

(Refer Slide Time: 31:27)

And cross he escape Kelvin-plank and Kelvin-plank statement and cross your statement and
close your statement now you see the equivalents of Kelvin plank and let us consider that means
equivalence mean if Kelvin-plank statement is not valid then Clausius statement will also not be
valid similarly the Clausius statement is not valid Kelvin plus statement will not be valid let us
consider the Clausius kelvin-planck statement is invalid that means there is a heat engine which
takes heat Q1 from a source t1 and develops what? W and develops work W here I write, there is
no other deserve one that means, the entire Q1 is converted to W high lighting the Kelvin -
Planck statement it operates with single fixed server. Now we consider a heat pump or are
refrigerator, a heat pump or a refrigerator.

Which takes it from a low temperature body t 2 which is lower than t 1 here in this case you lower
than t1 take some heat QL and this heat pump is run by this heat engine, that means the work
developed by the heat engine is given to this heat pump to run okay, this is the heat engine and
this is the heat from the opposite direction cycle and then we complete rejects heat engage. Now
this Q H is what QH is QL + W and W is what? W = Q Q H + w again from the heat engine
conservation of energy W is Q1 . So okay QH, so QH is you will plus QL +1 1okay.

Now therefore you see that the combined system as a whole does what this takes heat Q L from
the low temperature to the high temperature because the high temperature source receives the
heat it gives Q1 and takes QH it receives the heat, QH – Q1 IS QL that means if you see the reserved
source, the high temperature reservoir it gives it Q 1 receives it QH, so it this is the net heat Q H
minus t1 is QL that is what is being taken from the low temperature t2.

So therefore the combined system spontaneously takes it from t 2 and that to you on high
temperature without any other affecting the surrounding because this work an internal that means
this heat engine work is driving the heat pump, so combined system does not make any change in
the surrounding without making any change in the surrounding lifts it from low temperature to
high temperature. That means if the Kelvin Planck statement is not valid cross your statement is
also not valid.

Similarly we can show that if the Clausius statement is not valid that means spontaneously heat
can flow from low temperature to high temperature without any other affecting the surrounding
then Clausius statement will not be valid, so this is left as an exercise to you and you can see in
any thermodynamics book for this time is short, so I am not doing that, so only once I have
proved that if Kelvin Planck statement is invalid Clausius statement is invalid.

So it violates the Clausius statement, similarly Clausius statement is violated Kelvin Planck
statement is also violated, so after this I will show you a practical figured.
(Refer Slide Time: 36:12)
That this is of a typical steam power plant, you know the steam power plant from which we get
electrical energy but the steam power plant layout is like that from your popular knowledge you
know but I am not going into any details of that, there is a boiler where the combustion takes
place of a fuel is really coal and the high-temperature gas of that after the combustion heats the
water in the boiler, water is the working substance this is converted into steam and then this
expands into turbine to give work.

Then after expansion the low temperature and low pressure steam is passed through a condenser
where it rejects heat to the atmosphere usually the atmospheric water is a water from the
atmosphere is taken as the cooling water, which takes the heat from the steam to condense then it
is given to the pump where it takes work and pressure is boosted to that of the boiler pressure. So
this is the thermodynamic cycle and here you so see that energy source that is the furnace where
the combustion takes place and hot gas gives the heat.

That means here the working system water takes heat, so this is one reservoir and in the
condenser where the steam after expansion is condensed is the sink the low temperature
reservoir, that is cooling water from the atmosphere so you see that this is a heat engine where,
we have two deservers that furnace of the boiler and the cooling water from the ambient or
atmosphere at the condenser.

And as a result we get a network output which is the work output from the turbine the work input
to the pump which is much less compared to the turbine oil, so this is one good example of a heat
engine which is a typical steam power plant in practice okay now if we close this module here
next to you start the other thing thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 13: Second Law and its Corollaries (Part II)

Good afternoon and I welcome you all to this lecture section of the course laws of
thermodynamics, now last class we discussed the Kelvin plant statement and Corollaries
statement to formal statement of second law of thermodynamics, from the prospective of
mechanical engineering and we show that the equivalence of the two statement that means the
one statement is invalid then other statement is automatically invalid.

The we shown this in the case that Kelvin plant statement is invalid if we consider then we have
seen that the collision statement is also invalid and vice versa the other one left to you as an
exercise or you see in any book, now today we will start a very important concept which is
known as reversible process.

(Refer Slide Time: 01:05)

What is a reversible process by definition initially told you the directional constant that some
process are unidirectional in nature they cannot be brought back in the other way, they cannot be
made to occur in another way other way that means it occurs only in one way not the reverse
one, the reverse one takes place apparently it means those process switch by it is just definition
in this mean is reversible.

That means the process which can be which can take place in both the ways and the process
which cannot take place in both the ways that means it take place in one way or one direction
that is irreversible process no that is not the correct I told you earlier that there is some
permanent change in the surroundings when a process takes place a system from initial state to
final state and the back the reveres of the process that means from the final state to initial state
there is some change in the permanent change in the surrounding and that gives rise to the
concept of a revisable process you understand.

So therefore revisable process by it is formal statement you can tell like that a revisable process
is that process if at the conclusion of the process are formed by a system going from 1 state
initial state to the another final state the process is reverse back okay so that this system is
brought back to it is initial state the surrounding cannot come to the initial state or the initial state
surrounding cannot come to the initial state this is for all natural process if we can consider a
process which after it is conclusion from 1 state to other state is brought back in the reverse way.
To comer to the initial position and surroundings also comes to initial position that process is
known as reversible process that means we can restore both the system and surrounding at their
initial condition or initial state by occurring the process by making the process to occur in
direction form 1 state to other state and reverse back from the final state to initial state in such a
way that surrounding does not suffer any permanent change that means surrounding also comes
to it is initial state.

That process is known as reversible process but unfortunately all process in nature are reversible
they are all irreversible process now I tell you one example which told earlier that with respect to
heat transfer process you see that if we consider heat transfer natural case heat transfer t1 to t2
where t2 is ≤t1 heat transfer takes place but the reverse is not possible that means this the natural
process which occurs in one direction this way it is reversible but if we consider this one that a
body let us consider at a temperature t1 that 200 C.

For better understanding is heated finite body to a temperature of 80 0 C this heating and if it is
clod again cooling from 800C to 200C system come back to initial state that mean this process of
heating is not a unidirectional process the cooling is also possible but how does system
surrounding gets a formulate surrounding cannot come to the initial state let us consider this that
to heat it from 200 to 800C we have to put it, keep it in contact with the hot body th whose
temperature should be either 800C or > than 800C if you keep it at 800C then heat transfer at the
end will be very slow with the temperature will be close to 800C the rate of interest for will be
so.

Because of infinite small temperature difference so therefore for a natural process to occur to
within a infinite time , we take this th > 80 0 that 100C and they are put into contact thermal
contact by a the thermic one then if takes it okay and goes to 800 oh in this 800C body is cool
that means the reversible process to reveled back to 200C we take a body, let take this tl lower
temperature body which is equal to 100C and it gives takes heat from the body and cool it to
200C then you see though this system at the initial state.

But surrounding what is happen, the surrounding as given heat from his source at 100 0C that
means from a thermal deserver that 1000C and he has got the heat back to his thermal reserve
and 100C and this one is surrounding is not at the identical condition which it had initially no it
has they will heat from one part of this surrounding one reserves and taken it in another preserver
so if you want to make this surrounding to the initial state, that mean to restore this surrounding
to its initial state then we have to get back these heat.

Where from it was given this all this surrounding and this is another part of the surrounding we
together differ this surroundings that if we can get this heat to this body, then surrounding will
come to the initial state but this is not possible this is the cross statement without any other
external line we cannot do it. We can do it by the help of a heat pump or refrigerator that we have
to take one that is surroundings of final will change, so therefore these so surroundings offers a
permanent change.

Similar way I tell you that if you have cylinder in piston then if you compress the air and forms
some pressure and temperature to a high pressure and temperature and then expanding and if you
come back to the initial state, after compression then expansion then the compression process is
any reversible process why or other way if first expansion then compression, so that expansion
followed by compression or compression followed by expansion so that the initial state is less to
but in that case also surroundings offers in permanent change that in actual case the work
delivered in case of expansion and.

Work required or given in case of compression this is because of mechanical histories due to
friction and other deceptive effects, so therefore this way all natural process is when they come
back when the natural process is in a system changes from 1 state to other state is made to occur
in the river so it for the system to restore the initial position, initial state rather then this
surroundings offers say permanently change the surroundings state is permanently change, so
this way we define that all the natural process is the irreversible.

If we can make the process reversible then this is possible because the definition of reversible
process is that after the conclusion of a process if it is reversed back.

(Refer Slide Time: 09:24)

Both the system and surrounding can be raised to its initial state but this may ever happens that I
will show you that causes now why it does not happen causes so therefore we must know causes
of reverse all natural process are irreversible process irreversibility causes of irreversibility now
causes of irreversibility all natural irreversible process are irreversible process, process are
irreversible now this causes of irreversibility here is the lack of thermodynamic equilibrium you
have already come to know what is thermodynamic equilibrium lack of thermodynamic
equilibrium and this thermodynamic equilibrium consists of mechanical equilibrium so therefore
lack of mechanical equilibrium, lack of thermal equilibrium 3 equilibrium consists the
thermodynamic equilibrium.

That you have already read we have discuss it earlier and lack of chemical equilibrium, now lack
of mechanical equilibrium happens when ΔP not equal to 0, in case of mechanical equilibrium
ΔP is 0 there is no pressure difference between the system and the surroundings and the
mechanical work is delivered in that way that there is no dis-balance force acting on this system
so ΔP has to be 0 for mechanical equilibrium to be achieved.

But ΔP not 0 is the lack of mechanical equilibrium departure from mechanical equilibrium,
similarly the thermal equilibrium demands ΔT should be 0 but ΔT not 0 is the lack of thermal
equilibrium by virtue of which the system transfer heat to the surrounding by virtue of which
system transfers work that means interacts work with the surrounding interacts in terms of heat
transfer with the surrounding.
Similarly lack of chemical equilibrium is concentration difference is not 0 or chemical potential
which is responsible for chemical reaction this is responsible for mass transfer they are not 0 but
if all ΔP, ΔT, ΔC, Δμ as 0 the system is in thermo dynamic equilibrium does it interact with the
surrounding in terms of either work transfer, heat transfer, mass transfer or chemical reaction.

So therefore for a reversible process this has to be 0 so these are the causes of irreversibility with
it departs from the 0 value there has to be some pressure difference there has to be some
temperature difference there has to be some ΔC Δμ for irreversibility to be there for the existence
of the irreversibility. So one is lack of thermo dynamic equilibrium another is the dissipative
effects.

Dissipative effects are like this under this heading dissipative effects we have mechanical friction
we have mechanical friction you know these are the dissipative effect fluid viscosity these are
innovative lymph practice fluid viscosity inelasticity then magnetic hysteresis, electrical
resistance all these things are dissipative effect then in any process for example in mechanical
movement of piston and cylinder.

This is there is mechanical friction fluid viscosity appears inelasticity if you stretch aware
magnetic hysteresis in magnetic work transpose in electric resistance electric one work transpose
and the effect this all dissipative effects basic purpose is same what they do they convert the
mechanical energy or the work mechanical work electric work all constitutes the work in
thermodynamics into inter molecular energy.
By which the system becomes hot so therefore this is known as dissipative effect they dissipate
the energy and why the term dissipation is there I will tell you afterwards that mechanical energy
or work they are organized form of work and energy from the molecular point of view where the
inter molecular energy is disorganized form of energy, and these are called as low grade energy
that is high grade energy, and already we have seen earlier that heat cannot be converted
completely into the work.

But work can be converted completely into the heat in a heat compound refrigerator, so that is
another we define high grade and low grade energy that means work or mechanical energy is
high grade energy which is being transferred to the intermolecular energy by all this agents they
are the agents and they are always present in any process and they are known as dissipative
effects.
So this way we see that the thermodynamic equilibrium is distorted and the dissipative effects all
together calls make the system the, possess irreversible. Now what happen that means
irreversibility if we have to have a reversible process, P1 is reversible then this has to be 0 ∆P is
0, ∆T is 0, ∆C is 0 ∆μ is 0 that means there is no process at all, because they are the motive
forces for the process and obviously there will be no dissipative effect that means if you occur
any, even a process is occurred if you make to occur any process then automatically there will be
thermodynamic lack of thermodynamic equilibrium.

Therefore, this statement is very important the irreversibility of any natural process lies in it is
basic requirement for the process to occur, so therefore without any if there is no process without
any lack of equilibrium that means for complete thermodynamic equilibrium system is at rest and
there will be no dissipative effects, so therefore Po reversible process actual reversible process
pure reversible process can never occur.

But we can think of some process which is close to reversible process what are those let me see,
close to reversible process so from this concept we can think of process close to reversible
process why if we have the process where thermodynamic equilibrium departure is infinite small,
that means for process.
(Refer Slide Time: 17:26)

For any process where ∆P tends to 0 is very small, ∆T tends to 0 very small, ∆C tends to 0, ∆μ
tends to 0 and dissipative effect if it is tends to 0, now when this we will tend to 0 the process
will be extremely slow heat transfer under infinite small temperature differences is extremely
slow, what transfer under any infinite work pressure difference, mass transfer under the infinite
small concentration differ, chemical reaction under infinite small chemical potential difference
are extremely slow and obviously dissipative effects will tend to 0.

This process is known as Quasi reversible or Quasi static process and another condition is that
when this process will take place and that very small that means with the process takes place in
such a way that there is an infinite small thermodynamic potential, thermodynamic equilibrium
or if there is a infinite small departures from thermodynamic equilibrium and process is
extremely small and each and every state the process is in thermodynamic equilibrium, that
means for example if we expand the gash with a very small ∆P from a high pressure to low
pressure, first you expand from a high pressure to a very small ∆P difference, very close to the
high pressure then we keep the gash at rest for some time.

Well, so that the it comes to thermal equilibrium then again we expand to another lower pressure
which is very close to the initial pressure, very slowly and then at rest for some time so that it
attends a thermodynamic equilibrium, that means the process should pass through all
thermodynamic equilibrium states and it is extremely slow and takes place under infinite small
potential difference either ∆P, ∆T, ∆C, ∆μ this is like that. If I walk like that it is an irreversible
process, but if I walk like this that is slowly and take rest for some time thermodynamic
equilibrium exist within me, thermodynamic equilibrium exist so this is a reversible process.

But reversible process is extremely slow so that from one state to other state reaching the one
state to other state reaching one state to other state exist some state in finite time so this is known
as quasi reversible process now this can be explained in terms of the heat transfer let us explain
that there are there is a t1 temperature if you have to make it is a thermal reservoir source if you
have to make a reversible heat transfer to a body then this body temperature should be t1 – dt,
small difference where dt is extremely small that means infinite small temperature difference
heat transfer is the reversible heat transfer.

Or you can take that some t2 t2 + other way you can show that heat is transfer from a body at t2
to t2 + dt that means the heat has to be transfer when infinite small temperature difference. Now
we earlier consider that 200 C body was heated to 800 C and what do we did we first took it a
body of 1000 which is more than 800 to 200, so that in a finite time heated it is heated to 80 0 C that
is heating process.

And similarly if you cool replace a body at 10 0 C and allow the heat to flow from here and it will
come in your finite time 200 this is irreversible process we are seen because the surrounding does
not come its initial state after cooling but now if w make a reversible heat transfer this is the
reversible heat transfer but here the body is are at same temperature t1, t1 – dt t2 there the
thermal reversible source and sink finite its capacity infinite it capacity but her the body is a
finite heat capacity heating process that 20 to 80 in that case we can achieve the reversible heat
transfer if we consider in number of reservoirs with the very small difference 0.01 0 C20 20.01
20.02 20.03 like that in infinite number of reservoirs like 79.01 difference 99 then last two is like
that 800 C.
So if you consider this infinite number of reservoirs with 0.01 0 C differences then we just take
arbitrarily and finally to 800 and you first make this system to come to this contact so that it will
be heated extremely slowly with the temperature difference of 0.010 C that means which is a
limiting reversible process or quasi reversible process they leave it in case quasi static process
because the process is extremely slow when it reaches 20.01.

Then you wait for sometime so that entire system assumes a uniform temperature of 20.01then
you keep it in contact to it 20.02 reservoir it is heated that means I am doing full wrong so it is
heat is going so that it is heated top 20.02 then you bring this here [Link] it reaches 20.02 we
bring it here so that always what we do 20 to 20.01 take some time so that it reaches uniform
temperature then with the reservoir at 20.02 then we reaches 20.02 with the reservoir at 20.03 so
that it guess 20.03 and finally it gets 800 form this 79.9 then 800 okay that means here the body
you will attend 79.90 C then it is 800 C.

Which means that allow is the heat transfer take place with any finite small temperature
difference is not that initially I put 1000C huge temperature difference initially temperature
difference very large irreversible is very high, finally it goes down but still when it goes to 80°
still there is an irreversible because the heat transfer takes place with the temperature differences
of 20° but here always heat transfer takes place with varying infinite small temperature. If you
can reduce it into 0.001 differences then more number of irreversible are there that you can
conceive the infinite number of reservoirs it very small resolution with the temperature
difference and always keep the body to contact to reservoirs successively.

So that hit transfers takes place under infinite small temperature difference these way you can get
reversible hit transfer okay reversible hitting process because if you cool this thing similarly you
will pass through this infinite number of reservoir successive from another direction so that the
surroundings will get the hit back from where it get the hit and from which reservoir it get the hit
so it will get back.

So therefore you think over it and you will see that we concentrate reversible hit transfer process
similarly a reversible expansion and compression process mechanical what done I have told that
already so this is precisely the concept of reversible process which can never be achieved in
practice theoretical reversible process but it can be achieve in the limiting case that is quasi
reversible process or quasi-static process when the departure can come into a equilibrium its
extremely small and the process is excessive slow process to the number of equilibrium states.

Now we will come to very important theorem known as Carnot theorem but sometimes people
tell this is probably the most important we have in second law and from which the other
deductions take place to give bath to other corollaries so this is what let us see here the Carnot’s
theorem or Carnot principle.

(Refer Slide Time: 27:01)

There are two statements say for it the Carnot’s theorem or principle the efficiency of an
irreversible het engine is always less than the efficiency of reversible one that means reversible
heat engine operating between the same two reservoirs similarly the efficiencies of all reversible
heat engines operating between the same two reservoirs are the same.

Again I m telling the efficiency of an irreversible het engine is always less than the efficiency of
reversible one that means reversible heat engine operating between the same two reservoirs and
another one is that the efficiencies of all reversible heat engines operating between the same two
reservoirs are the same.

Now let me proof this one okay let me prove this one let us consider a heat source at temperature
t1 one is a reversible heat engine and another it takes heat let us consider Q 1 and rejects Q2R to a
sink t2 let us have a sink t2 and develops WR then we consider we have another heat engine which
is not reversible it takes heat Q1 and Q2 they are all different.

Now by reversible het engine we mean that heating in the working system operates in
thermodynamics cycle now thermodynamics cycle is composed of number of process such that
the initial study equal to final state and then all the process are reversible processes that
constitute reversible cycle and heat engine which operates on a reversible cycle is known as
reversibility engine.

And if any process of the thermodynamics cycle is irreversible so this is an irreversibility engine
now let us first consider that Q1R to prove that Q1 why because this Q1R minus Q2 are WR for
conservation of energy so here also Q 1-Q2 is W that means that is minus rejected in work done in
this equation two are independent one is dependent that means Q1 and Q2 are fixed.

So therefore if two are independent out of this two anyone we can choose as for our choice so
this is the logic for which we consider Q1R is Q1 so according to this is heat engine and this is for
reversible according to Carnot’s that η R is greater than η n but who is first start to it we will
show this is not possible is less than η R is W1/Q1 for this η W1/Q1 are in same then if we
consider this η then W1R is less than W1.

