For elementary reaction steps the rate law

can be inferred

unimolecular elementary step bimolecular elementary step

A → products A + B → products
d[A] d[A]
Rate = − = k[A] Rate = − = k[A][B]
dt dt
Molecularity: Number of particles coming together to react
in an elementary stepNils Walter: Chem 260
 An overall reaction often consists of
consecutive elementary steps
A→ I→ P Example: 2NO(g) + O2(g) → 2NO2(g)

Elementary steps: 1.) 2NO(g) → N2O2(g)

d[N 2 O 2 ]
reverse steps = k1[NO]2
dt
d[N 2 O 2 ]
2.) N2O2(g) → 2NO(g) − = k -1[N 2 O 2 ]
dt
3.) N2O2(g) + O2(g) → 2NO2(g)
d[N 2 O 2 ]
− = k 2 [N 2 O 2 ][O 2 ]
dt
d[N 2 O 2 ] 1 d[NO 2 ] problem: intermediate
and − = d[NO ]
dt 2 dt Þ 2
= 2k 2 [N 2 O 2 ][O 2 ]
dt Nils Walter: Chem 260
 The steady-state approximation
d[N 2 O 2 ] d[N 2 O 2 ] d[N 2 O 2 ]
= k1[NO]2 − = k -1[N 2 O 2 ] − = k 2 [N 2 O 2 ][O 2 ]
dt dt dt
d[N 2 O 2 ]
Overall: Σ =
dt
= k1[NO]2 − k −1[N 2 O 2 ] − k 2 [N 2 O 2 ][O 2 ] =0
Steady-state approximation =
[intermediate] remains small and constant

k1[NO]2 d[NO 2 ]
Þ [N 2 O 2 ] = and = 2k 2 [N 2 O 2 ][O 2 ]
k -1+ k 2 [O 2 ] dt
d[NO 2 ] 2k1k 2 [NO]2 [O 2 ]
Þ = and k -1>> k 2 [O 2 ] 2nd approximation
dt k −1 + k 2 [O 2 ]
Indeed observed Þ the
d[NO 2 ] 2k1k 2
Þ = [NO]2 [O 2 ] = k[NO]2 [O 2 ] proposed reaction
dt k −1 mechanism is correct!
Nils Walter: Chem 260
 The rate-determining step (RDS) and
reaching equilibrium
The RDS is the slow bottleneck k1
Reversible reaction A B
in consecutive elementary steps k -1
d[B]
Þ = k1[A] - k -1[B]
dt

@ equilibrium

d[B]
= k1[A]eq - k -1[B]eq = 0
dt
k1 [B]eq
= =K
k -1 [A]eq
Nils Walter: Chem 260
 Temperature dependence of the reaction
rate constant
Maxwell velocity distribution of a gas at temperature T

Critical velocity for reaction, vc

Nv |v| < vc No
Reaction
|v| > vc
Reaction
|v|
The minimum energy that must be supplied by a
T = 300 K collision as Ekin (= 1/2mv2) per mole reaction is the
activation energy Ea [kJ/mol]
T = 500 K
pre-exponential factor
T = 1000 K Population with Ea
Nv
T = 5000 K k = A∞ e-Ea/RT sufficient to drive
the reaction
Rate constant
|v|
Nils Walter: Chem 260
 The Arrhenius equation
Ea 1
k = A∞ e-Ea/RT Þ ln k = − + ln A∞
R T
A∞ = maximum possible rate at A plot of ln k vs 1/T will be linear!
infinite temperature Svante Arrhenius:
Chem. Nobel prize
1903 Arrhenius
ArrheniusPlot
Plot
ln A∞
k = A∞

ln k
k = 0.9 A∞
Slope = -Ea/R
k
RT = 10 Ea

k = 0.36 A∞
1/T
RT = Ea

Activation energies are determined

Temperature experimentally by measuring the rate over
as large a range of T as possible

Nils Walter: Chem 260

 Typical activation energies

An endothermic reaction
An exothermic reaction will occur
will normally have a large
rapidly if Ea < RT and only slowly if
activation energy, Ea
Ea >> RT

reactants products
products reactants

Potential Energy
Potential Energy

Ea

∆∆rE
H ∆rH Ea

Reaction Coordinate Q Reaction Coordinate Q

Nils Walter: Chem 260

 What is 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:

∅ K = exp 233.56 × 103 J = 1.15 × 1041

K = e-∆∆rG /RT 8.31451 J K-1 × 298 K
BUT: Very high
activation
energy Þ slow

Energy
H H
O–O → O–H + O•
∆rH
H
Q
React. Prod.
Nils Walter: Chem 260
 Adding a catalyst
MnO2 Add MnO2:
2 H2O2(l) 2 H2O (l) + O2(g)
The reaction becomes very fast

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

with a much smaller activation energy

Uncatalyzed Path
Energy Along
Energy

the Catalyzed
Path

H2O2 H2O + O2
Q

Initial and final states are unaffected by catalyst; but the

nature of the reaction coordinate is changed, reducing Ea
Nils Walter: Chem 260