THERMODYNAMICS AND ELECTROMAGNETSIM (STP 212)

▎Thermodynamics Overview ▎Concepts of Thermodynamics ▎Key Parameters of

Thermodynamics ▎ Mayer’s Relation ▎ Laws of Thermodynamics ▎Thermodynamic
Process ▎Heat Engine ▎Reverse Heat Engine ▎Second law of Thermodynamics ▎

Carnot’s Cycle (Carnot’s Engine) ▎

Thermodynamics Overview
Thermo means heat and Dynamics means movement. Thermodynamics is the study of the
relationship between heat energy and the motion. It provides a framework for understanding how
energy is transferred and transformed. Example, Heat Engines; devices that convert heat energy
into work, such as internal combustion engines and refrigerators. Thermodynamics is the branch
of physics that deals with the relationships between heat, work, and energy. It defines the
fundamental physical quantities, such as energy, temperature, and entropy, that characterize
thermodynamic systems at thermal equilibrium.

Concepts of Thermodynamics
- System: a system is a region of space where changes due to thermodynamic processes are being
studied.
- Surroundings: Everything outside the system is called the surrounding. In thermodynamics,
systems are classified based on how they interact with their surroundings. The two primary types
of systems are:
i. Open System: An open system can exchange both matter and energy with its surroundings.
This means that mass can enter or leave the system, along with energy in the form of heat or
work. A common example of an open system is a boiling pot of water, where steam (matter)
escapes into the air, and heat is transferred to the water from the stove.
ii. Closed System: A closed system can exchange energy but not matter with its surroundings. In
this type of system, the total mass remains constant, but energy in the form of heat or work can
still be transferred in or out. An example of a closed system is a sealed container of gas that can
be heated or cooled; while the gas cannot escape, it can still absorb or release heat.
These classifications help in analyzing and understanding the behavior of different systems in
thermodynamic processes.

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 Fig 1: thermodynamic system

- Wall: a wall refers to the boundary that separates a system from its surroundings. The wall can
influence the transfer of energy and matter between the system and its surroundings. There are
two primary types of walls in thermodynamic systems:
i. Diathermal Wall: A diathermal wall allows the transfer of heat (thermal energy) between the
system and its surroundings but does not permit the transfer of matter. This type of wall is often
used to model situations where temperature differences exist, and heat exchange occurs, such as
in a heat exchanger. An example of a diathermal wall could be a thin metal wall separating two
chambers at different temperatures.
ii. Adiabatic Wall: An adiabatic wall prevents the transfer of heat between the system and its
surroundings. This means that no heat can enter or leave the system through this type of wall,
making it ideal for analyzing processes where thermal energy is conserved. An example of an
adiabatic wall might be an insulated container that prevents heat exchange with the environment.
These two types of walls are essential for understanding various thermodynamic processes and
their implications on energy transfer and conservation within a system.

Key Parameters in a Thermodynamic System

1. Pressure (P): Pressure is the force exerted per unit area by the molecules of a substance on the
walls of its container. It is commonly measured in pascals (Pa) or atmospheres (atm). In a gas,
pressure can be influenced by temperature and volume according to the ideal gas law.
2. Volume (V): Volume is the amount of space occupied by a substance, typically measured in
cubic meters (m³) or liters (L). In thermodynamics, it is an important parameter that affects
pressure and temperature relationships in gases and liquids.
3. Heat Content (Enthalpy, Q): Heat content, often represented as enthalpy (Q), is a measure of
the total heat energy of a system at constant pressure. It accounts for the internal energy of the
system plus the product of its pressure and volume (Q = U + PV). Enthalpy changes are
particularly important in processes involving heat transfer.

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4. Energy (U): Energy, specifically internal energy (U), is the total energy contained within a
thermodynamic system due to the kinetic and potential energies of its molecules. It includes
thermal energy, chemical energy, and other forms of energy present in the system.
5. Temperature (T): Temperature is a measure of the average kinetic energy of the particles in a
substance. It determines the direction of heat transfer between systems and is measured in
degrees Celsius (°C), Kelvin (K), or Fahrenheit (°F).
These parameters are fundamental to understanding thermodynamic processes and the behavior
of systems in various conditions.

