Heat

&
Thermodynamics
 Content
•Platinum resistance thermometer, •Reversible and irreversible
• Thermo-electric thermometer, processes,
• Kinetic theory of gases, •Second Law of thermodynamics,
• Maxwell's distribution of molecular •Carnot cycle,
speeds,
•Efficiency of heat engines,
•Mean free path,
•Carnot's Theorem,
• Equipartition of energy,
•Brownian motion, •Entropy and disorder,
•Vander Waal's equation of state, •Thermodynamic functions,
• First Law of thermodynamics and its •Maxwell relations,
application, •Third Law of thermodynamics.
Thermodynamics: The branch of physical science that deals with the
relations between heat and other forms of energy (such as mechanical,
electrical or chemical energy) and the relationships between all forms
of energy.
 Differences between Heat and Temperature
Heat Temperature
Heat is a type of energy. Temperature is not energy. It is a thermal
condition of body.
Its SI unit joule. Its SI unit kelvin.
Heat depends on mass of the substance. One Temperature does not depend on the mass of
glass of boiling water and one teapot of matter. For example, temperature of one glass
boiling tea have different heat since they have of boiling water and one teapot of boiling tea
different masses. are equal to each other.

Heat cannot be measured with a device Temperature can measure directly with a
directly. You should know the mass, device called thermometer.
temperature and specific heat capacity of that
matter.

It is an cause. It is an effect.
 Thermodynamic System
A thermodynamic system is a quantity of matter of fixed
identity, around which we can draw a boundary. The boundaries
may be fixed or moveable. Work or heat can be transferred
across the system or boundary.
Examples: Refrigerator, air-conditioner, washing machine, heat
exchange, a utensil with hot water etc.
 Open system Closed system Isolated system
The system in which the transfer of mass as The system in which the The system in which neither
well as energy can take place across its transfer of energy takes place the transfer of mass nor that of
boundary is called as an open system. across its boundary with the energy takes place across its
surrounding, but no transfer of boundary with the
mass takes place is called as surroundings is called as
closed system. The closed isolated system. Here there will
system is fixed mass system. neither transfer of mass nor
that of energy.
Example: Open system is boiling water in an Example: The water being Hot water, coffee or tea kept in
open vessel, where transfer of heat as well as heated in the closed vessel, the thermos flask is closed
mass in the form of steam takes place when water will get heated but system.
between the vessel and surrounding. its mass will remain same.
 Thermometer
An instrument for measuring and Some Types of the thermometer
indicating temperature. Typically, it
consists of a narrow, hermetically Mercury thermometers
sealed glass tube marked with Alcohol in glass thermometers
graduations and having at one end a Constant pressure gas thermometers
bulb containing mercury or alcohol
Constant volume thermometers
that expands and contracts in the
tube with heating and cooling. Platinum resistance thermometers

Thermocouple thermometers

Pyrometer Thermometers
 Why mercury used mostly in
thermometers instead of water?
Mercury is used mostly in thermometers because of the following
properties:
• It is visible.
• It has a low freezing point (-39 °C).
• It has a very high boiling point (357 °C).
• It expands linearly.
• It gives accurate measurements.
• It is a good conductor of heat.
• Fast response time.
• It has a wide range of temperatures.
 Platinum resistance thermometer
The Platinum resistance thermometer is based on the principle that electrical
resistance of a metallic wire increase gradually and uniformly with increase in
temperature over a wide range. The scientist Clausius was first who develop a
relation as,
……………….. (1)
Where, and are the resistances of the conducting wire at and respectively and be
the coefficient of increase in resistance whose value depend on the nature and
property of the wire.
If, and be the resistances of a pure platinum wire at, and unknown
temperature respectively, then by using equation (1) we can write,

……………… (2)
And,

…………………. (3)
By knowing the values of, and we can determine the value of from
equation (3).
1. The resistance of the platinum wire of a platinum resistance thermometer at the ice point is 5  and
at the steam point is 5.93 . When the thermometer is inserted in a hot bath the resistance of the
platinum wire is 5.795 . Calculate the Celsius temperature on the platinum scale. [Ans:85.48 0C]
2. The values of resistance of a platinum resistance thermometer are 2.585 ohms and 3.510 ohms at 0 ̊ C
and 100 ̊ C respectively. When placed in a hot bath, the resistance is found to be 9.098 ohms. Calculate
the temperature of the hot bath on the platinum scale.
3. The resistance of a platinum resistance thermometer are 2.56 ohms and 3.56 ohms at 0 ̊ C and at
steam point. When the thermometer is placed in an unknown temperature bath, the resistance of the
thermometer is 6.78 ohms. Calculate the temperature of the bath?
4. What is the resistance of a platinum wire at 25 ̊ C? Here, resistance at 0 ̊ C, R0 = 2.585 Ω, α = 3.8 × 10-3
5. A platinum wire has resistances of 2 Ω and 3Ω respectively at and. Its resistance becomes 10.5 Ω at
the normal boiling point of sulphur. Calculate the value of boiling point of sulphur from the given data.
 
