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diff --git a/source/know/concept/laws-of-thermodynamics/index.md b/source/know/concept/laws-of-thermodynamics/index.md new file mode 100644 index 0000000..2d7af9e --- /dev/null +++ b/source/know/concept/laws-of-thermodynamics/index.md @@ -0,0 +1,103 @@ +--- +title: "Laws of thermodynamics" +date: 2021-07-07 +categories: +- Physics +- Thermodynamics +layout: "concept" +--- + +The **laws of thermodynamics** are of great importance +to physics, chemistry and engineering, +since they restrict what a device or process can physically achieve. +For example, the impossibility of *perpetual motion* +is a consequence of these laws. + + +## First law + +The **first law of thermodynamics** states that energy is conserved. +When a system goes from one equilibrium to another, +the change $\Delta U$ of its energy $U$ is equal to +the work $\Delta W$ done by external forces, +plus the energy transferred by heating ($\Delta Q > 0$) or cooling ($\Delta Q < 0$): + +$$\begin{aligned} + \boxed{ + \Delta U = \Delta W + \Delta Q + } +\end{aligned}$$ + +The internal energy $U$ is a state variable, +so is independent of the path taken between equilibria. +However, the work $\Delta W$ and heating $\Delta Q$ do depend on the path, +so the first law means that +the act of transferring energy is path-dependent, +but the result has no "memory" of that path. + + +## Second law + +The **second law of thermodynamics** states that +the total entropy never decreases. +An important consequence is that +no machine can convert energy into work with 100% efficiency. + +It is possible for the local entropy $S_{\mathrm{loc}}$ +of a system to decrease, but doing so requires work, +and therefore the entropy of the surroundings $S_{\mathrm{sur}}$ +must increase accordingly, such that: + +$$\begin{aligned} + \boxed{ + \Delta S_{\mathrm{tot}} = \Delta S_{\mathrm{loc}} + \Delta S_{\mathrm{sur}} \ge 0 + } +\end{aligned}$$ + +Since the total entropy never decreases, +the equilibrium state of a system must be a maximum +of its entropy $S$, and therefore $S$ can be used as +a [thermodynamic "potential"](/know/concept/thermodynamic-potential/). + +The only situation where $\Delta S = 0$ is a reversible process, +since then it must be possible to return to +the previous equilibrium state by doing the same work in the opposite direction. + +According to the first law, +if a process is reversible, or if it is only heating/cooling, +then (after one reversible cycle) the energy change +is simply the heat transfer $\dd{U} = \dd{Q}$. +An entropy change $\dd{S}$ is then expressed as follows +(since $\ipdv{S}{U} = 1 / T$ by definition): + +$$\begin{aligned} + \boxed{ + \dd{S} + = \Big( \pdv{S}{U} \Big)_{V, N} \dd{U} + = \frac{\dd{Q}}{T} + } +\end{aligned}$$ + +Confusingly, this equation is sometimes also called the second law of thermodynamics. + + +## Third law + +The **third law of thermodynamics** states that +the entropy $S$ of a system goes to zero when the temperature reaches absolute zero: + +$$\begin{aligned} + \boxed{ + \lim_{T \to 0} S = 0 + } +\end{aligned}$$ + +From this, the absolute quantity of $S$ is defined, otherwise we would +only be able to speak of entropy differences $\Delta S$. + + + +## References +1. H. Gould, J. Tobochnik, + *Statistical and thermal physics*, 2nd edition, + Princeton. |