Ch. 3. KINETIC VS. EQUILIBRIUM MODELING

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Ch. 3. KINETIC VS. EQUILIBRIUM MODELING 3-1. Definitions Kinetics? Dealing with processes (reactions) as a function of time on a certain pathway – for a given infinite time, the reaction should reach an equilibrium state Equilibrium? A state in which there is no further apparent change (it becomes stable) due to the equal rate of forward and reverse process (reaction) – should be reversible Modeling using either kinetics or equilibrium assumption in aqueous geochemistry.

Can you distinguish the following terms? Equilibrium vs. Disquilibrium Partial equilibrium Local equilibrium

3-2. Applicability of Kinetic or Equilibrium Modeling Residence time (tR): The time for a substance to stay in the given system (see eqn. 2.5 in the text). Half-life (or half time of reaction) (t1/2): The time required for half-completion of the process (reaction), assuming no reverse reaction and absence of initial products. (see eqn 2.6 in the text). If tR >> t1/2: Equilibrium model applicable. Otherwise, a kinetic model should be used. Fig. 2.2 on p.54 for the various tR. Table 2.1 on p.55 for reaction types and their t1/2.

3-3. Kinetics Elementary vs. overall reactions Order of an elementary reaction Order of an overall reaction (determined by a stoichiometry  eqn 2.18, 2.19 on p. 57) How to derive an kinetic equation? (in a differential equation form) See Table 2.2 and Fig. 2.3. for the kinetic expressions of some reactions Effect of T: Arrehnius equation (eqn 2.29, p.60) See Ea values for various reactions on p. 62.

Assignments: Read examples (from p.68 to 78), especially those corresponding to one’s thesis subject. Solve the Problems #2, #3, #4, #8