Mayer’s Relation.
Meyers relation tells us the relationship between heat required at constant pressure and heat
required at constant volume
Let us consider two scenarios
1. Consider one of an ideal gas that is enclosed in a cylinder by a light, frictionless airtight piston.
Let P, V, and T be the pressure, volume and temperature respectively of the gas. If the gas is
heated so that its temperature rises by dT, but the volume remains constant, then the amount of
heat supplied (dQ1) is used to increase the internal energy of the gas (dU). Since the volume of
the gas is constant, no work is done in moving the piston.
Therefore,
dQ1 = dU =CvdT (1)
where Cv is the molar specific heat of the gas at constant volume.
2. On the other hand, if the gas is heated to the same temperature, at constant pressure, the
volume of the gas increases by an amount say dV. The amount of heat supplied to the gas
increase the internal energy of the gas as well as to move the piston backward to allow expansion
of the gas. The work done to move the piston dw = PdV.
Therefore
dQ2 = dU + dw = CpdT (2)
where Cp is the molar specific heat of the gas at constant pressure.
From equation (1) and (2),
CpdT = CvdT + dw
(Cp – Cv)dT = PdV (3)
For one mole of gas,
PV = K = RT Boyles law.

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Therefore,
PdV = RdT, since pressure is constant (4)
Substituting equation (3) into equation (4)
(Cp – Cv)dT = RdT
Therefore,
Cp – Cv = R. This is known as Meyer’s relation between Cp and Cv
Specific Heat of a Gas: It is the amount of heat required to raise the temperature by 1 oC

Laws of Thermodynamics
A. Zeroth law of thermodynamics.
Assuming there are two system A and B connected to each other with a wall between them as
shown in fig-2a, the energy of A will flow to B and energy of B will also flow to A, depends on
whether the wall is diathermic or adiabatic. Suppose the wall is diathermic (allow heat to pass),
there will be transmission of heat between the two system but after sometimes, the heat
transmission will stop, at that time, the system is said to be in a state of thermal equilibrium. That
is, System A and B are in thermal equilibrium. Assuming there are another systems A and C in
thermal equilibrium as shown in fig-2b. Connecting systems B and C together across a
diathermic wall, and already in thermal equilibrium as shown in fig-2c. This means, system A =
system B, system A = system C, and therefore system B = system C.
Zeroth law state that if two system B and C are in thermal equilibrium, separately with system a
A, then B and C are also in thermal equilibrium with each other.
Zeroth law tell us about temperature. It defines temperature as the physical quantity which
determine the direction of flow of heat and it is the one which is equal in a state of equilibrium of
two systems

Fig 2: A block diagram describing the Zeroth Law of Thermodynamics

B. First Law of Thermodynamics: Energy cannot be created nor destroyed, but can be converted
from one form to another.

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This law is often expressed as:
ΔQ = ΔU + W or ΔQ = ΔU + pΔV
where ΔU is the change in internal energy, Q is the heat added to the system, W is the work done
on the system, P is the applied pressure and is the change in volume
Example 1: If a system absorbs 500 J of heat and does 200 J of work, what is the change in
internal energy?
Solution
ΔU = Q - W = 500J - 200J = 300J
Example 2: If a gas in a rigid container absorbs 400 J of heat, what is the change in internal
energy?
Solution
Δ U = Q = 400J
Example 3: Given heat of vapourization of water = 2256 J, and 1cm3 water on heating makes
steam of 1670x10-6 m3, calculate the internal energy when water convert to steam. (normal
pressure = 1.018x105)
Solution
2256 = ΔU + 1.013x105 x 1670x10-6
2256 = ΔU + 169.2
ΔU = 2086.8J

Thermodynamic Processes
A thermodynamic process is a transformation from one state to another. The main types of
processes include:
1. Isothermal Process: occurs at constant temperature T=0, while other parameters (volume,
pressure and heat content) change. It is a slow process and the container wall is diathermic.
Equation of process pV = k.
Indicator diagram.

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 Fig 3: indicator diagram of an isothermal process

Applying 1st law of thermodynamics:

ΔQ = ΔU + W,
In isothermal process, temperature remain constant, that is,
Δt = 0, ΔU = 0

Therefore,
ΔQ = ΔW, this means all the heat energy given is converted to work done.

Amount of work done in isothermal process Δw = pΔV,

therefore total work done,

= For one mole of gas

For mole of gas

Where is the number of moles, R is the gas constant, T is the temperature in Kelvin, V2 and V1
are final and initial volumes.

Example 4: Calculate work done during an isothermal expansion of 1 mole of an ideal gas at
300K from a volume of 10L to 20L.

