Thermodynamics - Dr. Hossen

CSE First Semester (Session: 2020-2021) Thermodynamics
Thermodynamics
By
Professor Dr. Khokon Hossen

Department of Physics and Mechanical Engineering, Faculty of Computer Science and Engineering,
Patuakhali Science and Technology University, Dumki, Patuakhali-8602, Bangladesh.
E-mail: khokon.pme@gmail.com
Cell: +8801791151601
Definition of Thermodynamics
Thermodynamics is a science and an important engineering tool used to describe processes that involve
changes in temperature, transformation of energy, and the relationships between heat and work.
Thermodynamics where thermo means “heat” and dynamics means “power” is the study of energy
conversion between mechanical work and heat, and the macroscopic variables such as temperature,
volume and pressure.
It can be regarded as a generalization of an enormous body of empirical evidence. It is used to describe
the performance of systems, power generation systems, and refrigerators, and to describe fluid flow,
combustion, and many other phenomena.
As for example, the focus of thermodynamics in aerospace engineering is on the production of work,
often in the form of kinetic energy (for example in the exhaust of a jet engine) or shaft power, from
different sources of heat.
The starting point for most thermodynamic considerations are the laws of thermodynamics, which
postulate that energy can be exchanged between physical systems as heat or work. They also postulate the
existence of a quantity named entropy, which can be defined for any isolated system that is in
thermodynamic equilibrium.
Thermodynamics is based on two generalizations called the first and second law of
thermodynamics which are based on human experience.
1
Internal Energy for Ideal Gas

Internal energy in general includes both kinetic energy and potential energy associated with the molecular
motion. But the potential energy is associated with intermolecular forces and is presumed to be zero in an
ideal gas where the only molecular interactions are the perfectly elastic collisions between molecules.
Therefore, the internal energy of an ideal gas is entirely kinetic energy.
While steam at 100 degrees Celsius is not strictly an ideal

gas, the diagram illustrates the fact that the phase change
to the gaseous state leaves only the kinetic portion of the
internal energy. For a monoatomic ideal gas this internal
energy is given by
If rotation and vibrational kinetic energies are involved

(i.e. polyatomic molecules), then
Study of the specific heats of gases provides evidence of

whether or not rotation and vibration play a significant
role in the molecular kinetic energy.
Specific Heats of Gases

The specific heat is the amount of heat per unit mass required to raise the temperature by one degree
Celsius. The relationship between heat and temperature change is usually expressed in the form shown
below where c is the specific heat.
2
The specific heat of water is 1 calorie/gram °C = 4.186 joule/gram °C which is higher than any other
common substance. As a result, water plays a very important role in temperature regulation. The specific
heat per gram for water is much higher than that for a metal, as described in the water-metal example. For
most purposes, it is more meaningful to compare the molar specific heats of substances.
The specific heats of gases are generally expressed as molar specific heats. For a monoatomic ideal
gas the internal energy is all in the form of kinetic energy, and kinetic theory provides the expression for
that energy, related to the kinetic temperature. The expression for the internal energy is
Two specific heats are defined for gases, one for constant volume (CV) and one for constant pressure (CP).
For a constant volume process with a monoatomic ideal gas the first law of thermodynamics gives:
Explanation: Specific Heat at Constant Volume
The molar specific heat at constant volume is defined by
3
at constant volume
Using the first law of thermodynamics this can be put in the form
but since ΔV = 0, the expression for CV becomes
For a monoatomic ideal gas, , so
This value agrees well with experiment for monoatomic noble gases such as helium and argon, but does
not describe diatomic or polyatomic gases since their molecular rotations and vibrations contribute to the
specific heat. The equipartition of energy predicts
Further application of the ideal gas law and first law gives the relationship
4
Explanation: Specific Heat at Constant Pressure:
The molar specific heat at constant pressure is defined by
at constant pressure
Using the first law of thermodynamics for a constant pressure process this can be put in the
form
From the ideal gas law (PV=nRT) under constant pressure conditions it can be seen that
Since the constant volume specific heat is
it follows that
5
For an ideal monoatomic gas
The ratio of the specific heats γ = CP/CV is a factor in adiabatic engine processes and in
determining the speed of sound in a gas. This ratio γ = 1.66 for an ideal monoatomic gas
and γ = 1.4 for air, which is predominantly a diatomic gas.
The First law of Thermodynamics

