Chapter 6: Thermodynamic Fundamentals and First Law

Basics of Thermal Physics ....................................................................................................................... 1

Thermodynamic Process .......................................................................................................................... 1

Reversible and Irreversible Process ......................................................................................................... 2

Reversible Process ............................................................................................................................... 2

Irreversible Process .............................................................................................................................. 3

Internal Energy (U) .................................................................................................................................. 3

First Law of Thermodynamics ................................................................................................................. 3

Applications of the First Law of Thermodynamics ............................................................................. 4

Heat and Work ......................................................................................................................................... 6

Relationship Between CV and CP ............................................................................................................. 7

Relationships of T, P and V ..................................................................................................................... 8

Work Done in Isothermal and Adiabatic Process .................................................................................... 9

Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU

 PHY103/Ch.6/2022-23

Basics of Thermal Physics

System, Walls and Surroundings: In thermodynamics, a system refers to certain portion of the
universe bound within some closed surface. The closed surface is called the boundary or wall.
Everything outside the boundary which has a direct bearing on its behavior is known as the surroundings.
There are three kinds of thermodynamic system:
1. Open system: A system that can exchange matters with its surroundings is called open system.
2. Closed system: If no matter can cross the boundary, the system is called closed system.
3. Isolated system: If no energy can interchange between surrounding and system then the system is
called isolated system.

State Variables: The state of a system is specified by the values of certain experimentally measurable
quantities called state variables or state functions on properties.
It can be divided into two classes.
1. Intensive variables: The state variables which are independent of mass of the system are called
intensive variables or properties. Examples: Pressure (P), Tension (𝜏), Surface tension (S), EMF etc.
2. Extensive variables: The state variables which are dependent on proportional to the mass of the
system are called extensive variables or properties. Examples: Volume (V), Length (L), Area (A),
Charge (q) etc.

Thermodynamic equilibrium: A thermodynamic equilibrium state is one in which all the bulk physical
properties (state variables) of the system are uniform throughout the system and do not change with
time. It has to be three conditions:
1. Thermal equilibrium: Thermal equilibrium means the temperature is same at all points between the
system and surroundings.
2. Mechanical equilibrium: Mechanical equilibrium means there is no unbalance forces are working in
the interior of the system or between the system of the surroundings.
3. Chemical equilibrium: In this equilibrium, no chemical reactions and transfer of matter are
happening.

Thermodynamic Process
In thermodynamic, we are concerned with the change of different state variables that occur when a
system changes from one equilibrium state to another. A process is the mechanism of bringing about
such a change. These initial and final equilibrium states are called the end points of the process.
The various types of thermodynamic process are:
1. Quasistatic process: During a process if at every instant the system departs only infinitesimally
from an equilibrium state, then the process is called quasistatic. A quasistatic process closely
approximates a succession of equilibrium states. If there are finite departures the process is non-
quasistatic. Quasistatic process is an idealized process. This process can never be obtained in
laboratory.
2. Isothermal process: A process in which temperature remains constant is called isothermal process.
For an isothermal process, 𝑑𝑇 = 0.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
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3. Isochoric process: A process in which volume of the system remains constant is called isochoric
process. In an isochoric process, 𝑑𝑉 = 0.
4. Isobaric process: A process in which pressure of the system remains constant is called isobaric
process. The process is also known as isopiestic process. In an isobaric process, 𝑑𝑃 = 0.
5. Adiabatic process: The process in which no heat can flow into or out of the system is called
adiabatic process. For an adiabatic process, 𝑑𝑄 = 0.
6. Reversible process: A reversible process can be defined as one whose direction can be reversed by
an infinitesimal change is some property of the system. Reversible process are quasistatic processes
where no dissipative effects such as friction, viscosity, electrical resistance are present.
7. Irreversible process: If there is a finite temperature difference between system and surroundings,
the direction of the heat flow cannot be reversed by an infinitesimal change in temperature of the
system, then it is said to be an irreversible process. This process is non-quasistatic process.

