Thermodynamic Process

When the system undergoes change from one thermodynamic state to final state due change in
properties like temperature, pressure, volume etc., the system is said to have undergone
thermodynamic process. There are various types of thermodynamic processes. Some examples
are: isothermal process, adiabatic process, isochoric process, isobaric process and reversible
process.

In Figure, 1-2 represents a thermodynamic process.

Types of processes:
A thermodynamic process can be carried out in different ways and under different conditions. The
processes can be classified as follows:

Reversible process:

The process in which the system and surrounding can be restored to the initial state from the final
state without producing any changes in the thermodynamic properties of the universe is called a
reversible process. There are two important conditions for the reversible process to occur. Firstly,
the process should occur infinitesimally slowly and secondly throughout the process, the system
and surroundings must be in equilibrium with each other.

Irreversible Process:

The process in which the system and surrounding cannot be restored to the initial state from the
final state is called an irreversible process. All the processes occurring in nature are irreversible
processes. During the irreversible process the system and surroundings are not in equilibrium with
each other.

Adiabatic process:

An adiabatic process is defined as one in which there is no exchange of heat between the system
and surrounding during the process. Those processes in which no heat can flow into or out of the
system are called adiabatic processes.

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This condition is attained by thermally insulating the system. In an adiabatic process if work is
done by the system its temperature decreases, if work is done on the system its temperature
increases, because, the system cannot exchange heat with its surroundings.

For an adiabatic process q = 0

When the adiabatic process is carried out reversibly then it is called isentropic process. Isentropic
process is just a process in which entropy of system remains constant.

Isothermal process:

An isothermal process is defined as one in which the temperature of the system remains constant,
during the change from its initial to final state. The system exchanges heat with its surrounding
and the temperature of the system remains constant. For this purpose the experiment is often
performed in a thermostat.

For an isothermal process dT = 0

Isobaric process

An isobaric process is defined as one in which the pressure of the system remains constant during
its change from the initial to final state.

For an isobaric process dP= 0 .

Isochoric process

An isochoric process (sometimes called isovolumetric or isometric process, Greek roots, 'choric'
translating to 'space' or 'volume') is defined as the one in which the volume of system remains
constant during its change from initial to final state. Combustion of a fuel in a bomb calorimeter
is an example of an isochoric process.

For an isochoric process, dV= 0.

Cyclic process / Thermodynamic Cycle:

When a process or processes are performed on a system in such a way that the final state is identical
with the initial state, it is then known as a thermodynamic cycle or cyclic process.

For a cyclic process dU = 0, dH = 0, dP=0, dV=0, dT=0

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In Figure, 1-A-2 and 2-B-1 are processes whereas 1-A-2-B-1 is a thermodynamic cycle or cyclic
process.

Table: Overview of processes and conditions

Quasi-static or Quasi-equilibrium Process

When the process is carried out in such a way that at every instant, the system deviation from the
thermodynamic equilibrium is infinitesimal, then the process is known as quasi-static or quasi-
equilibrium process and each state in the process may be considered as an equilibrium state.

Consider a system (gas) enclosed in a cylinder and piston arrangement as shown in Figure (a). Let
the system is initially in equilibrium state when the piston L at A, where the pressure is PA, volume
VA and temperature TA as shown in Figure (b). The weight (W) on the piston is composed of
number of small weights which balances the upward force exerted by the system. If the whole
weight is removed from the piston, then there will be unbalanced force between the system and
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the surroundings and the piston will move upwards till it hits the stops at B. At this point B the
system again comes to an equilibrium state where the pressure is PB, volume VB and temperature
TB. But the intermediate states through which the system has passed are non-equilibrium states
whose properties (pressure, volume and temperature) are not uniform throughout the system and
thus the state of the system cannot be well defined. Such a process is called irreversible or non-
equilibrium process, as shown by a broken line in Figure (b).

Now, if the small weights on the piston are removed one by one very slowly, then at any instant
of the upward movement of the piston, the deviation of the state from the thermodynamic
equilibrium will be infinitesimally small, if the gas system is isolated. Thus, every state passed
through by the system will be in equilibrium state. Such a process, which is the locus of all these
equilibrium points passed through the system, is known as quasi-static or quasi-equilibrium
process.

Note: The quasi-static or quasi-equilibrium process is also known as reversible process. A process
which can be reversed in direction and the system retraces the same equilibrium states is known
as reversible process.

A nonquasi-equilibrium process is denoted by a dashed line between the initial and final states
instead of a solid line.

QUASI-EQUILIBRIUM PROCESSES
A quasi-equilibrium process is one in which the system remains very nearly at equilibrium at all
times during the process.

NON-EQUILIBRUM PROCESSES
A non-equilibrium process is one in which only the initial and final states are states of equilibrium.
During the process (change of state), the system is not in equilibrium---the intensive properties
have different values in different locations in the system and vary with time at any one location.

Work:
In mechanics, work is defined as the product of the force (F) and the distance moved (x) in the
direction of the force. Mathematically, work done.

W= F × x

The unit of work depends upon the unit of force and the distance moved. In S.I. system of units,
the practical unit of work is newton-metre (briefly written as N-m). The work of 1 N-m is known
as joule (briefly written as J) such that l N-m = 1 J.

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In thermodynamics, work may be defined as follows:

1. According to Obert, work is defined as the energy transferred (without the transfer of mass)
across the boundary of a system because of an intensive property difference other than
temperature that exists between the system and surroundings.

In engineering practice, the intensive property difference is the pressure difference. The pressure
difference (between the system and the surrounding) at the surface of the system gives rise to a
force and the action of this force over a distance is called mechanical work.