If we consider η this Carnot’s Theorem we do not accept that is W1R is less than W1 whart we
consider what we do now here we just reverse this heat engine in the opposite direction and you
draw another figure here that I am doing like this I have this opportunity to heat pump
refrigerator reverse.

Now since this is the reversible heat engine operating on a reversible cyclic if we reverse all the
process, then the surrounding will come to the initial state that means it will resemble the same
magnitude of the heat transfer but in the opposite direction. That means it will take Q 2 R heat
from the sink and gives QnR heat to the source taking WR, your requirement will be here for the
heat pump the direction is changed, this will be same, the heat will be pumped to the source but
not taken from the source then the magnitude will be same.

Similarly heat will be taken from the sink not rejected to the sink to the operational heat pump or
refrigerator magnitude will be same because this is a reversible heat engine. This cannot be done
like that, this could be made to operate in the reverse direction but these quantities will be
changed. Now if we make this reversible heat engine or refrigerator has a reversible heat pump
reversible heat engine to a reversible heat pump or refrigerator.

Now since W1 are less than W I leave this and still I get W1R – sorry W1 – W1R amount of work.
W1 is the work by the reversible engine, that means since this irreversible engine work is more
than reversible engine work because we consider η < η, so therefore this less, so the part your
work is taken, so that we get heat amount of work W 1. Now you see this Q1R and this gives heat
to this thermal deserver or source and from the same source Q 1 it takes heat, there is no need of t 1
this reservoir.

Why? Simply we can eliminate the reservoir and can join these two that means you are working
through t1 we will act as this same, where the heat will be given by the heat pump and the
working fluid here, where from it will take heat as this source for this heat engine. So therefore
since this Q1R and they are taken from the same temperature, so they can be linked like this, so
the working fluid of this will act as the source for this and the working fluid of these act as sink
for this heat pump.

That means what happen? The combined assisted highlights the Kelvin plank statement, that
means it interacts with single fixed reservoir and develop the net amount of W1 – W1R. This is not
acceptable by the law of nature, the 2nd law which is Kelvin Planck statement, so therefore η R
cannot be less than η. So there are two opportunities, two possibilities η R η or ηR > η . Now how to
get rid of this opportunity by this condition there are two situation, two possible solution η R
cannot be > η because this Kelvin Planck statement.

So ηR cannot be < η not greater than, that this Kelvin Planck statement is highlighted, so
therefore ηR is either η or ηR > η , so η is η then what happens all the heat transfer and work done
will be same for the two engines, this is the logic only, there cannot be any analogical proof
because we consider the reversible and the irreversible engine in different, in terms of their
performance if η = η then if we take QR = Q1R earlier which I took in the another figure, that both
heat engines are there.

One reversible and the irreversible if ηR is η they will reject same heat and they will develop same
work whatever it be, that means the performance will be identical in terms heat and work
interaction that cannot happen, but this is the basic assumption or this is the basic realization that
the reversible engine and irreversible engine cannot interact with the surrounding with the same
heat and work interaction, so that their efficiency will be equal.

Otherwise the irreversible engine will become the reversible one, so that logic puts that logic
imposition the condition that it is not valid, that means the reversible engine efficiency cannot be
equal to the irreversible engine or other reversible engine efficiency cannot be equal to
irreversible engine, otherwise everything will be same irreversible engine will be reversible
engine because the reversible cycle is characterized by the performance.

That is efficient performance not distribution, okay so that first process with distribution cannot
reveal with the same efficient, this is not accepted so therefore the only solution is that η R that
means the efficiency of the reversible engine is greater than the efficiency of the irreversible
engine. So therefore the first statement is proved that the efficiency of the irreversible engine
work will be to same temperature levels to the same thermal reserve source sensing, the
reversible engine as the higher efficiency.

Next we have to prove that efficiency of all reversible engines operating between the same
source sensing cannot be same that I will do in the next class thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 14: Second Law and its Corollaries (Part III)

Good afternoon and I welcome you all to this lecture section of the course laws of thermal. Now
last class we discussed the connotes we discuss in the connotes to we arrived by logical detection
of truth.

(Refer Slide Time: 00:55)

That reversible in the efficiency of reversibility is this higher than that we reversible engine
operating in the…. Now the second statement is that efficiency of level civil engine operating
same source in this.
How do you protect to how do you protect it is very simple hoe you put the first one it will
automatically follow. That means there is two reversible engine R1 and R2 for the reversible
engines R1 and R2 both the reversal we discussed earlier. One reversible and another will
reversible. Let q1 arrow and is the taken by the reversible engine arrow one and Q1R2 is been
reversible engine.

And these are the keep rejected by the reversible engine 1 and reversible engine 2. Accordingly
these are this work never followed by the reversible engine1. This the work developed by the
reversible engine 2 okay. Now let us consider the all with the earlier that ηR1 < ηR2 ηR1 is less
than our we consider this is reversible this was revisable. Then by designation of episame and
you have the same time.

Consider that Q1R1 is similar with that means the hit taken by two reversible engines is but their
rejection is different accordingly the work done is different. Because we do not accept for that
efficiency is that. First we assume that ηR1 is less than ηR2. If I make this two operator is a hit
pump reversible hit pump or refrigerator. Then all this quantity will be same in the opposite
direction and it will demand then work WR1 from the surrounding and keep.

This is so WR1 is less that means the earlier proof W R1 is < WR2 therefore the part of WR2
will be taken by WR1 and will gativinate work output of wR2 – WR1. Clear because last proof if
recalled the last proof then you will see the WR2 is greater than WR1 so we take these and we
designate. That means by reverse this we can proof that ηR1 then or to be less than ηR2, because
in that it is will violetic element clustered.

We connect this and we proof, now the differences is that this is again in reversible engine now if
we reverse this now ηR1 cannot be greater than it cannot be less than η[Link] u consider ηR2 is
less than ηR1. This is less than then what happen what we do? We just reverse. This is the
reversibility engine and all this quantities will reveal by this same amount but the opposite
direction then it will QR2 from it will QR1 or Qr2 here. And it will take WR2.

So if ηR is less than ηR1 then WR2 in this case less than WR1 and we can connect this and then
that case we get WR1 – WR2 and we connect this two, this means violetic we mean consider that
means in that in this cas what we can do we can reverse this engine if we consider this efficiency
of this less than this and will prove that the only I that prove her. The efficiency are and this will
cannot be less than this otherwise the violet it will be consider by the this two.

Because this two and it is, if I consider ηR2 <ηR1 then we reverse this and here we are that
opportunity that advantage that seems it is a reversible engine if you reverse this quantity will be
same. And in the opposite direction since in the case WR2 < WR1 to it is WR1 is the part of this
and WR1 –WR2 is the main part of and will connect with this. So this so it will violet will be
construct this. So therefore ηR2 cannot be equal to ηR1, so ηR1 cannot be less than ηR2.

ηR2 cannot be less than sorry it will cannot be less than ηR1. So only opportunity only solution
is that ηR1. That means this can be prove that for any reversible engine operating between the
same source temperature and seen temperature. The same deserver operating between the same
two hit reserves is same. And now you can add a question are what the differences between
reversible engines are?

Yes the reversible engines two reversible engines may differ by the construction of their material
of construction by their design the process will be different. Reversible process may not be that
the reversible process can be constant pressure reversible process constant volume the reversible
process, isothermal reversible process. So the process is that means the thermolinamic cycle may
different for these two cases.

You working doing or working system may be different their material of prospection for the
engine may be different, so that may many ways in these two different. But thermolinamic cycles
on which be working system we can operate both the sides are have to be reverse. Then it will be
revisable in this and they will be different reversibility. That means whatever will be the working
system, whatever may be the processes in terms of the process caused.

But the keep the processes are all reversible that means the reversible cycle is reversible. Then
the reversible of the different types then the same efficient the results in the same efficiency that
will be the two temperatures. So therefore we can tell this thing is now you in this form that all
reversible engines of the same efficiency which ηR and all engine will be reversible engines. And
otherwise which where is in the working system material of construction processes.

But the reversible, not the all processes are revisable in the thermolinamic cycle. Thermolinamic
cycle is revisable, the vary of this revisable that means all of u designs have engine in fact this
will revisable engine technical engine then we will see the efficiency of the all the engines. Then
we will see all the engines developed by this entire individual will be different. What may be
smart enough to design efficiency in the engine 1.
Not that smart enough to revisable engine which is not that efficiency. That means all will
revisable engine in the η1, η2, η3, η4 all may in define. Then η1 ≠ η2 ≠ η3 ≠ η4 and so on is not
that they are equal. That means the reversible engine may be deficiency may where we given in
between the same source side. Which are but this is same and the highest of this efficiency or this
reversible class of engines but the class of the reversible engines is less than ηR.

That means ηR > η highs the highs value of the efficiency but one can achieve in practice are in the
reversible or natural engines is less than η, that means the revisable engine efficiency is the highs
put the performing this criteria for all the reversible engine. All the reversible engines when
where we are using their efficiencies but the highs one is the reversible engine efficiency to this
same for all reversible engines are in between same source and same temperature.

(Refer Slide Time: 08:56)

Now I will come to a very important concept or very important detection thermodynamics scale
of absolute scale absolute thermodynamic scale of temperature, absolute thermodynamic scale of
temperature. This is how do you define it was defined by lot scales in first. The absolute
thermodynamic scale of temperature then it was in this. Now this definition of absolute
thermodynamic scale of temperature comes for in directly or it is a direct comes directly from the
Carnot's theorem or principle or it is the direct consequence of Carnot's theorem or principle.

Now let us see now if there is a heat engine operating between t 1 x8 Q1 and rejects it Q2 at a
temperature t2 and develops or we know if it is the reversible heat engine then we know
efficiency is a function of temperature that means the Carnot's principle tells that all reversible
engines at same efficiency working between the same two temperatures Thermal reservist t 1 and
t2 t1 is greater than t2

That means analytically you can express that η is a function of t1 and t2 because this depends only
on temperature if you change that t 1 t2 then the reversible engine efficiency will change but again
with the same sink and source and sink same reservoir the efficiency of all reversible means that
means for a given t1 and t2 as the source and sink temperature if we see this is a function of t 1 t2
that we can write.

Now if we see in C can be written as W / Q 1 = Q1 this has been done earlier Q2 / Q 1 that means 1
- Q2 / Q1 so therefore one can write 1- Q 2 / Q1 = function of T1 that means this is a function of T 1
T this can be written in a different fashion that Q 1 /Q2 is some other function of T1 / T2 that means
T1 and T2 that means the ratio of heat interactions by the heat engine with the source sensing is a
function of 2 temperature this some other function that means we just write in this fashion 1 -
Q2 / Q1 is a function of T1 and T2 then Q1 / Q2 can be written as a function of T1 and T2 okay.

Now we will consider another heat engine let us consider this is heat engine number one this is
heat engine number 2 which rejects takes heat from T2 as Q2 and rejects heat Q3 at a
temperature T3 which is < than T2 which is < T2 that means T2 is < T1, T1 < T2 and T2 T3 is < T2
and it develops another or let this work is W1 and this work is W2 heat engine 2 then for heat
engine 2 we can write in the similar fashion that Q 2 / Q3 is the same function of T2 / T3 because it
is an unique function it is since the unique function who depends upon the temperature level if
you substances these arguments T1 T2 it to it will give the value of η

Because it is dependent on T1 T2 for the same function but with T 2 and T3 and if we consider the
combination of two engines together r1 and r2 together which develops W1 and W2 amount of
wall takes heat Q1 from t1 and rejects heat Q3 to T3 then with respect to the combined system we
can write Q1 / Q3 is a function of t1 t3 okay same function now we can write this thing in this way
but so long we do not know this functional form.

We only express in the form of an implicit function that Q 1 / Q2 is some function of t1 t2 Q2 / Q3 is

the same function of t2 t3 and Q1 / Q2 is the same function of t1 t3 okay, now if we write with
certain algebraic manipulation Q2 by Q1 as Q1 by Q2 rather Q1 / Q2 ask Q1 by Q3 divided by Q2 /
Q3 then we can write this Q1 /Q2 is Q1/ Q3 / Q2 by Q so therefore we can write function of t 1 t2
equals to function of Q1 t1 t3 divided by the function of t2 t3 from here that means if I just make an
algebraic rearrangement.
So that this gives some hints to the type of the function not the explicit form that explicit form of
the function in terms of the two temperatures but at least they give some idea because of
exploiting this relationship Q1 / Q2 function of t1 t2 Q2 / Q3 is a function of t2 t3 and Q1/ Q3 is the
function of Q1 T, so that we can write that function of t1 t2 is function of t1 t3 divided by the
function of t2 t3 this is only possible that means t3it should be canceled out such a way that t 3
terms from these to function.

So that it results into the function of t 1t2 and this is only possible provided the function is of this
type t1 t2 can be expressed in terms of product or quotient however you can tell I write this way is
a function of t1 divided only in terms of that is a product form or a quotient type that if function
of t1 t2 is function of t1 / t2 then it can happen because here it will be function of t1 by function of
t3 here it will be function of k2 by function then what is happening that function of t1 by function
of t2 if the function can be expressed this way then only this is function of t 1 divided by the
function of t3.

So this function can be expressed is this way that is function of t2divided by the function of t3 that
means the way in which the heat fluxes cancelled out Q 3 it becomes Q1 / Q2 the function t3
cancels out altogether so that it remains function of T 1/function of T 2 which is a function of T1
T 2 that means this function of two temperatures for the efficiency will be in this form, clear? So
this now okay, now these function of T 1 and T 2, Ø T1 and Ø T 2 this is if I now I write.
(Refer Slide Time: 17:28)

Q 1/Q2 so therefore we arrive this is some function of T1 by some function of T2, Now η is a
function of T 1 and T 2 from which we derived that Q 1 / Q 2 is some function of T 1, T 2 and
that has to be of this form from this deduction function of T 1 and T2 and this function is defined
as T1 this function of T 1, T 1is temperature measured in any conventional scale existing earlier
so in this absolute thermodynamic scale temperature was not discovered or was not deduced like
this.

That means it is temperature on any conventional scale this function itself is defined as the
absolute thermodynamic temperature that absolute thermodynamic scale up temperature that
means absolute thermodynamic scale of temperature, so the function itself is defined as T1 this
function itself of T2 is defined as another temperature this is conventional scale temperature
existing conventional scale this function is defined that temperature in some other scale which is
the absolute thermodynamic scale and this is T2.

So therefore this gives the bath of absolute thermodynamic temperature scale and this is the
definition of absolute thermodynamic temperature scale that the ratios of the temperatures equals
to the ratios of the heat interactions by a reversible heat engine that means if q1 is the heat taken
from temperature T1now if I express this and absolute temperature T1 and this is an absolute
temperature T 2.

Then T1/T 2 = Q 1 the heat taken from T1 to that given to T 2, so therefore this is the definition
of absolute thermodynamic scale of temperature that is the ratios of the temperature is equal to
the ratio of the heat interactions by the reversibility. Now the question will come this is the
concept these are the very routine logical deduction but concept is that, then to find out the
absolute thermodynamic temperature scale we have to measure the heat interaction by a
reversible engine.

But reversible engine does not occur in practice all natural or practical engines are irreversibly
yes this is a good question we come but here the answer is that this heat Q1/ Q 2 that is the heat
interaction by a reversible heat engine can be expressed in terms of other measurable properties
by the thermodynamic property relations from where we can measure this, so therefore it is not
always that it remains as a hypothetical since it is defined in terms of the heat transfer by
reversible heat engine, okay, so this defines the absolute scale of absolute thermodynamic scale
of temperature okay. Now we will define we will go to the definition of or the Carnot engine or
Carnot cycle.

(Refer Slide Time: 20:48)

Now Carnot was the first man Carnot engine who first realized how we can contribute practice
not in practice rather we can conceive physically a reversible engine, we can conceive physically
a reversible engine that was first given by Carnot, the concept is like that he first took a cylinder
and piston and some gash inside at a temperature T1and that if pressure P1 at a volume V1and he
took a body whose temperature is T1+dT and heat is allowed to transfer to this through this if
everything is insulated.

And while the heat is transferred since it is with infinite small temperature difference T1+dT to
T1 this process is an isothermal heat transfer process in addition process slowly heat is coming
and at the same way we make this temperature T1 fixed since T1+dT the source temperature is
fixed for this we expand or we push the piston outside okay, and let us consider the piston has
come to this state.

So this state is A and after this expansion the piston comes to this state, the piston comes to this
state this is this state B. Now while the piston expands what happens even if the heat transfer is
that it cannot raise the temperature because the gash expands and for expansion it cooling is there
so that it makes a balance to make the temperature constant that is isothermal process is possible
with heat transfer provided it does work so piston comes here and work is developed.

Now this is the system B now here we what we do we make everything insulated and allow the
piston to go allow the piston to go to a position where the gas is expanded like this is the another
position, this we can make dotted because it is the separate figure.
So from state a to state B then state B to state C here temperature remain same three one pressure
is little bit reduced and volume is little bit reduced I am not showing it but here the pressure is
tremendously reduced that in see and also temperature is reduced because this is insulated no
heat transfer is there and we let the piston expand from this position to this position in which we
get the work a greater amount of work we get.

Now here what happens after this, this is all insulated and this expansion we make extremely
slowly where heat transfer was made extremely slowly piston move extremely slowly a little
displacement is there for some amount of heat to be transferred then please turn of a very large
displacement and expansion but very slowly it is an extremely slow process when everything is
insulated no heat transfer is there.

Then at this state after reaching the state we remove the insulation and make the piston comes to
a contact with this cache not the piston this gas comes into contact to a cold reservoir later this
state temperature is t2 which is much less than t1, now I am writing this t1 and t2 in absolute
thermodynamic temperature scale, so this is T2 this is T2 temperature, so therefore this will be T2
- DT so that this temperature is very small compared to this T 2 that means the heat is transferred
to this temperature this accessing where the temperature difference is infinite small.

That means the heat transfer takes place at reversible condition limiting reversible quasi
irreversible condition and to make this T 2 constant just like the heating process we make a
displacement of this system piston like this that means while it rejects it the piston pushes their
rejection of heat will make the system cold that means this temperature may decrease but at the
same time that piston pushes the air to raise the temperature so that balance is there because T 2 –
dt2 is kept fixed.

So if t2 is going lowered then the temperature differential will be higher, so that we do not want
to make the temperature differential higher that means it will be an isothermal heat rejection like
that it is an isothermal heat addition do you want a system temperature escape constant here t 2
the system temperature is kept constant so this is the process of heat rejection when the piston
moves here then at the end last profit after this.

We again just similar to that insolate everything take away the sink, take away the sink and make
big piston from this position it could have been better if we could have drawn below it so that
this is the this position from this position it again comes back to its initial position that means in
this process what happened the gas is compressed a substantial compression of the gas but very
slowly just like the expansion takes place very slowly from this position that is the position to
this position.

Similarly from this position the gas is compressed to its initial state so that we regain again with
P1 t1 and t1 we remove this sink and make it insulated so that no heat transfer takes place so this
way we cannot sort of physically a reversible engine or reversible cycle it consists of four
processes you see this is an isothermal heat addition this is the way we consider that the some air
is there it is in contact with the T 1+ DT where DT is very small and T 1 is kept constant so by
expanding the gas to a little extent so that some heat is transferred at constant temperature t1and
always that infinite small temperature difference reversible thermal heat transfer.

Then after reaching this position everything is insulated this is removed and this is expanded
from this position to this position okay very slowly extremely slowly there is no heat transfer to
the surroundings so question of irreversibility cannot come then this comes here after the
expansion okay and we get work here, here also we get some work because of the expansion
major work comes here and this is an reversible expansion process and the process is adiabatic
because it is insulated then after this what happened just like heat addition.

