Geochemical kinetics
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Geochemical 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

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Geochemical kinetics
Geochemical 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



Reactions and kinetics
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


Extent of reaction
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 stoichiometric coefficient, and C is molar concentration of species i


Rate law
Rate Law

  • For any reaction: X  Y + Z

  • We can write the general rate law:

Rate = change in concentration of X with time, t

Order of reaction

Rate Constant

Concentration of X


Reaction order
Reaction Order

  • ONLY for elementary reactions is reaction order tied to the reaction

  • The molecularity of an elementary reaction is determined by the number of reacting species: mostly uni- or bi-molecular rxns

  • Overall reactions need not have integral reaction orders – fractional components are common, even zero is possible



Geochemical kinetics


Zero order
Zero Order interpret the order of rxn

  • Rate independent of the reactant or product concentrations

  • Dissolution of quartz is an example:

    SiO2(qtz) + 2 H2O  H4SiO4(aq)

    log k- (s-1) = 0.707 – 2598/T


First order
First Order interpret the order of rxn

  • Rate is dependent on concentration of a reactant or product

    • Pyrite oxidation, sulfate reduction are examples


First order1
First Order interpret the order of rxn

Find order from log[A]t vs t plot 

Slope=-0.434k

k = -(1/0.434)(slope) = -2.3(slope)

k is in units of: time-1


1 st order half life
1 interpret the order of rxnst-order Half-life

  • Time required for one-half of the initial reactant to react


Second order
Second Order interpret the order of rxn

  • Rate is dependent on two reactants or products (bimolecular for elementary rxn):

  • Fe2+ oxidation is an example:

    Fe2+ + ¼ O2 + H+ Fe3+ + ½ H2O


General rate laws1
General Rate Laws interpret the order of rxn


2 nd order
2 interpret the order of rxnnd Order

  • For a bimolecular reaction: A+B  products

[A]0 and [B]0 are constant, so a plot of log [A]/[B] vs t yields a straight line where slope = k2 (when A=B) or = k2([A]0-[B]0)/2.3 (when A≠B)


Pseudo 1 nd order
Pseudo- 1 interpret the order of rxnnd Order

  • For a bimolecular reaction: A+B  products

If [A]0 or [B]0 are held constant, the equation above reduces to:

SO – as A changes B does not, reducing to a constant in the reaction: plots as a first-order reaction


2 nd order half life
2 interpret the order of rxnnd order Half-life

  • Half-lives tougher to quantify if A≠B for 2nd order reaction kinetics – but if A=B:

If one reactant (B) is kept constant (pseudo-1st order rxns):


3 rd order kinetics
3 interpret the order of rxnrd order Kinetics

  • Ternary molecular reactions are more rare, but catalytic reactions do need a 3rd component…


Zero order reaction
Zero order reaction interpret the order of rxn

  • NOT possible for elementary reactions

  • Common for overall processes – independent of any quantity measured

    [A]0-[A]=kt


Pathways
Pathways interpret the order of rxn

  • For an overall reaction, one or a few (for more complex overall reactions) elementary reactions can be rate limiting

Reaction of A to P  rate determined by slowest reaction in between

If more than 1 reaction possible at any intermediate point, the faster of those 2 determines the pathway


Initial rate first order rxn example
Initial Rate, first order rxn example interpret the order of rxn

  • For the example below, let’s determine the order of reaction A + B  C

  • Next, let’s solve the appropriate rate law for k


Rate limiting reactions
Rate Limiting Reactions interpret the order of rxn

  • For an overall reaction, one or a few (for more complex overall reactions) elementary reactions will be rate limiting

Reaction of A to P  rate determined by slowest reaction in between

If more than 1 reaction possible at any intermediate point, the faster of those 2 determines the pathway


Activation energy e a
Activation Energy, E interpret the order of rxnA

  • Energy required for two atoms or molecules to react


Transition state theory
Transition State Theory interpret the order of rxn

  • The activation energy corresponds to the energy of a complex intermediate between product and reactant, an activated complex

    A + B ↔ C± ↔ AB

It can be derived that

EA = RT + DHC±


Collision theory
Collision Theory interpret the order of rxn

  • collision theory is based on kinetic theory and supposes that particles must collide with both the correct orientation and with sufficient kinetic energy if the reactants are to be converted into products.

  • The minimum kinetic energy required in a collision by reactant molecules to form product is called the activation energy, Ea.

  • The proportion of reactant molecules that collide with a kinetic energy that is at least equal to the activation energy increases rapidly as the temperature increases.


T dependence on k
T dependence on k interpret the order of rxn

  • Svante Arrhenius, in 1889, defined the relationship between the rate constant, k, the activation energy, EA, and temperature in Kelvins:

    or:

    Where A is a constant called the frequency factor, and e–EA/RT is the Boltzmann factor, fraction of atoms that aquire the energy to clear the activation energy


Arrhenius equation
Arrhenius Equation interpret the order of rxn

y = mx + b

Plot values of k at different temperatures: log k vs 1/T  slope is EA/2.303R to get activation energy, EA


Activation energy
Activation Energy interpret the order of rxn

  • EA can be used as a general indicator of a reaction mechanism or process (rate-limiting)