The first law of thermodynamics is a version of the law of conservation of energy, specialized
for thermodynamical systems. It is usually formulated by stating that the change in the internal energy of
a closed system is equal to the amount of heat supplied to the system, minus the amount of work done by
the system on its surroundings. The law of conservation of energy can be stated: The energy of an
isolated system is constant.
The first explicit statement of the first law of thermodynamics, by Rudolf Clausius in 1850, referred to
cyclic thermodynamic processes.
“In all cases in which work is produced by the agency of heat, a quantity of heat is consumed
which is proportional to the work done; and conversely, by the expenditure of an equal quantity
of work an equal quantity of heat is produced”.
Clausius stated the law also in another form, this time referring to the existence of a function of state of
the system called the internal energy, and expressing himself in terms of a differential equation for the
increments of a thermodynamic process. This equation may be translated into words as follows:
6
“In a thermodynamic process of a closed system, the increment in the internal energy is equal
to the difference between the increment of heat accumulated by the system and the increment of
work done by it”.
The first law of thermodynamics was expressed in two ways by Clausius. One way referred to cyclic
processes and the inputs and outputs of the system, but did not refer to increments in the internal state of
the system. The other way referred to any incremental change in the internal state of the system, and did
not expect the process to be cyclic. A cyclic process is one which can be repeated indefinitely often and
still eventually leave the system in its original state.
In each repetition of a cyclic process, the work done by the system is proportional to the heat consumed
by the system. In a cyclic process in which the system does work on its surroundings, it is necessary that
some heat be taken in by the system and some be put out, and the difference is the heat consumed by the
system in the process. The constant of proportionality is universal and independent of the system and was
measured by James Joule in 1845 and 1847, who described it as the mechanical equivalent of heat.
In any incremental process, the change in the internal energy is considered due to a combination
of heat added to the system and work done by the system. Taking dU as an infinitesimal (differential)
change in internal energy, one writes:
dU = δQ - δW
where δQ and δW are infinitesimal amounts of heat supplied to the system by its surroundings and work
done by the system on its surroundings, respectively. This sign convention is implicit in Clausius'
statement of the law given above, and is consistent with the use of thermodynamics to study heat
engines which provide useful work, which is regarded as positive.
In chemistry, however, it is conventional to use the International Union of Pure and Applied
Chemistry (IUPAC) convention where the first law is formulated in terms of the work done on the system.
With this alternate sign convention for work, the first law for a closed system may be written:
dU = δQ + δW
This convention follows physicists such as Max Planck, and considers all net energy transfers to the
system as positive and all net energy transfers from the system as negative, independently of any use for
the system as an engine or otherwise.
7
When a system expands in a quasistatic process, the work done by the system on the environment is the
product, P dV, of pressure, P, and volume change, dV, where as the work done on the system is -P dV.
Using either sign convention for work, the change in internal energy of the system is:
dU = δQ - PdV
Work and heat are expressions of actual physical processes which supply or remove energy, while U is a
mathematical abstraction that keeps account of the exchanges of energy that befall the system. Thus the
term heat for δQ means that amount of energy added or removed by conduction of heat or by thermal
radiation, rather than referring to a form of energy within the system. Likewise, work energy for δW
means "that amount of energy gained or lost as the result of work". Internal energy is a property of the
system whereas work done and heat supplied are not. A significant result of this distinction is that a given
internal energy change dU can be achieved by, in principle, many combinations of heat and work.
The internal energy of a system is not uniquely defined. It is defined only up to an arbitrary additive
constant of integration, which can be adjusted to give arbitrary reference zero levels. This non-uniqueness
is in keeping with the abstract mathematical nature of the internal energy. The internal energy is stated
relative to a conventionally chosen standard reference state of the system.
Limitations of the first law of Thermodynamics
Limitations of the first law of thermodynamics are discussed below:

(i) No restriction on the direction of the flow of heat: the first law establishes definite relationship
between the heat absorbed and the work performed by a system. The first law does not indicate whether
heat can flow from a cold end to a hot end or not. For example: we cannot extract heat from the ice by
cooling it to a low temperature. Some external work has to be done.
(ii) Does not specify the feasibility of the reaction: first law does not specify that process is feasible or not
for example: when a rod is heated at one end then equilibrium has to be obtained which is possible only
by some expenditure of energy.
(iii) Practically it is not possible to convert the heat energy into an equivalent amount of work.
To overcome this limitations, another law is needed which is known as second law of thermodynamics.
The second law of thermodynamics helps us to predict whether the reaction is feasible or not and also tell
the direction of the flow of heat.
8
It also tells that energy cannot be completely converted into equivalent work.
The Second law of Thermodynamics
The second law of thermodynamics states that the entropy of an isolated system never decreases,
because isolated systems spontaneously evolve towards thermodynamic equilibrium—the state of
maximum entropy. Equivalently, perpetual motion machines of the second kind are impossible.
The second law is a postulate of thermodynamics, but it can be understood and proven using the
underlying quantum statistical mechanics. It is an expression of the fact that over time, differences in
temperature, pressure, and chemical potential decrease in an isolated physical system, leading eventually
to a state of thermodynamic equilibrium. In the language of statistical mechanics, entropy is a measure of
the number of microscopic configurations corresponding to a macroscopic state. Because equilibrium
corresponds to a vastly greater number of microscopic configurations than any non-equilibrium state, it
has the maximum entropy, and the second law follows because random chance alone almost guarantees
that the system will evolve towards equilibrium.
The second law may be expressed in many specific ways, but the first formulation is credited to the
French scientist Sadi Carnot in 1824.
The first law of thermodynamics provides the basic definition of thermodynamic energy, also
called internal energy, associated with all thermodynamic systems, but unknown in classical mechanics,
and states the rule of conservation of energy in nature.
However, the concept of energy in the first law does not account for the observation that natural processes
have a preferred direction of progress. For example, heat always flows spontaneously from regions of
higher temperature to regions of lower temperature, and never the reverse, unless external work is
performed on the system. The first law is completely symmetrical with respect to the initial and final
states of an evolving system. The key concept for the explanation of this phenomenon through the second
law of thermodynamics is the definition of a new physical property, the entropy.
The second law of thermodynamics may be expressed in many specific ways, the most prominent
classical statements being the statement by Rudolph Clausius (1854), the statement by Lord
Kelvin (1851), and the statement in axiomatic thermodynamics by Constantin Carathéodory (1909).
9
These statements cast the law in general physical terms citing the impossibility of certain processes. They
have been shown to be equivalent.
A more recent statement, due to George N. Hatsopoulos and Joseph H. Keenan, is:
“Among all the states of a system with given energy, constituents and parameters, there exists a unique
stable equilibrium that can always be reached from any other state (with the same energy, constituents
and parameters) by a reversible weight process”.
The Kelvin-Planck, Clausius and Cathedory statements can all be shown to follow from the Hatsopoulos-
Keenan statement.
Clausius Statement
The German scientist Rudolf Clausius laid the foundation for the second law of thermodynamics in 1850
by examining the relation between heat transfer and work. His formulation of the second law, which was
published in German in 1854, is known as the Clausius statement: "Heat can never pass from a colder
to a warmer body without some other change, connected therewith, occurring at the same time". This
may be restated as
“No process is possible whose sole result is the transfer of heat from a body of lower temperature
to a body of higher temperature”.
Heat cannot spontaneously flow from cold regions to hot regions without external work being performed
on the system, which is evident from ordinary experience of refrigeration, for example. In a refrigerator,
heat flows from cold to hot, but only when forced by an external agent, the refrigeration system.
Kelvin statement
Lord Kelvin expressed the second law as “It is impossible, by means of inanimate material agency, to
derive mechanical effect from any portion of matter by cooling it below the temperature of the coldest
of the surrounding objects”. This may be restated as
“No process is possible in which the sole result is the absorption of heat from a reservoir and its
complete conversion into work”.
10
This means it is impossible to extract energy by heat from a high-temperature energy source and then
convert all of the energy into work. At least some of the energy must be passed on to heat a low-
temperature energy sink. Thus, a heat engine exhibiting 100% efficiency is thermodynamically
impossible. This also means that it is impossible to build solar panels that generate electricity solely from
the infrared band of the electromagnetic spectrum without consideration of the temperature on the other
side of the panel (as is the case with conventional solar panels that operate in the visible spectrum).
Note that it is possible to convert heat completely into work, such as the isothermal expansion of ideal
gas. However, such a process has an additional result. In the case of the isothermal expansion, the volume
of the gas increases and never goes back without outside interference.
Principle of Carathéodory
Constantin Carathéodory formulated thermodynamics on a purely mathematical axiomatic foundation.
His statement of the second law is known as the Principle of Carathéodory, which may be formulated as
follows:
“In every neighborhood of any state S of an adiabatically isolated system there are states
inaccessible from S”.
With this formulation he described the concept of adiabatic accessibility for the first time and provided
the foundation for a new subfield of classical thermodynamics, often called geometrical thermodynamics.
It follows from Carathéodory's principle that heat is a holonomic process function, in other words, δQ =
TdS.
The Third Law of Thermodynamics
“The entropy of all the perfect crystalline solids is zeros at absolute zero temperature”. The third law of
thermodynamics is also referred to as Nernst law. It provides the basis for the calculation of absolute
entropies of the substances.
Mathematically,
Lim T –>0 S = 0
11
Figure-1: Crystalline solids at temperature O K and T> 0 K.
Importance of third law of thermodynamics is given below