Reversible and Irreversible Process

Reversible Process
A reversible process is one which can be retracted in opposite direction by changing the external
conditions infinitesimally.
The reversible process involves a substance going through all stages of the direct process, repeating all
changes in the direct process in the opposite order, without any changes in the bodies or surroundings.
If heat is absorbed in the direct process, it will be released in the reverse process, and if work is done in
the direct process, there will be no energy wastage.
A gas enclosed in a cylinder and immersed in a constant-temperature water tank is compressed slowly
to maintain its temperature. This process requires small pauses to allow heat to escape. If the gas is
allowed to expand isothermally, the same amount of heat is received during expansion as during
compression. This reversible process occurs when the gas is expanded infinitely small and the
compression is repeated. However, this process is not reversible if heat loss occurs due to friction,
radiation, or conduction. Rapid changes in the gas's volume make the process unreversible, as the energy
used to overcome friction cannot be retraced.
The conditions of reversibility for any heat engine or process can be stated as follows:
➢ The pressure and temperature of the working substance must not differ appreciably from those
of the surrounding at any stage of the cycle of operation.
➢ All the processes taking place in the cycle of operation must be infinitely slow.
➢ The working parts of the engine must be completely free from friction.
➢ There should not be any loss of energy due to conduction, convection or radiation during the
cycle of operation.
It should be remembered that the complete reversible process or cycle of operation is only an ideal case.
In an actual process, there is always loss of heat due to friction, conduction, convection or radiation.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
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Irreversible Process
In nature all changes are irreversible because of the following reasons: (1) The conditions for
thermodynamic equilibrium i.e., mechanical, thermal or chemical equilibrium are not satisfied because
a natural process does not take place quasi-statically. (2) Dissipative effects, such as friction, viscosity,
inelasticity, electric resistance, eddy-formation etc. are always present.
Examples of some natural irreversible processes are: spontaneous expansion of a gas into an evacuated
space, spontaneous conduction of heat along a metal bar which is hot at one end and cold at the other,
transfer of heat by radiation from a hotter to a colder body, transfer of electricity through a resistor.
Nonetheless reversible processes are most important in thermodynamics because they can be handled
analytically.

Internal Energy (U)

The energy content of a system is called its internal energy. It is the sum of following forms of energy
of the system:
i. kinetic energy due to translational, rotational and vibrational motion of the molecules, all of which
depend only on the temperature,
ii. potential energy due to intermolecular forces, which depends on the separation between the
molecules, and
iii. the energy of electrons and nuclei.
In practice, it is not possible to measure the total internal energy of a system in any given state. Only
change in its value can be measured.
If the state of the system is changed from an initial state 1 to a final state 2, by supplying heat Q to the
system and if W is the work done by the system during the change, then increase in the internal energy
of the system is given by
(𝑈2 − 𝑈1 ) = 𝑄 − 𝑊
where 𝑈₁ is the internal energy in state 1, and 𝑈2 the internal energy in state 2.

First Law of Thermodynamics

Statement: Statement: When a certain amount of heat Q is supplied to a system which does external
work W in passing from state 1 to state 2, the amount of heat is equal to sum of the increase in the
internal energy of the system and the external work done by the system.
It also known as the energy equation.
Explanation: It is also known as the conservation of energy: if one has a system and puts heat into it,
and does work on it, then its energy is increased by the heat put in and the work done. We can write this
as follows: The heat Q put into the system, plus the work W done on the system, is the increase in the
energy U of the system; the latter energy is sometimes called the internal energy.
This is saying that the adiabatic work in a process is path independent, depends only on the end points.
As work is not a state function, there must exist a state function whose difference between two end
points is equal to the adiabatic work (𝑊𝑎𝑑 ). This state function is called internal energy, 𝑈 and

𝑊𝑎𝑑 = ∆𝑈 = 𝑈2 − 𝑈1 …………………..(6.1)
If the system is not thermally isolated, the work is then path dependent. Now for a given change,
∆𝑈 = 𝑈2 − 𝑈1 is fixed, but 𝑊 is not equal to ∆𝑈. In other words, there is a difference between adiabatic
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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
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work required to bring about a change between two equilibrium state and then non-adiabatic work
required to effect the same change, with the latter having an infinite number of possible values.

The difference between ∆𝑈 and 𝑊 is called the heat Q. The generalization of Eq. (6.1) is
𝑄 = ∆𝑈 + 𝑊 …………………..(6.2)
This is the mathematical statement of the first law. It tells us that the internal energy can be increased
either by doing work on the system on by supplying heat to it. It is true for all processes whether
reversible on irreversible.
For infinitesimal process, the first law is
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 …………………..(6.3)
For a reversible process, 𝑑𝑊 = 𝑃𝑑𝑉
Hence, 𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉 …………………..(6.4)

Limitation of the First Law

The first law is universal and exact. But it does not give us any information as to whether any particular
process can actually occur. For example, for a metal bar, hot at one end and cold at the other end the
heat always flows spontaneously from hot to cold end and until the bar attains uniform temperature. We
never observe the reverse happening spontaneously, even though it would not violate the first law since
one still has an energy balance before and after the change. Therefore, A directional law is needed which
limits the way energy may be transferred or transformed – that is where the second law comes in.

