Chap 22.

Molecular reaction dynamics

• Collision theory: reactions between simple species in the gas phase
• Reactions in solutions: diffusion-controlled, activation-controlled
• Activated complex theory: (transition state theory)
k in terms of thermodynamic parameters

• Potential energy surfaces and the motion of

molecules through these surfaces: the highest level of
sophistication

• The transfer of electrons in homogeneous systems

and at electrodes using transition state theory

(2015) Chemical Kinetics by M Lim 1

 Assigned Problems
Chapter 22 in the 9th edition
• Numerical Problems: 22.1, 22.3, 22.5, 22.7, 22.8, 22.10, 22.13

• Theoretical Problems: 22.15, 22.18, 22.19, 22.21, 22.22, 22.23

• Applications: 22.24, 22.25, 22.28, 22.29

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 Reactive encounters
Here we consider two elementary approaches to the calculation of
reaction rates (gas-phase reactions and reactions in solutions).
Both approaches are based on
1. reactant molecules must meet
2. they should have a certain Emin.

22.1 Collision theory

A + B 
kr
→P v = k r [ A][ B ]

v ∝ (steric requirement) × (encounter rate) × Emin × [ A][ B ]

∴ k r ∝ (steric requirement) × (encounter rate) × Emin

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 22.1 (a) Collision rates in gases
The collision density, ZAB, is the number of (A, B)
collisions in a region of the sample per V and t.

8kT
Z AB = σ N A2 [ A][ B ] 1
πµ =σ π d 2=
, d (d A + dB )
2

z for a single molecule B with the A molecules present

4kT z= σ crel N A [ A]
σ crel × ( NumberDensity ) A =
=σ N A [ A]
2 2
Z AA
π mA 8kT m AmB
=crel = where µ
πµ m A + mB
z ( NumberDensity ) B =
∴ Z AB =× zN A [ B ] =
σ crel N A2 [ A][ B ]
1 1
Z=
AA z × ( Numbe rDensity ) A
= σ crel N A
2
[ A]2

2 2

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 22.1 (a) Collision rates in gases
N2 at room T and p, with d=280 pm

4kT 4 RT
σ= N A2 [ A] σ N A2 [ A]
2 2
Z AA
π mA πMA
pN 2
[ N2 ] =
RT
4 ⋅ 8.314 ⋅ 298 
2
−3 
π ⋅ ( 2.80 × 10−10 m )
2 −1 1
= × 23

π ⋅ 28 × 10−3  
6.02 10 mol mol dm
0.0821 ⋅ 298 
kg m 2 s −2
m2 mol ( mol dm ) = m 2 ( m s −1 ) dm −6 = 106 m −3s −1
−2 −3 2

kg
= 5.00 × 1034 m −3s −1

(2015) Chemical Kinetics by M Lim 5

 22.1 (b) The energy requirement
Reaction occurs only when a collision occurs with sufficient energy
→ incorporate this requirement by writing σ as a function of KE of
approach of the two colliding species (i.e., σ → σ(E))
d [ A]
Z
− = AB =σ ( ε ) vrel N A [ A][ B ] vrel =vrel ( ε )
dt NA

= ( ∫ σ (ε ) v
0
∞
rel (ε ) f (ε ) dε ) N [ A][ B]
A

∞
N A ∫ σ ( ε ) vrel ( ε ) f ( ε ) d ε
∴ kr =
 εa 
σ (ε ) =
 1 −  σ for ε ≥ ε a
0

 ε 
= 0 for ε < ε a

kr = N Aσ crel e − Ea RT

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Reactive collision cross section
 εa 
σ (ε ) =
 1 −  σ for ε ≥ ε a
 ε 
= 0 for ε < ε a

d 2 − a2
=
vrel , A− B v= rel cos θ vrel
d2
2 d −a
2 2
µ ( vrel , A− B ) = µ vrel
1 2 1
2 2 d2
d 2 − a2
ε A− B = ε
d2
ε A− B a2  ε A− B  2
=1 − 2 → a 2 =− 1 d
ε d  ε 
 ε   ε 
∴ amax
2
= 1 − a  d 2 → π amax
2
= 1 − a  π d 2
 ε   ε 

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 1 2 2ε 2ε
ε= µ vrel → vrel= , d ε= µ vrel dv= µ dv= 2 µε dv
2 µ µ
 µ   µ  2ε dε
32 32

f ( v ) dv π
4= 2 − µ v 2 kT
π e −ε kT
2

 v e dv 4  
 2π kT   2π kT  µ 2 µε
32
 1 
π
2=  ε e −ε kT d ε f ( ε ) d ε
 π kT 
2ε
32
∞  1  ∞
kr A∫
N= σ ( ε ) v f ( ε ) d ε N 2π   ∫ σ (ε ) ε e −ε kT d ε
 π kT  µ
rel A
0 0

