Aquatic Chemical Kinetics：水的化学动力学.ppt

Aquatic Chemical Kinetics Look at 3 levels of chemical change: Phenomenological or observational Measurement of reaction rates and interpretation of data in terms of rate laws based on mass action Mechanistic Elucidation of reaction mechanisms = the ‘elementary’ steps describing parts of a reaction sequence (or pathway) Statistical Mechanical Concerned with the details of mechanisms ? energetics of molecular approach, transition states, and bond breaking/formation How can you tell if any system is at equilibrium? Beware of steady state (non-equilibrium) conditions where proportions of reactants are constant, but due to flux in-out and relative rates of reaction! Thermodynamic or kinetic descriptions? When a reaction is reversible and the rate is fast compared to residence time ? thermodynamic description When a reaction is irreversible, OR it’s reaction rate is slower than the residence time ? kinetic description Partial Equilibrium ? system where some reactions fast, others are slow – sound familiar? Time Scales Reactions and Kinetics Elementary reactions are those that represent the EXACT reaction, there are NO steps between product and reactant in between what is represented Overall Reactions represent the beginning and final product, but do NOT include one or more steps in between. FeS2 + 7/2 O2 + H2O ? Fe2+ + 2 SO42- + 2 H+ 2 NaAlSi3O8 + 9 H2O + 2 H+ ? Al2Si2O5(OH)4 + 2 Na+ + 4 H4SiO4 Equilibrium and reversible kinetics For any reaction AT equilibrium, Keq is related to the forward (k+) and reverse (k-) reaction rates Example: Fe2+ + H+ + 0.25 O2 = Fe3+ + 0.5 H2O Log K=8.48, if k+=100 mol/min, then k-=3x10-7 mol/min Extent of Reaction In it’s most general representation, we can discuss a reaction rate as a function of the extent of reaction: Rate = dξ/Vdt where ξ (small ‘chi’) is the extent of rxn, V is the volume of the system and t is time Normalized to concentration and stoichiometry: rate = dni/viVdt = d[Ci]/vidt where n is # moles, v is