We have to reject it by Kelvin-plank statement one reservoir engine cannot operate then here if
the temperature is t2 at this position that is t2 then this thing has to be t 2-DT and to make the same
infinite small temperature difference DT for heat to flow to the same we make it a constant
temperature or isothermal heat rejection by pushing the piston slowly and it comes to this
position when some heat is transferred.

Then at this position we again insulate it and very slowly compress the gas to its initial position
this way we consider a Carnot cycle or Carnot engine if we draw this on P V diagram if we draw
this on PV diagram you will see that state a let us like this P 1 V1 and t1 okay now state A to B to
be C okay C to D and final state is E that is again a final status is or that is again A so A to B is
an isothermal process it looks like that in a PV diagram where the volume is increased.

Then pressure is decreased due to this, for an ideal gas you know PV = RT or PV is equal to
MRT, B is the total volume then a isothermal process gives in PV diagram a rectangular
hyperbola, here P is the pressure P is the specific volume per unit. So this is the this is taking
place at a constant temperature T1 then from B to C is an slow expansion process to a very low
pressure and temperature and this is a reversible adiabatic process.

So reversible isothermal process this is reversible adiabatic expansion why adiabatic insulated?
No heat transfer then c to d again from c to d is a heat rejection but at an isothermal, that we see
if this temperature is t2 at states this remains at t2, then again and this is isothermal heat rejection
this process is isothermal heat rejection. This is isothermal heat rejection okay and then again
from d to a. This is the direction of the process d to a is again this is the d state this is that this
state you see this state this is the d state to a state again in the initial state.

This is adiabatic compression that means we see the Carnot cycle consists of two isothermal
process at t1 and t2 two temperatures t1 is higher than t 2 and two adiabatic process reversible
adiabatic process adiabatic expansion and reversal sorry reversible adiabatic compression, now at
this temperature heat is added let Q 1 and at this temperature heat is rejected net key and in this
Wbc work from b to c, we get and here we give our W B to a, W B to a.

So this way a Carnot cycle is concept and if we write the efficiency of the Carnot cycle as we
know is 1 - Q2 / Q1 this is because this is the network if WBC is higher than Wba so Wbc - Wb okay
divided / Q1 that means and this = Q 1- Q2 Wbc - W = Q 1- Q 2, so 1 - Q 2 by Q as you have already
seen for a reversible heat engine. So this so if you write and with the definition of the absolute
temperature we can write t2 by t1, so therefore the efficiency of any reversible engine can now be
expressed in terms of absolute temperatures as 1- t2 / t1 because Q2 by Q 1 is t 2 / 2 and all it is
proof and this is by the definition of thermodynamic scale of temperature.

We have deduced from the directly from the Carnot's principle or theorem that the absolute
thermodynamic temperature scale is defined as that the ratio of the temperatures in that scale is
the ratio of the heat interactions by a reversible engine with the thermal reservoir, so Q2 by Q1 is
t and this is not for this type of reversible engine as conceived by car nodes for any reversible
engine working between a sink temperature t2 and source temperature t1 its efficiency is given by
1 - t2 by t1 okay this is the way car nodes first consider a reversible heat engine okay thank you
for this model.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 15: Definition of Entropy and

Entropy Change in
Closed Systems

Good afternoon I welcome you all this lecture section of the course loss of thermo dynamics now
today we will come very important topic that is the concept of the entropy in the perceptive of
classical thermodynamic,so its definition by the heat transfer in the reversible process okay .

(Refer Slide Time: 00:44)

If you do this now entropy is concept in the perspective of the classing the thermodynamics so
its definition of the heat transfer in the reversible process how it is done now we have already
learned if there it is a heat engine reversible heat engine operating between the source T 1
reversible heat engine operating between the source E 1 and the sink T 2 this T 1 and the T2
absolute thermo dynamic scale temperature taking the heat cube Q1 rejected to the heat Q 2, we
know that the Q 1 /T 1 or other the Q 1 /Q2 first tied in this can be written as Q 1 /T 1 = to Q 2
this can be written as the Q / T 1 +(-Q2 /T2 )=to 0.

What is this with the respect to the heat engine that is the cyclic integral integration in the cyclic
process of δ QR /t cyclic integral it is the cyclic integral δ Q are the simple formula concept
comes Q 1 /T 1 q! is the heat that it Q 2 is the heat rejected it is the – and the algebraic sum of
the Q / t in the cyclic process for the reversible heat is engine is 0 this is the great concept this
you can also prove in the general reversible cyclic engine in the operating on the reversible
cycle.

Which does not take the engine in the constant temperature the source is not also in the constant
temperature because if the system goes on the constant temperature I have already told that the
surrounding at the body from body from the ware it will take the reservoir of the source that the
T also varies in this temperature that also I have discussed earlier similarly for the T 2 in this
case we can derive the same equation it is the very simple caser we derived it concept. So the
concept derived let us consider in the thermo dynamic plane P V A close loop like that which is
in the general represent is cycle.

Now in this case we can derive the cycle thermo dynamics in this cycle in to finite small number
of the infinite small element and other infinite number of the communist cycle of cycle like this.
If this we have the number of the reversible adiabatic if we divide this like this all the reversible
adiabatic and by reversible isothermal process as you know the comminute cycle in the
reversible isothermal cycle processes and reversible adiabatic process.

Similarly here low temperature region you can divide like that means we can divide this cycle in
to the number of the elemental communize cycle so that though the temperature varies in the any
elemental cycle for this the temperature is T 1and the T added is δ for this elemental cycle the
heat added is δ Q and the – and the temperature T 1 -. Or this elemental cyclic the heat added the
elemental and the heat added the δ is the double and the temperature id the T 1 double.

So now for this all elemental portion of this process we will cause that means when we divide it
the cycle in to the elemental and the comminute cycle then we can consider the in the constant
values and the heat is added like that in this case the heat rejection also the δ Q 2 and the
temperature T 2 for this elemental cycle the δ Q 2‘at the temperature and the T 2‘for this
elemental cycle the element Q double ‘in the T 2.

So on it is the very simple just the extension of this and each elemental cycle we can write δ Q
1 / t1 T is δ T 1 this is the δ Q 2 / T 2 simply this is similarly the δ 2 and the T 1‘ and the δ Q 2‘
/ T 2‘ and the δ Q 1 double‘ and ‘ and for all this δ Q and the double ‘ and so on ‘ so that if we
add this a we get Σ δ Q 1 / T 1 is Σ δ Q 2 / T 2.

So there for by adding we get the Σ δ Q 1 / T 1 = to Σ and the δ Q / t 2 which means the Σ the δ Q
1 / t1 – δ Q 2 / T 2 over a cycle = to 0 and – Q 2 because of the heat rejection you take like
within the that is algebraic sum of the δ Q 2 / t over the cyclic which can be retain as the cyclic
integral δ Q / t here all the heat transfer is not reversible writing the suppose the reversible
actually final expression I Wright the reversible so the δ Q / t is 0.

So therefore from this simple logical proof we get that for the reversible heat engine the
reversible thermodynamic cycle δ Q R / t =. Now in this case I will okay I can rub this one. And
very important concept is that this δ Q r for a cycle δ Q T. now if the cycle reversible totally
reversible now reversible is in the two types internally reversible and externally reversible now
what about the temperature is it the temperature is the source are the thermal reservoir are the
temperature of the heat engine.

Now the question the heat transfer is not the reversible may be the temperature different now in
the heat transfer for the reversible process and then the temperature difference will be their not
their source temperature of the temperature system this is the same similarly it is the C
temperature or the temperature of the working system during the heat reject it does not matter
and the name but this not may not be the case how the question comes the tell the heat transfer as
the reversible heat engine.

The heat transfer process is not reversible it is not take under the finite and the temperature
difference in this context there are two thing which is very important to you look you know one
is internal reversibility discussed earlier also internal reversibility and external reversibility now
internal reversibility and the many process due to the internal dis appointment and the
mechanical history and the fluid viscosity and all this things it is the distance but the external
reversibility the concept as the reversibility due to the heat transfer for the finite difference that
menus if you consider the surrounding and the system as the temperature difference so therefore
the hearty engine may be internal reversible that means there is not internally due to all this
friction and the fluid viscosity and all their thing .

It may take heat under the finite temperature where it will be externally reversible that means the
cycle as to totally reversibly test to the both internally reversible and externally reversible is that
birth the internally and externally will be 0 that means there is no within the system there is no
internally reversibility and there will be no heat transfer takes place across it infinite the small
temperature okay this is the case for a simple single process also for example take you for this it
is a important concept also.

That is the mass of the gas expands gas and the expands and there piston cylinder arrangements
in the piston goes out because of the pressure and also it takes the heat from the surrounding
temperature T h for example hot body the gas temperature is that at the any time the gas
temperature and the piston and the process is always less than the T H the finite amount of the
heat goes to the gas you understand therefore you see this heat transfer T H and system boundary
heath transfer and the system temperature.

It will passes through the and in the equilibrium state then should be the infinite because the heat
which is transfer now consider the process that this process is infinite is slow free from the
internally reversible no friction nothing but the heat is transfer from the high temperature source
to the gas in the finite temperature difference this process is has externally reversible internally
reversible.

But if the heat transfer takes place from the temperature which is the which is the hollow is the at
the same temperature of the infinite small difference with the gas temperature if the gas
temperature varies the accordingly is the out side temperature so that is always will be there
infinite small temperature then it is externally difference and that the same time is free from
internally and the free from the reversible it is totally reversible now with this similar concept
when the cycle operate we internally reversible but externally reversible that means the cycle
which is internally reversible.

internally reversible but externally reversible that means it takes the heat from source or sink
which as the different temperature than the temperature of the working temperature which
receives the regencies in the turn cycle is known as the that means which as the internally
reversible very useful concept in the reversible side and for the heat engine appropriate in the end
of the reversible cycle then the cyclic integral δ Q r / T is again the 0 where the reversible means
the end of the reversible process and this is the temperature of the working system during the
reversible process.

Not these are the values and the but the cycle is totally reversible not in the reversible and this
temperature of the system and the temperature of the source of the same okay so now with this
we will proceed further therefore you consider in to the reversible cycle and but the cycle is
totally reversible in this temperature and this source or the same in the same so now with this
therefore you consider in the reversible and we will see and we call as the reversible process and
the bother much about the externally reversible.

(Refer Slide Time: 14:17)

So that δ Q /T cyclic integral is 0- now this keeps the beautiful idea that when the someone the
cycle is 0 then if you define now δ Q R / T as the we can define exact differential of the point
function is y if you express this substitute this then δ Q R is the D S has to be 0 so when ever we
substitute the D s let us consider the very parameter is if the differential change then we
substitute this is the cyclic integral is 0. The cyclic and the integral of the nay paremeteristhe 0
this is the point function and become the property of the system the way we disused and that
when se replace by the D of the A and the exact function is D of F the cyclic point is the o
between nth je and the cyclic or the point function is the o that were define in the integral energy
came of okay similarly.

In that case now the we found that Q – in the cyclic process is W so if yousubstitue this as the of
the parameter is the 0 it means state function that they two are the path full in the diffrencesis the
function and the first law similarly those the Q is the point function and the Q is the T that
becomes the point function and therefore by the definition that entropy is this D S is the or the
finite change in the entropy is r / t okay now see this will be the birth so the entropy and the
designation comes like this three change and the differential change and the finite change and the
δ Q R /t process in the confecting in the two state son the two 2-1c is this quantatity and the δ Q
R /t is the integral 1 to 2 and this is the point is the little function of the entropy and that is
be4cause it satisfies the relation integral in that comes 0 .

And it is like the δ Q R /T enjoys the characteristic it can be expressed in the terms of the
differential of the point function which is the property entropy that means the δ Q are the two by
the T from the one state point to the other state point is independent of the path because it is the
property and it is the function of the independent the path that is most pital thing that means if
we have two state point on the one and the two and if they are connected the point number of the
reversible process.

Let us consider 1 or 2 are all reversible process okay in the one it is the reversible process and R
is the this is the R B this is R C from the state one to the two if the value of this we will send
which means that the integral δ Q R / T 2 1 are the two of the ray of this path = δ Q R / T 1 R B 2
= δ Q R / 1 R C 2 that means which are the path we follow if we connect in the two pints in this
the integral point is function is the obviously and this is define like that is the S 2 – S 1.

So the S 2 – is fixed and the entropy is fixed in the state point so this is the point function and
this one is fixed so whatever we will go the change in the just like work done in the conservative
force field so the whatever path we take the change of the entropy is given by thisintergal and
this integral is T respect and the p of the path that means if we connect the two points is and the
reversible process and the value of the δ Q R /t and the reversible path in the change of therapy
of this process.

And the now the big question come what happens in the process and the reversible one for the
reversible process now for the reversible cycle which is internally reversible why there it is
externally reversible not it is does not matter I the cycles internally reversible and you can
consider the reversible internally reversible also internally reversible it is the reversible cycle
here and the system temperature so that is why I am bother to it is the internally reversible
insister reversible cycle δ cyclic integral δ Q / R is not equal to 0 because the cyclic integral is
not the 0 provide the cycle is reversible.

So in case of the reversible cycle weather the temperature is the source of the same temperature
or the temperature is not the working system in the cyclic integral never in the 0 now the
questions come what is the value of cyclic integral δ Q / T in the reversible process as compared
to the cyclic integral δ Q/T in the reversible process or the integral δ Q /T in the single process
with the compared to the revisable process now these question comes in The picture now what
comes one thing the since is not equal to 0 this is true that the integral δ Q / t is a path function
not a point function now the two question come first question.

what is the value of the δ Q / t and in the reversible process if we have the reversible processed
us consider are eversible process one is and the 2 and it is done in the dot area the first question
is that if you have the system in the reversible process and the process and the one to two and if
I evaluate in the and the integral δ Q / T one and the two is the δ S is now the definition and the t
is the reversible process that mean I have to connect in the reversible which means you can tell
the or the value that the entropy[y change in the reversible process connecting in the integral of
the δ Q / 2 and the t is the value if the states could have the connecting by an reversible process
then what could be the value of the δ Q / p in that the reversible process in the entropy change in
the δ Q / pis the process .

So therefore the next question comes what is the value of the δ Q / p for the reversible process
compared to the it revisable path the δ Q / pin a reversible path and similarly in the cyclic path
what is the value as compared to this and it is 0 and now I write that this thing you can better
understand this is the process and if we had the number of reversible path δ Q / p of the each path
A B C and not equal that means it is not equal in theintergal of the δ Q / p 1 D 2 and the note
equal to δ Q / t and C Q are not equal.

And the path function and the but the entropy change will be δ by any reversible with the
connecting any the two state is S1 is giving by the δ Q R 1 are the any two reversible process
because they are same that means δ Q arte by any reversible process is same because they are the
point function they define the entropy change while reversible process is δ Q/ P is not the
entropy change it is simply Q / t integral over the process and these are different in the different
reversible process now again I am telling questions come out is compare with their counter per
these question was answer by clauses and these know as clauses in equality .

(Refer Slide Time: 23:56)

Now this was answered buy the clauses and it is known as in equality and it is very simple prove
its concept I tell you the reason the cyclic integral and the T for the reversible process is less that
the δ Q / t do r the reversible process and the reversible it is the constant temperature of the work.
Since this is o so the cyclic integral and the δ q / T and less than three. This is clauses inequality
in the trams of the and the cycling and hence it follows the δ Q r Q /t in may process for example
1 to 2 is less than 1 to 2 in the reversible process.

That means this is less than the differentiate in the 2- or we can tell δ Q / T find that is the less in
the terms tart is therefore this is the in this format cyclic integral δ Q / T is less than its
counterpart in the reversible cyclic it is less than the 0 it is similar integral to δ Q / T giving the
process is the less that the counterpart integral δ Q R/ t.

If over the process it is the nothing but inches this T is give you the concept of the δ classis
answer done by them it is very simple to prove in lies in the since in the river engine is less than
that over the reversible process that is simple like that that means the reversible engine it is the
consider the a is reversible engine T 2 take the Q 1 in the reversible heat engine and in the same
temperature T 2.

Consider the engine is totally reversible then Q1 / T 1 = to Q 2 / T 2 or simply you can write this
is better this is Q 1 / Q2 and the reversible engine you cannot write this sorry we cannot write
this in the reversible engine on the efficiency and the δ is 1 – by the definition of the first law and
that is by the conservation of the δ and the you know the δ in the by the definition can we give
the first law of the conservation of the energy in the δ and the thermal efficiency is1- Q2 – Q1
and the Q 2 – Q 1 is what is divided1.

By the now if we have the reversible heat engine in the same source T 1 same source And the
same temperature the n the efficiency is defined as the, and in that and the 2 R and the Q r are is
the heat rejection and then the heat received by the heat engine that become in the 1 – T 2 – T 1
this is for the reversible engine so it is less and the reversible that means 1- Q 2 / Q 1 is less than
1 - Q2 – Q 1 that means the Q 2 / Q 1 is greater than the Q 2 / Q 1 and again we can write and
the Q 1 / Q2 is less than T 1 / T 2 which give Q 1 / T 1 – Q 2 – t2 = 0 .

So you see the proof that simple the concept is that he reverse engine is less the n the reversible
process T 1v T 2 is the source thing in the source temperature in the efficiency is define like that
from the conservation of the energy you know it .

Earlier discussed we have earlier reversible engine it is dissolved also like that you at the Q 1 and
the Q 2 and it is rejected for the reversible for the reversible in the it can replace like thi9s Q 1 /
T1 but since δ is less than the notes of the principle 1- Q/Q 1 is less than the Q 1 / Q 2 is less that
means Q1 that means Q 2 –Q1 and the higher than T 2 / Q1 are Q2 is less than T 1 / T 2 Q1 / Q2
is less than that means the t is less than the Q 2 by T so that Q 1 T 1 – Q 2 / T 2 less than the 0
not equal less than the 0 that means the cyclic integral δ Q t is less than it.
Again it can provide by taking a general loop as the thermal thermodynamic cycle for the
reversible cycle and the comparing to the reversible one and you get the same answer this is the
for the ;logical proof I do it is the formation like and this is very important information from the
fundamental concept of view clauses equality tell that δ Q / T cyclic integral is less than that the
consider part that in the counter in the reversible process and the δ Q for the giving process is
less and the less than the counterpart do the R / T in the reversible process that is = to δ and it is
like concept we alive the this once in a different way this way were can write in a different way
for an reversible process and the reversible process we can write just now let us consider and the
reversible process which is internally.

(Refer Slide Time: 30:04)

For the reversible process δ is other I can write differential term D S is greater than δ Q / T for
that the reversible process from the clauses in equality δ Q is less than the δ S or the δ S is
written than the δ Q R / T process, that means the change of the entropy that means the
corresponding the δ Q / R in the reversible process is always greater than the reversible process
the differential form in the finite difference from and in the change of the entropy, I am the
process is always greater than the δ Q R / T clear.

Now if I write for an reversible process δ is always reversible δ is greater than the δ Q / T is the
is greater than the integral by the integral and the reversible process we can write this some
positive quantities which I write as Δ S I , which is always greater than 0 the Δ is an any process
is more than the Δ Q / T is over than they process is integral + Δ is greater than the 0 this can be
written in the differential form , D S is Δ Q/ T= D S I where the D S I differential form greater
than 0 and this is known as entropy change due to an internally reversible.

This is known as entropy change due to reversibility it is this kind were in due to the internal
reversibility it which is the hollow entropy change due to the reversibility is always greater than
0 so this is one very important relation in classical reversal thermodynamics, that the Δ is process
entropy it is the Δ Q and the δ Q/T.