Thermoelectric or Thermocouple Thermometer
• Thermo Electric Thermometer is a device used to measure temperature using a
thermocouple which generates a voltage proportional to temperature difference.
The range in which it can measure the temp is nearly -200oc to 1600oc.
• A thermocouple uses two different metal wires. They are joined at one end. The
other end is attached to a voltmeter calibrated to read temperature according to
the know relationship between the difference in temperature between the joined
end (sensing tip) and the open end, connected to the meter.
• Principle: It is based on the principle of Seebeck effect, in which a temperature
difference between two dissimilar electrical conductors  produces a voltage
difference between the two substances.
 FOUR MAJOR TEMPERATURE SCALES
The Fahrenheit scale of temperature is the common form of temperature measurement used in the United States and
some parts of the Caribbean. It was created by the German scientist Daniel Gabriel Fahrenheit in the early 18th century,
and adapted its measurements standards from a previous scale created by Ole Roemer. Water freezes at 32 degrees
Fahrenheit, and boils at 212 degrees F. The Fahrenheit temperature scale includes negative temperatures, below 0 degrees
F. The coldest possible temperature, absolute zero, is -459.67 degrees F.

Two versions of the Celsius scale were created in the early 18th century – one by Swedish scientist Anders Celsius, and
another by the French Jean Pierre Cristin. The Celsius scale is sometimes referred to as the centigrade scale, because it is
based on a 100 degree division between the freezing and boiling points of water. Water freezes at 0 degrees Celsius and
boils at 100 degrees C.

The Kelvin scale was adapted from the Celsius scale in the 19th century by the British scientist William Thompson, later
Lord Kelvin. Kelvin was designed in order to set the zero point of the temperature scale at absolute zero. Because of this,
absolute zero is located at 0 K – Kelvin does not use degrees in its notation. You can convert from Celsius to Kelvin by
adding 273.15 to a Celsius temperature. Water freezes at 273.15 K, and boils at 373.15 K .

While not widely used – apart from some U.S. engineering fields – the Rankine scale provides an absolute zero-based
equivalent to the Fahrenheit scale. The scale was created by Scottish scientist William John Rankine in the 19th century,
shortly after the creation of the Kelvin scale. Temperatures can be converted from Fahrenheit to Rankine by adding 459.67.
Absolute zero is thus located at 0 degrees Rankine. Water freezes at 491.67 degrees R, and boils at 671.67 degrees R.
Temperature Scale
1. The temperature of the surface of the sun is about 6500℃. What is the
temperature a) On the Rankin scale? b) On the Kelvin scale.
2. The normal boiling point of liquid oxygen is -183 ̊ C. What is this
temperature on i) Kelvin scale and ii) Rankine scale?
3. One day when temperature is 15 ̊ F. What will be the temperature on
Celsius and Kelvin scale?
4. At what temperature do the Kelvin and Fahrenheit scales coincide?
5. At what temperature do the Celsius and Fahrenheit scales coincide?
6. Which temperature has 400 differences in Celsius and Fahrenheit scale?
 KINETIC THEORY OF GASES
The kinetic theory of gases is a simple, historically significant model of the 
thermodynamic behavior of gases, with which many principal concepts of
thermodynamics were established. The model describes a gas as a large
number of identical submicroscopic particles (atoms or molecules), all of which
are in constant, rapid, random motion. Their size is assumed to be much
smaller than the average distance between the particles. Kinetic Theory of
Gases is based on the following assumption, first stated by Clausius in 1860.
1. A gas consists of large number of tiny, rigid particles called molecules.
2. The gas molecules are identical in all respects, like mass, size, etc.
3. The volume of the molecules is negligible when compared to the volume of
the gas.
4. Molecules are perfectly elastic spheres and do not exert forces on each other.
5. The molecules are in random motion and obey Newton‟s law.
 Maxwell's Distribution of Molecular Speeds
In the context of the Kinetic Molecular Theory of Gases, a gas contains a
large number of particles in rapid motions. Each particle has a different
speed, and each collision between particles changes the speeds of the
particles. An understanding of the properties of the gas requires an
understanding of the distribution of particle speeds.
If we were to plot the number of molecules whose velocities fall within
a series of narrow ranges, we would obtain a slightly asymmetric curve
known as a velocity distribution. This velocity distribution curve is
known as the Maxwell-Boltzmann distribution. The Maxwell-
Boltzmann distribution law was first worked out around 1850 by the
great Scottish physicist, James Clerk Maxwell and Later, the Austrian
physicist Ludwig Boltzmann. Notice that the graph is not symmetrical.
There is a longer "tail" on the high speed right end of the graph. The
graph continues to the right to extremely large speeds, but to the left the
graph must end at zero (since a molecule can't have a speed less than
zero
The Maxwell-Boltzmann equation, which forms the basis of the
kinetic theory of gases, defines the distribution of speeds for a
gas at a certain temperature. The Maxwell-Boltzmann
distribution is used to determine how many molecules are
moving between velocities v and v+dv . the Maxwell-Boltzmann
distribution is given by,