Solution

= 1 x 8.314 x 300 ln(20 / 10) = (2494.2)(0.693) = 1726.5J

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2. Adiabatic Process: Definition: No heat exchange with surroundings (Q = 0).
Heat content in adiabatic remain constant, it is a quick process. The container wall is adiabatic
wall.
Equation of the process: PVγ = k (constant)

PVγ = k = RT

where gamma γ is the ratio of the specific heat of the gas which are specific heat at constant
pressure and specific heat at constant volume, that is,

γ=

Indicator diagram.

Fig 4: indicator diagram of an adiabatic process

Applying first law of thermodynamics: ΔQ = ΔU + ΔW.

In adiabatic process, heat doesn’t change, that is ΔQ = 0,
0 = ΔU + Δw or pΔV = -ΔU.
How much work is done?
Δw = pΔV.
Work done from volume v1 to v2

=k

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Example 5: For an ideal gas undergoing adiabatic expansion where P₁ = 100 kPa, V₁ = 0.5 m³,
V₂ = 1 m³, Assuming γ = 1.4

find P₂

Solution

Using P1V1γ = P2V2γ

P₂ = P₁ (V₁ / V₂)γ = 100kPa (0.5 / 1)1.4

= 100kPa (0.3536) = 35.36kPa

3. Isochoric Process: Volume remains constant (V = 0). All other parameter may change. So, if
the volume is not changing, how much work is done,
Δw = pΔV, since V=0, Δw = 0.
Applying first law,
ΔQ = ΔU, heat given is used only for rise in temperature, no work is done.

Fig 5: indicator diagram of an isobaric process

Hence, all the heat transferred to or from the system contributes to a change in internal energy.
Based on the ideal gas model, the internal energy is:

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 ΔU = TΔS = m Cv ΔT

Where, Cv specific heat capacity at constant volume, m: mass of the gas, ΔT: change in
temperature, ΔS: change in entropy

Example 6: 2 kg of water is heated from 50°C to 80°C in a closed vessel. What will be the
change in the internal energy of the water? (specific heat of water = 4184 J/kg.K)

Solution:

Given: mass of water = 2 kg, T1 = 50°C = 323K, T2 = 80°C = 353K, cv = 4184 J/kg.K

In an isochoric process, work done is 0. Hence the internal energy is only dependent on the heat
absorbed. Thus,

ΔU = ΔQ = mCvΔT

= 2 × 4184 × (353 – 323)

= 2 × 4184 × 30 = ΔU = 251.04 kJ

4. Isobaric Process: Pressure remains constant (P = 0), if P is constant, how much work is done.
Δw = PΔV= p(V2-V1).

Applying 1st law;

ΔQ = ΔU + P(V1-V2),

that is, some of the heat is used to raise the temperature and part of it is used to do the work

ΔQ = nCₚΔ T

Example 7: If 2 moles of gas absorb heat at constant pressure and its temperature rises from 300
K to 400 K (Cₚ = 29 J/(mol⋅ K) ):

Solution

Q = nCₚΔ T = (2) (9) (100) = 5800J

Example 8: During an isobaric expansion, a gas absorbs 100 J of heat and the pressure of gas
is 10 atm. If the initial volume is 1 m3 and the final volume is 4 m3, find the change in internal
energy.

Solution

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 Given, Q = 100 J, P = 10 atm, V1 = 1 m3 V2 = 4 m3

Change in internal energy U for an isobaric process is given by △U = Q - W

where, W = P(V2 - V1)

W = 10(4 - 1) = 10.3 = 30

U = 100 – 30 = 70J

5. Cyclic Process: It is a combination of processes so that final parameters ss the same as initial
parameters. It is the process in which the initial and final states are the same.

Figure 6: cyclic process

When a system undergoes a cyclic process, its initial and final internal energies are equal. Hence,
the internal energy change in any cyclic process is zero. Applying the first law of
thermodynamics to a cyclic process, we get,
ΔQ = ΔU + W as ΔU = 0
Therefore, ΔQ = W.
hence the work done by the system in a cyclic transformation is equal to the heat absorbed by the
system. The network involved in a cyclic process is the area enclosed in a P-V diagram. If the
cycle goes clockwise, the system does work. If the system goes anticlockwise, then the work is
done on the system every cycle. An example of such a system is a refrigerator or air condition.

Heat Engine
A heat engine is a machine that converts heat energy into work (mechanical energy). It
withdraws heat from the reservoir, a hot body, and then carries out some work using it. Some
heat energy is released to the sink, a cold body. Hence, some part of heat energy will be wasted-

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fuel, fuels like coal, gasoline, and wood release energy when burnt in the engine. Since engines
work by burning the fuels to release heat, they are termed heat engines. The figure below shows
a block diagram of a working of heat engine.