Now you consider certain special and in the certain case for example in the certain case it is
reversible heat transfer process that means the heat transfer process with but the process it is
reverses then the δ is a be the 0 then the Δ S I will be o and the result will be Δ Sis the integral
which is the basic definition of the Δ S change in the enthalpy entropy is always define from it
inception in the change and the Δ S δ Q R/T so for any reversible process for the heat transfer it
is the added to the system and the Δ S is positive and the system that is negative now you
consider reversible in the reversible heat transfer in it.

You consider it heat transfer process the heat reversible heat transfer process it will be the
reversible process in that case the ∂it is the reversible heat transfer that is the reversible heat
transfer and the equation on the and the Δ S is and the ΔV / t now you consider reversible
without the heat transfer and the adiabatic process and these are the special case now in the
reversible adiabatic process it is beautiful because of the reversible internal reverse in the land
that is the 0 and the form is also this also 0 but in this case is that is the o.

And the entropy is the and we get in the reversible and the change in the reversible process with
it without the heat transfer it is the adiabatic process and the simple adiabatic v f we want the
reverse adiabatic and the adiabatic simple and the adiabatic proceeds without the reversible in the
that is the natural adiabatic process if you add the reverse able it is the reversible adiabatic
process without the process and the process in the without the reversible is that case and that is
always greater than the end it has the value in there for the adiabatic process in the without the
heat transfer to the surrounding and the change of the entropy is always greater than the 0.

So these two these one and this one very reversibleadiabtic process entropy and the in that case
it will be the reversible process for the definition and the reversible heat transfer process and that
will be that is the important thing in this case that is the certain and the special case it will be the
reversible case in the which expect to the surrounding this is the negative in the internal
reversible rigidity this is positive always there is greater than the o.

And the it all will be the final entropy is the same as this and there will be the reversible possible
with the passes through the series of the equilibrium and it takes in the reversible adiabatic
process entropy remains in the entire process and there in the this is known as isometric process
that means that all points of the process in entropy remains here but here in the change will be 0
be balancing here and the reversible process in the regain s at the same is positive in explain this
now today it is up to this.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 16: Entropy Change in Closed

Systems (Contd.)

Good afternoon I welcome you all to this lecture secession of the course loss of thermodynamics.

(Refer Slide Time: 00:27)

Last class we have seen that the change of interrupted with Δs in a an adiabatic process is > than
0 always because of internal irreversibility if in heat there is no heat transfer if the process is
reversible that internal irreversibility is 0 then reversible adiabatic process now question of
external irreversibility because the process is adiabatic = 0.
This 2 important things we have come to know at the conclusion of the definition of the entropy
through cross inequality now an isolated system and isolated system which does not interact with
this surrounding may be considered as an adiabatic system there may be changes that can take
place within the system, system may not be at equilibrium state and this changes EPT is
irreversible we consider the Δs we can consider as isolated system is > than 0.

If we consider the change inside the isolated system that take place from one part of the system
to other part if you consider a single system Δs isolated in case of reversible change = 0 so this
two combine we can write Δs of an isolated system of an is ≥0 means that the change of entropy
of an isolated system is > 0 if the changes with the system is reversible or if the change within
the system is revisable then equality sing now in this context is very important thing is that if we
have two system, system A and system B interact with each other in terms of energy mass
everything.

This two system as a whole and if they do not interact with anything else in this surrounding the
two system itself consider constitute and isolate system when this is not for two system if we
have number if system A, B, C they are mutually interacting with each other can make an
isolated system and this type of isolated system in a very loss term is known as universe that
means we consider in our universe there are process take place between system to system
between we interact with each other there is number of interaction there are number interaction
take place.

But universe is such that it does not interact outside the universal entire thing is within the
universe so if that limited sense in classical thermodynamics and isolated system which
constitutes interacting systems constitute the interacting systems in the surrounding as universe
and therefore and they behave like an isolated system obviously I told that constituting this
interacting systems and therefore we can write with this that Δs universe is ≥0.

That means if we consider an isolated system consisting of interacting systems either two or
more number then Δs of this combined system is >0 when the interactions will be each other
when the interactions will be when the interactions will be irreversible when the interactions will
be revisable Δs is universe will be equals to 0.

And Δ universe that means of this isolated system is nothing but some Δs of all the interacting
system AA + ΔsB+ Δs all the interacting system algebraic sum of all the that means sum may be
positive sum may be negative in such way that there algebraic sum is always either 0 for a
irreversible process or greater than 0 for nay natural process for example 2 bodies exchange heat
I will show you now if the two bodies exchange heat 1 body which rejects it is entropies decreased
but one body which gets CD entropies increased but the algebraic sum is greater than 0.

If the process is irreversible and natural process otherwise it is 0, if it is irreversible process of there are
two system one is consider that system another is considered that surrounding to that system sometimes
we write these expression so Δs universe = ΔS system + ΔS surrounding that also can be written ΔS is
universe ΔS but two system one system another is surrounding.

Now you see this concept how as it work now let us consider in irreversible heat transfer let us now
consider an irreversible heat transfer and irreversible heat transfer.

(Refer Slide Time: 06:03)

T1 and irreversible and natural heat transfer process will take place if two systems are made into contact
through that thermal wall, so that heat can transfer in this case where T 1 is > T2 heat may occur so now
entropy change of this system this is system A this is system B there is A is – Q / T 1 why ΔQ / T is Q / T 1
okay, and this is δSB is Q / T 2 and if you consider the changes internally here irreversible so that we can
write the ΔQ / d is δSA and since T remains constant that T 1, T1 comes out of the integral this becomes Q
and the same Q is transferred hereQ2.

So ΔS universe will be equal to Q x 1 this is – 1 / Q1 + 1/ T 2 so this is always > this because it is < T 1, T1
is > T2 that means this is less that means this is always > 0 another example I give it in the two bodies are
finite capacity here you have considered thermal reserve here, whose heat capacity is infinitely high and
keeps at constant temperature, but if I may contact of two finite bodies T1 and T2 and heat transfer takes
place so that T1 gets decreased temperature get decreased as rejects heat and T2 gets increase that it takes
and the heat transfer will go and decreasing the temperature.

Difference goes on decreasing and finally the process will naturally stop oh that will I will tell a mean
temperature if we consider the heat capacity is that same then you know the mean temperature is nothing
but the arithmetic mean by the energy balance T 1 + T2 / 2 that means heat rejected by this body is equal to
like heat gain by this body and if we consider T f is the final temperature as we know that it be heat
capacities are same Tf is there arithmetic mean, but now instead of so this a natural process this is a Tf is
T1 + T2 / 2 now how do we find out the ΔS universe.

So ΔS universe equals to ΔS this is body A then this is body B ΔS A + ΔS now what is ΔS in this case
ΔSA if we consider this is internally reversible, is integral δQ / t for the body and heat is equal to CP is
the heat capacity total heat capacity mass into specific heat CP x dT is the reversible heat transfer / T and
it is from T1 to Tf and this becomes is equal to CP ln Ta / T1 see Tf is < T1 this is negative obviously if
ΔS is negative because for A it is reject heat it is cool so therefore we cannot take T out because ΔQ is
CPdT and t is changing.

So therefore we have to integrate like this similar way if ΔS becomes around ΔQ / T this is for A this for
B and that becomes is equal to at the similar way CP ln TF/T2 and this is positive because TF > T2,
So Δ is universe is equal to Δ is say plus Δ is B, C p ln TF 2 /T1 T2 and Tf 2 is what? Cp ln (T1 + T2)2
(T1+ T2/2)2 /T1 T2 this is always positive we can prove this is because we know that geometric
mean root over T1 T2 is always greater than the arithmetic mean.

This we have proved now this we can prove that (T1+ T2) 2 is always greater than T1 and T1 that
means it is always greater than 0 that means it is greater than 0, so we can prove since the
arithmetic mean is greater than the geometric mean that is T1 + T2/2 is always greater than T1 ,
T2 root of R, T1 or T2 or this whole square is greater than T1, T2 we can prove simple school
level algebra so that entropy change is greater than 0 for a finite word.

Now another very interesting thing comes into picture that if the two finite bodies re attach or
connected through a reversible heat engine then what will be its final temperature this is a very
interesting problem.

(Refer Slide Time: 11:48)

That if two bodies A at temperature T1 another body B at temperature T2 if they are connected
through a reversible heat engine sometimes this is a problem that it takes it Q1 which is going on
changing because their finite capacity body, so what will be TA and what will be Δx units, TA is
not the arithmetic mean so you have to find out TA because they are not in direct thermal contact,
now here to find out TA we must know this thing this will act as a clue to find out TA since this is
the internally irreversibility taken to is 0 for both these things and since this is connected to a
reversible heat engine which takes also heat reversibly from this two reserves.
So the entire process is reversible this system reversible heat engine reversible this that means Δ
is universe is Δ is A + Δ is heat engine + Δ is B, now for a heat engine whether it is reversible or
irreversible the entropy change is always 0 because entropy is a property and it needs operates on
a thermodynamic side 0 and Δ SA and ΔB they are all operates on a reversible process so that
ΔSA and ΔSB summation algebraic summation will become 0so ΔS is universe will be 0.

That means ΔSA + ΔSB becomes 0, we take this clue to find out TF what is ΔSA, that means Δ
is universe = ΔS it will be the same equation L n Tf \T1 integral ΔQ/T + Cp LN TF/T2 so that this is
Cp LN, this expression will remain same earlier one because this comes from the integral dq/ ΔQ/T
and in this case this becomes equal to 0, that means TF 2 /T1 T2 is 1 L and TF 2 T1, T2 0 that
means TF is geometric mean.

So in case of direct thermal conduct of two finite bodies of same capacity is arithmetic mean
while it is connected by a reversible heat engine internally reversible it is of the system at 0 then
the mean temperature is root over T1, T2 is the geometric mean okay. Now after this I will solve
few problem okay I think the concept is clear to you therefore you see before I close this I tell
you that it is now concluded that for all natural processes in this universe which is considered as
an isolated system takes place in such a way.

That the ∆ is of the universe is great than 0 and this is the direction of constant I told at the
beginning of this class that there is directional constant for any process, any natural process
occurs in such a way that it makes a permanent indentation to the surrounding, that means
entropy change of the process plus the entropy change of the interacting systems are surrounding
algebraic sum of this two mass be greater than 0.

If the processes are natural, that means if you consider an entropy band of in an universe the
entropy is monotonically increasing that means entropy change of the universe always increases
for example, I am teaching to you this is a process in this process I increase the entropy of the
universe, so there is an increasing the entropy of the universe, entropy is generated in the
universe so this is the directional constant of any natural process, okay in general. Now I will
solve some problem, let u see this problem.
(Refer Slide Time: 16:24)

A heat pump has a coefficient of performance that is 50% of the theoretical maximum, it
maintains a house at 20°C which leaks energy of 0.6 kW per degree of temperature difference to
the ambient, that means temperature difference from the house and the ambient. For a maximum
of 1.0kW power input to the heat pump find the minimum outside temperature for which the heat
pump is a sufficient heat source, okay. Now let us come to the board and see what this tells.

(Refer Slide Time: 17:16)

Now there is a house this is the house and there is a heat pump let the temperature of the house is
TH which is 20°C it means 293K actually it is 273.15 you have to add because the
thermodynamic scale of temperature is define, which has defined, which has been defined as I
told but the scale is like that 0°C corresponds to 273.15K but you can neglect this 0.15 293K and
heat from gives heat QH to this house and it takes heat from this surroundings, this is the
surrounding temperature Ta which we have to find out, so this takes heat from the surrounding
let this is QA we have to find out Ta.

And it takes work as 1kW, let us work with the 1kW heat and find out what is the value of TH
and that will ne Ta and that will be the minimum value, why I will tell you afterward. This house
leaks energy which is QL is the heat at which the heat leaks from the house to the surrounding.
Now to maintain the house at 293K Ma will be automatically by common sense this much less
than 293K it is the heating the house in knowing tank in Western countries.

Now this QH will be such to maintain the house at 293K must equal Ql that means the heat
which it leaks must be giving by Qh a study state when the house as attend 293K that means Q h =
Ql and Ql is it is what 0.6kw Qw what is this Ql is 0.6 KW per degree of temperature difference
that means 0.6 x Th – Ta that much KW, because by definition 0.6kw per degree difference T h- Ta
Ql this is Qh. Now we have to express Qh now in terms of this temperature T a and Th so that we
can find out the T, minimum temperature T.

How you will find out now this Qh you can be written as the coefficient of performance of the
heat pump in to w because coefficient of performance is defined as Q h / w and w = 1 so therefore
it is simply this cop of the heat pump. That much KW why because w is 1kw now we have to
express cop in terms of temperature and it is written in the problem the heat pump as a
coefficient of performance which is 50% of the ideal one that means cop of heat pump is 0.5 of
the cop of the ideal.

Now ideal cop we can write cop is usually can be written w/Q h or I am sorry extremely Qh/ w or
Qh/ - Qa and for a ideal cop this is the basic definition then they are proportional to their
temperature, so therefore cop will be 0.5 of this so therefore we can write Q h = 0.5 of this that
means Qh = cop of heat pump w is one so Q h = 0.5 Th /Th – Ta very simple problem Ta small am I
have given small a sorry.

Th – Ta and that must be equal to 0.6 T h – Ta okay so therefore it must be equal to 0.5 T h, Th – Ta
must = 0.6 Th - Ta because this is Qh = qa so therefore we get (Th – Ta)2 = 0.5 / 0.6 x Th this is very
simple 0.5 / 0.6 Th is Th – Ta and if you solving Th is 293 K you get the value of Ta the negative
value you just in ignore which will give a value of T a higher than Ta so we take the positive value
the answer is 277.4 K that means T a is in the usual centigrade for Celsius scale is 4 o Celsius so
this is simply this problem okay I think you have understood this problem well so how I have
done this QH is equal to QL is by definition is QH is COP*W is 1 kilo watt so they are simply it is
COP kilo watt.
So then right COP of the hit pump is .50% of this is ideal we cannot right in terms of temperature
for non ideal hit pump but it is .5 of the ideal hit pump COP so therefore Q H is equal to COP is
equal to this 60% okay.

(Refer Slide Time: 24:22)

Now come to the next problem, now we come to the next problem now this is the same problem
we wish to produce refrigeration at -30 oC a reservoir is available at 200 o C and the ambient
temperature is 30oC a reservoir is a 200oC and the ambient temperature is 30OC thus work can be
done by a cyclic heat engine operating between 200 OC reservoir and the ambient this work is
used to drive the refrigerator determine the ratio of the heat transferred from the 200 OC reservoir
to the het transferred from -30OC reservoir assuming all processes are reversible.

(Refer Slide Time: 25:08)

Now this is like this we have ambient we have a hot source at 200 OC that means 473k this is TH
hot source then we operate the heat engine with the ambient the heating takes heat Q 1 and rejects
it Q2 to an ambient temperature TH which is how much TH and ambient 30OC Ta which is equals
to 30O that means 303K 30+273 303K.

Now this heat engine drives a heat pump refrigerator here you write refrigerator, refrigerator
which takes a same thing heat pump the same device heat pump or refrigerator takes heat from –
cool temperature TL low temperature which equals to -30OC that means this is what is the -30OC
okay.

Let me see the -30OC that means it is 243K it takes Q L and it gives to the ambient temperature,
ambient temperature in this case here see it Cit pumps heat from the low temperature and gives
to the ambient temperature which is 303K and this heat you consider as Q H which it gives here so
Q1 Q2 are the heat taken by the heat engine giving by heat engine this is by refrigerator given by
the refrigerator to this were it access the heat part.

Now our problem is that we have to find out Q 1/ QL what is Q1/ QL. So it is very simple W is the
connecting it, that means we connect W with Q1 and then we connect W with QL and equate it
and then we get the result, because the same W driving the refrigeration, we have temperature
this from where the refrigeration has to be made and we have an ambient where the refrigerator
will reject.
But do we a source, so that with this as source and the ambient as your seeing a heat engine can
operate at that heat engine can drive the refrigerator that means the same W. So from the heat
engine, we get W is Q1 x η and here all process are reversible. It is told in the problem that
assumes all process as reversible, so η is what? Q 1 x 1 x – η is TA/ TH. W is Q1 x 1 x – η is TA/ TH,
from here W how can I find out? W here COP is defined as from refrigerator, from refrigerator
COP is what? COP is QL / W.

So QL = W = QL / COP okay and at the same time COP since this is a reversible heat pump COP
is QL / Qh - QL that is TL / TA - TL because this is reversible heat pump or refrigerator, so we can
express this in terms of the temperatures TL / TA - TL okay. So now W = what from the
refrigeration from the refrigerator? We get W = Q L / COP and COP is that, so W = QL x 1 / COP,
that means TA – TH// TA - TL / TL that is this temperature.

So these two are equal W, so therefore Q1 x 1- TA/ TH that is the efficiency QL x TA - TL / TL here
we get everything, so we get Q1/ QL if you take this side divided by this, we know T A 303 we
know TH 473 and we know TL is 243. So you know all the temperatures, so therefore we can get
the ration Q1/ QL which is = 0.687, okay today up to this thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 17 – Tutorial: 4 Entropy

Good afternoon I welcome you all to this lecture section of the course laws of thermodynamics
now in this section last section we solved two problems this section also we will solve two
interesting problems let us see the problem.

(Refer Slide Time: 00:36)

This is the problem we have discussed earlier regarding the entropy change now this is a problem
a 12 kg steel container has 0.2kg super heated water vapor in super heated steel at 100 kPa both
at 2000 C both this steel container and the super heated steel water vapor the steam at 200 0 C, the
total mass that is both this steel and the steam that is water vapor is now cool to ambient
temperature of 300 C how much heat transfer took place was taken out of the system and what is
this steel water both these things upon makes a systems steel water entropy change so let us
come to the board and understand the problem.

(Refer Slide Time: 01:33)

The problem is like this there is a steel container this is the steel container and there is steel, this
is steel container let the initial state is 1 is the initial state and let 2 is the final state now in initial
state the temperature T is what is given in the problem temperature T is 200 0C that means 473K
now the pressure of this steam that is the initial pressure because now the steel and this steam
combine contains the system, so steel as a temperature of 2000 C that is 473K and steam is also
473 K.

And P1 is given by 1000kPa that means 1000kPa now we have to find now to find the property
we have to go through steam table but first let us write the equation for 1 st law okay 1st law what
is 1st law now if we consider Q is given to the system actually it is taken out but we will find the
if we get a negative sign then it will be taken out in general we do like this Q 12 is U1, u2- U1 that
is the change in the internal energy of the system plus W1

But in this case W12 is 0 there is no heat transfer because it is rigid steel container and steel heat
is transferred out but we have taken it is strong in so that we can write the general link equation
so this can be written as Q12 now this aim U2- U1 consists of both steel and the water vapor so
for steel it is m steel change in the internal energy of the steel is m steel C steel into t 2- t1 for
solid to change in energy this specific heat into mass into temperature change + the m steam into
U2 – U1 steam.

So now we know c steel c steel is not given but we know it is value I will tell you afterwards m
still is known mass of steel is m steel, m steel is 1.2kg m steel is given what is that 0.2kg, 0.2kg
so m steel will know T2 we know T1 also T1 we know and T2 is also we know that T2 is here I
write T2 is 200C 300 since here that means 303 so therefore this part is known this part m steel is
known but we neither known U1 known U2 how to find out, now from steam table you check that
1000kp and this temperature of 73k that is 200C here it is super heated.

How to check it if you see this steam table 1000kp you will see the saturation temperature is less
than that means it is a super heated steam that means if I draw a diagram TS diagram we come to
know this in your earlier class that this a constant pressure line in TS diagram this is the liquid
line this is the liquid line saturated liquid state, all the points in this line and this is the vapor line
that saturated vapor, now this if this is 1000kp pressure line my state is like this it is at a
temperature this is the saturation.

