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5.60 Thermodynamics & Kinetics

Spring 2008

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 5.60 Spring 2008 Lecture #34 page 1

Temperature Dependence of Rate Constant

Arrhenius Law

k = Ae −Ea / RT

where Ea ≡ Activation Energy

A ≡ Pre-Exponential Factor

k(T) lnk(T) k=A

Slope=-Ea/R

T T

Typically: Ea ~ 50-300 kJ/mole

A (unimolecular) ~ 1012–1015 sec-1

(bimoledular) ~ 1011 liter/(mole sec)
5.60 Spring 2008 Lecture #34 page 2

Physical Interpretation of Ea

Consider A+B→C

A→ ←B ⇒ (A B)* ⇒ C

Reactants Activated Complex Product

(A B)*

Eaforward

Energy Eabackward

Reactants

Products

Reaction Coordinate

Small Ea ⇒ Weak T dependence ⇒ Fast reaction

Large Ea ⇒ Strong T dependence ⇒ Slow reaction

5.60 Spring 2008 Lecture #34 page 3

Catalysis

A catalyst speeds up a reaction but is NOT destroyed or

used up in the process

k1
Consider A B (k1,k-1) both slow
k-1

Let C be a catalyst
k2
A+C B+C (k2,k-2) both fast
k-2

C acts to LOWER the Ea for the reaction, often altering the

mechanism.

A ⇒ A* ⇒ B

Uncatalyzed

A+C ⇒ (A C)* ⇒ B+C

Catalyzed
5.60 Spring 2008 Lecture #34 page 4

A*
Ea
(A C)*
Energy E aC

Reaction Coordinate

The Equilibrium Keq = [B]eq/[A]eq is unaltered

Only the rate is changed through a lowering of Ea.