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13.7—Reaction Rates and Temperature:

The Arrhenius Equation
• Recall the rate law expression:
Reaction rate = k[A][B]
k[A][B] = pfZ[A][B]
k = pfZ
Recall that Activation energy
f = e-Ea /RT in J/mol

-Ea /RT
k = pZe Fraction of
collisions with
sufficient energy
for reaction
Steric factor Collision frequency
Rate constant (fraction of collisions
with proper
2
orientation)
 13.7—Reaction Rates and Temperature:
The Arrhenius Equation
• The Arrhenius equation quantifies the relationship
between reaction rate and temperature.
Ea Activation Energy
ln k = ln A -
RT Temperature, K
rate constant gas constant,
Pre-exponential
factor = pZ 8.3145 J/molK

Two other forms of the equation are:

Ea k ' Ea æ 1 1 ö
- ln = ç - ÷
k = Ae RT
k R èT T 'ø
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 14.9—Altering an Equilibrium Mixture:
Changes in Temperature
• The effect of temperature on the equilibrium
composition arises from the dependence of
equilibrium constant on temperature.
æ K 2 ö DH°rxn æ 1 1 ö
ln ç ÷ = ç - ÷
è K1 ø R è T1 T2 ø
ΔH°rxn in J/mol
R = 8.3145 J/molK
The van’t Hoff equation demonstrates mathematically the reason
that temperature causes a shift in equilibrium.
Temperature is the only factor that changes the value of K
 14.10—The Link Between Chemical
Equilibrium and Chemical Kinetics

• Kc (and K) is really just the ratio of the rate constants of the forward
and reverse reactions:

kf
Kc =
kr