Temperature corresponding to this is the constant temperature corresponding to this pressure so

this temperature is higher than this temperature, this is the saturation temperature corresponding
to this temperature 1000kp so this is the super heated steam so from super heated steam table I
found I find U2 sorry U1 here I write I find U1 I find S1 these are all specific values this small u
are the specific values this will be required and also I find the specific volume of b steam at
initial state.

This will be required so this 3 things I found I fond from the super heated steam table, now I
have to find out U2 now how to find out U2 this is very interesting now only thing I know that
this an 303k final state is at 303k now the point I do not know anything else now whether this
will be in super heated region and this temperature then this pressure will be lower then this will
be it is existing pressure, this may be dry saturated vapor this may be liquid or this may be
somewhere here.

Intermediate weight vapor that means a mixture of liquid and steam weight vapor how to do how
to check one thing is that this process is a constant volume process because volume remains
constant and since the mass remains constant that means this specific volume remains constant
that is the flow is that V2 is V1 that means I know V2 this V2 is same as V1 now we check this V2
against Vg and Vf that is the dry saturated liquid and dry saturated vapor in the saturated steam
table and we will see in this problem that V l > V2 < Vg Vl now Vf that means the specific volume
of saturated liquid is less than V2, V2 is higher than that but less than Vg that means it is not super
heated it is not saturated liquid that is in between.

That means heat as a dryness fraction x2 with some dryness fraction x2 now when we determine
this it is in this state so dryness fraction x2 can be calculated by equating these,V 2 is 1 – x Vf + x
Vg these two things we get from steam table and V2 we know so that V2 is V1 from which we
have checked that it is in the saturated that is vapour domed that means saturated state but with
mixture of liquid and vapor so if we quit this then we get the value of x2 sorry x2.

When we know x2 point is here for u2 also we can find out 1 – x2 x U f + x2 x Ug and for S2 also
specific entropy 1 – x2 x he wave x2 x Ug so this U f Ug sorry SF it is SF x SG so these are from
steam tables that the saturated liquid and dry saturated vapor for specific volume for internal
energy and for entropy that means I get V2 U2 S2 similar to these V2 V1 S1 U1 like this so this
sets are known at both inlet and outlet.

So therefore if I put this U2, U1 and in steam we get the value of Q12 and this value equals to if
you put all these value that is T2, T1 m-steal C- steal and if you consider these till specific it as
point this as 0.46 the applicant and this value equals to -1434.8 kilo joule minus that means the
minus sign is the heat is coming out, now the entropy part is very simple I can rub these thing so
entropy change is entropy change of this steal + the entropy change of the total entropy change
total system is ΔS steal + ΔS steam.

(Refer Slide Time: 12:26)

And this is equal to mass of steal is specific heal L n T2/T1 + mass of steam x specific heat x Oh
no, mass of steam specific heat I am sorry so this is ΔS steam is M. M steam x S2 – S1 this is
already obtained S2 value you know S1 value we know because from the superheated steam
table I get this from the saturated steam table I get this with this check and then we can find out
and this becomes equal to I tell you that equals to -3.699 kilo joule\K.

Now one interesting thing is there that this problem has not told you to find out the entropy
change of the universe this is the entropy change of the system this is minus because obviously
heat has been lost this is minus sign that mean heat has come out it is ΔS of this system is like
that, if you find out ΔS surrounding then you have to find out that is a heat that is rejected that is
Q12 that is received by the surrounding.

Divided by the surrounding temperature that is 300 C, 303 the value of Q1 to which I got earlier
1434.8 this is be plus sign because surrounding is taken, so this quantity minus this quantity is
always positive we do it kept as an exercise so Q2, Q12 if you put that value 1434.8 that is
1434.8/303 then you will get this is more than this by magnitude, so this minus this is positive
that means entropy change of the reverse is positive.

This is not aspect of course in this problem okay I hope you have understood this problem well
okay, now I can rub this. Next problem is tremendously interesting.

(Refer Slide Time: 15:39)

This problem you see very carefully this gives you the concept of internally reversiblility
externally reversibility and entropy generated very, vert conceptual problem see that. A computer
chip dissipates 2kJ of electrical work, electric work over time over some time and rejects that as
heat transfer from its surface at a steady state temperature of 50°C to the ambient air at 25°C.
Now what we have to find out entropy change of the chip, entropy change of the universe,
entropy genearated within the chip, entropy generated outside the chip, total entropy genearted
all these things entropy change of the chip, entropy change of the universe, entropy genearated
within the chip, entropy genearated outisde the chip and total entropy generated which is
obviously C+D. This problem is very, very interesting problem, now you come to the board
work.
(Refer Slide Time: 16:56)
The problem is like this there is a chip which is at steady state temperature 50°C because of an
electrical work transffered to be that means work electrical work, that means some voltage some
electric current passes through it i across the voltage, that means some electrical work simply
register concept you consider a chip which gets heated, heated means this electrical work is
converted into heat molecular elements.

But at the same time it gives heat Q to the surrounding which is at work temperatures surounding
at 25°C temperature Ta at 25°C and in such a way that the temperature 50°C at the chip surface
consider at in the of the chip itself, chip is a very thin material that it is at 50°C the steady state
does not change that means the heat which is transferred is given by the electrical work steady
state that means by first law that Q= if you write the first law Q=∆u+W chip is at steady state
means ∆u0 that means Q it is from common sense that keep the temperature cost and for the chip

Electrical work at a must be equal to the heat transfer that means electrical work change the
intermolecular energy but at the same time heat transfer out makes the intermolecular energy
remains the same so chip is at this steady state and the steady state temperature is 50°C this is
very important point that chip is at steady state, so ∆u0 so Q=W that means inter electical work
is finally transferred as heat to the surrounding.

First dissipated in terms of intermolecular energy which raise this temperature then dissipated to
the surrounding and they are equal so that temperature remains same. Now we write this
expression ∆s, now this is a highly irreversible process because of this internal irreversiblilty in
the chip the temperature is increased. Well, by virtue of which it transfers heat to the surrounding
so there is a which is highly and irreversible process I told you the example this exist, this is
because of the chip resistnace.

That electrical work is being dissipated in terms of or transferred in terms of converted in terms
of intermolecular energy, highly irreversible process so ∆si but now since the chip is at steady
state ∆s is 0 so first question is Δs chip = 0 since = 0 Δ si is Δ q/ t now in this case we can write δ
Q / T + Δ si = 0 or Δ si that entropy change due to internal irreversibility is equal to this is first
time I am writing this plus this ΔQ / T is negative since it is going out and since t is constant it is
q/T chip.

I am writing this her and this here, so Δ si is q/ T chip that means q which is going out to this
surrounding divided by the chip temperature gives you the Δ si that means this is the entropy
generated due to internal irreversibility within the chip. So another answer is there one answer is
there. So this is the entropy change due to internal irreversibility of the chip but this is not the
entropy change of the chip entropy change of the chip is this so this is entropy generated sorry
not entropy change I am sorry entropy generated if the watt is not entropy change sorry entropy
generated during the chip because of inter that means within the chip entropy is generated
because of the internal irreversibility but the entropy change is 0 this is because Δ si and Δq / T
balance each other.

Δ is 0 I have got is your steady state from other point of view we can explain that entropy is
generated due to internal irreversibility and I told you in the last class just last but one class last
before the last class that there may be a situation that heat lose and the internal irreversibility
may balance each other so the Δs is 0. So that this is balance so entropy generated is q / T which
you can find out by this q is 2kilo joule 2000j / 273+50 and this becomes equal to you can find
out the value that entropy change entropy generated in the chip is 6.19j/k.

Now what is the entropy generated next one outside the chip entropy generated that means this
we call this is because of the external irreversibility I told because of the heat transfer due to a
finite temperature difference 50 and 25 that means this will be q/T chip this is minus plus the
same q / Ta now q = 2000j q = w = 2kj 2000j and you put the value of T chip that is 50+273 and
value of Ta what is ta, ta 25, 273 + 25 and you get that value of entropy generated externally that
is entropy generated internally due to internal irreversibility and this is entropy generated due to
external entropy generated due to external irreversibility.

This is due to internal irreversibility due to external so total entropy generated total the entropy
generated Δ is total I am not writing total generated total is entropy generated due to internal
irreversibility and external irreversibility. So internal irreversibility entropy generated is q / T
Chip and external generated you can calculated in that but I am writing in this –Q/Tchip+Q/Ta
and this cancels out so the total insufficient becomes Q/Ta this entropy generated externally if
you calculate you get this value, you get this value that .519Joule per K entropy generated
externally .519 that means if you equal it.519joule per K.

So you can add this two but it is written in first equation to show that it simply becomes Q/Ta if
you calculate Q/Ta it will be this plus this obviously because this and this cancels out so this plus
this can get but by formula it is Q/Ta here now if you see from other point of view if I write ∆S is
universe that is without the concept of entropy generation internally and externally just I find out
entropy change of universe.

I know the entropy change of the universe which is chip plus entropy change of the surroundings
and entropy change of the chip is 0 surrounding will be Q/Ta Q is equal to 2000 Joule that means
we see that entropy change of the universe are total entropy generated are the same that means
the classical statement in classical reversible thermodynamic in terms of entropy generated of the
universe becomes the equal to the ∆S generated total entropy generated which equals to ∆Si+∆Se

That means if you look this problem from two angle one is reversible thermodynamics angle we
find out that is why so many things have been asked to find out that entropy change of the COP
is 0 so entropy generated due to internally reversibility is by this equations very important
equation I have told you the earlier class that ∆S is 0 then ∆Si is -∆Q/t here in this case ∆Q/t is
negative so this is ∆Q/t becomes Q/t.

Because this temperature is constant otherwise you have to integrated if this temperature put a
barrier it is simply Q/ta this is the numerical value now entropy change due to externally
reversibility I told that you externally reversibility theses re similar due to heat transfer through
infinite temperature difference so therefore through a finite temperature difference heat transfer
through the entropy change for this type of reversibility heat transfer to a finite temperature
difference will be like this.

The chip has this entropy decrease and this has entropy increase so therefore ∆S is like this, this
is the boundary temperature of the chip were you transfers the heat through the immediate
surroundings so this is ∆S entropy generated due to externally reversibility so total entropy
generation both due to internal and external reversibility is this that this cancels out ∆Si+∆Se this
is ∆Se.

And this is ∆Si so that becomes Q/t now if you calculate ∆ is universe at ∆S chip is surrounding
that is chip plus surrounding then this becomes equal to again Q/Ta because ∆S chip is 0 that
means ∆S is universe is equal to ∆S generated ∆Si+∆Se so therefore we will see that all these
aspects have been covered here that entropy generated and the entropy change of the universe.

So in the conclusion of this lecture I like to tell this aims your lecture on entropy has whole of
this second law thermo dynamics I just summaries it in brief that we started from second law
concept has a directional constraint or the uni-relation characteristics of a process and there we
saw, that there are some process occurring spontaneously in nature or man mad which are one
directional, but process which are both way possible to occur the make a permanent indentation,
that we will finally come at the end, that occurs in such way that entropy is generated in the
universe is greater than 0. We learnt Kelvin Planck statement and the celosia statement that a
heat engine to develop work continuously from heat it has to interact with 2 reservoirs.

Heat had to be rejected that continuously conversion heat into R is not possible in a cyclic
process but heat can be converted into work by it is not possible by the same amount that means
the same heat the equal amount of heat cannot be converted into the same amount of the work.
Heat cannot be converted into work by the same amount in a continuous process by a cycle,
thermodynamic cycle required for continuous conversion but any process heat can be converted
into work.

That concept should be there after that I will tell you certain little bit of concept of
thermodynamic many people have that Q = ∆ u + W in any process single process. Now there me
a process where ∆ may be 0, for example if you take an ideal gas and if you supply heat and get
work in a way that the temperature remains constant and ideal gas internal energy of temperature
source, so therefore internal energy remains constant, so there may be process where ∆is 0 Q can
be converted into W in the same amount.

But you cannot be converting into W continuously in the cycle process that is the restriction in
the Kelvin Plank statement, celosia statement is very simple it cannot be converted
spontaneously from low temperature to high temperature, the most important theorem of the
second law is the canots theorem, that the reversible engine operating between two temperature
level source and sink.

As the higher efficiency then the irreversible engine and all reversible engine have the same
efficiency, whereas all irreversible engine efficiency has different efficiency, even the maximum
of that is less than that of reversible engine same as the thermal engine from which we finally
reduced the concept of absolute temperature which is define as ratio of the absolute temperature
two system equal to the heat added and heat rejected by a heat engine.

From one the heat is added and from other the heat is rejected and then from that we had the
concept of entropy which is defined in the terms of change in entropy change in process is given
by the integral δ2/t if the process connecting to two states is connected by the reversible process,
that means it is defined as ∆Q/t in a reversible process integral of ∆Q/t in a reversible process is
less than ∆Q/t reversible process and therefore it is less than ∆S.

Just now we solve the problem entropy is the change of the system is express ∆Q/t
+ some quantity which entropy change internal irreversibility okay, so this is the concept celosias
this is celosias in equality cyclic integrating of ∆Q/t is 0, if t is the temperature of the working
system operating in the cycle then this is indo reversible cycle, that means internal reversibility is
0, so that case you can tell that ∆Q/t = 0 t is the working system temperature.

But if t is the temperature of the surroundings source and sink the cycle has to be both internally
and externally reversible, so this is very good concept, very useful concept you have to
remember for the 2nd law the thermodynamics. We have solved some problem in 2 nd law the
thermodynamics and I think this is all and for 2 nd law upto this but next class, this is all for not
2nd law but in the next class we will be discussing entropy transport for the open system.

So long which I have discussed related entropy change and entropy generated in a close sytem
but you will discuss the entropy transport in a open system which is very important. In oa we
discussed the first law apply to the close system and the first law conservational energy principle
apply to a open system and then we will discuss that our discussion of second law will end okay
thank you.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 18: Entropy And its Transport

So far we have discussed various phases of entropy transport and we will continue with that and
the specific agenda of today’s discussion we will to mathematically discuss the various aspects
that come with the deception of change in entropy of a system for a control mass system as well
as for a flow process so to began with I will try to draw your attention on the following in
equality.

(Refer Slide Time: 01:06)

Ds system is ≥ ∂ Q / T so this is something which is I think the most important inequality that
we talk about when we discuss about the change in entropy so what is this T something which is
very important and we will go through that though various teasing questions and exercises in the
subsequent two three modules but this T conceptually is the temperature of the system bounded
here cross which this Δ heat transfer is taking this, so it is not any orbiter T it is the temperature
of that system bounded here across which the heat transfer is taking place for which you're
calculating this ds system.

So now you can also write this or convert this inequality in the form of a equality so you can
write ds system is equal to ∂ Q / T + entropy generation which is ≥ 0m this is for a system now of
course the mathematical objective is satisfied here that we all are understand that this
terminology is introduced to convert the inequality to 1 equality but what is the physical
significant of this in the context of heat and work we have to understand that entropy generation
is a general conceptual paradane it should not always be associated with heat transfer.

It could be associated with flow of information in an information system and so but here we are
considering the heat transfer as an example, so now we can write so let us do let us do a different
exercise let us write the 1st law for a system as ∂Q again we are not considering the change in
kinetic energy and potential energy because we are considering that the thermal effects are more
important.

So now in place of ∂Q can we write TDS the answer is we can write TDS only for reversible
process if it is not reversible process we cannot write ∂Q = TDS now what is ∂W so in place of
∂W we can write the following the first question that let me ask me you that can be write this
Pdv, okay so can we write as Pdv what is your answer, so let think about it let us say that we are
instead of this we are writing ∂Q = TDS so if we do that then in place of ∂W we can write Pdv
with an understanding that we are talking about a simple complex substance.

So that the work is only Pdv work but the Pdv wok is not the work that you can get as output
when that you get as output when the process is irreversible so the question is when the process
is irreversible what is the work that you get when the process is irreversible the work that you get
as an output should be less than Pdv that means because of irreversibility the irreversibility may
be associated with fraction free expansion whatever you are losing an opportunity of doing work
so you can write Pd vans your actual ∂ W + some δLW which is something positive so the last
work is 0 when it is reversible process.
So that it will be pdV but if it is not a reversible process then you have last work, so technically
speaking you cannot write LW = pdV always so when you write this TdS = dU + δW + δLW let
me show let me try to use here so dU + δW this together from here you can write δQ so TdS =
δQ + δLW, so that means dS so when we write dS we mean dS system not always we are writing
the sub secrete dS system so dS = δQ over T + δLW over T.

So now compare this * with ** okay compare the * with ** okay so we can write if you compare
the * with the ** we can clearly write that this entropy generation is nothing but this LW/ T that
means entropy generation is always associated with the last opportunity of doing one that can be
taken as a physical interpretation of entropy generation in a system where you are trying to use
some heat transfer to convert that into work so if you are using some heat transfer to convert that
into work there is a maximum potential of that heat to be converted to work, but you may not be
able to utilize that maximum potential.

Because of entropy generation or irreversibility in the system, so physically you may have last
opportunity of doing work for last work, so this is the first physical interpretation that I want to
give and then using the same inequality let me try to give you a different prospect let us give an
example.

(Refer Slide Time: 09:14)

Where you have process with P = P 0 and T = T0 that is pressure and temperature they are kept as
constant but still there is a change within the system how is it possible, remember that for
system to be in equilibrium it has to be mechanically equilibrium thermal equilibrium and phrase
and chemical equilibrium, so these two indicate mechanical and thermal equilibrium but it does
not guarantee in phase and chemical equilibrium, so they are put still be a change within the
system even if you keep.

These two same and let us consider certain such a change so we can write again for such a
system dS > = δQ over T and again this T is absolute temperature by this time you know very
well that in when you are considering something in the context of second law that T is absolute
temperature, so now you can write δQ < = TdS if you apply the first law in place of δQ you can
write dU + δW neglecting changes in kinetic energy and potential energy when can you write
this δW as pdV.

When it is a internally reversible process or pass equilibrium process so pass equilibrium or

internally reversible these two terms are equivalent or internally reversible, so now this is a
process where T is kept as constant so you can write TdS or rather sorry I have written δU by
mistake, so dU d of U + now this pdV you can write d of P0V because P0 is a constant you can
take it within the difference here, so d of U + P0V similarly this you can write as d(TOS) so u+
P0V – TOS <= 0 this means d of what is u+ pv, U + PV is the enthalpy H so d(H) with reference
to pressure P0 – T0S <= 0, so here we come up with another mathematical function which is a
combination o properties this we call as Gibb’s function or Gibb’s free energy of the system.

So DG so that means we can say that any spontaneous process will take place if at a constant
temperature and pressure the Gibb’s function or Gibb’s free energy is decreasing so a
spontaneous process cannot take place if the Gibb’s free energy is increasing and it comes to
equilibrium when it is a minimum that there is no further change in the Gibb’s free energy.

So why I am telling you this because in this particular course we do not have a lot of scope of
discussing about the Gibb’s function and its interpretation in the context of phase and chemical
equilibrium but I want to give you a very basic elementary physical picture on the Gibb’s
function its physical interpretation so you can see that these G therefore is the driving force for a
chemical change to take place or driving force for a phase change to take place.

And we have already discussed that for a phase or chemical equilibrium the chemical potential
concept with the picture and that chemical potential is linked with the partial moral Gibb’s
function. Now in the two examples that we have consider in this today’s lecture so far we have
considered the cases of irreversible situations but let us consider an example where we consider
reversible adiabatic process of an ideal gas.

(Refer Slide Time: 14:29)

So let us apply the first law and second law for this, so let us apply the first law. �Q = DU + �W
now because it is reversible you can write this PDV Ideal gas we consider it to be a simple
compressible substance with the pressure volume temperature changes are more important than
other changes and because it is adiabatic this is 0 so you can say so this PDV is for reversible and
this is for adiabatic.

