Categories: Physics, Thermodynamics.

# Fundamental thermodynamic relation

The **fundamental thermodynamic relation** combines the first two
laws of thermodynamics,
and gives the change of the internal energy $U$,
which is a thermodynamic potential,
in terms of the change in
entropy $S$, volume $V$, and the number of particles $N$.

Starting from the first law of thermodynamics, we write an infinitesimal change in energy $\dd{U}$ as follows, where $T$ is the temperature and $P$ is the pressure:

$\begin{aligned} \dd{U} &= \dd{Q} + \dd{W} = T \dd{S} - P \dd{V} \end{aligned}$The term $T \dd{S}$ comes from the second law of thermodynamics, and represents the transfer of thermal energy, while $P \dd{V}$ represents physical work.

However, we are missing a term, namely matter transfer.
If particles can enter/leave the system (i.e. the population $N$ is variable),
then each such particle costs an amount $\mu$ of energy,
where $\mu$ is known as the **chemical potential**:

To generalize even further, there may be multiple species of particle, which each have a chemical potential $\mu_i$. In that case, we sum over all species $i$:

$\begin{aligned} \boxed{ \dd{U} = T \dd{S} - P \dd{V} + \sum_{i}^{} \mu_i \dd{N_i} } \end{aligned}$## References

- H. Gould, J. Tobochnik,
*Statistical and thermal physics*, 2nd edition, Princeton.