Applications of the First Law of Thermodynamics

1. Adiabatic processes: An adiabatic process is one that
occurs so rapidly or occurs in a system that is so well
insulated that no transfer of energy as heat occurs between
the system and its environment. Putting Q = 0 in the first law
(6.2) yields
∆𝑈 = −𝑊 … … … … … … … (6.5)
This tells us that if work is done by the system (that is, if W
is positive), the internal energy of the system decreases by
the amount of work. Conversely, if work is done on the
system (that is, if W is negative), the internal energy of the
system increases by that amount.
Figure 6.1 shows an idealized adiabatic process. Heat cannot
enter or leave the system because of the insulation. Thus, the
only way energy can be transferred between the system and
its environment is by work. If we remove shot from the Fig. 6.1: An adiabatic expansion can
piston and allow the gas to expand, the work done by the be carried out by slowly removing
system (the gas) is positive and the internal energy of the gas lead shot from the top of the piston.
Adding lead shot reverses the process
decreases. If, instead, we add shot and compress the gas, the
at any stage.
work done by the system is negative and the internal energy
of the gas increases.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.6/2022-23

2. Constant-volume processes: If the volume of a system (such as a gas) is held constant, that system
can do no work. Putting W = 0 in the first law (Eq. 6.2) yields
∆𝑈 = 𝑊 (constant-volume process) …………..(6.6)
(6.2) Thus, if heat is absorbed by a system (that is, if Q is positive), the internal energy of the system
increases. Conversely, if heat is lost during the process (that is, if Q is negative), the internal energy of
the system must decrease.

3. Cyclical processes: There are processes in which, after

certain interchanges of heat and work, the system is restored to
its initial state. In that case, no intrinsic property of the
system—including its internal energy—can possibly change.
Putting ∆𝑈 = 0 in the first law (Eq. 6.2) yields
𝑄 = 𝑊 (cyclical process) ……………. (6.7)
Thus, the net work done during the process must exactly equal
the net amount of energy transferred as heat; the store of
internal energy of the system remains unchanged. Cyclical
processes form a closed loop on a p-V plot, as shown in Fig. Fig. 6.2: The net work 𝑊𝑛𝑒𝑡 done by
6.2. the system during a complete cycle
is represented by the shaded area.

4. Free expansions: These are adiabatic processes in which no

transfer of heat occurs between the system and its environment
and no work is done on or by the system. Thus, Q = W = 0, and
the first law requires that
𝑑𝑈 = 0 (free expansion)………………(6.8)

Figure 6.3 shows how such an expansion can be carried out. A

gas, which is in thermal equilibrium within itself, is initially
confined by a closed stopcock to one half of an insulated
double chamber; the other half is evacuated. The stopcock is
opened, and the gas expands freely to fill both halves of the Fig. 6.3: The initial stage of a free
chamber. No heat is transferred to or from the gas because of expansion process. After the
the insulation. No work is done by the gas because it rushes stopcock is opened, the gas fills
into a vacuum and thus does not meet any pressure. both chambers and eventually
reaches an equilibrium state.
A free expansion differs from all other processes we have
considered because it cannot be done slowly and in a controlled way. As a result, at any given instant
during the sudden expansion, the gas is not in thermal equilibrium and its pressure is not uniform. Thus,
although we can plot the initial and final states on a p-V diagram, we cannot plot the expansion itself.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.6/2022-23

Heat and Work

If the system is not thermally isolated, then the work W done in taking the system between a pair of
equilibrium points depends on the path. For a given change, 𝛥𝑈 = 𝑈2 − 𝑈1 is fixed, but W is not now
equal to ΔU. In other words, there is a difference between the adiabatic work required to bring about a
change between two equilibrium states and the nonadiabatic work required to effect the same change,
with the latter having an infinite number of possible values. The difference between ΔU and W is called
the heat Q.
The first law says that the internal energy can be increased either by doing work on the system or by
supplying heat to it. In this form, it is true for all processes whether reversible or irreversible.
There has to be a sign convention for heat, just as there is for work. Heat Q is defined to be positive
when it enters the system.
The exchange of energy just described happens quite naturally whenever there is a temperature
difference between a system and its surroundings, unless prevented by an adiabatic barrier. The direction
of heat flow is always from higher to lower temperature. Thus, an alternative definition of heat is the
energy that flows spontaneously from an object with higher temperature to an object with lower
temperature.