So we have used both the considerations of reversible and adiabatic now for an ideal gas DU is
CVDT this we already discussed in one of our previous lectures and we know for an ideal gas the
equation of state is PV = RT so let us apply it for a unit mass so if you so this will be M CVDT if
it is total mass so if you apply per unit mass it will be CV0 = CVDT + P x d of specific volume,
right.

So for an ideal gas you can write P x specific volume = RT so if you take the differential of both
sides you have PDV + VDP is RDT. So you can write DT is PDV + VDP/R, let us substitute this
here so if you substitute this here then you get 0 = CV PDV + VDP /R + PDV. So you can write 0
= CV + R PDV + CV VDP, CV + R is CP and if you divide both sides by CV then you have
CP/CV = γ. So 0 = γ PDV + VDP so you can divide both sides by PV and what you get is 0 = γ
dv/v + dp/p so you can divide both sides by pv and what you get is 0=γdv/v+dp+p so if you
integrate now you will get γlnv+lnp=lnc or this means pv γ=constant, so this shows that for a
reversible adiabatic process of an ideal gas the pressure volume will essentially shows that
pvγ=constant.
With this back ground now let me give you a teaser, so let me relax the condition that it is a
reversible process, this is the next example it is an adiabatic process of an ideal gas but need not
be reversible that is the next example, so what happens here.

(Refer Slide Time: 19:16)

So δQ=du+W by the way for the reversible adiabatic process of an ideal gas if you have pv γ=
constant the work done we have already seen that is integral pdv so p2v2-p1v2/1-γ in the chapter
of heat and watt we have derived this, we can example of a reversible polytrophic process we
have air we have use the index n here just use γ instead of n. Now we will find out the work done
here, so it is a adiabatic therefore δQ is 0 it is not reversible.

So we cannot write δW=pdv so W12=∫δW from state 1 to state 2 is equal to –du integral of this,
so –(u2-u1). So as an example, assume so du is what so this is per unit mass so [Link] so m.u2-u1
so assume Cv=constant, so this if you assume Cv=constant this is then becomes mCv(T2-T1). So
now you know that you can write Cp/Cv=γ and Cp-Cv=R so from this you can write Cv in terms
of R Cp you can write as γCv so γ-1 Cv=R so Cv=R/γ-1.

So –mR/ or minus you can absorb okay, -mR/γ-1 so you can write R(Tspv) so this you can write
(p2v2-p1v1)/1-γ this is something which is bound to create a confusion within you that with the
reversible adiabatic process whatever answer we got as work done the same answer we have got
as work done when we relax the requirement of reversible process, so the work is becoming
same for reversible and irreversible process so where is the fallacy.
Actually the work done p2v2-p1v1/1-γ is true for a reversible process even if Cp and Cv are
functions of temperature, but for an irreversible process we show that this is true only if Cp, Cv
are constants otherwise this integration cannot be done in this way. So this is true only for
calorically prefect gas, but not for all ideal gases. Calorically prefect means only when Cp, Cv is
constant but if Cp, Cv is not constant then we cannot use this, okay. The next agenda will be to
discuss about.

(Refer Slide Time: 23:30)

Entropy transport for a flow process, so let us say that there is a control volume there is some
inflow boundary there is some outflow boundary, so we can write the entropy transport across
the control volume in terms of the entropy transport of a control mass system, why we intend to
write it in this way is because we already know how to describe the entropy transport trough
across a control mass system. So we want to use that to extend it to the entropy transport for a
control volume so for control mass assister we have already read the ds = ∂q/ T + d of entropy
generation.

So that means we know what is ds of with respect to system so now we want to apply that to ds
with respect to control volume so what w e want to do is something like this let us say that we
apply the Reynolds transport theorem, so I am straight away writing it for taking the property as
s it could be any general extensive property so ds dt for with respect to the system is ∂s / ∂t with
respect to the control volume plus rate of outflow minus inflow of entropy across the control
volume.

So instead of entropy we could use any property but as an example we are using entropy as a
property now what is ds dt of the system this is ∂q/ T + ds gen this ∂q / T is the ∂q system but in
the derivation of Reynolds transport theorem what is considered is that there is a control mass
system which is go inside with this control volume in the limit as that time ∂t that is under
consideration is 10 x 0. So when the control mass system is almost coincident with this control
volume that means the δq of the system will be same as δq control volume, so this will become
δq cv / t + dsj.

(Refer Slide Time: 27:37)

Therefore we can write δqcv / t + Ds gen = ∂s ∂t cv + rate of outflow – inflow of entropy is Σ m°

e se – Σ m°I si this gives what is m° is the mass flow rate this is waste on the assumption that
across the inflow and the outflow boundaries this is inflow boundary this sis out flow boundary
there could be many inflow and many outflow boundaries across each boundary the property is
uniform so that the total property you can just simply write mass flow rate times the entropy that
particular section so this can be thought of as an average specific entropy over the section across
which the transport is taking place.

So this is so you can write so you can write this equation or this particular equation as an
equation that commands the entropy transport during a flow process, so let me give you one
example we will talk about two examples first example reversible and adiabatic flow process
with single inlet and exit, so because it is adiabatic you have so one particular in this expression
one particular thing which we have missed is that the right hand side is expressed on the rate
equation.

So left hand side should also be expressed as a rate equation so instead of ds this it will be s dot
gen that is the rate of entropy generation and this will be [Link]/t so the important thing that we
have made important consideration we have made is that right hand side we have expressed on
the rate equation in a transport theorem so that left hand side should also be expressed on the rate
equation.

The expression for the second law that we have used S2-S1=Q/t+ entropy generation that is not
the rate that is the total change so we divide that by time ∆t and take the Kelvin as ∆t is used so
[Link] IS 0 reversible means entropy generation is here let us consider that in addition to this
reversible adiabatic steady state steady flow process this is very important.

A reversible adiabatic steady state steady flow process so if you considering this steady state
steady flow process what is essentially means that there is no change of property within the
control volume so steady state steady flow process there is no change in the property within the
control volume and single in let and single outlet means this £ will be replaced by just you can
write 0 is equal to m.e Se- m.i Si.

And the mass conservation is m.e is equal to m.i so you can write Se is equal to Si so this is true
for reversible and adiabatic process so this kind of process is also called as isotropic process
because the entropy remains constant throughout the process now let us applied the Tds
relationship you can apply the Tds relationship for any process so you can write Tds equal to D H-
Tdp so now you apply this there is no change in the entropy during the process, so this is 0 so D h
is equal to Tdp so i to e this is I to e so He-Hi is equal to integral of Tdp from i to e
(Refer Slide Time: 33:44)

Now let us apply the first law so Qcv+m.*Hi+Vi 2/2+gzi+m.*He+Ve2/2+gze+wcv what is [Link] is
[Link] / m dot okay. Now look at this equation hi – he = - integral of Vdp so you can write w. cv
integral of Vdp from I to e + Vi 2 - Ve2/ 2 + gzi – ze, this is true for reversible adiabatic process. If
you consider the isothermal process reversible + isothermal + steady state steady flow, so for the
isothermal process so we are replacing the adiabatic process by isothermal process, so isothermal
process because it is reversible isothermal process you can write Q. = or ΔQ = Tds.

And Tds you can write as dh – vdp, so this you can always write okay, so in place of the heat
transfer now you could, now you cannot write 0 but you can write Tds in place of Tds you can
write dh – Vdp. So if you write dh – Vdp then you will see that the work done expression comes
out to be the same. You just substitute this ΔQ as Tds ad dh – vdp and put it in the expression for
the first law. So instead of it will come out to be m dot x h2 – h1 – m dot integral x vdp, where
small v is the specific volume.
So you will see that you will get the same expression for the work done, so we are consider two
limiting cases one reversible adiabatic and one is reversible infact any reversible process it does
not need to be isothermal because here we are not consider any where the t is constant, we have
just used Tds this t itself could be a variable therefore we have not committed the t is the constant
so reversible isothermal is a special case but it could be any general process.

So for any reversible process, so as a matter of fact for any reversible steady state steady flow
process with single inlet and outlet, this is the expression that we get for the work done per unit
mass, it is very important expression and we will take up with this expression and go further for
our next lecture thank you very much.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

by
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 19: Tutorial 5: Entropy and

its Transport

(Refer Slide Time: 00:19)

In the previous lecture we were discussing about the entropy transport in a flow process and we
were talking about a typical example which is still there in the board that we are considering a
reversible steady state, steady flow process with single inlet and outlet. So now we will consider
a special case of this.

(Refer Slide Time: 01:03)

Wcv=0 and V=constant, so a special case when there is no work done and the specific volume
remains constant, it is a constant density incompressible fluid. So in that case this equation will
boil down to 0 is equal to now you can take V out of the integral, because it is a constant, so you
can write –(Pe-Pi) V you can write as 1/ρ so +Vi 2-Ve2/2+g(zi-ze). So you can write
Pi/ρ+Vi2/2+g(zi)=P/ρ+Ve2/2+g(ze).

Amazingly, it looks very much like the Bernoulli’s equation. But again illusively this is not the
Bernoulli’s equation, this looks like Bernoulli’s equation, but this is actually a mechanical energy
conservation equation. The Bernoulli’s equation you apply between two points here you apply
the stead state, steady flow energy equation between two sections, i and e are not two points,
they are two sections and you are assuming that the properties like velocity, pressure are uniform
over those sections.

Otherwise, you may have to give a correction factor to these which are known as kinetic energy
correction factors in fluid mechanics. So I am trying to draw a perspective also, here you see we
are bridging the inter linkage between fluid mechanics and thermodynamics. And you see that
this looks like the Bernoulli’s equation. And therefore, this can be interpreted as a mechanical
energy conservation equation for a steady state, steady flow reversible steady state, steady flow
process with single inlet and outlet with no work done and constant density fluid.

So these are the assumptions based on which this equation can be applied okay. With this little
bit of background on entropy transport for non flow and flow processes let us try to work out
some examples, some problems on entropy transport. So we will go to the tutorial problems
chapter 4.

(Refer Slide Time: 04:24)

(Refer Slide Time: 04:27)

(Refer Slide Time: 04:30)
So we will start with the problem number 4.1.

(Refer Slide Time: 04:34)

So we have about 7 to 8 problems in this particular chapter. And what I plan to do is I planned to
discuss about these problems in brief so that you know how to solve the problems instead of
getting into the numbers, I give you the principle of solving the problems, the concept of solving
the problems which you can use and work out the numbers. So the first example one look at this
screenshot, 1kg of ammonia in a piston cylinder at 500 C and 1000 kilo Pascal is expanded in a
reversible isothermal process to 100 kPa.

Find the work done and the heat transfer. So this kind of problem is a very illusive problem,
because by looking into this it is given reversible isothermal process.

(Refer Slide Time: 05:34)

So you will have, let me write temptation, you will have a temptation of using the formula
W12=P1V1LnV2/V1, this temptation come from school level approach of solving these
problems where everything is ideal gas. Now whether this is correct or not let us evaluate this for
this problem. So now let us look into the problem data.

So state 1 is given as 50 0C P1 as 1000kPa then how do you get state 2 because it is a revisable
process you can write ∂Q = Tds this is for a reversible process so we can write that Q1 2 now it is
an isothermal process so T(s2- s1) okay so what is the state 2 is till the temperature is 50 0C and
the pressure is 100kPa so from the property table of ammonia you can get what is s1 and you can
get what is s2.

So MT(s2- s1) by the way entropy of if it is a two phase mixture entropy of a two phase mixture
can be calculated by the same mixture rule which is used for calculating the specific volume
internal energy enthalpy the same rule of mixtures can be used so this is the heat transfer this T is
273.15 + 50K, so now first law if you write Q 12 = m (u2 – u1), so from the table you can get u1, u2
also + W12 so if you substitute the heat transfer and u 2 – u1 you will get w12 and the answer is
363.75kJ and clearly this is not P1, v1 ln v2/ v1 you can check from the data why because although
this is isothermal process and reversible isothermal process for this process PV is not equal to
constant because the ammonia considered in this problem may not be treatable as an ideal gas.

(Refer Slide Time: 09:07)

This we must keep in mind, next problem we go to problem number 4.2, it is projected in the
screen water in a piston cylinder is at 1MPa 5000C there are two stops a lower one which is
corresponding to a volume of 1m3 and upper one which is corresponding to a volume of 3m 3 so
the piston floats when the pressure is 500kPa initially the pressure is 1mPa so the heat as to be
transferred from the system so that the pressure comes down from 1 MPa to 500kPa and then the
piston will come down. And it will reject it is rejecting heat the surroundings find the total
entropy generated in the process.

(Refer Slide Time: 10:21)

So let us try to work out this problem first we draw the PV diagram, so state 1 is super heated
vapor which is 1MPa 5000C the it comes down from 1MPa to 500kPa okay because the piston
can float when only when the pressure comes down to 500kPa so from here to 500kPa let us say
this is state 1A this is 500kPa then heat is rejected so it will come at a constant pressure it is
volume will decrease. How much it will decrease it will decrease when it encounters the stops so
it comes to the V stop the lower stop.

(Refer Slide Time: 11:44)

So if you look at this picture you will see there is a upper stop[ and there is a lower stop so I am
talking about this stop by calling V stop so this V stop is 1m3

(Refer Slide Time: 11:59)

So at this volume now it cannot when a heat is continuously rejected its pressure will come down
at constant volume so until it is cold until it becomes 100 0C, so state 2 how do you specify it V 2
= 1m3 and T2 is let us call this 2a 1000C. So this will tell you what is V 1 what is U1 what is S1 all
these you can get from table similarly if you know V2 you know the mass how do you know the
mass, mss is so instead one the volume is given which is 3m 3 so m is 3m3 sorry V1 / 3 sorry 3m3/
V1 so you can get V2 as V2 / m so from table you can get V2 U2 S2 okay.

So now you apply the first law U12 = m x U2 – U1 + W12 okay what is W12 is the area under this
PV diagram okay this is the shaded area, so you get what us Q12 now second law S 2 – S2 = Q12 /
T + entropy generation, so this is the integral form of dS = δQ / T + dsJ if you integrate this,
between states 1 and 2 so S2 – S1 is = Q12 / T + Sjl where is what T will substitute here and this is
the golden question so it depends on entropy generation due to which effective 12 capture here if
you want to capture the entropy generation due to internal irreversibility is only then this should
be the temperature.

Of the boundary of the system but if you want to capture the entropy generation because of the
net change in entropy if the system and the surroundings, the this should be the surrounding
temperature so if this includes the effect of both external and internal irreversibility this should
be the surrounding temperature, but if it includes the effect of only the internal irreversibility this
should be the system boundary temperature. Now the problem that is asked it says that what the
total entropy is generated in the process.
So it is the combination of internal entropy generation due to internal and external irreversibility
so in that case Sj in total, is this 2 – S1 – Q12 / T0 but T0 is the surrounding temperature, so this is
sometimes written as ΔS system + ΔS surrounding it is just another way of looking into the same
equation why this is ΔS surrounding because when heat Q12 is transferred from system to
surrounding with respect to surrounding, it is a negative heat transfer whatever comes from
surrounding to the system that means surrounding gets depilated of it.

So and for the surrounding we are considering it to be a such a lots thermal dissolver that for the
change in entropy you can use ds = δQ / T so you can use that TDS relationship for the
surrounding no matter whether it is irreversible for the system or not for the surrounding you can
use the heat transferred divide by it is absolute temperature so this is the this becomes the ΔS of
the surrounding so this is just another way of interpreting the same result and if you substitute it,
it comes out to be 19.45kj/ k sorry k/ k okay.

(Refer Slide Time: 17:43)

Next let us consider problem 4.3, so problem 4.3 there is a vertical cylinder piston this contains
R-22 at -200 C, 70% quality and the volume is 50 liters as shown in the figure, the cylinder is
brought in a 200 C room that means T0 is 20 + 273.15 so 293.15 Kelvin and an electric current of
10 ampere is passed though the registered inside the cylinder, so it is a very interesting problem
where you also have electrical effect so this is something beyond the parading of simple
compressible substance.

Where you also have electrical work associated the voltage drop across the register is 12 volt it is
claimed that after 30 minute the temperature inside the cylinder is 40 0C and that increase in
temperature is because of the Joule heating effect, so question is, is its possible? So the question
that is asked is that is it possible is this claim possible, so whenever there is a question that
comes that is any claim possible we have to assess the claim in the perspective of the first law
and the second law.

So we have to see whether this claim violates first law and whether this claim violates second
law, so typically we can create a situation when the claim will satisfy the first law but when the
first law is satisfied we also have to guarantee that the second law also satisfied that means how
do you know whether the second law is satisfied or not you calculate the entropy generation and
show that it is positive.
If the entropy generation is positive that means it is a feasible process if the entropy generation
comes out to be negative that means it is not a feasible process, so let us work out this problem
so for the system which is the R-22.

(Refer Slide Time: 20:12)

There are two types of work, one is this is problem 4.3 the work done is w moving boundary + w
electrical, so what is the moving boundary work mp (v2 – v1) it is a constant pressure process if
you look into the figure of the problem you will see that there is a piston which is floating and
because the resistance pressure does not change the inside pressure also does not change as it is
moving in a quasi- equilibrium process.

And what is the electrical work, the electrical work is minus the voltage into current into time
this Δt is given as 30 minutes that is 30 x 60 seconds so now the first law you can apply Q 12 =
m(u2 – u1) = w12 and the second law s2 – s1 = Q 12 /T + Sjn so this T you can put the temperature
of the thermal reservoir which is 293.15 Kelvin, the reservoir is the room temperature which is
200C so 293.15 Kelvin.

And the states are given state1 R-22 at -200C 70% quality, so from the table of R-22 you can
identify state 1 you know internal energy entropy all these from the table and state 2 the
temperature is 400C and the pressure at state 2 is same as pressure at state 1, how do you know
the pressure at state 1, pressure at state 1 is the saturation pressure corresponding to -20 0C
because it is inductive two phase region.
Saturation temperature of ammonia, so the pressure at state 2 will be same as the pressure at state
1 which is Psat (ammonia at -200C) from ammonia table, so state 1 is identified by T1 and X1
state 2 is identified by P2 and T2, so you know all the properties and you can calculate the
entropy generation so if you calculate the entropy generation it becomes 0.768 kilo joule /Kelvin
so this is greater than 0 that means this process is feasible, okay. So let us work out the next
problem that is problem number 4.4.

(Refer Slide Time: 23:51)

There is a rigid container with a volume of 200 liter it is divided into two equal volumes by a
partition, both sides contain nitrogen one side at 2MPa, 200 0C another side as 200Kpa 1000C, so
the situation is like this.

(Refer Slide Time: 24:27)

Problem 4.4, so there is a rigid container with the volume of 200L it is divided in to 2 equal
portions both contain nitrogen the patrician raptures and the nitrogen comes to a uniform state.
And the surroundings are 200 C that is 293.15K.

What is the, what done a net entropy change during the process, so to calculate the net entropy
change during the process we can consider that the nitrogen is an ideal gas so you can calculate
the change in entropy of the system. This is the change for a so using by integrating the TDS
relationship for an ideal gas with constant cp and cv yu get s2 – s1 = cp ln t2/ t1 – Rln p2 / p1
okay.

So this you can do by integrating TDS = Dh – VDP for an ideal gas with constants cp and cv. So
this is for A and this is for B, now what is the heat transfer ion the process? There is no watt done
so the watt done is 0. Why there is not watt done? Because your control mass system is this one
and that does not change in volume. So u2 – u1 is Ma (cv x t2 – t1 a) + Mb cv (t2 – t1B) and you
can use the second law s2 – s1 = q12 / t where you can substitute t =\ t0 to get the entropy
generation.

So s2 – s1 you can use form this formula q1 to use this from this formula and if you substitute
this you will get the entropy generation which is 0.2947 kj/ k. so let us consider the next
problem, problem 4.5 now this problem is a problem for flow process. Steam enters a turbine at
3MPa 4500 C.

