LAWS OF THERMODYNAMICS

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BHANU PRAKASH

0205-027, B.Tech (4/4)

C.B.I.T
 The four laws of thermodynamics are as follows:

1. ZEROTH LAW OF THERMODYNAMICS:

Scientists: Ralph. H. Fowler

Year: First third of the 20th century

Statement: If two thermodynamic systems are in equilibrium with a third, they are also in thermal
equilibrium with each other.

Basic Principle: This law emerged during the development of temperature and temperature scales,
which is in turn based on the concept of an ideal gas, the second law of thermodynamics and from
statistical mechanics and kinetic theory.

Explanation: It states that if system A is in thermal equilibrium with system B and system B is in
thermal equilibrium with system C then the system A is also in thermal equilibrium with system C.
Actually when two systems are put in contact with each other, there will be a net exchange of energy
between them unless they are in thermal equilibrium i.e., they contain the same amount if thermal
energy for a given volume.

Mathematical Expression:

A ~ B ~ B ~ C => A ~ C

2. FIRST LAW OF THERMODYNAMICS:

Scientists: James Prescott Joule was the one who first gave the foundation of the first law of
thermodynamics. But the exact statement was given by Rudolph Clausius.

Statement: This can be expressed in many ways, but the actual statement is

“In any process, the total energy of the universe remains constant.”

Basic Principle: This law is based on conservation of total energy.

Mathematical Expression: The mathematical statement of first law is given by:

dU= δQ – δW
 Where,

dU is the infinitesimal increase in the internal energy of the system.

δQ is the infinitesimal amount of heat added to the system.

δW is the infinitesimal amount of work done by the system on the surroundings.

The expression of the first law can also be written by taking

δW = P dV

where P is the pressure and dV is the infinitesimal volume change.

For a reversible process, the amount of heat added to a close system can be expressed as

δQ = T dS

where T is temperature and S is entropy. So, it can be restated as

dU = T dS – P dV

Explanation: Firstly, it postulates that there exists state functions of a system that are dependent only
on the initial and the final states of a system and are independent of the path from state-1 to state-2.

It also states that for a cyclic process where the initial and final states of a system are the same, the
change in these state functions is zero.

3. SECOND LAW OF THERMODYNAMICS:

Scientists: The first principle of thermodynamics to be established was the second

law of thermodynamics. The first theory on the conversion of heat into mechanical work is due to
Nicolas Leonard Sadi Carnot. It was formulated by Sadi Carnot.

Statement: There is no process that, operating in a cycle produces no other effect than the subtraction
of a positive amount of heat from a reservoir and the production of an equal amount of work.

In a simple manner, we can state that energy systems have a tendency to increase their entropy rather
than decrease it. The most common statement of second law of thermodynamics is essentially due to
Rudolph Clausius i.e.,
 “The entropy of an isolated system not in equilibrium will tend to increase over time, approaching a
maximum value at equilibrium.”

An equivalent statement by Lord Kelvin is,

“A transformation whose only final result is to convert heat extracted from a source at constant
temperature into work is impossible.”

Basic Principle: It is based on conversion of heat into mechanical work.

Mathematical Expression: The second fundamental theorem is the mechanical theory of heat. It is
generally written as:

∫ δQ/T = -N

Where, N is the equivalence-value of all the transformations involved in a cyclical process.

In terms of time variation, the mathematical statement of the second law of a closed system
undergoing an adiabatic transformation is

dS/dt ≥ 0

where , S is the entropy.

Explanation: In a general sense, the second law says that temperature difference between systems in
contact with each other tend to even out and that work can be obtained from these non- equilibrium
differences, but that loss of heat occurs in the form of entropy. When work is done, pressure
differences, density differences and particularly temperature differences all tend to equalize if given
the opportunity. This means that an isolated system will eventually come to have a uniform
temperature.

4. THIRD LAW OF THERMODYNAMICS:

Scientists: Walther Nernst and Max Plant.

Year: Stated in 1905 and extended in 1913.

Statement: It is stated as,

“As temperature approaches absolute zero, the entropy of a system approaches a constant.”
 An alternate version of the third law of thermodynamics as stated by Gilbert N. Lewis and Merle
Randall as:

“If the entropy of each element is some (perfect) crystalline state be taken as zero at the absolute zero
of temperature energy substance has finite positive entropy, but at the absolute zero of temperature
the entropy may become zero and does so become in the case of perfect crystalline substances.”

It can also be represented as,

“The entropy of the universe tends to maximum.”

Explanation: In simple terms, the third law states that the entropy of a pure substance approaches
zero as the absolute temperature approaches zero.

This law provides an absolute reference point for the determination of entropy. The entropy
determined relative to this point is the absolute entropy.

Mathematical Expression:

T -> 0 , S -> c

5. FOURTH LAW OF THERMODYNAMICS:

Scientists: Lars Onsager

Statement: Systems increase entropy at maximum rate available to them.

Explanation: If a system receives a thorough flow of energy (produce entropy or dissipate energy).

a. The system will utilize the energy flow to move away from thermodynamic equilibrium.

b. If it has more than path away to move away is offered from thermodynamic equilibrium.

Mathematical Expression:

Ju = Luu ∇(1/T) – Lur ∇(m/T)

Jr = Lru ∇(1/T) – Lrr ∇(m/T)