--- title: "Fundamental thermodynamic relation" firstLetter: "F" publishDate: 2021-07-07 categories: - Physics - Thermodynamics date: 2021-07-05T17:39:57+02:00 draft: false markup: pandoc --- # Fundamental thermodynamic relation The **fundamental thermodynamic relation** combines the first two [laws of thermodynamics](/know/concept/laws-of-thermodynamics/), and gives the change of the internal energy $U$, which is a [thermodynamic potential](/know/concept/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**: $$\begin{aligned} \dd{U} = T \dd{S} - P \dd{V} + \mu \dd{N} \end{aligned}$$ 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 1. H. Gould, J. Tobochnik, *Statistical and thermal physics*, 2nd edition, Princeton.