236 PHYSICS
Eq. (11.1), the total heat absorbed equals the 11.10 REVERSIBLE AND IRREVERSIBLE
work done by the system. PROCESSES
11.9 SECOND LAW OF THERMODYNAMICS Imagine some process in which a thermodynamic
system goes from an initial state i to a final state
The First Law of Thermodynamics is the
f. During the process the system absorbs heat Q
principle of conservation of energy. Common
from the surroundings and performs work W on
experience shows that there are many
it. Can we reverse this process and bring both
conceivable processes that are perfectly
the system and surroundings to their initial
allowed by the First Law and yet are never
states with no other effect anywhere ? Experience
observed. For example, nobody has ever seen
suggests that for most processes in nature this
a book lying on a table jumping to a height by
itself. But such a thing would be possible if is not possible. The spontaneous processes of
the principle of conservation of energy were nature are irreversible. Several examples can be
the only restriction. The table could cool cited. The base of a vessel on an oven is hotter
spontaneously, converting some of its internal than its other parts. When the vessel is removed,
energy into an equal amount of mechanical heat is transferred from the base to the other
energy of the book, which would then hop to a parts, bringing the vessel to a uniform
height with potential energy equal to the temperature (which in due course cools to the
mechanical energy it acquired. But this never temperature of the surroundings). The process
happens. Clearly, some additional basic cannot be reversed; a part of the vessel will not
principle of nature forbids the above, even get cooler spontaneously and warm up the base.
though it satisfies the energy conservation It will violate the Second Law of Thermodynamics,
principle. This principle, which disallows if it did. The free expansion of a gas is irreversible.
many phenomena consistent with the First The combustion reaction of a mixture of petrol
Law of Thermodynamics is known as the and air ignited by a spark cannot be reversed.
Second Law of Thermodynamics. Cooking gas leaking from a gas cylinder in the
The Second Law of Thermodynamics gives kitchen diffuses to the entire room. The diffusion
a fundamental limitation to the efficiency of a process will not spontaneously reverse and bring
heat engine and the co-efficient of the gas back to the cylinder. The stirring of a
performance of a refrigerator. In simple terms, liquid in thermal contact with a reservoir will
it says that efficiency of a heat engine can convert the work done into heat, increasing the
never be unity. For a refrigerator, the Second internal energy of the reservoir. The process
Law says that the co-efficient of performance cannot be reversed exactly; otherwise it would
can never be infinite. The following two amount to conversion of heat entirely into work,
statements, one due to Kelvin and Planck violating the Second Law of Thermodynamics.
denying the possibility of a perfect heat engine,
Irreversibility is a rule rather an exception
and another due to Clausius denying the
in nature.
possibility of a perfect refrigerator or heat
Irreversibility arises mainly from two causes:
pump, are a concise summary of these
one, many processes (like a free expansion, or
observations.
an explosive chemical reaction) take the system
Kelvin-Planck statement to non-equilibrium states; two, most processes
No process is possible whose sole result is the involve friction, viscosity and other dissipative
absorption of heat from a reservoir and the effects (e.g., a moving body coming to a stop and
complete conversion of the heat into work. losing its mechanical energy as heat to the floor
and the body; a rotating blade in a liquid coming
Clausius statement
to a stop due to viscosity and losing its
No process is possible whose sole result is the mechanical energy with corresponding gain in
transfer of heat from a colder object to a the internal energy of the liquid). Since
hotter object. dissipative effects are present everywhere and
It can be proved that the two statements can be minimised but not fully eliminated, most
above are completely equivalent. processes that we deal with are irreversible.
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