Fig. 6.4: An illustration of the difference between work and heat. The
input of energy into the system is in (a) as work and in (b) as heat.

In some cases the distinction between heat and work is obvious. For example, if a gas is compressed or
expanded by motion of a piston, any change in internal energy resulting from the piston’s motion is due
to work W. If the process is an isothermal one, the gas must in the same process experience a flow of
heat Q with its surroundings. Just to be clear, under isothermal compression W is positive and Q is
negative, and under isothermal expansion W is negative and Q is positive, so that in either case the
internal energy is unchanged by the first law (Equation 3.2).
As another example, consider Figure 6.4 showing a gas in a container with rigid diathermal walls. A
current I flows through the heating coils of resistance R wrapped around the container. In Figure 6.4a,
the system denoted by the dashed line, includes the heating coils.Work is being done on the system at
the rate I2R because the current I enters the system. The energy crossing the system boundary is in the
form of work. In Figure 6.4b, the system is the gas and container alone, excluding the coils. Here, no
work is done on the system but there is energy flow across the system boundary in the form of heat
because the temperature of the coils is higher than that of the gas. This simple example shows that, in
distinguishing between heat and work, it is very important to be clear as to what constitutes the system.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.6/2022-23

Relationship Between CV and CP

The amount of heat required to raise the temperature of unit mass of a substance by 1 Kelvin is called
specific heat.
Let us apply the first law of thermodynamic to a substance of unit mass. As the substance absorbed dQ
amount of heat and expands by a volume dV against the uniform external pressure P, we write the first
law as,
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 … … … … (6.9)
Let us consider, 𝑈 = 𝑈(𝑉, 𝑇)
Hence,
𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( ) 𝑑𝑉 + ( ) 𝑑𝑇 … … … … (6.10)
𝜕𝑉 𝑇 𝜕𝑇 𝑉
From Eq. (6.9) and Eq. (6.10), we can write
𝜕𝑈 𝜕𝑈
𝑑𝑄 = ( ) 𝑑𝑉 + ( ) 𝑑𝑇 + 𝑃𝑑𝑉
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑈 𝜕𝑈
= ( ) 𝑑𝑇 + [( ) + 𝑃] 𝑑𝑉 … … … … (6.11)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
For an isochoric process, 𝑑𝑉 = 0 and so that
𝜕𝑈
𝑑𝑄 = ( ) 𝑑𝑇
𝜕𝑇 𝑉
𝑑𝑄 𝜕𝑈
⇒( ) =( )
𝑑𝑇 𝑉 𝜕𝑇 𝑉
Therefore,
𝑑𝑄 𝜕𝑈
𝐶𝑉 = ( ) = ( ) … … … … (6.12)
𝑑𝑇 𝑉 𝜕𝑇 𝑉
where CV is the specific heat for constant volume.

For an isobaric process, 𝑑𝑃 = 0 and so that

𝜕𝑈 𝜕𝑈
𝑑𝑄 = ( ) 𝑑𝑉 + ( ) 𝑑𝑇 + 𝑃𝑑𝑉
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑈 𝜕𝑈
⇒ 𝑑𝑄 = ( ) 𝑑𝑇 + {𝑃 + ( ) } 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝜕𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
⇒ ( ) = ( ) + {𝑃 + ( ) } ( )
𝜕𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑃
Therefore,
𝜕𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
𝐶𝑃 = ( ) = ( ) + {𝑃 + ( ) } ( ) … … … … (6.13)
𝜕𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑃
where, CP is the specific heat for constant pressure.
Subtracting Eq. (6.12) from Eq. (6.13),
𝜕𝑈 𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = {𝑃 + ( ) } ( ) … … … … … … (6.14)
𝜕𝑉 𝑇 𝜕𝑇 𝑃
This is the general expression for any system.
We use Mayer's hypothesis for an ideal gas which states that there is no change in internal energy with
the change in volume for the ideal gas if the process is isothermal, i.e.,
𝜕𝑈
( ) =0
𝜕𝑉 𝑇

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
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Thus Eu. (6.14) becomes,

𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = 𝑃 (
) … … … … … (6.15)
𝜕𝑇 𝑃
We know 𝑃𝑉 = 𝑅𝑇 for one mole of an ideal gas.
𝑅𝑇
∴𝑉=
𝑃
𝜕𝑉 𝑅
⇒ =
𝜕𝑇 𝑃
𝜕𝑉
⇒ 𝑃( ) = 𝑅
𝜕𝑇 𝑃
Therefore,
𝐶𝑃 − 𝐶𝑉 = 𝑅
where R is the universal gas constant. i.e., the difference in the specific heat of a perfect gas at constant
pressure and constant volume, respectively is equal to the universal gas constant, R.