(Refer Slide Time: 28:39)

And expands in a reversible adiabatic process and exhaust at 10kPa, changes in kinetic energy
and potential energy are small and power output of the turbine is 800 KW. What is the mass flow
rate of steam through the turbine?

(Refer Slide Time: 28:59)

So in the turbine what happens let us write problem 4.5 so this is the schematic of a turbine
normally we show the schematic with an expansion in the turbine conceptually shown by this
expanded section. So this is I and this is e so first law Q0cv so this is the steady state steady flow
process and this is the control volume which is the turbine, so it is given that the process is
adiabatic.

So this is 0 you neglect the changes in kinetic and potential energy that is also given so W 0cv/m0
is equal to hi-he so it is given that the rate of watt done by the power output of the turbine is
800kg watt so state I is given that the steam is at 3MPa 4500 centigrade this is super heated steam
3MPa 4500 centigrade.

The state e how do you specify state e the exit pressure is 10kPa and s e=si because it is a
reversible adiabatic so using this two from table you can calculate what is he you can find out
what is he this will give what is hi so from here you can find out what is m o this is 0.728kg per
second next problem, problem number 4.6.

(Refer Slide Time: 31:42)

You have a counter flow heat exchanger as shown in the figure so the heat exchanger is what it
does it essentially uses the hot fluid to heat a cold fluid or it uses cold fluid to cool down a hot
fluid so there is an exchange of heat between this two by the system if you look into the figure
the system is insulated so that there is no let heat transfer between the system and the
surrounding so if you draw this figure.

(Refer Slide Time: 32:32)

So there is air which enters the state one and leaves at state two and there is water which enters at
state three and leaves at state four so it is so the water is used to cool the air so now we have
identify the various states so state one so is 5040 Kelvin 400kPa so this two properties are there
540 Kelvin and 400kPa state two it is 360 Kelvin air.

If you assume ideal gas then the property will be function of temperature only okay then state
three water state three is water at 20o centigrade 200 kilo Pascal and state four so assuming
negligible pressure drop across this pipe line 3 to 4 you have P4= P3 and you have to calculate
basically what is the other property that is needed to specify the state four.
So here control volume is the combination of the two streams this one so the first law let us write
the first law in the second law Q0cv+£(moi hi neglecting changes in kinetic energy and potential
energy there is no watt done there is no let het transfer so m oi hi is mo1 h1+mo3 h3= mo2h2+mo4
h4and mo1 is same as mo2 and mo3 is same as mo4 so from here you can calculate what is h4, an h4
and p4 will give state 4 and that will give what is entropy and state 4 specifically entropy.

So now to calculate the entropy generation in the process, you refer to this equation, it is a steady
state steady flow process so this term is not there and there is no need of heat transfer across the
boundary of the system because it is just heat exchange between two streams. So if you use this
you will get what is the entropy generation for this system.

For here you can use the ideal gas property, for water you have to use stable, so this a very
typical problem, there are two fluids, foe one you have to use ideal gas consideration for other
you have to use the trim okay. So I am giving you the final answer, the total entropy generation is
0.02017 kw/kg the rate of entropy generation. We will work out couple of more problems
quickly; the next problem is just a one liner, problem number 4.7.

(Refer Slide Time: 37:27)

A small pump takes in water at 200 C 100 kPa and pumps it to 2.5 MP at a flow rate of
100kg/min; find the required pump power input? So the key word for this problem is that it is a
small pump. When it is small pump what it, means? When it is small pump it, means you may
neglect the losses and you may assume it to be a reversible pump, reversible pump with single
inlet and outlet.

(Refer Slide Time: 38:03)

The work done is –∫ cdp if you neglect the changes in kinetic energy and potential energy, you
recall that for a steady state, steady state flow process with at the reversible consideration and
single inlet and single outlet this is the work done, if you neglect the changes in kinetic energy
and potential energy. That pump is handling the liquid for which is v is the constant, so you can
take this out of the integral and this is approximately = - vf x dp, vf at 2 20 0 C, so this is – vf x P2
– Pi, so this is 100kPa and this is 2.5 mp. So the total work done, so this is small w w. m. where
m. is the mass slow rate 100kg/min, you have to convert kg/sec.

So this – 4 kw -4 means – means you have to energizes the pump, you have to waltz the pump to
run the flow, so we can see here we have seen two example one is the energy producing the
device and another consuming the device. The work producing device rather work producing and
work consuming energy producing is not the correct terminology here, so the work producing
device is the turbine and work consuming device is the pump and these two examples have
already covered. The last example we will consider.

(Refer Slide Time: 39:57)

In this tutorial session this is problem number 4.8 which is projected on the screen.

(Refer Slide Time: 40:07)

So you have a household refrigerator which has a freezer at TF and a cold space at TC at you see
that this refrigerator takes heat Q.c from the whole space and Q.f from the freezer and it rejects
the heat from Q.a m end, because it is a refrigerator it can operate in a cycle while transferring
the heat from the lower temperature body to higher temperature body only if it does the work
input and the work input in the figure you see the work input is w.

You have to find out the what is the minimum work input for the pump, for the refrigerator, so
the minimum work input will be there only if it is reversible process because if it is not a
reversible cycle, if it is the work consuming device it will consume more work because of loses,
so we have to assume the reversible process. So if it is a reversible process, so first of all you will
use for the cyclic process, cyclic ∫ of heat = cyclic integral of what? That is Goss law, so see this
problem; we will solve the problem from the fundamental.

So cyclic integral of heat is Q.f + Q.c + Q.a in terms rate equation if we write and the cyclic
integral of waltz is – w. that actual integral is the rate times the time but times get cancelled on
both sides. So why – because it is the watt observing cyclic device it is not a work producing
device and the second law because it is reversible cycle you have the cyclic integral l of the δ
Q/T=0 ,so that means Q.F / T F = Q. C /T C +Q. A /TA that is =o. So look at this figure now.

(Refer Slide Time: 42:42)

I am just trying to going to explain which is very important when you write the cyclic integral of
the δ Q / T you are writing Q. A but the temperature here what I am showing in the mouse but
actually it is the temperature here which is temperature at the system boundary but because we
are considering in the externally reversible process that is the temperature difference between the
system boundary and this one is consider with the very small but this is the T A this is T^ A +δ T
A So this is as good as T A.

So we can write here that this is a T AS +δ T A this is T C +δ T C and this is the T A +δ T F okay,
so there is a little bit of the problem with the figure may be that this is the sign of Q . A way is
not shown correctly in the figure that is displayed here I have watch out this problem with this
with this direction of the Q. A Q .C and Q. F so please contact the figure that his directions given
in the board so this is the heat transfer to the system that is why I am consider as the both as the
positive all as the positive okay this is T A and this T C and this T F.

So here because this is T A and this should be actually and this actually _δ T A not +if that is
according to the diagram and it is the Q direction and it should opposite and T A +δ T A and here
according to these diagram what I have shown here if this is T A this should be T A – δ T because
this is smaller than the heat transfer is taking place so we are considering al amount the stories
we are considering the temperatures a system already in the heat transfer is taking place okay.

Because this is ending to 0 this is the reversible process that is why we write this and what
additionally formation is given is that the Q. F = Q .C so by combining this is equation and this
equation you can find out the W. and answer is 0.504kilowatt okay so what we are apply
basically is the first law of the cycle second law of the reversible cycle we have shown that the
correct of the direction and the heat transfer and the watt done by considering the adiabatic sign
and we have consider and the temperature of the system boundary.

But because it is externally reversible in the temperature differences is small so we have consider
only the thermal reservoir temperature here so this completes the present tutorial and in the next
section you have the review section and we will discussed about and the various concept and
direct to the outstanding of the entropy and that will be take up in the next section thank you very
much.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
on
Laws of Thermodynamics

by
Prof. Sankar Kumar Som
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 20: Introduction to Third Law

Good afternoon and I welcome you all to this lecture session of the course laws of
thermodynamics now today I will give you a brief introduction to the third law of
thermodynamics.

(Refer Slide Time: 00:35)

Third law of thermodynamics in fact the people working in the field of engineering science know
very little about third law and its concept not much this is because of its limited use in
engineering calculations but definitely it has contribution in the calculations of engineering
science I will tell you and then I will explain as much as I can the concept of third law.
So far we have defined entropy from the classical thermodynamics point of view through the
heat transfer in irreversible process and we have seen that this definition has come out that is
very fast rate in terms of the difference of entropy or change of entropy in a process from one
state to other state that s is integral of del Q reversible by T that means if a process executes if a
system is the process at internally reversible condition then what is the amount of integral del Q
by T del s.

So always we define the entropy in terms of its changes okay and in all engineering calculation
the changes are required but sometimes we require the absolute entropy but even if we do not
require absolute entropy the changes unknown but if you have to ascribe the value of entropy it
is not exactly the absolute entropy from an absolute data but you have to fix a common data the
third law of thermodynamics is that common bottom where the entropy can be taken as zero or
entropy is actually zero of it substance.

So this statement to understand we have to understand little bit of microscopic point of view of
thermodynamics or microscopic thermodynamics though this is totally beyond your scope of
calculation or usefulness of thermodynamics in your at your level but we can discuss this little
bit now we know from the kinetic theory of matter that molecules moves at random indifferent
direction and they collide with each other in any matter.

Now this randomness or disorderliness of the molecule is actually the measure of entropy the
randomness of this organism are made by the variation of velocities over a higher spectrum large
variations and they are change very fast there they are change that means more randomness or
more disorder needs means the velocity is a magnitude and the direction changes very fast and
over a large spectrum.

If it happens in any matter we tell that this ordinance or randomness is more so more is the
disorder less more is the randomness more is the entropy now what happens because of this
disorder needs or randomness of the molecular motion it becomes difficult to predict a particular
molecular configuration for a given macroscopic state that means with this randomness the
predictability of molecular configuration or the molecular position or we can tell the molecular
state sometimes it is told as microscopic state.
To define a particular microscopic State for a given macroscopic state it becomes very difficult it
becomes much less predictable which means that with this randomness and disorder names of the
molecules a given macroscopic state at thermodynamic equilibrium which so far we have
discussed we have a number of possible molecular configuration or microscopic and more is the
disorder more is the randomness more is this number of microscopic states that means the
uncertainty of defining the microscopic state increases becomes less predictable okay.

And that way entropy increases so it is not surprising at this stage at this stage to understand that
substance in solid phase will be having less entropy than that in gas phase because of the fact that
in solid phase the randomness is much less compared to that in gas phase and the molecules in
solid phase usually oscillate continuously about an equilibrium position.

So therefore absolute entropy in solid phase is less than that of gas phase where randomness is
much more and they collide frequently the molecules collide frequently and the randomness is
much more in statistical thermodynamics this is explained or this is written in a mathematical
form through a parameter known as thermodynamic probability it is very simple concept very
preliminary and simple concept the thermodynamic probability is the number of probable
microscopic states with respect to a given macroscopic state and it depends upon the state
variables at that macroscopic state.

For an example I am telling you we have considered an isolated system you know what is
isolated system which does not interact with the surrounding the isolated system is at equilibrium
it does not interact with the surrounding it properties remain invariant with time and uniform
throughout the mass of the system but it may have a very high absolute entropy because the
randomness of B or disorderneeds of the molecules so therefore you see microscopic state is
different from that of the macroscopic state in which were that here for a given macroscopic
equilibrium state of an isolated system we have a large number of probable microscopic States or
molecular configure.

So this is expressed in terms of thermodynamic probability in statistical thermodynamics that

probability indicates the number of possible microstates for a given microstate of a system and
the absolute entropy is in that case is expressed by a very well-known equation K LN P where P
is the thermodynamic probability and K is the Boltzmann constant and this equations known as
volts man equation this equation is known as Boltzmann equation and K is case Boltzmann
constant Boltzmann constant.

Boltzmann constant whose value is one point three eight zero six into 10 to the power minus
23June 30 which is the unit of entropy so this is the absolute entropy in statistical
thermodynamics expressed by the well-known Boltzmann equation in terms of thermodynamic
probability that means the possible or probable microstates for a given microstate and where this
probability is more means we can have more microstates more number of microstates for a given
microstate so at the absolute entropy is more.

So therefore absolute entropy depends upon the number of probable microscopic States which in
turn depends upon the molecular disorder is randomness more is the disorder Nina’s mode is the
randomness more is the probability of the microstate okay. Number of microstates now with this
equation we can understand that how then absolute entropy is expressed now you consider a
solid where the randomness is much less because the molecules continuously oscillate about
equilibrium position and this randomness where the less random that means uncertainty is list
also decreases or fades out at the temperature increases so this randomness or this uncertainty
even for solid which is much less also fades out or decreases with the decrease in the temperature
absolute temperature any temperature decrease in the temperature okay.

And when it approaches towards absolute zero it becomes the uncertainty becomes minimum
and in this respect I can tell that we assume that when absolute zero is approached all molecular
motion ceases out all molecular motions cease out that means are stopped there is no molecular
motion and this is sometimes called as ultimate molecular order that means the order of the
molecule reaches this maximum value and uncertainty is zero and certainty is 100% that means
molecular configuration is fixed.

But if you proceed towards absolute zero for a solid substance the uncertainty is reduced the
molecular randomness or disorder needs is reduced and these substance approaches an absolute
zero entropy and this is more so for a crystalline solid this is because for other solids non
crystalline solid still there are fewer certain uncertainties even if the temperature absolute
temperatures approaches zero so it is for a crystalline solid substances where when the absolute
temperature approaches zero we can tell the randomness approaches 0 that means uncertainty
approaches 0 and molecular order reaches is maximum.
So this concept this concepts were derived from experiments from chemical reactions data from
chemical reactions at very low temperature data from heat capacities of substances at very low
temperature by collecting the data and through deduction it has been established and this law
actually was formulated by two scientist arced and simony and known asnarsimha statement
which steps like that the absolute entropy of a crystalline substance approaches zero as the
absolute temperature approaches zero this is known unsacred Simon statement.

I will show it afterwards the statement now with this narsimha statement we can have some idea
about the absolute entropy how it is useful in engineering calculation that to have a common
bases that we can ascribe the entropy values at different states from its changes calculated by our
well-known formula in classical thermodynamics through reversible heat transfer we can ascribe
if we know this base and that common base.

And that is very important I am telling in chemical reactions which has not been taught in your
discourse that if you read the thermodynamics of reactive systems then you will see it is very
important to have a common base for calculations of entropy at different states of the substances
known as reactants or products in a chemical reaction and that base is at zero absolute
temperature base where the entropy absolute entropy is zero.

This is of very practical use for in engineering calculations now this is one approach of defining
the third law there is another approach of defining the third law this comes from the attainability
ofabsolute zero in fact I have told that absolute zero is approach but exactly we cannot have
absolute zero we cannot attain absolute zero in fact is this has-been found you know that there
are probably you know this has not been also taught that there are various ways overcooling.

So if you pull a system how much cooling you can do or at what temperature you can go you can
never got absolute zero in this respect I will tell you in brief what are the methods there is a
method known as joule-Kelvin effect the method which uses the joule-kelvineffect joule-Kelvin
effect is like this if a gas is coming at a high pressure and temperature is allowed to pass-through
a small restriction or constriction where there is a pressure drop because of the mechanical
friction then it is found that temperature of the gas is decreased if we isolate the entire
constricted systems decreased provided the initial temperature is below certain temperature
known as inversion temperature.
I am not going into that detail that is known as dual Kelvin effect and if you think from the
steady flow energy equation that the first law of thermodynamics applied to control volume and
if the constricted system is totally insulated then the enthalpy at the inlet will be equal to the
enthalpy at the outlet if you consider the kinetic energy and potential energy changes are
negligible that means in this case the enthalpy at the inlet and outlet remains same.

But this is highly an irreversible process where the pressure is reduced and the temperature is
reduced provided the inversion in the initial temperature is less than the inversion temperature
most of the gases are cooled by utilizing this effort this effect where initial temperature is usually
lower than the inversion temperature to realize thiscooling effect otherwise the gas has to be pre
cooled to a temperature below the inversion point temperature of that gas okay.

Now this process is known as bottling process and by throttling a gas like this we can produce a
low temperature and this is utilized for liquefaction of air okay and we can produce liquefaction
of any gas and by joule-Kelvin effect wean produce helium at five Kelvin today now again there
is another process to go for a further cooling to reduce the temperature which is the adiabatic
vaporization that means if you have an helium at five K if you make an adiabatic vaporization
that means entire system is insulated there is no heat transfer with the surrounding and because
of the vaporization the cooling effect okay.

So this is another way by go to go for further cooling another way overcooling a system is by
magnetocaloriceffect this effect is known not much this is that on a paramagnetic substance by
decreasing the adiabatically the magnetic field we can go on changing the temperature to a very
low value but in all these processes of cooling it is observed and it comes from the commonsense
also that as you cool the cooling becomes more tough for example when you compress a gas the
compression becomes more tough as the pressure is increased as you compress the next
compression becomes tough similarly as the cooling proceeds.

If you cool the next cooling is more tough so this way if you have finite number of processes
you can never achieve to Absolute Zero cooling becomes gradually difficult so that you can
never achieve zero key and this has been established from several experiments so therefore this
statement that the absolute zero can never be achieved in any finite number of processes
executed by any system is also another way of defining the third law of thermodynamics.
So therefore we have two ways one by defining the absolute entropy its base where the absolute
entropy is zero we use it at a base for entropy to ascribe the entropy a different state for our
calculation engineering calculation similarly the third law is also explained in terms of
unattainable 'tiphenomena that absolute zero can never be approached .So I now show you and
the two statements of thermodynamics.

(Refer Slide Time: 17:51)

Not statement not shaman statement this statement is the entropy of a pure crystalline substance
approaches zero as absolute temperature approaches zero that as I have explained and another is
the unattainable it statement which is the statement by no this is the statement of unattainable 'it
phenomena what is that that is by no finite series of processes is the absolute zero attainable.

So therefore these are the true statements of thermodynamics third law we do not have to put
much you need much effort in it only an overall understanding and a brief introduction of third
Locke for the completeness of the course it is required so you must know there're four laws of
thermodynamics one is zeros law which defines the concept of temperature which defines the
temperature gives the concept of temperature another is the first law which is nothing but
typically the law of conservation of energy okay.

The second law which is the law that puts a directional constant which imposes the directional
constraint on unidirectional characteristics of process occurring in nature which has-been dealt
elaborately how this constraint or you variationalcharacteristics is imposed on any natural
process and last one is the thermodynamics third law which defines the absolute entropy at
Absolute Zero.
State which is again not attainable through two statements on is not Simon statement which
defines that absolute entropy which tells that the absolute entropy of a fist aligned substance
approaches zero when the absolute temperature approaches zero an absolute temperature cannot
be attained in any finite series of processes which is unattainable ax T statement okay by this I
conclude thank you all.
 NPTEL

NPTEL ONLINE CERTIFICATION COURSE

Course
On
Laws of Thermodynamics

by
Prof. Suman Chakraborty
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur

Lecture 21: Review of Learning Concepts

So today we are going to have a review session where we will essentially try to divide certain
concepts on entropy by asking some short questions.

(Refer Slide Time: 00:39)

So I have projected the questions on the screen, but I will read these questions out and we will
discuss these questions one by one. So these questions are relating to state whether the following
statements are true or false. So certain statements are given you have to say whether these are
true or false and in case you are able to give the correct answer you also have to justify it okay.
So the first question is all isothermal processes must be reversible, this is the first statement, so
true or false. So let us try to analyze this.
(Refer Slide Time: 01:23)

Let us say there is a piston cylinder arrangement and there is a heat transfer from a thermal
reservoir. Let us say the temperature within the system is T1 which is less than T reservoir. So
that there is a heat transfer, so if this temperature T1 of the system remains the same there is an
isothermal process for the system and if it is isothermal it is suppose to be a very slow process,
so that it is a reversible isothermal process.

