A precise, simple and general basic Le Châtelier principle based on elementary calculus: what Le Châtelier had in mind? (Q2201018)

The author first recalls the basic Le Châtelier principle considering the minimization problem \(\min f(x;\mathbf{p})\) where \(\mathbf{p}\) is a \(P\)-dimensional parameter vector and \(f\) is supposed to be twice continuously differentiable with respect to \(x\). This principle proves that if \(\frac{\partial ^{2}f}{\partial x^{2}}>0\) at a minimizer \(x^{\ast }\) (regular minimum point), the sign of \(\frac{\partial x^{\ast }}{\partial p_{j}}\) is the opposite of that of \(\frac{\partial ^{2}f}{\partial x\partial p_{j}}\) at \(x^{\ast }\) and that of \(\Delta x^{\ast }\) is the opposite of that of \(\frac{\partial ^{2}f}{\partial x\partial p_{j}}\Delta p_{j}\) at \(x^{\ast }\). The author illustrates this principle with examples in economics and mechanics. He then considers chemical reaction equilibrium problems which may be written as minimization ones for the Gibbs energy \(G\): \(\min_{\xi }G(\xi ;p)\) where \(\xi \) denotes the vector of dimension \(R\) of reaction extents and \(p\) that of parameters. In the case of a single reaction, the author describes the parameters to be considered and the applicability of Le Châtelier principle. In the case of multiple variables, the author considers a chemically reacting system in an ideal solution phase at specified temperature and pressure. He proves that for every feasible point \(\mathbf{n}^{0}\) satisfying the mass conservation and non-negativity constraints, then \(\sum_{j=1}^{R}\sum_{k=1}^{R}\frac{\partial ^{2}(G/RT)}{\partial \xi_{j}\partial \xi _{k}}\delta \xi _{j}\delta \xi _{k}>0\), where \(n_{i}=\mathbf{n}_{i}^{0}+\sum_{j=1}^{R}\nu _{ij}\xi _{j}\), for stoichiometric coefficients \(\nu _{ij}\). He finally discusses the influence of finite variations of the parameters.