(i) It helps in calculating the thermodynamic properties.
(ii) It is helpful in measuring chemical affinity. Because of this it is known as Nernst theorem.
(iii) It explains the behavior of solids at very low temperature.
(iv) It helps in analyzing chemical and phase equilibrium.
Limitations of third Law
(i) Even at 0 K Glassy solids have entropy which is greater than zero.
(ii) Solids that have mixtures of isotopes do not possess zero entropy at 0 K. For example: Solid
chlorine does not have zero entropy at 0 K.
(iii) Crystals of CO, N2O, NO, H2O, etc., do not possess perfect order even at 0 K, thus their
entropy is not equal to zero.
(iv) It is impossible to reach a temperature of absolute zero.
(v) It is impossible to have a (Carnot) efficiency equal to 100% (this would imply Tc = 0).
Thermodynamic Process
The operation by which a system changes from one state to another is called a process. Whenever a
system changes from one state to another it is accompanied by change in energy. In case of open systems,
there may be change of matter as well.
12
The following types of process in thermodynamics are well known:
(i) Isothermal Process
(ii) Adiabatic Process
(iii) Isochoric Process
(iv) Isobaric Process
(v) Isentropic process
Isothermal Process
Definition: An isothermal process is a thermodynamic process in which the temperature of the system
remains constant. The heat transfer into or out of the system typically must happen at such a slow rate that
the thermal equilibrium is maintained.
Note that a process being isothermal does not imply anything about the heat transferred or work done, i.e.
heat transfer may take place during an isothermal process. An isothermal process implies that the product
of the volume and the pressure is constant for an ideal gas. i.e.
PV = Constant
Isothermal processes can occur in any kind of system, including highly-structured machines, and even
living cells. Various parts of the cycles of some heat engines are carried out isothermally and may be
approximated by a Carnot cycle.
Other Factors in an Isothermal Process
In general, during an isothermal process there is a change in internal energy, heat energy, and work. The
internal energy of an ideal gas, however, depends solely on the temperature, so the change in internal
energy during an isothermal process for an ideal gas is also zero (0).
Heat, Q = δU + W
δU= 0
So Q = W
V2
dV V
Note that during an Isothermal process, the work done, W = RT   RT loge 2
V1
V V1
13
Isothermal Processes & States of Matter
In the diagram, an isothermal process is indicated by following a vertical line is pressure and horizontal
line is volume with a constant temperature.
Therefore, if the pressure and volume change, it is possible for a substance to change its state of
matter even while its temperature remains constant, if you're careful about how you apply or remove heat
from the system.
Figure-2: For a simple substance, during an adiabatic process in which the volume increases, the internal energy of
the working substance must decrease.
Adiabatic Process
Definition: An adiabatic process is a thermodynamic process in which there is no heat transfer (Q) into
or out of the system. In other words Q = 0.
An adiabatic process is generally obtained by surrounding the entire system with a strongly insulating
material or by carrying out the process so quickly that there is no time for a significant heat transfer to
take place.
Applying the first law of thermodynamics to an adiabatic process, we obtain:

δU = -W
Since δU is the change in internal energy and W is the work done by the system, we see the following
possible outcomes:
14
(i) A system that expands under adiabatic conditions does positive work, so the internal energy
decreases.
(ii) A system that contracts under adiabatic conditions does negative work, so the internal energy
increases.
There is often, though not always, a change in temperature associated with the change in internal energy.
The compression and expansion strokes in an internal-combustion engine are both approximately
adiabatic processes. What little heat transfers outside of the system is negligible and virtually all of the
energy change goes into moving the piston.
Conversely, a process that involves heat transfer (addition or loss of heat to the surroundings) is
generally called diabatic.
Note that during an adiabatic process the gas equations:
(i) PVγ = constant

(ii) TVγ-1 = constant
P  1
(iii)  constant
T
and the work done during an adiabatic Process, W = Cv (T1-T2)
dU C
where Cv = at constant volume V and P  
dT CV
Isochoric Process
Definition: An isochoric process is a thermodynamic process in which the volume remains constant.
Since the volume is constant, the system does not work and W = 0.
This is perhaps the easiest of the thermodynamic variables to control, since it can be obtained by placing
the system in a sealed container which neither expands nor contracts.
Applying the first law of thermodynamics to this situation, we find that:

