PROF.

RAKESH RATHI’S CHEMISTRY TUTORIALS

SECOND LAW OF THERMODYNAMICS:
First law of thermodynamics is merely the law of conservation of energy.
The law allows all the transformations in which energy is conserved.
According to the first law of thermodynamics, it is possible to use ice for heating water. If heat supplied by ice at
lower temperature is equal to heat gained by water at higher temperature the energy is conserved and the process
can take place.

We know that heat flows spontaneously, from hot end to cold end but not in the opposite direction. However, the
reverse process, flow of heat from the cold end to hot end is allowed by first law.
If heat supplied by the cold end is equal to heat gained by the hot end, the energy is conserved and hence the
transformation is allowed by the first law. However, we see that such transformations are not possible.
These examples indicate that the first law is insufficient in the respect that it does not place any restrictions on
the direction of heat flow.

It is the second law of thermodynamics based on human experience that fixes the direction of heat flow.
It states that “the spontaneous flow of heat is always unidirectional, from higher temperature to low
temperature?

Another respect in which the first law of thermodynamics is insufficient is that it demands the conservation of
energy in all types of transformations but does not clarify the extent of convertibility of one form of energy into
another.
According to first law of thermodynamics, heat can be completely converted into work. The second law of
thermodynamics in this respect states that ‘heat cannot be completely converted into an equivalent amount of
work without producing permanent changes either in the system or its surrounding’.

Consider a machine such as heat engine that continuously converts heat in work. It takes up heat from a source at
higher temperature, converts some part of it into work and transfers the remainder to the sink. The efficiency of
machine is the ratio of work done to the total heat absorbed. If heat absorbed is completely converted into work
without producing changes in the system, the efficiency must be unity. However, no machine has yet been
made that has an efficiency, unity. This is another statement of second law of thermodynamics.

ENTHALPY (H):
The enthalpy of a system is defined as the sum of the internal energy of the system and the energy that arises due
to its pressure and volume. It is the total heat content of the system. Like U even H is extensive and state function
like U its not possible to find the absolute valuie of H
Mathematically, the enthalpy is given by the equation.
H = U + PV
Since, U, P and V are state functions, H is also a state function.
H = H2–H1
Where, H1 is the enthalpy of the system in the initial state and H2 in the final state.
Now, H1 = U1 + P1V1 and H2 = U2 + P2V2

H = (U2 + P2V2) – (U1+ P1V1)

= U2 + P2V2–U1–P1V1
= (U2−U1) + (P2V2–P1V1)
= U + (PV)

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