Laws of Thermodynamics

Laws of thermodynamics evolved during 19th century to meet the engineering demands of use
of steam power in industries. The success of laws of thermodynamics even till now lies in the
fact that they are stated for macroscopic systems and hence unaffected by quantum revolution.

Laws of thermodynamics uses defined fundamental physical quantities such as temperature,

energy, entropy to describe thermodynamic systems and also explains the transport and
conversion of heat and work in a thermodynamic process.

To discuss further about thermodynamics it is essential to understand terms used in

thermodynamics:

System: it is a particular defined region of the universe separated from its surroundings by a
boundary.

Work: response of the system to external macroscopic influence in which energy is either
supplied or removed from the system.

Heat: response of the system to microscopic influence in which energy is either supplied or
removed from the system via molecular motion.

Isolated system: if a system neither exchanges energy or matter with its surroundings then it is
called isolated system.

Closed system: if a system exchanges energy but not matter with its surroundings then it is
called closed system.

Open system: if a system exchanges both energy and matter with its surroundings then it is
called open system.

Classical example of open system is living organisms; they exchange both energy and matter
from their surroundings.

Thermodynamic equilibrium: a equilibrium state of the system could be defined by the values
of thermodynamic such as pressure and volume of gas.

Reversible process: Each infinitesimal change to the state of the system takes the system from
one equilibrium state to another. Thus, each infinitesimal change can be exactly reversed.

Number of degrees of freedom: the number of thermodynamic variables required to define

the thermodynamic state of the system. This number is defined as number of degrees of
freedom.
Having discussed the fundamental concepts in thermodynamics lets focus on laws in
thermodynamics. There are four principles or laws of thermodynamics:

1. The zeroth law of thermodynamics 

2. The first law of thermodynamics 
3. The second law of thermodynamics 
4. The third law of thermodynamics

1. The zeroth law of thermodynamics 

It states that if two systems are in thermal equilibrium with the third system then they are in
thermal equilibrium with each other as well.

The zeroth law can be used to infer the existence of a quantity, the equality of which for two
different systems, defines the systems to be in thermal equilibrium and this quantity is
temperature.

2. The first law of thermodynamics (law of conservation of energy)

It states that all the real processes occurring in this world involves transformation of energy
form one form to other. These transformations are such that the total amount of energy is
always conserved. The amount of energy lost in a steady process cannot be greater than the
amount of energy gained. It expresses time translation symmetry.

1st law is defined as “If the state of a thermally isolated system is changed by the performance
of work, the amount of work required depends only on the initial and final states of the
system”.

1st law defines the energy as the stored quantity which is independent of any particular process
path. Energy Is a state function.

The first law could be expressed as:

Increase in internal energy of a system = heat supplied to the system + work done on the system
δU = Q + Wsystem
where U is internal energy, Q is heat and W is work

δU = Q - Wsurroundings
From the above equations we can say that work is work done by the system on its
surroundings. It could also be stated as amount of heat of the process.
δU = TdS – pdV

where energy Q (heat) is the product of the temperature (T) and it conjugate

variable entropy (S), Q = TdS, and similarly work is the product of pressure (p)
with volume (V), W = -pdV.

3. The second law of thermodynamics (the entropy principle)

Second law states that “the total entropy of the universe is continually increasing”.

When two systems which are at different temperatures are placed in contact, heat will be
exchanged until the systems are in thermal equilibrium. Energy would be conserved by a
process in which heat is exchanged from a cooler to a hotter system, but this is never observed.
Thus, thermal processes in nature have a particular directionality, and it is described by second
law.

A second function of the second law is to describe the process by which useful work may be
produced from heat.

Randomness or disorder of the components of a system is expressed as entropy, S. any change

in the randomness of the system is expressed as ΔS. It was Gibbs who developed the theory of
energy change during the chemical reactions, showed that the free energy content G, of a
system can be defined in terms of enthalpy, entropy and absolute temperature.

Free energy is G = H – TS.

At a constant temperature, free energy change (ΔG ) could be defined by enthalpy (H = U + pV)
change ΔH, and entropy change ΔS.

ΔG = ΔH – TΔS

If ΔG is negative for a process then the process tends to occur spontaneously.

Most of the cell function depends on molecules, such as proteins and nucleic acids. The free
energy for the formation of these macromolecules is positive, which means the process of their
formation is not spontaneous; the molecules are less stable and more highly ordered than a
mixture of their monomeric components. Hence these reactions are thermodynamically
unfavorable, energy-requiring (endergonic) reactions. But since formation of these
macromolecules is essential for vital functions of cell, cells couple them to other reactions that
liberate free energy (exergonic reactions), so that the overall process is exergonic: the sum of
the free energy changes is negative and process becomes spontaneous. The usual source of
free energy in biological reactions is the energy released by hydrolysis of adenosine
triphosphates (ATP).

Gibbs showed that ΔG for any chemical reaction is a function of the standard free-energy
change, ΔG°— a constant that is characteristic of each specific reaction where

aA + bB → cC + dD
It is expressed as:

[Ci ]c [Di ]d
ΔG=ΔG °+ RT ln a b
[ Ai] [Bi]

where [Ai] is the initial concentration of A, and so forth; R is the gas constant; and T is the
absolute temperature.

When the reaction reaches equilibrium no driving force is left hence no work can be done ΔG =
0. So on substituting 0 for ΔG and Keq (equilibrium constant) for [Ci]c [Di]d/ [Ai]a [Bi]b a new
relation is obtained.

ΔG° = -RT ln Keq

When Keq >> 1, ΔG° is large and negative; when Keq << 1, ΔG° is large and positive.

Since Keq and ΔG° are experimentally determined values, it tells us which reactions tends to
complete and which do not.

Law of maximum entropy production (LEMP)

This law states that “A system will select the path or assemblage of paths out of available paths
that minimizes the potential or maximizes the entropy at the fastest rate given the constraints”.

The Second Law says that the world acts to minimize the potentials it does not say which out
available paths it will take to do this. This is the question the Law of Maximum Entropy
Production answers.
The Law of Maximum Entropy Production thus has deep implications for evolutionary theory,
culture theory, macroeconomics, human globalization, and more generally the time-dependent
development of the Earth as a ecological planetary system as a whole.

4. The third law of thermodynamics

As temperature approaches absolute zero, the entropy of a system approaches a minimum.

References-

1. Newman, T.J. (2006). Equilibrium Thermodynamics.

2. Swenson, R (1989), Emergent Evolution and the Global Attractor: The Evolutionary
Epistemology of Entropy Production Maximization.

3. Glansdorff, P., Prigogine, I. (1971). Thermodynamic Theory of Structure, Stability and

Fluctuations, Wiley-Interscience, London, ISBN 0-471-30280-5.

4. Nelson, D.L and Cox, M.M. (2005). Principles of biochemistry. 4th Edition.