δU = Q
15
Since δU is the change in internal energy and Q is the heat transfer into or out of the system, we see that
all of the heat either comes from internal energy or goes into increasing the internal energy.
Constant Volume, But W is Non-zero
It is actually possible to do work on a system without changing the volume, as in the case of stirring a
liquid. Some sources use "isochoric" in these cases to mean "zero-work" regardless of whether there is a
change in volume or not. In most straightforward applications, however, this nuance will not need to be
considered ... if the volume remains constant throughout the process, it is an isochoric process.
Isobaric Process
Definition: An isobaric process is a thermodynamic process in which the pressure remains constant. This
is usually obtained by allowed the volume to expand or contract in such a way to neutralize any pressure
changes that would be caused by heat transfer.
In an isobaric process, there are typically internal energy changes, work is done by the system, and heat is
transferred, so none of the quantities in the first law of thermodynamics readily reduce to zero. However,
the work at a constant pressure can be fairly easily calculated with the equation:
W =P * δV
Q = δU + P * δV
Since W is the work, P is the pressure (always positive) and δV is the change in volume, we can see that
there are two possible outcomes to an isobaric process:
 If the system expands (δV is positive), then the system does positive work (and vice versa)
 If the system contracts (δV is negative), then the system does negative work (and vice versa)
Isentropic Process
An Isentropic process is a thermodynamic process which occurs at constant entropy. For a reversible
process this is identical to an adiabatic process if a system has entropy which has not yet reached its
maximum equilibrium value, a process of cooling may be required to maintain that value of entropy.
16
Table-1: Comparative study of thermodynamical process.
Reversible Process
The processes in which both the system and its surroundings can be simultaneously returned to their
initial states after the process has been completed is known as reversible process.
The basic concept is that most of the thermodynamic processes have a preferred direction just as Heat
always flows from hotter object to colder object. Once a gas is released in a room, it expands in room and
never contracts without indulgence of any external force etc.
But in some systems, the reverse occurs. Normally it happens when that system is close to
thermal equilibrium. This equilibrium has to be inside the system itself and also within the system and its
surroundings. When this stage is reached, even a small change can change the direction of the process and
therefore such a reversible process is also known as an equilibrium process.
A very simple example can be of two metal jars A and B which are at a thermal equilibrium and are in
contact with each other. Now when we heat jar A slightly, heat starts to flow from Jar A to Jar B. This is
the direction of this process. Now this process can be reversed just by cooling Jar A slightly. When Jar A
is cooled, heat flows from Jar B to Jar A till thermal equilibrium is reached.
17
Figure-3: Reversible and Irreversible Process.
Irreversible Process
The process is said to be an irreversible process if it cannot return the system and the surroundings to
their original conditions when the process is reversed. The irreversible process is not
at equilibrium throughout the process.
For example, when we are driving the car uphill, it consumes a lot of fuel and this fuel is not returned
when we are driving down hill. Many factors contribute in making any process irreversible. The most
common of these are
i) Friction
ii) Unrestrained expansion of a fluid
iii) Heat transfer through a finite temperature difference
iv) Mixing of two different substances.
Entropy: Entropy and its characteristics
Entropy is a thermodynamic property that can be viewed as the quantitative measure of disorder in a
system. A measurement of the degree of randomness of energy in a system. The lower the entropy the
more ordered and less random it is, and vice versa.
Examples: gallon of gas, prepared food, sunlight have low entropy. When these are “used” their entropy
increases. The concept comes out of thermodynamics, which deals with the transfer of heat energy within
18
a system. Instead of talking about some form of "absolute entropy," physicists generally talk about the
change in entropy that takes place in a specific thermodynamic process.
Figure-4: Entropy and disorder of the crystal.
In an isothermal process, the change in entropy (δS) is the change in heat (Q) divided by the absolute
temperature (T):
δS =Q/T
A change in the entropy (dS) of a system is the infinitesimal transfer of heat (δQ) to a closed
system driving a reversible process, divided by the equilibrium temperature (T) of the system.
Q
dS =
T
The entropy of an isolated system that is in equilibrium is constant and has reached its maximum value.
Empirical temperature and its scale is usually defined on the principles of thermodynamics equilibrium by
the zeroth law of thermodynamics. However, based on the entropy, the second law permits a definition of
the absolute, thermodynamic temperature, which has its null point at absolute zero.
The SI units of entropy are J/K (joules/degrees Kelvin).
Characteristics of Entropy are as follows
1. It increases when the heat is supplied irrespective of the fact whether temperature changes or not.
2. Whether temperature changes or not the entropy decreases when heat is rejected.
3. In all the adiabatic processes, the entropy remains constant.
4. Everything that we do increases entropy and makes our environment worse.
19
Figure-5: Entropy in nature.
Calculate the entropy changes of an Ideal Gas in different processes
There are three types of processes in which entropy changes of an ideal gas. These three processes are:
(i) Isothermal process
(ii) Isobaric process
(iii) Isochoric process
i. Isothermal process
The process in which there is no change in temperature is known as Isothermal process. Entropy changes
from S1 to S2 when gas absorbs heat during expansion. The heat taken by the gas is given by the area
under the curve which represents the work done during expansion.
In other words, Q = W.
S2
But Q = 
S1
Tds = T(S2 – S1)
And W = P1 V1 ln (V2 / V1)

= R T1 ln (V2 / V1)
Therefore, T (S2 – S1) = R T1 ln (V2 / V1)
S2 – S1 = R ln (V2 / V1)
∆ST = R ln (V2 / V1)
= – R ln (P2 / P1)
= R ln (P1 / P2)
20
Hence, ∆ST = R ln (V2 / V1)

= R ln (P1 / P2)
Hence, isothermal expansion of an ideal gas is accompanied by increase in entropy.
ii. Isobaric Processes

The process in which there is no change in pressure is known as Isobaric process. Consider an ideal gas at
constant pressure and its temperature changes from T1 to T2 and entropy changes from S1 to S2.
Then, Q = Cp (T2 – T1)
Differentiating to find small increase in heat, dQ of the ideal gas when temperature rises is dT.
dQ = Cp.dT
dividing both sides by T, we will get:
dQ / T = Cp. dT / T
dS = Cp. dT / T
Integrating both sides, we will get:
S2 T2