12
 8  1 ∞
= NA   ∫ σ (ε ) ε e −ε kT d ε
 πµ kT  kT 0
 εa 
σ (ε ) =
 1 −  σ for ε ≥ ε a
 ε 
= 0 for ε < ε a
12
 8  1 ∞  ε a  −ε kT
NA  
 πµ kT  kT ∫ε a
σ 1 −
 ε  εe dε

12
 8  1 ∞
N Aσ  ∫ε (ε − ε ) e
ε

− kT
dε
 πµ kT 
a
kT a

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 12
 8  1 ∞
kr N Aσ   ∫ε ( ε − ε ) e −ε kT
dε
 πµ kT  kT a
a

∞ ∞ ∞
∫ε (ε − ε ) e ∫ε ε e d ε − ε a ∫ e −ε kT d ε
−ε kT
a dε = −ε kT
a a εa

∞ ∞
−ε kT ε =∞ 1 − aε a
∫ε → ∫ e − aε d ε =
−ε kT −ε a kT
e d ε = −kTe = kTe 1 kT → a
e
a ε =ε a εa a
d
da (∫ ∞

εa
e − aε d ε =) d  1 − aε a 

da  a
e 

→ − ∫ε
∞

a
ε e − aε
d ε = −
1 − aε a ε a aε a
a 2
e − e
a
∞
∴ ∫ ε e −ε kT d ε = ( kT ) e −ε a + ε a kTe −ε a
2 kT kT
εa

∫ε (ε − ε a ) e d ε = {( kT ) } ( ) = ( kT )
∞
−ε kT
e −ε a + ε a kTe −ε a − ε a kTe −ε a e −ε a
2 kT kT kT 2 kT

12 12
 8  1 ∞  8  1
∫ε a ( a ) ( kT ) e−ε a
−ε kT
N Aσ  ε − ε
= ε σ
2 kT
kr  e d N A  
 πµ kT  kT  πµ kT  kT
12 12
 8kT  −ε a kT  8kT  − Ea
N= σ
A   e N σ
A   e
RT

 π µ   π µ 
k2 = N Aσ crel e − Ea RT

(2015) Chemical Kinetics by M Lim 9

22.1 (b) The energy requirement
8kT
=kr N Aσ e − Ea RT
→ Ae − Ea RT

πµ

A: weak temperature dependence, A ∝ T

d ln k2 21 1 Ea  1
RT 2
=
RT  + 2 
=+
Ea RT
dT  2 T RT  2

Ea: the minimum KE along the line of approach that is

needed for reaction
A: a measure of the rate at which collisions occur in the gas

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 22.1 (c) The steric requirement
Experimental σ may be different from theoretical σ obtained
for non-reactive collisions or tables of molecular radii:
To compensate for the disagreement,
Steric factor, P. (ex, due to relative orientation of the colliding species)

A harpoon mechanism

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 Reactive cross-section, σ * : σ * = Pσ
(target area for reaction)

=∴ k r Pσ c=
rel N A e − Ea RT
PZ AB f

P : local peoperties of the reaction

(orientation, how close they must come to react)
Z AB : transport property (how often particles come together)
f : energy criterion

Ex 22.1 Estimate steric factor for the reaction H2 + C2H4 → C2H6

at 628 K when experimental A = 1.24×106 M−1s−1 at 298K.
8kT  σ H 2 + σ C2 H 4  8kT
= σ
Atheoretical =
NA   =
N 7.37 × 1011
M − 1 −1
s
πµ  2  πµ
A

∴ P = 1.7 × 10−6 (the more complex the molecule, the smaller the value of P )
(2015) Chemical Kinetics by M Lim 12
 P 4.5 for the reaction K + Br2 → KBr + Br
Harpoon mechanism: when the two are close enough an electron
flips across from K to Br2 → ions → Columbic interaction takes place
Ex 22.2 Estimate P for the harpoon mechanism of K + Br2 → KBr + Br
by calculating the distance at which it becomes energetically favor
able for the electron to leap from K to Br2.
+ − e2
K + Br2 → K + Br E = I K − EABr2 −
4πε 0 R
2

e2
When E ≤ 0, harpooning occurs ∴ ≥ I K − EABr2 σ * = π Rmax
2

4πε 0 Rmax
2
σ R* 2  e 2  1
P= = =
max
 d =RK + RBr2 =400 pm
σ d 2
 (
 4πε 0 I K − EABr  d 2
2  )
I K = 420 kJ mol −1 = 7.0 × 10−19 J , EABr2 = 250 kJ mol −1 = 4.2 × 10−19 J
P = 4.2
(2015) Chemical Kinetics by M Lim 13
(recall) 21.8 Unimolecular reactions-> RRK
21.8(a) Lindermann-Hinshelwood mechanism
→
ka
A + A ← A * + A
k− a

A * 
kb
→ P (slow, rds)
d [ A *] ka [ A]
2

≈ 0 ka [ A] − k − a [ A *][ A] − kb [ A *] ∴[ A
= = *]
2

dt kb + k − a [ A]
d [ P] kbka [ A]  kbka [ A] 
2

= k= b[ A *] = k [ A]  k ≡ 
dt kb + k − a [ A]  k b + k −a [ ] 
A
d [ P] kk
If k − a [ A] >> kb , ≈ k [ A] and k = b a
dt k− a
1 k− a 1 1 1
= + → vs straight line is expected
k kb k a k a [ A] k [ A]
low [ A]: bimolecular high [ A]: unimolecular
(2015) Chemical Kinetics by M Lim 14
 22.1 (d) The RRK model
The steric factor P for unimolecular gas phase reactions.

s −1
 E* 
P= 1 − 
 E 
s −1
 E  *
kb ( E ) =  1 −  kb
 E 
for E* ≥ E

s: # of modes of motion over which E may be dissipated.