n = density of the gas,

kB = Boltzmann constant,
T = temperature of the gas,
V = velocity of the gas molecule
The total number of molecules in the gas can be obtained by,
Three speed expressions can be derived from the Maxwell-
Boltzmann distribution: A plot of n against v is given below--
• Most probable speed: The most probable speed is the speed
associated with the highest point in the Maxwell distribution.
Only a small fraction of particles might have this speed, but it is
more likely than any other speed.

• Average speed: The average speed is the sum of the speeds of

all of the particles divided by the number of particles

• Root-mean-square speed: The root-mean-square speed is

square root of the average speed-squared.

Where, M=Molar mass which is the mass of one mole of a

substance. Molar mass is reported in grams per mole or g/mol
 Mean Free Path
The average distance travelled by a molecule between two collisions
is called the mean free path ( λ). If S is the total distance travelled
during N collisions, then

Problem: Calculate the values of Vmp , Vavg , and Vrms for xenon
gas at 270 C
Problem: Calculate the root mean square, average and most
probable speed of oxygen at 270C
 Degrees of Freedom
“The total number of independent variables required to describe completely the state of motion
of a body are called its degrees of freedom”.
An ant moving along a straight line, it has only one degree of freedom (x).
If it moves on a plane it has two degrees of freedom (x,y).
A flying mosquito has three degrees of freedom (x,y,z). Also a monoatomic molecule, e.g., Neon
(Ne), Helium (He) etc., has three degrees of freedom (all are translational)
A diatomic molecule having a dumbbell shape e.g., HCl, Cl2, O2 etc., has six degrees of freedom
(3 translational, 2 rotational and 1 vibrational), as shown in figure.
 Principle of Equipartition of Energy
Equipartition of energy is an equal amount of energy will be
associated with each degree of freedom. The average kinetic energy
associated with each degree of freedom is
Statement: “For any dynamical system in thermal equilibrium, the
total energy is divided equally among all the degrees of freedom and
the energy associated per molecule per degree of freedom is where
is Boltzmann‟s constant and is absolute temperature of the gas”.
 Brownian Motion
• Particles in both liquids and gases (collectively called
fluids) move randomly. This is called Brownian motion.
They do this because they are bombarded by the other
moving particles in the fluid. Larger particles can be
moved by light, fast-moving molecules.
• Brownian motion is named after the botanist Robert
Brown, who first observed this in 1827. He used a
microscope to look at pollen grains moving randomly in
water. At this point, he could not explain why this
occurred. But in 1905, physicist Albert Einstein explained
that the pollen grains were being moved by individual
water molecules. This confirmed that atoms and
molecules did exist, and provided evidence for particle
theory.
 Vander Waal's Equation of State
In thermodynamics, the Van der Waals equation (or Van der Waals equation of state) named after Dutch physicist Johannes Diderik van der
Waals, is an equation of state that generalizes the ideal gas law based on plausible reasons that real gases do not act ideally. The ideal gas
law treats gas molecules as point particles that interact with their containers but not each other, meaning they neither take up space nor
change kinetic energy during collisions. The ideal gas law states that volume (V) occupied by n moles of any gas has a pressure (P) at
temperature (T) in kelvins given by the following relationship, where R is the gas constant:

To account for the volume that a real gas molecule takes up, the Van der Waals equation replaces V in the ideal gas law with , where Vm is
the molar volume of the gas and b is the volume that is occupied by one mole of the molecules. This leads to

The second modification made to the ideal gas law accounts for the fact that gas molecules do in fact interact with each other (they usually
experience attraction at low pressures and repulsion at high pressures) and that real gases therefore show different compressibility than
ideal gases. Van der Waals provided for intermolecular interaction by adding to the observed pressure P in the equation of state a term
where a is a constant whose value depends on the gas. The Van der Waals equation is therefore written as:

and, for n moles of gas, can also be written as the equation below

 Zeroth Law of Thermodynamics
• Zeroth law of thermodynamics is one of the four laws of thermodynamics. The credit for formulating the
law goes to Ralph H. Fowler. Interestingly, the zeroth law of thermodynamics was actually developed much
later than the original three laws. However, there was some confusion regarding the nomenclature,
whether it should be named the fourth law or some other name. The complication arose because the new
law gave a much clearer definition of the temperature and basically replaced what the other three laws
had to state. Fowler finally came up with the name to end this conflict.
• The zeroth law of thermodynamics frames an idea of temperature as an indicator of thermal equilibrium.
• Thermal Equilibrium: Temperature is a property that distinguishes thermodynamics from other
sciences. This property can distinguish between hot and cold. When two or more bodies at different
temperatures are brought into contact then after some time they attain a common temperature and they
are said to exist in thermal equilibrium. Systems are said to be in thermal equilibrium if there is no heat
transfer, even if they are in a position to transfer heat, based on other factors. For example, if we put food
in the refrigerator overnight then that food is in thermal equilibrium with the air of that refrigerator. Heat
no longer flows from food to the air or from the air to the food, this state is known as thermal equilibrium.
 Zeroth Law of Thermodynamics
Statement:
“The zeroth law of thermodynamics states that if two
thermodynamic systems are each in thermal equilibrium
with a third, then the two systems are in thermal
equilibrium with each other also”.
When a body ‘A’ is in thermal equilibrium with another
body ‘b’, and also separately in thermal equilibrium with a
body ‘C’, then body ‘B’ and ‘C’ will also be in thermal
equilibrium with each other. There are also various ways
to state the zeroth law of thermodynamics. However, in
simple terms, it can be said, “Systems that are in thermal
equilibrium exist at the same temperature”.
 Application of the Zeroth Law
• Let’s say Object A is in “India” and Object B is in “Bangladesh” and we want some Information
about the temperature of both. What will you do ? Here comes the Body C (Assume it to be
mercury Thermometer). In both these country Body C is available. We measured the Height of
Mercury Column in India after contacting it with Object A and also measured the same in
Bangladesh after Contacting it with Object B. At both these places the Height of Mercury Comes
out to be same. Therefore without bringing in contact physically the Object A and Object B we
can easily conclude that they are at a same temperature or in a thermal Equilibrium.
• Measuring our body temperature using mercury thermometer: When mercury
thermometer is placed on our body, the glass wall of the thermometer first attains equilibrium
with our body due to heat conduction. Then equilibrium is attained between the glass wall and
the mercury. So if our body and mercury are in thermal equilibrium with the glass wall. then
our body and mercury are in thermal equilibrium with each other ie.,mercury shows the exact
body temperature.
• Another example of the zeroth law of thermodynamics is when you have two cup of coffee. One
cup will have hot coffee and the other have cold coffee. Now if we leave them in the table for a
few hours they will attain thermal equilibrium with the temperature of the room.
 First Law of Thermodynamics
• Before we get into the first law of thermodynamics we need to understand the relation
between heat and work and the concept of internal energy. Just like mass, energy is always
conserved i.e. it can neither be created nor destroyed but it can be transformed from one
form to another.
• Internal energy is a thermodynamic property of the system that refers to the energy
associated with the molecules of the system which includes kinetic energy (due to
translational, rotational and vibrational motion of molecules which only depends on T) and
potential energy(due to intermolecular force) which depends on the separation between
the molecules.
• Whenever a system goes through any change due to interaction of heat, work and internal
energy, it is followed by numerous energy transfer and conversions. However, during these
transfers, there is no net change in the total energy. So, the first law of thermodynamics
affirms that heat is a form of energy. The first law of thermodynamics tells that the
energy of the universe remains the same. Though it may be exchanged between the system
and the surroundings, it can’t be created or destroyed. The law basically relates to the
changes in energy states due to work and heat transfer. It redefines the conservation of
energy concept.
 First Law of thermodynamics
Statement: “ If some heat is supplied to a system which can do work, then the quantity of heat
absorbed by the system is equal to the sum of increase in internal energy of the system and the
external work done by the system”.
Explanation: If be the amount of heat absorbed by a system and be the change in internal
energy and is the work done by the system due to absorption of heat, then according to the 1st
law of thermodynamics,
 Application of the First Law
(a) A common example is heat engine. In a Heat engine, the thermal energy is converted into mechanical
energy and the process also is vice versa. Heat engines are mostly categorized as an open system. The
basic working principle of a heat engine is that it makes use of the different relationships between heat,
pressure and volume of a working fluid which is usually a gas. Sometimes phase changes might also
occur involving a gas to liquid and back to gas.
(b) Metabolism.
(c) Photosynthesis.
 Limitations of
First Law of thermodynamics

