D + H2 → HD + H

Simplest possible “reaction”

Potential Energy Surfaces Potential Energy Curves

2 of 3 Symmetric
Stretch

Energy
3-d plot coordinates

r
V(rHH) → H2 as H - D
Contour distance increases.

Energy
Plot

rHH
Endothermic Exothermic
Activation Ea Ea
Activation Energy,
Energy, EEaa
Energy

Energy

Energy
∆E or
∆E or ∆H ∆H
Reac. Q Prod. Reac. Q Prod. Reac. Q Prod.
Reaction
Reaction Coordinate
Coordinate
Temperature
Temperature Dependence
Dependence of
of aa Reaction
Reaction Rate
Rate Constant:
Constant:

Velocity distribution in gas phase at temperature T

Critical velocity for reaction, vc

Nv |v| < vo No
Reaction
|v| > vo
Reaction
|v|
The minimum energy that must be supplied
by a collision is the Activation Energy.
T = 300 K
KE = ½mv2 ≥ Ea
T = 500 K Pre-exponential Boltzmann
T = 1000 K factor Constant
Nv
T = 5000 K k = A∞ e-Ea/kBT Population with
KE sufficient
to drive the
|v| Rate constant reaction.
 Arrhenius A plot of ln k vs 1/T will be
Arrhenius Equation
Equation linear.
k = A∞ e-Ea/k
/RTBT ln k = -Ea 1 + ln A∞
R T

A∞ = maximum possible rate at

infinite temperature Intercept = ln A∞

k = A∞ Arrhenius
Arrhenius Plot
Plot
k = 0.9 A∞

ln k
k Slope = -Ea/R
kRT
BT =
= 10

k = 0.36 A∞
10 EEaa
kRT
BT = Eaa

1/T
= E

Temperature
Ea = Joules/molecule
for Ea = Joules/mole
Activation barriers are determined
experimentally by measuring the rate
over as large a range of T as possible.
 An endothermic reaction
An exothermic reaction will occur
will have a large activation
rapidly if Ea < RT and only very
energy, Ea.
slowly if Ea >> RT.

Potential Energy
Potential Energy

Ea

∆∆H
E ∆H Ea

Reaction Coordinate
Reaction Coordinate

But
But What
What About
About Entropy?
Entropy? Entropy accounts for the
number of different
states that contribute all
along the reaction path.
We plot Gibbs energy
along reaction coordinate ∆Gŧ is the free energy or
to account for entropy.
Gibbs energy of activation.

k ŧ/RT
k = kBT e -∆
∆G
Gibbs Energy

∆Gŧ h
ŧ-T∆
∆Sŧ)/RT
= kBT e-(∆∆H
∆rG h
ŧ/R ŧ/RT
= kBTe∆S e-∆∆H
Reaction Coordinate h
Pre-exponential
factor A∞
h = Planck’s Constant
∆Sŧ = Entropy of Activation

∆Hŧ = Enthalpy of Activation ⇒ microscopic Ea

Sample
Sample Problem:
Problem:

If a reaction doubles its rate when the temperature is increased

from 305 K to 315 K, what is the activation energy?

k = A∞ e-Ea/RT
A∞ is approximately T independent

k(315 K) = A∞ e-Ea/R(315 K) = 2
k(305 K) A∞ e-Ea/R(305 K)

2 = e-Ea(1/305 – 1/315)/R
ln2 = -Ea(1/305 – 1/315)/R

Ea = ln2 (8.3145 J mol-1 K-1) 10-3 kJ = 55.4 kJ/mol

0.0001041 K-1 J
Catalysis:
Catalysis:
Consider: 2 H2O2(l) → 2 H2O (l) + O2(g)
∅
∆rG = 2(-237.13) + 0 - 2(-120.35) = -233.56 kJ
∅
∆rH = 2(-285.83) + 0 - 2(-187.78) = -196.10 kJ
This reaction is exothermic and spontaneous!
In fact the equilibrium constant is huge.

∅
233.56 × 103 J
K = e-∆∆rG /RT K = exp = 1.15 × 1041
8.31451 J K-1 298

Very high
activation
H

Energy
H energy
O – O → O – H + O• ∅
H ∆rH
Q
Reac. Prod.
 MnO2
2 H2O2(l) 2 H2O (l) + O2(g) Add MnO2

MnO2 acts as a catalyst – that is, it provides a mechanism

with a much smaller activation energy.

Old Path
Energy Along
the Catalyzed
Energy

Path

Energy
T
Q CA
H2O2 H2O + O2
Q “Q”

Initial and final states are unaffected by catalyst. The

nature of the reaction coordinate is changed.
 Heterogeneous Catalysis:
Catalyst is in a different phase than reactants.
Usually a solid surface catalyzing gas or liquid
phase reactions.
Examples:
Rhodium, Platinum, Zeolites, Metal Oxides, …
Homogeneous Catalysis:
Catalyst is in the same phase as the reactants.
Usually in liquid solution.
Examples:
Complexes of Rhodium and Platinum, Enzymes,
Strong Acids, …

Catalase
2 H2O2(l) 2 H2O (l) + O2(g) In the presence of Catalase

Manganese Catalase in certain Lactobacillus type bacteria.