E*: E required for the bond of interest to break
E: E available in the collision

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 22.2 Diffusion-controlled reaction
Collision in gases
Encounter in solution (cage effect): less frequent collision but longer stay
→
kd
A + B ← AB 
ka
→ P AB : encounter pair
k− d

d [ AB ]
= kd [ A][ B ] − k − d [ AB ] − ka [ AB ] ≈ 0
dt
k
∴[ AB ] =d [ A][ B ]
ka + k − d

d [ P] ka kd  ka kd 
= k= a[ AB ] [=
A][ B ] k2 [ A][ B ]  2
k ≡ 
dt ka + k − d  k a + k −d 

(i) ka >> k − d , k2 ≈ kd "diffusion - controlled limit"

≈ 109 M -1s -1 (Enzyme catalyzed, the recombination of radicals)
kk
(ii) ka << k − d , k2 ≈ a d = Kka "activation - controlled reaction"
k− d
(2015) Chemical Kinetics by M Lim 16
(2015) Chemical Kinetics by M Lim 17
 22.2(b) Diffusion and reaction
When the two reactants molecules react if they come within a distance R*.

kd = 4π R* DN A = DA =
kT
6πη RA
DB
kT
6πη RB
8RT kT  1 1 
kd ≈ D = DA + DB =  +
6πη  RA RB 

3η
R*
kd is independent of R* RA ≈ RB ≈
2
→ independent of the identities of the reactants kT 4
D≈
6πη R*
Abl. kd for recombination of I atoms in kT 4
kd = 4π R* DN A = 4π R* NA
hexane (0.326 cP) at 298K. 6πη R*
8kT 8RT
8RT 8 ⋅ 8.314 ⋅ 298 = = NA
=
kd = 3η 3η
3η 3 ⋅ 3.26 × 10−4
kT
=
2.03 × 10 m mol s =
7 3 −1 −1
2.03 × 10 M s 10 −1 −1 =D = f 6πη a
f

(2015) Chemical Kinetics by M Lim 18

 When the two reactants molecules react if they come within a distance R*.
Let a A molecule is at the center (r = 0) B
∂c ∂ [ B]
Recall that =D∇2c → DB ∇2 [ B ] = A R*
∂t ∂t
∂ [ B]
When a system reached a steady state, = 0 → ∇ 2 [ B ]r = 0
∂t
∂ 2
2 ∂ 1 1 ∂ ∂ 1 ∂2 
Since ∇=2
+ +  sin θ + 
∂r 2 r ∂r r 2  sin θ ∂θ ∂θ sin 2 θ ∂φ 2 
∂2 2 ∂
= + in spherically symmetric system
∂r 2
r ∂r
d 2 [ B ]r 2 d [ B ]r b
+ = 0 → [ B ] =
a +
dr 2 r dr r
r
B.C. [ B ]∞ = [ B ] bulk value
d [ P]
[ B ]r = R = 0
* react within a distance R* = A [ A] N A
v= 4π R* DB N A [ A][ B ]
dt
 R *
 d [ B ]r  [ B] A is not stationary: DB → DB + DA ≡ D
∴[ B ]=  1 −  [ B ] →   =
d [ P]
r *
 r   dr  r = R* R
= 4π R* DN A [ A][ B ]
 d [ B ]r  [ B] dt
J r = R* = − DB   =
− DB
 dr r=R * R*
v A 4= π R*2 J r = R* 4π R* DB [ B ] for a A molecule ∴ kd = 4π R* DN A

(2015) Chemical Kinetics by M Lim 19

 Review 22-1
8kT 4kT
= N A2 [ A][ B ] , Z AA σ
density: Z AB σ= N A2 [ A]
2
• Collision
πµ π mA

∞
A ∫ σ ( ε ) vrel ( ε ) f ( ε ) d ε
N= N Aσ crel e − Ea RT
 k2
0

→ Pσ crel N Ae − Ea RT

The more complex the molecule, the smaller the value of P

A harpoon mechanism

• →
kd
A + B ← AB 
ka
→ P AB : encounter pair
k− d

d [ P] ka kd
[ A][ B ] diffusion - controlled limit (ka >> k − d )
dt ka + k− d
activation - controlled reaction (ka << k − d )
8RT
=kd 4π R* DN A ≈
3η

(2015) Chemical Kinetics by M Lim 20