The first law states that whenever a system undergoes any thermodynamic process it always holds
certain energy balance. But it fails to give the feasibility of the process or change of state that the
system undergoes. For instance, the first law fails to explain why heat flows from hot end to cold
end when a metallic rod is heated at one end and not on the other and vice-versa. The first law
only quantifies the energy transfer that takes place during this process. It is the second law of
thermodynamics which provides the criterion for the feasibility of the various processes.
Work Done in the Thermodynamic System
The work, done by the gas is given by,

Where, and

And

In a finite change of volume from

Problem: Some gas are confined in a cylinder having movable piston. The system has
done 1200 J work when 800 J heat energy is given keeping pressure constant at 400
Pa. What are the change in volume and internal energy?
Specific Heat (S): The specific heat of material is defined as the quantity of heat
required to raise the temperature of unit 1 gm of that material through 1 degree
Celsius.
Specific heat,
The unit of specific heat is in C.G.S. is and in S.I. is .
Molar Specific Heat at Constant Volume (Cv): It is defined as the amount of heat
energy required to raise the temperature of one mole of a gas by at constant
volume. It is represented by and given by,

Molar Specific Heat at Constant Pressure (Cp): It is defined as the amount of

heat energy required to raise the temperature of one mole of a gas by at constant
pressure. It is represented by and given by,
 Relation between and
Let us consider one mole of an ideal gas enclosed in a cylinder provided with a frictionless piston of
area A. Let P, V and T be the pressure, volume and absolute temperature of gas respectively as shown
in below figure.

A quantity of heat dQ is supplied to the gas. To keep the volume of the gas constant, a small weight is
placed over the piston. The pressure and the temperature of the gas increase to P + dP and T +
dT respectively. This heat energy dQ is used to increase the internal energy dU of the gas
……………………. (1)
where, is the molar specific heat at constant volume. According to first law of thermodynamics

…………………. (2)
Since the volume is constant, .
From (2) we get,
…………….. (3)
From (1) and (3) we have,
…………… (4)
Now, keeping the pressure constant, the temperature of the system is raised by the same amount by supplying heat
So, we get the amount of heat,
………………. (5)
Using equations (4) and (5) in (2) we get,
………. (6)
But, for n moles of ideal gas,
………………. (7)
Differentiating (7) we get,
……………….. (8)
Using (8) in (6) we get,

or,
or,
…………….. (9)
Therefore, the difference between the two specific heats of an ideal gas is equal to the molar gas constant,. Now,
from equation (9) we can write,

For an ideal gas the ratio between and is denoted by.

From experiment we have seen that, is 1.67 for one atomic gas, for two atomic gas and for three atomic gas.
Problem: For an ideal gas. Calculate the values of molecular specific heats of
the gas?
Solution:
We have,
And

Substituting this in (1)

