Degrees of Rate Control at Non(pseudo)steady-State Conditions
Brandon Foley, Aditya Bhan
Abstract
The degrees of rate control enable identification of rate-controlling transition states and species during (pseudo)steady-state reaction. We demonstrate a method for identifying rate-controlling transition states and species at non(pseudo)steady-state conditions by modifiying of the definitions for degrees of rate control and sensitivities to superimpose the condition that time constants of the analytical rate function are kept constant when taking the partial derivatives of rate with respect to the rate constants/free energies. The utility of transient degrees of rate control is demonstrated for catalytic reaction networks to rationalize features of the transient rate including extrema and discontinuities.
Topics & Concepts
Steady state (chemistry)Reaction rate constantClassification of discontinuitiesConstant (computer programming)Transient (computer programming)ThermodynamicsCatalysisReaction rateTransition state theoryMaxima and minimaChemistryControl theory (sociology)Control (management)PhysicsPhysical chemistryKineticsMathematicsComputer scienceClassical mechanicsMathematical analysisBiochemistryArtificial intelligenceProgramming languageOperating systemCO2 Reduction Techniques and CatalystsElectrocatalysts for Energy ConversionElectrochemical Analysis and Applications