Fig 7: indicator diagram of an isobaric process

 Source or reservoir; source of the heat, it provides heat to the engine.

 Sink or cold reservoir: it absorbs waste heat from the engine
 working substance: the fluid or gas that undergoes thermodynamics process within the
engine. It takes heat from source, expand (perform work) and then rejected to the sink.

Here, the heat, Q1 is taken from the source, which is at high temperature T1. The engine performs
work, W using that heat, and the remaining heat, Q2 is dumped into the sink at the low
temperature T2. Hence, it can be concluded that not all the heat energy taken from the source is
used to perform work, but some part of the energy is also dumped into the sink. So, how much
work is done?

P-V diagram of heat engine: figure 6, shows the working of heat engine with the help of a
Pressure-Volume (P-V) diagram

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 Fig 8: indicator diagram of an isobaric process

The loop of the P-V diagram depicts the amount of work done by the heat engine. Let us try to
understand each step one by one-

o A→B (Isothermal Expansion): During this process, the temperature of source is T 1 and ideal
gas will draw Q1 amount of heat from it. Here, the expansion is isothermal so there is no
change in internal energy. So, the heat absorbed by the gas will be equal to the work done by
it on the environment.
o B→C (Adiabatic Expansion): During this step, the temperature of an ideal gas decreases
from source temperature, T1 to the sink temperature, T2. The pressure reduces but the volume
increases as no amount of heat energy is being supplied to gas as it expands.
o C→D (Isothermal Compression): During this process, the sink temperature, T2 further
reduces as it rejects Q2 amount of heat to the sink.

o D→A (Adiabatic Compression): In this step, the temperature naturally rises from T 2 to T1
and as a result, the working substance returns to its original state and that’s how one cycle of
the heat engine is completed.

Efficiency of a Heat Engine:

The efficiency of heat engine is mathematically defined as the fraction of the work done by the
working substance to the amount of heat input (at high temperature).

Efficiency, η =

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Thus,

Therefore,

Example 9: A heat engine receives 800J of heat from the hot reservoir and does work of 300J.
calculate the efficiency of the engine and the heat rejected to the cold reservoir
Solution

i. Efficiency, η = =

Therefore, the efficiency of the engine is 37.5%

ii. Heat rejected

Therefore, the heat rejected to the cold reservoir is 500J

Example 10: Consider a Carnot engine operating between a hot reservoir at T = 600K and a
cold reservoir at T = 300K. If the engine absorbs heat of 1200J from the hot reservoir. Calculate
(i) the efficiency of the engine (ii) The work done by the engine (iii) the heat rejected to the cold
reservoir

Solution

(i) Efficiency, η of the Carnot engine:

Thus, efficiency is 50%

(ii) Work done by the engine (W)

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(iii) Heat rejected to the cold reservoir ( )

Using the law of thermodynamics,

Reversed Heat Engine

Heat transfer naturally occurs only from higher temperature bodies to lower temperature ones but
never in the reverse direction. Heat transfer in the direction is only possible with the addition of
external work.
Reversible heat engine uses the same working principle as heat engine that include a heat transfer
between a cold region and a hot one. However, reverse heat engines also transfer energy in reverse
direction. Instead of transferring energy from a higher region to a lower one, reverse heat engine
transfer energy from the colder reservoir to the higher temperature system by adding work.
Reverse engines convert thermal energy into mechanical work by transferring energy between a hot
reservoir and a cold reservoir using a cyclical process. The flow of energy is shown below in figure
7, where the energy is transferred from a lower temperature region to the surroundings (a higher
temperature region) by adding work. As this process cannot happen naturally, an electric
compressor is used to pump heat out of the system.

Figure 9: Reversible heat engine energy flow diagram

The amount of energy discharged into the surroundings (Q1) in Joules by a reverse heat engine is
expressed as the sum of the work (W) and the heat transfer from a lower temperature (Q2) measured
in Joules.

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Applications of Reverse Heat Engines
There are two main reverse heat engine applications: heat pumps and refrigerators, which are
designed to remove heat from a cold region and transfer it to a hotter one.
Refrigerators
Refrigerators and air conditioners are used to cool down a space by removing heat. Work is done on
the system, using a motor to pump warm air inside the fridge to the environment, which is a higher
temperature region. The process involves a fluid that is circulated through a closed system:

1. The fluid passes through a nozzle and expands, which turns it into a gas that cools down. This is
known as an adiabatic expansion, where energy or mass is not transferred to the environment.
2. The cooler gas is transferred into the inner space of the fridge, which has a higher temperature.
Heat is transferred from the fridge to the gas, increasing its temperature. This is known as an
isobaric expansion, which means that the pressure is constant.
3. The gas is then transferred to a compressor, which adds work to the system. The compressed gas
is heated and becomes a liquid again.
4. The hot liquid goes through coils located on the outside of the fridge, and heat is transferred to
the room. This is known as isobaric compression.