S1
dS = Cp 
T1
dT / T
S2 – S1 = Cp ln (T2 / T1)
∆SP = Cp ln (T2 / T1)
Hence, increase in temperature of an ideal gas at constant pressure is accompanied by increase in
entropy.
iii. Isochoric Processes
The process in which there is no change in volume is known as Isochoric process. Consider an ideal gas
at constant volume and its temperature changes from T1 to T2 and entropy changes from S1 to S2.
Then, Q = Cv (T2 – T1)
Differentiating to find small increase in heat, dQ of the ideal gas when temperature rises is dT.
dQ = Cv .dT
dividing both sides by T, we will get:
dQ / T = Cv. dT / T
dS = Cv. dT / T
Integrating both sides, we will get:
2 T2
 dS = Cv 
T1
dT / T
1
21
S2 – S1 = Cv ln (T2 / T1)
∆SP = Cv ln (T2 / T1)
Hence, increase in temperature of an ideal gas at constant volume is accompanied by increase in entropy
of an ideal gas.
Derive the Entropy changes for a reversible process
Let us consider entropy at the initial state 1 is S1 and entropy at the final state 2 is S2. Hence, the
change in entropy of a system, as it undergoes a change from state 1 to 2, becomes
2
S2 – S1 = 
1
(δQ / T) R …………….. (1)
If two states1 and 2 are infinitesimally near to each other, the we can omit the integration sign and hence,
S2 – S1 becomes equal to dS.
Therefore, the above equation can be written as:
dS = (δQ / T) R ………………… (2)
Where dS is an exact differential.
Thus, from equation (2), we conclude that the change of entropy in a reversible process is equal to δQ/T
which is the mathematical formulation of the second law of thermodynamics.
The third law of thermodynamics states” when a system is at zero absolute temperature, the entropy of the
system is zero”.
It is clear from the above law that the absolute value of entropy corresponding to a given state of the
system could not be determined by integrating (δQ / T) R between state at absolute zero and the given
state. Zero entropy, however, means the absence of all molecular, atomic, electronic and nuclear disorders
Equation (2) indicates that when an exact differential δQ is divided by an integrating factor T during a
reversible process, it becomes an exact differential.
Hence, practically we determine the change in entropy and not the absolute value of the entropy.
Entropy and the Second Law of Thermodynamics
One way of stating the second law of thermodynamics is:
“In any closed system, the entropy of the system will either remain constant or increase”.
22
One way to view this is that adding heat to a system causes the molecules and atoms to speed up. It may
be possible (though tricky) to reverse the process in a closed system (i.e. without drawing any energy
from or releasing energy somewhere else) to reach the initial state, but you can never get the entire system
"less energetic" than it started ... the energy just doesn't have any place to go.
This view of the second law of thermodynamics is very popular, and it has been misused. Some argue that
the second law of thermodynamics means that a system can never become more orderly. Not true. It just
means that in order to become more orderly (for entropy to decrease), you must transfer energy from
somewhere outside the system, such as when a pregnant woman draws energy from food to cause the
fertilized egg to become a complete baby, completely in line with the second line's provisions.
Some Problems
(1) Calculate the final volume of one mole of an ideal gas initially at 0oC and 1 atm pressure. If
it absorbs 2000 cal of heat during reversible isothermal expansion.
The gas is in the standard temperature and pressure condition i.e. at S.T.P
Hence V1 = 22.4 dm3 and V2 have to be calculated.

As given expansion is isothermal and reversible therefore, ∆U = 0
We know that ∆U = q + w
But ∆U = 0
Hence q = – w = 2000 cal
= 2000 X 4.184 J = 8368 J
As work done in reversible isothermal expansion is given by:
w= -nRT ln (V2/ V1)
Therefore nRT ln (V2/ V1) = – w = 8368 J
(I mol) X (8.314 J K- mol-) X (273 K) ln (V2/ 22.4 dm3) = 8368 J
V2 = 242.50 dm3
Hence the final volume of one mole of an ideal gas initially at 0oC and 1 atm pressure is equal to 242.50
dm3.
23
(2) One mole of an ideal gas is heated at constant pressure from 0oC to 200oC.
(a) Calculate work done.
(b) If the gas were expanded isothermally & reversibly at 0°C from 1 atm to some other
pressure Pt, what must be the final pressure if the maximum work is equal to the work
involved in (a).
(a) Work done:

Work done during heating of gas from 0oC to 200oC
Here,
T1 = 0oC = 273 K, T2 = 200oC = 473 K
Now
W = – PΔV = -P (V2 – V1)
= – P [(nRT2/P)-(nRT1/P)] = – nR (T2–T1) = –1 × 1.987 × (473 – 273)
= – 397.4 cal
(b)If work equivalent to 397.4 cal is used for gas at 0oC, causing its isothermal expansion, from 1 atm to
pressure Pt
w = – 2.303nRTlog (P1 /P2)
-397.4 = – 2.303 × 1.987 × 273log (1/Pt)
Therefore, Pt = 1.272 atm
Hence, final pressure is 0.694 atm.
(3) Calculate q, w, ∆U and ∆H for the reversible isothermal expansion of one mole of an ideal gas
at 37oC from a volume of 20dm3 to a volume of 30 dm3.
Temperature T = 37oC = 37 + 273 = 310 K

Since the process is Isothermal,
Therefore, ∆U=0 and ∆H = 0 (as for an isothermal expansion of an ideal gas ∆U=0 and ∆H = 0)
w= -nRT ln (V2/ V1)
= – (1 mol) (8.314 J K-1 mol-1) (310 K) ln (30 dm3 / 20dm3)
= – 1045.02 J
24
From first law, ∆U= q + w

Since ∆U=0, q = – w = 1045.02 J
Carnot´s Cycle
Nicolas Léonard Sadi Carnot (1 June 1796 – 24 August 1832) was a French military engineer who, in
his 1824 book Reflections on the Motive Power of Fire, gave the first successful theoretical account
of heat engines, now known as the Carnot cycle; his book also laid the foundations for the second law of
thermodynamics. He is often described as the "Father of thermodynamics", being responsible for such
concepts as Carnot efficiency, Carnot theorem, the Carnot heat engine, and others.
Basic Concepts
Cyclic process:
• A series of transformations by which the state of a system undergoes changes but the system is
eventually returned to its original state.
• Changes in volume during the process may result in external work.
• The net heat absorbed by the system during the cyclic process is equivalent to the total external
work done.
Figure-6: Transformations along A-B-C-D-A represents a cyclic process. The entire process
is reversible since equilibrium is achieved for each state (A, B, C, and D).
25
Carnot’s Heat Engine
Figure-3: Carnot’s Heat Engine
The Components
• A “working substance” (blue dots) is in a cylinder (Y) with insulated walls and a conducting base
(B) fitted with an insulated, frictionless piston (P) to which a variable force can be applied.
• A non-conducting stand (S) upon which the cylinder may be placed to insulate the conducting
base.
• An infinite warm reservoir of heat (H) at constant temperature T1.
• An infinite cold reservoir for heat (C) at constant temperature T2 (where T1 > T2).
Figure-7: The Components of Carnot’s Heat Engine
The Four Processes:

1. Adiabatic Compression
26
The substance begins at location A with a temperature of T2. The cylinder is placed on the stand and the
substance is compressed by increasing the downward force on the piston. Since the cylinder is insulated,
no heat can enter or leave the substance contained inside. Thus, the substance undergoes adiabatic
compression and its temperature increases to T1 (location B).
Figure-8: Carnot’s Cycle of Adiabatic Compression
Heat Q = ∆U + W
QAB = 0
Internal work ∆U AB = Cv (T1-T2)
Work done from A to B is WAB = -∆UAB
WAB = - Cv (T1-T2)
2. Isothermal Expansion
The cylinder is now placed on the warm reservoir. A quantity of heat Q1 is extracted from the warm
reservoir and thus absorbed by the substance. During this process the substance expands isothermally
at T1 to location C. During this process the substance does work by expanding against the force
applied to the piston.
Heat Q = ∆U + W
∆T = 0, QBC = Q1
Internal work ∆UBC =0
∆UBC = 0
27
WBC = ∆QBC
VC
Work done from B to C is WBC = RT1log
VB
Figure-9: Carnot’s Cycle of Isothermal Expansion
3. Adiabatic Expansion
The cylinder is returned to the stand. Since the cylinder is now insulated, no heat can enter or leave the
substance contained inside. Thus, the cylinder undergoes adiabatic expansion until its temperature returns
to T2 (location D). Again, the cylinder does work against the force applied to the piston.
Figure-10: Carnot’s Cycle of Adiabatic Expansion

28
Heat Q = ∆U + W
QCD = 0
Internal work ∆UCD = Cv (T2-T1)
Work done from A to B is WCD = -∆UCD
WCD = - Cv (T2 - T1)
4. Isothermal Compression
The cylinder is now placed on the cold reservoir. A force is applied to the piston and the substance
undergoes isothermal compression to its original state (location A). During this process the substance
gives up the resulting compression heating Q2 to the cold reservoir, allowing the process to occur
isothermally.
Figure-11: Carnot’s Cycle of Isothermal Compression.

Heat Q = ∆U + W
∆T = 0, QDA = Q2
Internal work ∆UDA =0
WDA = QDA
VA
Work done from D to A is WDA = RT2log
VD
Net Effect
The net work done by the substance during the cyclic process is equal to the area enclosed within
ABCDA. Since the process is cyclic, the net work done is also equal to Q1+Q2. The work is performed by
transferring a fraction of the total heat absorbed from the warm reservoir to the cold reservoir.
29
Figure-12: Net Effect of Carnot’s Cycle.
VC V
WNet = WAB+WBC+WCD+WDA = - Cv (T1-T2) + RT1log +(- Cv (T2 - T1))+ RT2log A
VB VD
WNet = Q1+ Q2 where Q1> 0 and Q2<0
Efficiency
We can define the efficiency of the heat engine (η) as the ratio between the net work done (WNET) and the
total heat absorbed (Q1), or:
WNET Q1  Q 2
η 
Q1 Q1
By considering the relations valid during each process, it can be shown that:
T2
η  1
T1
Important Lesson
 It is impossible to construct a cyclic engine that transforms heat into work without surrendering
some heat to a reservoir at a lower temperature.
Examples of Carnot Cycles in Practice
• Steam Engine → has a radiator
• Power Plant → has cooling towers
Examples of Carnot Cycles in Nature
• Hadley Cell
• Hurricane
• Thunderstorm
30
Figure-13: Examples of Carnot Cycles in Practice.
Heat Engines
31
Refrigerators
32
Some Problems
1. An ideal monatomic gas is taken through a cycle in the PV diagram.
(a) If there are 0.0200 mol of this gas, what are the temperature and pressure at point C?
(b) What is the change in internal energy of the gas as it is taken from point A to B?
(c) How much work is done by this gas per cycle?
(d) What is the total change in internal energy of this gas in one cycle?
(a) From the graph: Pc = 98.0 kPa
33
Using the ideal gas law
PcVc
Tc   1180 K.
nR
(b) This is an isochoric process so W = 0 and U = Q.
 3  P V PV 
U  Q  nCV T  n R  B B  A A 
 2  nR nR 
 PBVB  PAVA 
3
2
 V PB  PA   200 J
3
2
(c) The work done per cycle is the area between the curves on the PV diagram. Here W=½VP = 66 J.
(d)
 3  P V PV 
U  nCV T  n R  f f  i i 
 2  nR nR 
 Pf Vf  PiVi   0
3
2
The cycle ends where it began (T = 0).
2. An ideal gas is in contact with a heat reservoir so that it remains at constant temperature of
300.0 K. The gas is compressed from a volume of 24.0 L to a volume of 14.0 L. During the
process, the mechanical device pushing the piston to compress the gas is found to expend 5.00
kJ of energy. How much heat flows between the heat reservoir and the gas, and in what
direction does the heat flow occur?
This is an isothermal process, so U = Q + W = 0 (for an ideal gas) and W = Q = 5.00 kJ. Heat flows
from the gas to the reservoir.
3. An ice cube at 0.0 C is slowly melting. What is the change in the ice cube’s entropy for each
1.00 g of ice that melts?
To melt ice requires Q = mLf joules of heat. To melt one gram of ice requires 333.7 J of energy.
Q 333.7 J
The entropy change is S    1.22 J/K.
T 273 K
4. A Carnot heat engine receives 500 kJ of heat per cycle from a high-temperature heat reservoir at
652oC and rejects heat to a low-temperature heat reservoir at 30oC. Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature heat reservoir.
(a)
34
TL
 th , rev  1 
TH
( 30  273) K
 1
(652  273) K
 0.672 or 67.2%
(b)
QL T
 L
QH TH
(30  273) K
  0.328
( 652  273) K
QL  500 kJ (0.328)
 164 kJ
5.An inventor claims to have invented a heat engine that develops a thermal efficiency of 80 percent
when operating between two heat reservoirs at 1000 K and 300 K. Evaluate his claim.
TL
 th , rev  1 
TH
300 K
 1
1000 K
 0.70 or 70%
The claim is false since no heat engine may be more efficient than a Carnot engine operating between the
heat reservoirs.
6. An inventor claims to have developed a refrigerator that maintains the refrigerated space at 2oC
while operating in a room where the temperature is 25oC and has a COP of 13.5. Is there any truth
to his claim?
35
QL TL
COPR  
QH  QL TH  TL
(2  273) K