Relationships of T, P and V
Whenever a system consisting of a unit mass, absorbs dQ amount of heat and performs dW amount of
external work against a uniform external pressure P, we know from the first law that,
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 … … … … (6.16)
and also
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 … … … … (6.17)
𝑑𝑈
[Since 𝐶𝑉 = ]
𝑑𝑇
From Eq. (6.16), we can write
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉 … … … … (6.18)
We know, 𝑃𝑉 = 𝑅𝑇 for one mole of an ideal gas.
'N
Differentiating,
𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑅𝑑𝑇
𝑜𝑟, 𝑃𝑑𝑉 = 𝑅𝑑𝑇 − 𝑉𝑑𝑃
So that Eq. (6.18) becomes,
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑑𝑇 − 𝑉𝑑𝑃
⇒ 𝑑𝑄 = (𝐶𝑉 + 𝑅)𝑑𝑇 − 𝑉𝑑𝑃
⇒ 𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑉𝑑𝑃 … … … … … (6.19)
Since we are concerned about an adiabatic process, we have 𝑑𝑄 = 0.
Then from Eq. (2) and Eq. (3), we get
𝐶𝑉 𝑑𝑇 = −𝑃𝑑𝑉 … … … … (6.20)
𝐶𝑃 𝑑𝑇 = 𝑉𝑑𝑃 … … … … … (6.21)
Dividing Eq. (6.21) by Eq. (6.20) we have
𝐶𝑃 𝑉𝑑𝑃
=−
𝐶𝑉 𝑃𝑑𝑉
𝐶𝑃 𝑉𝑑𝑃
⇒𝛾= =−
𝐶𝑉 𝑃𝑑𝑉

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU
 PHY103/Ch.6/2022-23

𝑑𝑉 𝑑𝑃
⇒ 𝛾. =−
𝑉 𝑃
On integration the both sides, we get
𝛾 ln 𝑉 = − ln 𝑃 + ln 𝐶
where ln 𝐶 is a constant.
⇒ ln 𝑉 𝛾 + ln 𝑃 = ln 𝐶
⇒ 𝑃𝑉 γ = constant … … … … … (6.22)
Using 𝑃𝑉 = 𝑅𝑇
𝑅𝑇 𝑅𝑇
𝑜𝑟, 𝑉 = , 𝑜𝑟 𝑒𝑙𝑠𝑒 𝑃 =
𝑃 𝑉
Now from Eq. (6.22),
𝑅𝑇 γ
𝑃. ( ) = constant
𝑃
𝑅𝛾 𝑇 𝛾
⇒ 𝑃. 𝛾 = constant
𝑃
⇒ 𝑇 𝛾 𝑃1−𝛾 = constant
1−𝛾
⇒ 𝑇𝑃 𝛾 = constant … … … … … (6.23)
And,
𝑅𝑇 γ
. 𝑉 = constant
𝑉
⇒ 𝑅𝑇𝑉 γ−1 = constant
⇒ 𝑇𝑉 γ−1 = constant … … … … … (6.24)
Equations (6.22), (6.23) and (6.24) are the adiabatic equations of a perfect gas.

Work Done in Isothermal and Adiabatic Process

Home Work

Problems
1. Problem: A quantity of air at 27°C and atmospheric pressure is suddenly compressed one third of its
original volume. Find the final pressure and temperature.
2. Air is compressed adiabatically to half its original volume. If the air was initially at 27°C and at
atmospheric pressure, then calculate the final temp. and pressure.
3. At 290 K, 15 m3 gas was compressed adiabatically from 1 atm to 6.5 atm pressure. Calculate the
final temp. and volume. (𝛾 = 1.2)
4. A certain mass of gas at NTP is expanded to double its volume under adiabatic conditions. Calculate
the resulting temp. and pressure. (𝛾 = 1.40)
5. Calculate the work done in adiabatic expansion of one mole of an ideal gas.

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Arpon Chakraborty, Lecturer, Department of Physics, BSMRSTU