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3-d Plot 2 of 3 Coordinates: Potential Energy Surfaces Potential Energy Curves
3-d Plot 2 of 3 Coordinates: Potential Energy Surfaces Potential Energy Curves
3-d Plot 2 of 3 Coordinates: 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:
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
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
Activation barriers are determined
Ea = Joules/molecule experimentally by measuring the rate
over as large a range of T as possible.
for Ea = Joules/mole
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
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
∅
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
Old Path
Energy Along
the Catalyzed
Energy
Path
Energy
T
Q CA
H2O2 H2O + O2
Q “Q”
Catalase
2 H2O2(l) 2 H2O (l) + O2(g) In the presence of Catalase