(25  2) K
 1196
.
The claim is false since no refrigerator may have a COP larger than the COP for the reversed Carnot
device.
7. A heat pump is to be used to heat a building during the winter. The building is to be maintained
at 21oC at all times. The building is estimated to be losing heat at a rate of 135,000 kJ/h when the
outside temperature drops to -5oC. Determine the minimum power required to drive the heat
pump unit for this outside temperature.
36
The heat lost by the building has to be supplied by the heat pump.
8. A Carnot engine converts one fifth of the heat input into work. If the sink temperature is reduced
by 80o C, the efficiency gets doubled. Find the source and the sink temperature. Also give the
consequences of the Carnot cycle.
Maximum efficiency of an engine working between temperatures T2 and T1 is given by the fraction of the
heat absorbed by an engine which can be converted into work is known as efficiency of the heat engine.
Mathematically,
Efficiency, η = (T2 – T1) / T2 = 1/5
37
5 T2 -5 T1 = T2
Therefore, T2 = 1.25 T1 ……………………….. (1)
Where T2 is the source temperature and T1 is the sink temperature.
If the sink temperature (T1) is reduced by 80o C, the efficiency gets doubled i.e.
η= T2 – (T1 – 80) / T2 = 2 X 1/5 = 2/5
5 T2 – 5 T1 + 400 = 2 T2
5 T2 – 2 T2 – 5 T1 + 400 = 0
3 T2 – 5 T1 + 400 = 0
Substituting the value of T2 from equation (1), we will get,
3 (1.25 T1) – 5 T1 + 400 = 0
3.75 T1 – 5 T1 + 372 = 0
400 = 1.25 T1
T1 = 320 K
Therefore, T2 = 1.25 X 320 = 400 K
Hence, temperature of the source and the sink is 400 K and 320 K respectively.
Consequences or impartibility of the Carnot cycle:
(1) It is impossible to perform a frictionless process.
(2) It is impossible to transfer the heat without finite temperature difference.
(3) During isothermal process the piston must move very slowly so that the temperature remains constant
and during adiabatic process it must move very fast so that the heat transfer is negligible due to short span
of time. The variation speed during same cycle is not possible.
9. A Carnot engine has the same efficiency (i) between 100 K and 500 K and (ii) between T K and
900 K. Calculate the temperature T of the sink.
Mathematically,
In First case:
Efficiency, η = (T2 – T1) / T2
T2 = 500 K (temperature of the source)
T1 = 100 K (temperature of the sink)
38
Therefore,
η = (T2 – T1) / T2
= (500 – 100) / 500
=4/5
In second case:
T2 = 900 K (temperature of the source)
T1 = T K (temperature of the sink)
Therefore,
η = (T2 – T1) / T2
= (900 – T) / 900
It is given that the Carnot engine has the same efficiency. Hence equating the efficiency of both the cases
we will get:
(900 – T) / 900 = 4 / 5
5 (900 – T) = 3600
4500 – 3600 = 5T
900 / 5 = T
T = 180 K
Hence the temperature T of the sink is equal to 180 K.
10. Three real heat engines have the same thermal efficiency and are connected in series. The first
engine absorbs 2400 kJ of heat from a thermal reservoir at 1250 K and the third engine ejects its
waste of 300 kJ to a sink at 150 K. determine the work output from each engine.
Data given:
Q1 = 2400 KJ
Q4 = 300 KJ
For engine E1,
Efficiency η1 = (Q1 – Q2) / Q1
= 1 – (Q2 / Q1)
I.e. Q2 / Q1 = 1 – η1
Similarly for engine E2,
Q3 / Q2 = 1 – η2
39
For engine E3,

Q4 / Q3 = 1 – η3
Therefore,
(1 – η1) (1 – η2) (1 – η3)
= (Q2 / Q1) X (Q3 / Q2) X (Q4 / Q3)
= Q4 / Q1 = 300 / 2400 = 1 / 8
For same thermal efficiency of each engine:
(1 – η)3 = 1 / 8
1–η=1/2
η = 1 / 2 = 50%
Now, Q2 / Q1 = 1 – 1 / 2 = 1 / 2
Q1 = 2 Q2
Q2 = Q1 / 2 = 2400 / 2 = 1200 kJ
And
Q3 / Q2 = 1 / 2
Q3 = Q2 / 2 = 1200 / 2 = 600 kJ
Hence work output from first engine (W1) = Q1 – Q2
= 2400 – 1200 = 1200 kJ
From second engine (W2) = Q2 – Q3
= 1200 – 600 = 600 kJ
From third engine (W3) = Q3 – Q4
= 600 – 300 = 300 kJ
Total work done W = W1 + W2 + W3
= 1200 + 600 +300 = 2100 kJ
Hence the total work output of the engines in series is equal to 2100 kJ.
11. Calculate the maximum efficiency of an engine operating between 120o C and 35o C.
Mathematically,
40
T2 = 120o C = 120 + 273 = 393 K