In some cases, the intensive property difference may be the electrical Potential difference between
the system and the surrounding, In this case, the resulting energy transfer across the system and
boundary is known as electrical work.

2. According to Keenan, work is said to be done by a system during a given operation if the sole
effect of the system on things external to the system (surroundings) can be reduced to the
raising of a weight.

The weight may not be actually raised but the net effect external to the system should be the
raising of a weight.

For example, consider a system consisting of a storage battery, as shown in Figure. The terminals
connected to a resistance, through a switch constitute external to the system (i.e. surroundings).
When the switch is closed for a certain period of time, then the current will flow through the
battery and the resistance, as a result the resistance becomes warmer. This clearly shows that the
system (battery) has interaction with the surroundings. In other words, the energy transfer
(electrical energy) has taken place between the system and the surroundings because of potential
difference (not the temperature).

Now according to the mechanics definition of work, there is no force which moves through a
distance. Thus no work is done by the system. However, according to the thermodynamic
definition, the work is done by the system because the resistance can be, replaced by an ideal
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motor (100% efficient) driving a winding drum, thereby raising a weight. Thus, the sole effect
external to the system (surroundings) has been reduced to the raising of a weight. Hence,
thermodynamic work is done by the system.

Note. The work done by the system is considered as positive work, while the work done on the
system is considered as negative work.

State (Point) Functions and Path Functions

A state (Point) function is a property describes a particular state (Point), without depending on the
path taken to reach this state (Point). In contrast, functions whose value depends on the path taken
to get between two states are called path functions.

To understand the difference between the two, think of two cities, A and B that are 100km away
from each other along a straight line. Roads are rarely built in long straight lines, we may have
two roads linking A and B, with lengths 150km and 200km. So, while the displacement between
the two towns is the same for each route (it is a state/point function), the distance you need to
travel to get from A to B depends on which road you take (it is a path function).

Both path and state functions are often encountered in thermodynamics.

Heat and Work—A Path Function

Consider that a system from an initial equilibrium state 1 reaches to a final equilibrium state 2 by
two different paths 1-A-2 and 1-B-2, as shown in Figure. The processes are quasi-static. When
the system changes from its initial state 1 to final state 2, the quantity of heat transfer will depend
upon the intermediate stages through which the system passes, i.e. its path. In other words, heat
is a path function. Thus, heat is as inexact differential or imperfect differential and is written as
δQ.

Note: An inexact differential or imperfect differential is a type of differential used in

thermodynamics to express changes in path dependent quantities. In contrast, an integral of an
exact differential (a differential of a function) is always path independent since the integral acts
to invert the differential operator. Consequently, a quantity with an inexact differential cannot be
expressed as a function of only the variables within the differential; i.e. its value cannot be inferred
just by looking at the initial and final states of a given system. Inexact differentials are primarily
used in calculations involving heat and work because they are path functions, not state functions.

On integrating, for the path 1-A-2,

2
∫1 δQ = [𝑄]12 = 𝑄1−2 or 1Q2

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 2
It may be noted that ∫1 δQ ≠ Q2 - Q1, because heat is not a point function. Thus, it is meaningless
to say 'heat in a system or heat of a system'. The heat can not be interpreted similar to temperature
and pressure.

The work, like heat, is not a thermodynamic property, therefore it is a path function as its value
depends upon the particular path followed during the process. Now if we consider the path 1-A-
2, then the work done during the process 1-A-2 will be equal to the area under the curve 1-A-2
and if we consider path 1-B-2, then the work done during the path 1-B-2 will be equal to the area
under the curve 1-B-2.

Since the areas under the curves 1 -A-2 and 1 -B-2 ate different, therefore work done by these two
processes will also be different. Hence, work is an inexact differential or imperfect differential
2
and is written as δW. On integration, for the path 1-A-2, ∫1 δW = [𝑊]12 = 𝑊1−2 or 1W2

2
As discussed above, ∫1 δW≠W2–W1, because work is 'not a point function. Thus, it is meaningless
to say 'work in a system or work of a system'. Since the work cannot be interpreted similar to
temperature and pressure of the system, therefore it is a path function and it depends upon the
process. It is not a point function as the temperature and pressure. The work done in taking the
system from state 1 to state 2 will be different for different paths.

Thermodynamic properties are point functions:

A thermodynamic system can be defined by using the variables P, V, T and `n'. A state function is
a thermodynamic property of a system, which has a specific value for a given state and does not
depend on the path (or manner) by which the particular state is reached.

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Example : Pressure (P), Volume (V), Temperature(T), Internal energy (U), Enthalpy (H), free
energy (G) etc.

Thermodynamic properties are point functions, since for a given state, there is a definite value for
each property. During change of states, the values of the properties will change and this change in
values of the properties does not depend on path, but it depends upon end states and hence all the
properties are point functions.

The differentials of point functions are exact or perfect differentials and the integration is simply,
e.g.,
2
∫1 𝑑V = V2 - V1
Operator δ is used to denote inexact differentials, operator d is used to denote exact differentials.

Difference between point function and path function

Point Function Path Function

Its values are based on the state of the system Its values are based on how that particular
(i.e. pressure, volume, temperature etc.) thermodynamic state is achieved.

No matter by which process the state is obtained, Different processes to obtain a particular
its values will always remain the same. state will give us different values.

Only initial and final states of the process are We need to know exact path followed by
sufficient the process

Its values are dependent on the path

Its values are independent of the path followed followed

It is an exact or perfect differential It is an inexact or imperfect differential.

Its cyclic integral is always zero Its cyclic integral may or may not be zero

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It is property of the system It is not the property of the system

Its examples are density, enthalpy, internal

energy, entropy etc. Its examples are Heat, work etc.

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