However, the reversible isothermal process by reversible we mean internally reversible, but if
you look at this temperature difference between the thermal reservoir and the system boundary,
there may be a finite temperature difference. So isothermal may assure internal reversibility, but
it will never assure total reversibility. It will be totally reversible process if this T reservoir minus
T1 is some ∆T very small tending to 0, then it is reversible, externally reversible.

Otherwise, it is not externally reversible and we can say that it is just an internally reversible
process. So all isothermal processors must be reversible this statement is not correct. Let us
consider the second statement, cyclic integral of δQ may tend to 0 for irreversible heat engines.
So cyclic integral of δQ, so let us say that there is a heat engine which takes heat QH rejects heat
QL and thus some work W in a cyclic process.

So cyclic integral of δQ is QH-QL, can it tend to 0 for an irreversible heat engine? Surely,
because the difference of this is work done, and if the engine is highly reversible the work done
will be less unless and therefore, in the limiting condition for a highly reversible situation this
may tend to 0. The third question is a process with no net change in the system entropy must
necessarily be reversible and adiabatic. So a process with no net change in entropy must
necessarily be reversible and adiabatic.

(Refer Slide Time: 04:39)

See let us write the expression for change in entropy of the system. S2-S1=Q12/T+Sgen, so what
is saying is that this is 0, how can this be 0? There are some possibilities one is, it is a reversible
adiabatic process, if it is reversible entropy generation is 0 if it is adiabatic Q12 is 0. However,
there would be some other case also when this is 0, when this is 0, for example, this is some
minus positive number a when this is negative when heat is transferred from the system to the
surroundings.
And let us say this is +a so then the total is 0, but it is not a reversible and adiabatic process. So
net change in entropy is 0 does not mean it is an isentropic process, isentropic means the entropy
remains same throughout the process not just the final entropy minus initial entropy is 0. So this
is the case when the change in entropy at the end of the process is 0, but it is not reversible and
adiabatic.

(Refer Slide Time: 06:05)

So a process with no net change in system entropy need not necessarily be revisable and
adiabatic let us consider the 4th question all slow process must necessarily be revisable so this is
also not true because all slow process must necessarily be internally reversible but they may be
externally revisable so if they are externally revisable that means that net process becomes
irreversible. The next question is throttling of an ideal gas is approximately an isothermal
process.

So throttling the process of throttling something like this so you have a throttle volve and across
the volve the fluid is flowing in such a way that there is no scope of any heat transfer or work
done and if you neglected changes in kinetic energy and potential energy the first law for a
steady flow process will tell that hi = he remember that this does mean that it is an isentropic
process.

The enthalpy does not remain same it is just the enthalpy before immediately before throttling
same as enthalpy immediately after throttling but we are talking about an ideal gas so now this
means that dh so hi- he =0 so if it is a constant specific heat even if it is a constant specific heat it
means Cp (Ti – Te) = 0 not for all ideal gas only for ideal gas with constant specific heat but
even then you cannot say that it is an isothermal process.

Why because it is for an ideal gas with constant Cp Cv this means that the temperature before
throttling is same as temperature after throttling but this does not mean that temperature remains
same throughout the process, so it is an isothermal process.
Next question area under the close loop representing a thermodynamic cycle in Ts diagram
signifies the net work done in a cycle process so if you have a Ts diagram and you have a area
enclosed in the Ts diagram.

(Refer Slide Time: 08:51)

So the area enclosed in the Tds in the Ts diagram in a cyclic process, so that is integral of Tds
that will be ∂Q provided it is a revisable process, so if it is a revisable process the of course this
area also represents the work done because cyclic integral heat = cyclic integral of work from the
1st law of thermodynamics but if the process is such that it is not totally a revisable process then
you cannot write ∂ Q = Tds and then this equivalence will not be there.

(Refer Slide Time: 09:38)

Next question a process with 0 net change in entropy must necessarily be isentropic so this is the
same question that we had here 0 net change in entropy means s2 – s1 = 0, so s2 – s1 is = 0 does
not mean it is an isentropic process because it just indicates that the final entropy is same as the
initial entropy but it does not assure that entropy remains constant throughout the process. Next
question a piston cylinder arrangement contains water at 400C heat is transferred into the cylinder
from a heat sources at 1000C.

And water expands in a cross equilibrium process the process is revisable clearly the process the
cylinder the water expands in a cross equilibrium process that means it is internally revisable
however there is a temperature difference between the system and the heat source is 100 0C and
system bounded is at 400C so because of this finite temperature difference cross which heat
transfer is taking place it is an externally irreversible process.

Therefore the process is not irreversible it is only internally irreversible but not externally
revisable next question a system undergoes change in state from state1 to state 2 by a revisable
and irreversible process that change in entropy of the system is greater in the irreversible process
this is not true. Because when the system goes from state 1 to state 2 that change in entropy s2-
s1 does not depend on the path it depends only on the end state 1 and 2 because it is a point
function the entropy is a point function the next question the entropy of a fixed mass of ideal gas
decreases in every isothermal compression so entropy of a fixed mass of an ideal gas decreases
in every isothermal compression, so let us try to address these question so let us try to use this.
(Refer Slide Time: 12:20)

TdS relationship TdS = dh – Vdp for an ideal gas dh is Cpdt isothermal means dt is 0 so ds is –
vdp / T compression means pressure increases right, so decrease positive specific volume is
positive and this is absolute temperature it is always positive so dS is negative that means
entropy of a fixed mass of an ideal gas decreases in every isothermal compression next question
the specific internal energy enthalpy and entropy of an ideal gas are each functions of
temperature alone.

So internal energy and enthalpy of an ideal gas are functions of temperature alone but entropy is
not right, we call the formula for change in entropies if an ideal gas with constant CP CV so S 2 –
S1 is Cp and T2 – T1 – Rln P2 / P1 so you can see that entropy of an ideal gas will depend on
temperature, so entropy of an ideal gas is not is a function of temperature as well as pressure
whereas internal energy and enthalpy of functions of temperature only, but entropy is a function
of temperature and pressure or temperature and specific volume right.

So this statement is not correct again I am repeating the specific internal energy and enthalpy are
functions of temperature only for an ideal gas but entropy is the function of the temperature as
well as pressure next question are process that highlights second law highlights the first law to
this is not correct because second law talks about the directionality of available process, so
according to first law if energy balance is satisfied you can still have heat transfer from a lower
temperature body to a higher temperature.
Body without any work input however according to second law such a process will not be visible
until that analyze will give a work input, so even though you satisfy energy balance which is the
essence of first law and second law may not be satisfy so a process that while a second law
violates the first law to is not correct, in a sense that a process that violated second law may not
violate first law energy balance is satisfied but second law is not satisfied. Next question one
correlated.

Of the second law states that the change is entropy of a close system must be greater than or
equal to 0, so the change in entropy of a close system if you see this is the change in entropy of a
close system can we guarantee whether this is positive negative or 0, we do not give a guarantee
see where it many times we loosely say that entropy always increases but we do not mention that
it is entropy of the universe system + surrounding together that increases, entropy of a system or
surrounding separately.

Those might either increase or decrease or remain the same sum total of entropy of the system
and surrounding if you consider that will always increase so for example entropy of system can
decrease how it can decrease like if you have heat rejection then this negative for this is always
positive for all cases so some total may be positive negative or 0 so entropy of a close system
just change in entropy of a close system must be greater than or equal to 0 this is not a correct
statement.

Next question a close system can experience and increase in entropy only when there is energy
transfer by heat to the system during the process, so a close system that experience and increase
in entropy only when there is energy transfer by heat to the system during the process that is not
correct even this heat transfer is not there or there is heat transfer from the system a close system
can in experience that an increase in entropy because of generation right.

So this statement is not correct next question number 15 constant pressure lines in ages diagrams
have negative slope ages diagrams are very important and for steam this particular diagram is
also known molecular diagram moldier chart which is used commonly in industry so why this
diagram is important is because for working out various changes in thermodynamic properties
for analyzing devices in power plants you may often may required the enthalpy and entropy data.
So if you have enthalpy what it is entropy diagram, by looking into the diagram you can
immediately read out the data, so the question is constant pressure lines in the ages diagram have
negative slopes so let us write this.

(Refer Slide Time: 18:52)

Tds = dh vDP constant pressure line means Dp is 0. So you can write in the HS diagram the
slope of the constant pressure line is the absolute temperature and the absolute temperature is
always positive, so constant pressure lines in the HS diagram will have positive slope because
this is absolute temperature this is always positive. The next question entropy of a system can
decrease or increase during heat rejection process? So during heat rejection process this us
negative entropy generation is always positive some total may be positive negative or 0 so during
heat rejection entropy of a system may decrease it may increase or it may, may not change.

All these three possibilities are there during a heat rejection process so entropy of a system can
decrease or increase during heat rejection process this is possible even it may remain same, okay.
Now I will come to a difference set of short questions.
(Refer Slide Time: 20:34)

So this set of short questions so because this is a review section I want you to review this
following concepts and I do not want to give you the answers to these learning concept because
we have already discussed in great details but just consider this isolated system so a system that
does not interact with the surrounding close system simple compressible substance pure
substance phase thermodynamic equilibrium law of corresponding state, state postulate flow
work, uniform state.

So please try to revise these learning concepts so these concepts are important because I mean
based on these concepts you can basically develop a foundation on the basic laws of
thermodynamics, these are not exactly the laws of thermodynamics but these are concepts which
act as preludes to the practical application and realization of the various intricacies of the laws of
thermodynamics.

Next the next questions we will discuss state the assumptions behind the equations that are given,
first equation δw = Pdv so what are the assumptions for δw = pdv? The assumptions are very
straight forward simple compressible substance and quasi equilibrium process these are just the
two Important assumptions there is no other assumption that goes behind this, next δQ = du +
pdv. So basically it is a first law where you have neglected first law for a close system where you
have neglected the changes in kinetic energy and potential energy. That is why du and not d and
in place of δw you have written pdv that means you have assume it is a quasi equilibrium
process.

So it is a first law for a closed system with negligible changes in kinetic energy and potential
energy and quasi equilibrium process δQ = du + δw so δQ = d u + δw is the first law for any
process for a close system then next tds = so this s will be capital S, TDS = du + pdv so TDS =
du + pdv this is the TDS relationship that is valid for any process now I want to discuss a little
bit of this because there are confusions on this in almost all students. That why th3e TDS
relationship is valid for all process.

(Refer Slide Time: 23:37)

So if you write ∂ q = du + ∂ w for a reversible process for a simple compressible substance you
write pdv, reversible process for simple compressive is substance you write TDS so that means
this you are considering a reversible process of a simple compressible substance but then how do
you claim that is true for any process is true for any process in a sense that if you use this to
calculate the change in entropy between two states one and two you just construct a reversible
hypothetical reversible process and calculate s2 – s1 using this formula by integrating this.
Once you have evaluated this that s2 – s1 will remained valid even if you have any other
arbitrary process which is not reversible because it is point function, and all the parameters here
in this formulas are point functions. Therefore it is valid for any process, so the integration of this
formula has to be carried over a reversible path but once the integration has been carried out that
result can be applied for any process that is the spirit of calling that or mentioning that this is
valid for any process provided it is a simple compressible substance.

Next one TDS = du + ∂w again here ds will be D capital S TDS = du + ∂w, so what are the
assumptions? See this is first law where you have substitute a ∂q = TDS that means this must be
a reversible process you may argue that if it must be a reversible process why you have not
written ∂w as pdv the reason is that it might not be a simple compressible substance it could be
another case where other forms of worker also there so you are actually not committing what is
∂w.

But as you have committed that ∂ q = TDS that means you have committed it is a reversible
process. The last one state the assumptions w = - integral of vdp so this is any reversible steady
state steady flow process with single inlet and single outlet with negligible changes in kinetic
energy and potential energy. The derivation of this formula we have done in the in one of the
lecture, so you already know but the assumptions we can summarize that steady state steady flow
process with single inlet and single outlet and negligible changes in kinetic energy and potential
energy, okay next question.

(Refer Slide Time: 26:34)

There is a Ts diagram given here you can see where there are sudden lines which are drawn for
an ideal gas and the may be ideal gas as a special case you may consider ideal gas with constant
cpc. So what do these lines represent so VA, VA is what so this you can tell very clearly? So it is
an isentropic process no doubt about it but expansionary compression so let us see, let us use the
TDS relationship here, so TDS = Dh – vdp. So reversible adiabatic process means ds = 0.

(Refer Slide Time: 27:42)

So Dh = vdp dh is for an ideal gas is cp D t, so as you go from b to a if you look in to the diagram
here if you go from b to a the temperature is decreasing that means D t is negative, that means
itself expansion so it as an isotropy expansion.

(Refer Slide Time: 28:16)

Next AC and DA so we are trying to consider whether out of this two I give a choice one is a
constant volume and another is constant pressure so out of this two which one is constant volume
line which one is constant pressure line so you have Tds=dh-bdp so for constant pressure now dh
is Cp dT so constant pressure means dp is equal to 0.

So ∂T/∂S at constant pressure is equal to T/Cp similarly if you see Tds is du/pdQ and for ideal
gas is du is Cv dT for constant volume dv is 0 that means ∂T/∂S is T/ Cv so out of this two
which one is because Cv is less than Cp so T/ Cv is better than T/Cp so constant volume line in
a Ts diagram must be cheaper than the constant pressure line.

So if you look into the diagram here AC must be constant volume and AT must be constant
pressure so out of this two one is heat addition and the heat rejection so if you have entropy
increases that will be necessary in heat addition but if you have entropy decrease that one also
must be heat rejection so AC is constant volume heat addition and DA is constant pressure heat
rejection.

If you have an option between constant volume and constant pressure EA is what is EA, EA the
temperature is constant so it is isothermal process from E to A if you are going it is heat rejection
so it is an isothermal heat rejection process okay now we will work out a couple of short
questions and this questions are short problems this questions are typically very short problems.

(Refer Slide Time: 31:39)

So the question is this is question number two given in the screenshot but I am repeating this
question a spring is slowly stretched by a tensile force of one kilo neutron isothermally at 300
Kelvin what is rate of change of entropy of the spring per unit length so this is the case where
you have to use Tds =du instead of pdv now it is a spring stretching watt minus fdx why this
minus this is minus because when the pdv work is done work leaves the system and when does
spring is stretched.

So when the displacement of the spring with the force this is watt come by the force and when
you come to the pdv that is watt done against the registers so it is just a different watt of looking
into so you can write so du is cdT under isothermal condition this is 0 so ∂S/∂x constant
temperature is minus F/T so the spring force is given as 1 kilo neutron and the absolute
temperature is 300 Kelvin. So you can calculate this one so the entropy decreases because this is
negative.

So on stretching of spring the entropy decreases why? Because if the spring is coiled there are
large number of possible micro state for the given micro scope state, if the spring is stretched,
then the number of micro states for given micro state that decreases, if it is stretched, so less
number of probably micro state for given micro states, next question, question number 3.

(Refer Slide Time: 33:34)

Liquid vapor phase change process of the single compressible pure substance is plotted in the
di9agram. The phase change takes place at 400kv with hfg value given. What is the scope of the
hs diagram for quality = 0 and quality = 0.5. so basically we are talking about the hs diagram for
the phase change process.

(Refer Slide Time: 34:04)

So we will use Tds = dh – vdp for change process of the single compressible pure substance this
is 0, so phase change of pure substance takes place at constant pressure , so ∂h /∂s at constant
temperature or constant pressure rather constant pressure here means constant temperature also,
that is T. So this does not depend on the fraction on quality, it depends only on absolute
temperature, so because the absolute temperature same during the phase change process this
slope means constant during the phase change process, so it is a essential a straight line. Now the
final question of this particular session, heat is transfer from a heat source at 100kv to a simple
compressible system.

With the system already temperature of 500kv, during this process there is heat transfer of 1500kj
to the system entropy of the system increases by 5kj/kv and internal energy increases by 100kj,
the system mass is 1 kg. State whether the following is true or false, the work done = ∫pdv x
500kj and the entropy generation due to external is 2kj/kg. So let us see whatever these
statements are correct or not. So let me try to draw a schematic of this.

(Refer Slide Time: 36:03)

Heat is transferred from the heat source and 100k to a system with the boundary temperature
500k, so this T system boundary this is T reservoir, there is a total heat transfer of 1500kj during
the process entropy of the system increases by 5kj/k and internal energy of the system increases
by 100kj sorry, 1000kj. So first law if you apply Q 12 = U2 – U1 for the system this is the system
let us say, + W12. It may be a piston cylinder, so the heat transfer is 1500 and work is 1000, sorry
change in internal energy is 1000 so what is the work? That is 1500 -1000 that is 500kj.

Now let us do the 2nd law analysis and take the entropy generation, so we can write S2 – S1 =
Q12/T + entropy generation S2 – S1 IS given as 5 the question is what T you will substitute her it
depends on as I told are you interested only calculate the internal reversibility and the reality
generation and the total entropy generation and we can calculate the to6tal entropy generation
then this should be the temperature of reservoir.

And you are interest to calculate only the entropy generation due to the internal reversibility then
this is the temperature of the system boundary and this is due to the internal reversibility. So this
is what the Q 1` is 15 and the reservoir temperature is one thousand write so this is fifteen
hundred / one thousands and it is 1.5 5- 1.5 is 3.5 I am not writing the units.
For this is 5 this is fifteen hundred and the temperature of the system boundary is 500 so this is 3
5-3 this is 2 so what are the heat transfer and what is the entropy generation and due to the
external reversible is and this is the total entropy generation and this is the total entropy
generation due to revisable, so the remaining entropy generation is due to the external revisable
and the 3.5 – 3 and that is 1.5 kilo joule per Kelvin.

(Refer Slide Time: 40:07)

so the part v of the answer is given and the entropy generation due to the externals reversibility is
2 kilojoules perceiving that is wrong it should be 1.5 kilojoules per Kelvin and the first question
w1 2 integral P D = to 500 and this is very typical question and the W 1 and 2 and this 500
kilojoules and this incorrect but this not equal and the integral P D V because it is not a
quadrillion process and this is not equal to the quadrillion process and this is the equilibrium
process see there is entropy generation due to the internal revisable.

What is there posses equilibrium it6 is such as three process bust be internally reversible if it is
internally reversible the entropy generation due to the internally reversibility must be 0 so it has
been 0 that means I could be have the formula and this P V formula but because it is not 0 you
cannot use the pv formula so although the watt is = to 500 kilo joule but it is not equal to the
integral p d v so the first transfer is also not correct okay so we have come to the end .

And this is the course we have to summarize we have discussed various law of the thermo
dynamics to begin with we have discussed the some of the basis consideration like the system
control volume and the concept of macroscopic and microscopic approach then in the properties
posses states then pure substances space and the concept of the quadratic equilibrium and it is the
compressible substance which is the equilibrium posses all these concept we have developed
using these concept.

We have to the specify the and the properties and the fix the pure substance using the property
data or the equation of the states and then using the bend law we have learned various law of
thermodynamic so the primary law that is understood to the covert of the thermal equilibrium of
the zeroth law of thermodynamic and mix then we have studied the first law of thermodynamics
then we have studied second law of thermo dynamic mix the eventually the third law of
thermodynamic.

And we have watch out the various problem stats these law of thermodynamic and these are
very critical because no matter what ever the Brach of the science of the engineering I am talking
about the very biological science and these are the chemical science and the mechanically
sciences whatever the met logical and the material sciences and the basic building blocks are the
thermodynamics remain to the basic law of the thermodynamic so that was the abject of this
course I believe it was enjoyable for all you go through this cause it was pleasure on my personal
to deliver lecture is close I wish all of you a great time ahead thank you very much.