T1 = 35o C = 35 + 273 = 308 K
Therefore,
η = (T2 – T1) / T2
= (393 – 308) / 393
= .21628 = 21.62%
Hence maximum efficiency of the engine is 21.62%
12. Carnot engine working between a source temperature of T2 and sink temperature of T1 has
efficiency of 25%. If the sink temperature is reduced by 20o C, the efficiency is increased to 30%.
Find the source and the sink temperature.
Mathematically,
Efficiency, η = (T2 – T1) / T2 = 25% = 0.25
T2 – T1 = 0.25 T2
T1 = 0.75 T2
In the second case, if the sink is reduced by 20o C, then
η= T2 – (T1 – 20) / T2 = 30% = 0.3
T2 – T1 + 20 = 0.3 T2 ………………………………. (1)
Putting the value of T1 in equation (1), we will get:
T2 – 0.75 T2 + 20 = 0.3 T2
0.25 T2 + 20 = 0.3 T2
20 = 0.3 T2 – 0.25 T2 = 0.05 T2
T2 = 20 / 0.05 = 400o C
Hence, T1 = 0.75 T2
T1 = 0.75 X 400 = 300o C
Hence, temperature of the source and the sink is 400o C and 300o C respectively.
13. A Carnot engine converts one sixth of the heat input into work. If the sink temperature is
reduced by 62o C, the efficiency gets doubled. Find the source and the sink temperature.
41
Mathematically,
Efficiency, η = (T2 – T1) / T2 = 1/6
6 T2 -6 T1 = T2
Therefore, T2 = 1.2 T1 ………………….. (1)
If the sink temperature (T1) is reduced by 62o C, the efficiency gets doubled i.e.
η= T2 – (T1 – 62) / T2 = 2 X 1/6 = 2/6
6 T2 – 6 T1 + 372 = 2 T2
6 T2 – 2 T2 – 6 T1 + 372 = 0
4 T2 – 6 T1 + 372 = 0
Substituting the value of T2 from equation (1), we will get,
4 (1.2 T1) – 6 T1 + 372 = 0
4.8 T1 – 6 T1 + 372 = 0
372 = 1.2 T1
T1 = 310 K
Therefore, T2 = 1.2 X 310 = 372 K
Hence, temperature of the source and the sink is 372 K and 310 K respectively.
Maxwell Relations in Thermodynamics
In thermodynamics, the Maxwell equations are a set of equations derived by application of Euler's
reciprocity relation to the thermodynamic characteristic functions. The Maxwell relations, first derived
by James Clerk Maxwell, are the following expressions between partial differential quotients:
42
The characteristic functions are: U (internal energy), A (Helmholtz free energy), H (enthalpy),
and G (Gibbs free energy). The thermodynamic parameters
are: T (temperature), S (entropy), P (pressure), and V (volume).
As an example of a derivation, consider
Euler's reciprocity relation reads:
which indeed gives
In thermodynamics, enthalpy (also known as thermodynamic potential) is the sum of the internal
energy U and the product of pressure p and volume V of a system,
The Helmholtz energy is defined as
A = U- TS
where
43
A is the Helmholtz free energy (SI: joules, CGS: ergs),

U is the internal energy of the system (SI: joules, CGS: ergs),
T is the absolute temperature (kelvins) of the surroundings, modelled as a heat bath,
S is the entropy of the system (SI: joules per kelvin, CGS: ergs per kelvin).
where:
U is the internal energy (SI unit: joule),

p is pressure (SI unit: pascal),
V is volume (SI unit: m3),
T is the temperature (SI unit: kelvin),
S is the entropy (SI unit: joule per kelvin),
H is the enthalpy (SI unit: joule).
44

Thermodynamics - Dr. Hossen

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Thermodynamics - Dr. Hossen

Uploaded by

Copyright:

Available Formats

CSE First Semester (Session: 2020-2021) Thermodynamics

Professor Dr. Khokon Hossen

Internal Energy for Ideal Gas

While steam at 100 degrees Celsius is not strictly an ideal

If rotation and vibrational kinetic energies are involved

Study of the specific heats of gases provides evidence of

Specific Heats of Gases

Explanation: Specific Heat at Constant Volume

The molar specific heat at constant volume is defined by

but since ΔV = 0, the expression for CV becomes

For a monoatomic ideal gas, , so

Explanation: Specific Heat at Constant Pressure:

The molar specific heat at constant pressure is defined by

Since the constant volume specific heat is

For an ideal monoatomic gas

The First law of Thermodynamics

Limitations of the first law of Thermodynamics

Limitations of the first law of thermodynamics are discussed below:

The Second law of Thermodynamics

The Third Law of Thermodynamics

Figure-1: Crystalline solids at temperature O K and T> 0 K.

Importance of third law of thermodynamics is given below

Limitations of third Law

The following types of process in thermodynamics are well known:

(i) Isothermal Process

(ii) Adiabatic Process

(iii) Isochoric Process

(iv) Isobaric Process

(v) Isentropic process

Other Factors in an Isothermal Process

Isothermal Processes & States of Matter

Applying the first law of thermodynamics to an adiabatic process, we obtain:

Note that during an adiabatic process the gas equations:

(i) PVγ = constant

and the work done during an adiabatic Process, W = Cv (T1-T2)

Applying the first law of thermodynamics to this situation, we find that:

Constant Volume, But W is Non-zero

Table-1: Comparative study of thermodynamical process.

Figure-3: Reversible and Irreversible Process.

Entropy: Entropy and its characteristics

Figure-4: Entropy and disorder of the crystal.

The SI units of entropy are J/K (joules/degrees Kelvin).

Characteristics of Entropy are as follows

Figure-5: Entropy in nature.

Calculate the entropy changes of an Ideal Gas in different processes

And W = P1 V1 ln (V2 / V1)

Hence, ∆ST = R ln (V2 / V1)

ii. Isobaric Processes

Derive the Entropy changes for a reversible process

Entropy and the Second Law of Thermodynamics

One way of stating the second law of thermodynamics is:

Hence V1 = 22.4 dm3 and V2 have to be calculated.

(a) Work done:

Temperature T = 37oC = 37 + 273 = 310 K

From first law, ∆U= q + w

Carnot’s Heat Engine

Figure-3: Carnot’s Heat Engine

Figure-7: The Components of Carnot’s Heat Engine

The Four Processes:

Figure-8: Carnot’s Cycle of Adiabatic Compression

Figure-9: Carnot’s Cycle of Isothermal Expansion

Figure-10: Carnot’s Cycle of Adiabatic Expansion