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On violations of Le Chatelier's principle for a temperature change in small systems observed for short times

Dasmeh, Pouria; Searles, Debra J.; Ajloo, Davood; Evans, Denis J.; Williams, Stephen R.


Le Chatelier's principle states that when a system is disturbed, it will shift its equilibrium to counteract the disturbance. However for a chemical reaction in a small, confined system, the probability of observing it proceed in the opposite direction to that predicted by Le Chatelier's principle, can be significant. This work gives a molecular level proof of Le Chatelier's principle for the case of a temperature change. Moreover, a new, exact mathematical expression is derived that is valid...[Show more]

CollectionsANU Research Publications
Date published: 2009-12-02
Type: Journal article
Source: The Journal of Chemical Physics
DOI: 10.1063/1.3261849


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