And,
 Second Law of Thermodynamics
The second law of thermodynamics put restrictions upon the
direction of heat transfer. The second law of thermodynamics that
provides the criterion for the feasibility of any process. It states that
any spontaneously occurring process will always lead to an
escalation in the entropy (S) of the universe. It is also known as the
Law of Increased Entropy.
Mathematically, the second law of thermodynamics is represented
as,
ΔSuniv > 0
where ΔSuniv is the change in the entropy of the universe.
 Second Law of Thermodynamics
Different Statements of The Law:
Kelvin- Plank Statement
It states that practically a reservoir never gives a positive
net amount of work from the heat extracted from a thermal
reservoir. So, basically, you cannot have a heat engine that
operates between the two temperature levels and it has no
heat rejection.
It is not possible to achieve a continuous supply of work
from a body by cooling it to the temperature below the
coldest of its surroundings.
Clausius Statement
It is impossible to construct a device operating in a cycle
that can transfer heat from a colder body to warmer
without consuming any work. Refrigerator works on
Clausius’s statement. In other words, unless the compressor
is driven by an external source, the refrigerator won’t be
able to operate.
 Entropy
Entropy is a measure of the randomness of the system or it is the measure of energy or chaos within an
isolated system. Entropy is a State Function because it depends only on the initial and final
thermodynamic states and not on the path followed.
There are few factors that cause an increase in entropy of the closed system. Firstly, in a closed system,
while the mass remains constant there is an exchange of heat with the surroundings. This change in
the heat content creates a disturbance in the system thereby increasing the entropy of the system.
Secondly, internal changes may occur in the movements of the molecules of the system. This leads to
disturbances which further causes irreversibilities inside the system resulting in the increment of its
entropy.
It is denoted by ‘S’. Mathematically,. Here, dQ is the energy transferred as heat, T is the temperature of
the system in Kelvins. and stands for initial heat and final heat of the system respectively.
 Entropy change of a Perfect gas
Suppose that the initial temperature, pressure and volume of m kg of a gas be T1, P1 and V1
respectively. Let this gas be heated to final temperature, pressure, volume T2, P2, V2 respectively.

Now, according to the 1st law of thermodynamics we can write,

Again, we can write,

And,
Putting these two values in Eqn. (i) we get,

From ideal gas law we know,

Inserting this value in Eqn. (ii) we get,

Integrating,

This the required expression for change in entropy.

Problem: Calculate the increase in entropy of 2 gm of O2 when its
temperature is raised from 200 C to 1000 C and its volume is
doubled. [Cv=25.5 Jmole-1K-1 and R=8.31Jmole-1K-1 ]
Difference Between Isothermal Process and Adiabatic
Processes
Isothermal Process Adiabatic Process
An isothermal process is a While an adiabatic process is the one in
thermodynamic process in which there which there is no transfer of heat or
is no change in the temperature of the mass in-between the system and the
system. The temperature of the system surrounding throughout the
remains constant throughout the thermodynamic process. Hence, in an
thermodynamics process i.e. ΔT = 0. adiabatic system ΔQ = 0.

From a thermal reservoir near the By definition, there is no change in the

system, heat can be added or removed heat in an adiabatic process and so there
from the system, in order to keep the is no addition or subtraction of the heat.
temperature constant.

Any transformation in such a process is Any transformation in such a process is

slow. fast.
Boyle’s law holds good. i.e. PV=constant Boyle’s law doesn’t hold good. i.e.
PVγ=constant
 Differentiate between reversible and irreversible
process.
Reversible process Irreversible process
1) It is a slow process which goes through (1) It is a comparatively fast process. Here,
various smaller stages which maintains no equilibrium is maintained between the
equilibrium between the system and the system and the surroundings.
surroundings.
2) Reversible processes can take place 2) Irreversible processes can take place only
either in forward direction or in backward in one direction.
direction.
3) Reversible process proceeds in smaller 3) Irreversible process proceeds in larger
steps because the driving force is small. steps in comparison with reversible process
because there is definite driving force
required for the progress of the process.

4) Work done in a reversible process is 4) Work done in an irreversible process is

greater than the work done in an always lower than the work done in an
irreversible process. irreversible process.

(5) A reversible process can be brought back 5) An irreversible process cannot be

