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corresponds to a molecule in which the A-B bond is partly made and the B-C bond is partly broken. 2.5 THERMODYNAMIC FORMULATION Transition-state theory rate constant Thermodynamics applied to chemical reactions yields useful thermodynamics quantities such as G(change in Gibbs free energy of the chemical system), H (change in enthalpy or heat of the reaction) and S (change in entropy). These quantities refer to the starting and ending states of the system. A general reaction is represented by the form αΑ + βΒ ... T# Product The transition state is in equilibrium with the reactants, and the rate of the reaction is the rate of the product formation from the transition state, given by rdCp 1dCA kBTC kBTK C aC ... dtadthT hCAB So the rate constant (concentration based) can be expressed as Lenoble, 1978)), kB is Boltzmann’s constant (1.381 * 10-23 J K-1) , T is absolute temperature, h is Planck’s constant (6.626 * 10-34 J s), and K is the concentration- C based equilibrium constant for the reaction involving the reactants and the transition state. Equation (2.8) uses the concentration-based equilibrium constant, which combines all chemical and physical effects between the reaction species and the solvent. As already stated above, one of the most important things is to locate the transition state along the reaction coordinate, which corresponds to maximum energy kTST kBTK chC (2.8) where κ is the transmission coefficient (01 and always positive (Asano and 19PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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