Coefficient of Performance (COPreff)

The amount of heat removed from the fridge per work is given by the coefficient of performance
(COPref). It is a measure of the amount of heat transfer from the cold region compared to the work
input to the system.
Using the relation between work and heat transfer in a reverse heat engine, we get the following
equation for the coefficient of performance:

Efficiency
The efficiency of a reverse heat engine is the amount of heat transfer that is actually converted into
work. This is determined by dividing work by the heat transfer Q2. Then, a relation can be written
for the COPreff and the efficiency determined, as seen below.

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 and

Example 11: A refrigerator has a COP of 4.8 and uses 400 J of work. Determine the heat
transferred and the efficiency of the refrigerator.
Solution

= x W = 4.8 x 400 =1920J

efficiency

Where
= 400 + 1920 = 2320J

Second Law of Thermodynamics

While the first law of thermodynamics gives information about the quantity of energy transfer as
a process, it fails to provide any insights about the direction of energy transfer and the quality of
the energy.
The second law clearly explains that it is impossible to convert heat energy to mechanical energy
with 100 per cent efficiency. For example, if we look at the piston in an engine, the gas is heated
to increase its pressure and drive the piston. However, even as the piston moves, there is always
some leftover heat in the gas that cannot be used for carrying out any other work. Heat is wasted,
and it has to be discarded. In this case, it is done by transferring it to a heat sink or in the case of
a car engine, waste heat is discarded by exhausting the used fuel and air mixture to the
atmosphere. Additionally, heat generated from friction that is generally unusable should also be
removed from the system.
Different Statements of the Law
There are two statements on the second law of thermodynamics, and they are
1. Kelvin- lank Statement
2. Clausius Statement
Kelvin-Planck Statement

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It is impossible for a heat engine to produce a network in a complete cycle, if it exchanges heat
only with bodies at a single fixed temperature.
Clausius’s Statement
The second law of thermodynamics states that heat transfer naturally only occurs from higher
temperature bodies to lower temperature ones. A reverse direction transfer is only possible with the
addition of external work.

The Carnot engine is a theoretical thermodynamic cycle proposed by Leonard Carnot. It

estimates the maximum possible efficiency that a heat engine during the conversion process of
heat into work and, conversely, working between two reservoirs can possess.
Carnot Theorem
According to Carnot Theorem:
Any system working between T1 (hot reservoir) and T2 (cold reservoir) can never have more
efficiency than the Carnot engine operating between the same reservoirs.
Also, the efficiency of this type of engine is independent of the nature of the working substance
and is only dependent on the temperature of the hot and cold reservoirs.

Carnot Cycle
A Carnot cycle is defined as an ideal reversible closed thermodynamic cycle. Four successive
operations are involved: isothermal expansion, adiabatic expansion, isothermal compression, and
adiabatic compression. During these operations, the expansion and compression of the substance
can be done up to the desired point and back to the initial state.

Figure 10: Four cylinder depicting Carnot cycle process

Following are the four processes of the Carnot cycle:

Step 1:

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Isothermal expansion: The gas is taken from P1, V1, T1 to P2, V2, T2. Heat Q1 is absorbed from
the reservoir at temperature T1. Since the expansion is isothermal, the total change in internal
energy is zero, and the heat absorbed by the gas is equal to the work done by the gas on the
environment, which is given as:

Step 2:
Adiabatic expansion: The gas expands adiabatically from P2, V2, T1 to P3, V3, T2.
Here, work done by the gas is given by:

Step 3:
Isothermal compression: The gas is compressed isothermally from the state (P3, V3, T2) to (P4,
V4, T2).
Here, the work done on the gas by the environment is given by:

Step 4:
Adiabatic compression: The gas is compressed adiabatically from the state (P 4, V4, T2) to (P1, V1,
T1).
Here, the work done on the gas by the environment is given by:

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 Figure 11: Carnot cycle P-V diagram

Hence, the total work done by the gas on the environment in one complete cycle is given by:

Since the step 2–>3 is an adiabatic process, we can write T1v2Ƴ-1 = T2v3Ƴ

or

Similarly, for the process 4–>1, this can be written as

This implies,

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So, the expression for net efficiency of Carnot engine reduces to:

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