Noah Bessard

Statistical Mechanics Homework 1

1. 0th law: Two systems in thermal equilibrium with a third system are in thermal equilibrium with
each other. This means that if system 1 is exchanging no heat with system 3 and system 2 is
exchanging no heat with system 3, then systems 1 and 2 will also exchange no heat with each
other.
1st law: ∆𝑈 = ∆𝑄 − ∆𝑊. This means that if a system undergoes some change in internal energy
it must be the result of either the heating of the system or work being done on or by the system.
𝑑𝑄
2nd law: 𝑑𝑆 ≥ 𝑇
. This law states that the entropy of a closed system is always greater than or
equal to the heat added or lost from the system divided by the initial temperature of the
system. While this does allow for a decrease in local entropy it still must be greater than the
terms on the right.
3rd law: The entropy of a system at T = 0 is approaches some constant which is assumed to be
zero. This implies that there is some universal l ground state that all systems approach as their
temperature approaches zero

2. Enthalpy: The internal energy of a system plus the work done by the system to the environment
to establish itself. A real system can’t spontaneously appear in a non-vacuum without displacing
the matter that was initially occupying the space. As a result of this the system must do work on
its environment to come into existence. So the enthalpy in can be thought of as the total energy
required to create a system.

Hemholtz Free Energy: The energy of a system that can be used for work assuming the system is
confined to some volume and is always able to remain in thermal equilibrium with its
environment.

Gibbs Free Energy: This is the energy of a system which can be extracted in the form of heat in
the case where the temperature and pressure are fixed. This again requires an interaction with
an environment to maintain constant temperature.