How much may the equilibrium be shifted in a chemical relaxation experiment?

摘要: A simple method for determining the largest permitted displacement of an equilibrium in a chemical relaxation experiment is described. The rate equation can always be put form –d Δ[Xi]//dt=τ–1Δ[Xi](1 +r), where r dimensionless parameter which positive, negative or zero. This depends on extent perturbation, constant and concentrations species involved reaction. It related to Δ[Xi] by fundamental r=vitext-decoration:overlinerΔ[Xi] text-decoration:overliner only concentrations, vi being stoichiometric coefficient. Convenient expressions are given most common unimolecular bimolecular reactions. new linearization condition |r| 1. generally satisfied, whatever equilibrium, whenever small compared concentrations. However, many cases, above also fulfilled even if shift large (low values). case dimerization reaction 2A ⇌ A2 considered detail.