rxn1 - Thermodynamics and kinetics of transformation...

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Unformatted text preview: Thermodynamics and kinetics of transformation reactions Chapter 12 Chemical transformation reactions bonds breaking and forming 3 types: chemical photochemical biological Questions Can a given compound be transformed in the environment by one or more pathways? what are the reaction products? what are the kinetics? what is the influence of variables such as pH, light intensity, redox condition, ionic strength, etc, on products and kinetics? Thermodynamics vs. Kinetics We have already discussed one type of transformation reaction: proton transfer. Proton transfer was considered to be fast and reversible, i.e. equilibrium was established. We could therefore ignore kinetics and deal only with products and equilibrium. the reactions we will now discuss will generally be under kinetic control, therefore focus on kinetics, not equilibrium (although eqbm considerations may be useful in predicting kinetics!) Thermodynamics Use infinite dilution state in water as reference ' ' ] [ ] [ ln i i RT i i i + = reference state, o i 1 ) ( ' aq G i f i General reversible chemical reaction qQ pP bB aA + + where A, B, P, Q are chemical species and a, b, p, q are stoichiometric coefficients The free energy change of this reaction is equal to the free energies of the products minus reactants: b B a A q Q p P Q P B A r B A Q P RT q p b a G ]) [ ( ]) [ ( ]) [ ( ]) [ ( ln ' ' ' ' ' ' ' ' + + +-- = Q P B A r q p b a G + +-- = This is related to the standard free energies of the product minus the reactants: Reaction quotient, Q r b B a...
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rxn1 - Thermodynamics and kinetics of transformation...

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