to the initial state without making any brought back to its initial state without
change in the surroundings making a change in the surroundings.
 Carnot’s Ideal Heat Engine
we have seen that the heat engine cannot have 100% efficiency. What is the
maximum possible efficiency can a heat engine have?. In the year 1824 a
young French engineer Sadi Carnot proved that a certain reversible engine
operated in cycle between hot and cold reservoir can have maximum
efficiency. This engine is called Carnot engine.
A reversible heat engine operating in a cycle between two temperatures in a
particular way is called a Carnot Engine.
The carnot engine has four parts which are given below.
i. Source: It is the source of heat maintained at constant high temperature
TH. Any amount of heat can be extracted from it, without changing its
temperature.
ii. Sink: It is a cold body maintained at a constant low temperature TL. It can
absorb any amount of heat.
iii. Insulating stand: It is made of perfectly non-conducting material. Heat is
not conducted through this stand.
iv. Working substance: It is an ideal gas enclosed in a cylinder with perfectly
non-conducting walls and perfectly conducting bottom. A non-conducting
and frictionless piston is fitted in it.
 Carnot’s cycle
The working substance is subjected to four successive
reversible processes forming what is called Carnot’s cycle.
Let the initial pressure, volume of the working substance
be P1,V1.
Step A to B: Isothermal expansion from (P1,V1,TH) to
(P2,V2,TH):
The cylinder is placed on the source. The heat (QH) flows from
source to the working substance (ideal gas) through the
bottom of the cylinder. Since the process is isothermal, the
internal energy of the working substance will not change. The
input heat increases the volume of the gas. The piston is
allowed to move out very slowly.
W1 is the work done by the gas in expanding from
volume V1 to volume V2 with a decrease of pressure
from P1 to P2. This is represented by the P-V diagram along the
path AB.
Step B to C: Adiabatic expansion from (P2,V2,TH) to (P3,V3,TL)
The cylinder is placed on the insulating stand and the piston is
allowed to move out. As the gas expands adiabatically from
volume V2 to volume V3 the pressure falls from P2 to P3. The
temperature falls to TL. This adiabatic expansion is represented
by curve BC in the P-V diagram. The work done by the gas in an
adiabatic expansion is given by W2.
Step C to D: Isothermal compression from (P3,V3,TL) to
(P4,V4,TL).
The cylinder is placed on the sink and the gas is isothermally
compressed until the pressure and volume become P4 and V4
respectively. This is represented by the curve CD in the PV
diagram. Now the work done on the gas is W3. Work is done on the
gas so that work done is negative
Step D to A: Adiabatic compression from (P4,V4,TL) to
(P1,V1,TH).
The cylinder is placed on the insulating stand again and the gas is
compressed adiabatically till it attains the initial pressure P1,
volume V 1 and temperature T H. This is shown by the curve DA in
the P-V diagram. In the adiabatic compression also work is done on
the gas so it is negative
Let ‘W’ be the net work done by the working substance in one cycle

∴W=Work done by the gas – work done on the gas

= W1+W2-W3-W4 [since, W2=W4]
=W1-W3
Efficiency: The ratio of part of heat converted into work to the part of
heat absorbed from the source is the efficiency of the engine.
 
 
Also we can write,
 REFRIGERATOR
A refrigerator is a Carnot’s engine working in the reverse order. The
working substance (gas) absorbs a quantity of heat QL from the cold
body (sink) at a lower temperature TL. A certain amount of work W
is done on the working substance by the compressor and a quantity
of heat QH is rejected to the hot body (source) ie, the atmosphere at
TH. When you stand beneath of refrigerator, you can feel warmth air.
 
Also we can write,
1. Find the efficiency of a Carnot engine working between 127 ̊ C and 27 ̊ C .
2. Find the efficiency of a Carnot engine working between steam point and ice point .
3. A Carnot engine whose low temperature reservoir is at 7 ̊ C has an efficiency of 50 %. It is desired to increase the
efficiency to 70 %. By how many degrees should the temperature of the high temperature reservoir be increased?
4. A Carnot engine whose temperature of the source is 400 K, takes 200 calories of heat at this temperature and rejects
150 calories of heat in the sink. What is the temperature of the sink? Calculate the efficiency of the engine.
5. A Carnot engine is operated between two reservoirs at temperatures of 450 K and 350 K. If the engine receives 1 kcal of
heat from the source in each cycle. Calculate i) amount of heat rejected to the sink in each cycle. i) efficiency of the
engine and iii) work done by the engine in each cycle.
6. A Carnot engine working as a refrigerator between 260 K and 300 K receives 500 calories of heat from the reservoir at
the lower temperature. Calculate i) amount of heat rejected to the reservoir at the higher temperature and ii) the
amount of work done in each cycle to operate the reservoir.
7. A Carnot engine is operated between two reservoirs at temperatures 400 K and 300 K. a) If the engine receives 1200 Cal
from the reservoir at 400 K in each cycle, how many calories does it reject to the reservoir at 300 K ? b) If the engine is
operated in reverse as a refrigerator and receives 1200 Cal from the reservoir at 300 K, how many calories does it
deliver to the reservoir at 400 K ?
 Third Law of Thermodynamics

• The third law of thermodynamics states that the entropy of a perfect crystal at a
temperature of zero Kelvin (absolute zero) is equal to zero. This law was
developed by the German chemist Walther Nernst between the years 1906 and
1912.

• At a temperature of zero Kelvin, the following phenomena can be observed in a

closed system:
i. The system does not contain any heat.
ii. All the atoms and molecules in the system are at their lowest energy points.
iii. Therefore, a system at absolute zero has only one accessible microstate – it’s
ground state. As per the third law of thermodynamics, the entropy of such a
system is exactly zero.
 Thermodynamic Functions
• Thermodynamic potential or fundamental function is a quantity
used to represent the state of a system. We have four fundamental
functions: internal energy U, enthalpy H, Helmholtz free energy F
(or simply the free energy), and Gibbs free energy G (or simply the
Gibbs function).
 Internal energy Enthalpy
• The internal energy of a thermodynamic system is the • Enthalpy is a property of a thermodynamic
energy contained within it. It is the energy necessary system, defined as the sum of the system's
to create or prepare the system in any given internal internal energy and the product of its pressure
state. It does not include the kinetic energy of motion and volume. It reflects the capacity to do non-
of the system as a whole, nor the potential energy of mechanical work and the capacity to release heat.
the system as a whole due to external force fields,
• The enthalpy H of a thermodynamic system is
including the energy of displacement of the
surroundings of the system. It keeps account of the defined as the sum of its internal energy U and
gains and losses of energy of the system that are due to the work required to achieve its pressure and
changes in its internal state. volume: H = U + pV

• The internal energy is an extensive property, and Where,

cannot be measured directly. The thermodynamic p is pressure, and V is the volume of the system.
processes that define the internal energy are transfers
of matter, or of energy as heat, and thermodynamic Enthalpy is an extensive property; it is proportional
work. These processes are measured by changes in the to the size of the system (for homogeneous
system's extensive variables, such as entropy, volume, systems).
and chemical composition.
• For a closed system, with matter transfer excluded, the
changes in internal energy are due to heat transfer dQ
and due to thermodynamic work dW done by the
system on its surroundings.
• Accordingly, the internal energy change dU for a
process may be written dU = dQ – dW
 Helmholtz free energy Gibbs free energy
In thermodynamics, the Helmholtz free energy is a In thermodynamics, the Gibbs free energy is a thermodynamic
thermodynamic potential that measures the useful work potential that can be used to calculate the maximum of reversible
obtainable from a closed thermodynamic system at a constant work that may be performed by a thermodynamic system at a
temperature and volume (isothermal, isochoric). The negative constant temperature and pressure.
of the change in the Helmholtz energy during a process is equal
to the maximum amount of work that the system can perform The Gibbs energy (symbol G) is also the thermodynamic potential
in a thermodynamic process in which volume is held constant. that is minimized when a system reaches chemical equilibrium at
If the volume were not held constant, part of this work would constant pressure and temperature. Its derivative with respect to
be performed as boundary work. This makes the Helmholtz the reaction coordinate of the system vanishes at the equilibrium
energy useful for systems held at constant volume. point. As such, a reduction in G is necessary for a reaction to be
Furthermore, at constant temperature, the Helmholtz free spontaneous at constant pressure and temperature.
energy is minimized at equilibrium. The Gibbs free energy is defined as
The Helmholtz energy is defined as G (p,T) = U + pV - TS
F = U-TS which is the same as
where G (p,T) = H - TSWhere,
F is the Helmholtz free energy (sometimes also called "A") (SI: U is the internal energy (SI unit: joule),
joules, CGS: ergs),
p is pressure (SI unit: pascal),
U is the internal energy of the system (SI: joules, CGS: ergs),
V is volume (SI unit: m3),
T is the absolute temperature (kelvins) of the surroundings,
T is the temperature (SI unit: kelvin),
S is the entropy of the system (SI: joules per kelvin, CGS: ergs
per kelvin). S is the entropy (SI unit: joule per kelvin),
H is the enthalpy (SI unit: joule).
 Maxwell relations

Maxwell relations are the set of

thermodynamics equations derived from
a symmetry of secondary derivatives and
from thermodynamic potentials. These
relations are named after James Clerk
Maxwell, who was a 19th-century
physicist.
These are derived from Euler’s
reciprocity relation. The relations are
expressed in partial differential form. The
Maxwell relations consists of the
characteristic functions: internal energy
U, enthalpy H, Helmholtz free energy F,
and Gibbs free energy G and
thermodynamic parameters: entropy S,
pressure P, volume V, and temperature T.