Atkins & de Paula:

Atkins Physical Chemistry 9e

Chapter 22: Reaction Dynamics

 Chapter 22: Reaction Dynamics
REACTIVE ENCOUNTERS
22.1 Collision theory
rate constant, kr encounter rate minimum energy requirement steric requirement.
A BP v k r [A][B]
1/ 2
8 RT
c c (T / M ) v (T / M ) N AN B (T / M ) [A][B]
1/ 2 1/ 2 1/ 2

M
k r (T / M )1/ 2 e Ea / RT
k r P (T / M )1/ 2 e Ea / RT
22.1(a) Collision rates in gases
collision density, the number of (A,B) collisions in a region of the sample in an interval
of time divided by the volume of the region and the duration of the interval:
1
8kT
2
m A mB
Z AB N A2 [A][B], d 2 d 12 (d A d B ),
m A mB
1
4kT
2

Z AA N A2 [A]2
m A
 Chapter 22: Reaction Dynamics
1
8kT
2

collision frequency, z crel N A crel

collision density, Z AA 12 zN A 12 crel N 2A
Z AB crel N AN B collision cross-section
1
volume of tube
8kT
2

Z AB N A2 [A][B] N 1 / 1 / crel t

z 1 / t crel N
22.1(b) The energy requirement
dN A
( )vrel N AN B ( ) 0 when a
dt
d[A]
( )vrel N A [A][B]
dt
( )vrel f ( )d N A [A][B]
d[A]
f ( ); Boltzmann distributi on of energy
dt 0

k r N A ( )vrel f ( )d
0
Chapter 22: Reaction Dynamics

k r N A ( )vrel f ( )d
0
1
d 2 a2
2

12 v 2
rel vrel , A B vrel cos vrel 2

d
2
d 2 a2 2
1

d 2 a2
2 (vrel , A B ) 2 vrel
1 2 1
A B
d
2
d2
amax , above which reactions do not occur
a amax A B a

1 a d 2
( ) amax
, d 2
( ) 1 a
2
amax
2
vrel , A B

a ( ) 0 & a ( )
Chapter 22: Reaction Dynamics

k r N A ( )vrel f ( )d
0

2 / kT d
3/ 2 3/ 2
12 v 2 , dv d /( 2 )1 / 2
f (v)dv 4 v 2 e v f (v)dv 4 e
2

/ 2 kT

2kT 2kT (2 )1/ 2

3/ 2
1 1 / 2 / kT
f (v)dv 2 e d f ( )d
kT
1/ 2 1/ 2
2 8 1
3/ 2
1

0
( )vrel f ( )d 2
kT

0
( ) 1/ 2 e / kT d

( )e / kT d
kT kT 0
e ax e ax xe ax
a / kT e dx a C , xe dx a 2 a C
ax ax

d 1 e d (kT ) 2 e a / kT
/ kT
( )e
0 a

1/ 2
8kT a / kT

0
( )vrel f ( )d

e


k r N A ( )vrel f ( )d N Acrel e Ea / RT
0
 Chapter 22: Reaction Dynamics
22.1(c) The steric requirement
steric factor, P = */.
reactive cross-section, *, the area within which a molecule must approach another
molecule for reaction to occur. 1/ 2
8kT
rate constant from collision theory, kr P N Ae E / RT
a

harpoon mechanism, a process in which electron transfer precedes atom extraction.
(Exercise Example 22.2!)
 Chapter 22: Reaction Dynamics
22.1(d) The RRK model
The RiceRamspergerKassel model (RRK model), a model that takes into account
the distribution of energy over all the bonds in a molecule.
s 1 s 1
E E
P 1 kb ( E ) 1 kb for E E
E E

s; the # of modes of motion, E ; energy required for the bond breakage, E ; energy available in the collision

Lindemann-Hinshelwood
mechanism
RRK model

Exp. data for

s
unimolecular
isomerization of
trans-CHD=CHD
 Chapter 22: Reaction Dynamics

22.2 Diffusion-controlled reactions

cage effect, the lingering of one molecule near another on account of the hindering
presence of solvent molecules.
 Chapter 22: Reaction Dynamics
22.2(a) Classes of reaction
diffusion-controlled limit, a reaction in which the rate is controlled by the rate at which
reactant molecules encounter each other in solution.
activation-controlled limit, a reaction in solution in which the rate is controlled by the
rate of accumulating sufficient energy to react.

A B AB v k d [A][B] AB : encounter pair, d : diffusion

AB A B v k d [AB]
AB P v k a [AB] a : activated process
d [AB] k d [A][B]

k d [A][B] k d [AB] k a [AB] 0 [AB]
dt k a k d
d [P] kk
k a [AB] k r [A][B] , k r a d
dt k a k d
When k d k a k r k d : diffusion - controlled limit
ka kd
When k a k d k r ka K : activation - controlled limit
k d
 Chapter 22: Reaction Dynamics
22.2(b) Diffusion and reaction
A B AB in solution!
c 2 c 3dimension [B]
D 2 DB 2 [B] ; diffusion equation (Fick' s second law of diffusion)
t x t
[B]
At steady state; 0 2 [B]r 0; r signifies a quantity that varies with the distance r
t
d 2 [B]r 2 d [B]r b
[B]r
2

spherically symmetry system
0 General solution : [ B] a
r 2 r r
r
r

[ B]r [B] ([B] is bulk value) as r , [ B]r 0 at r R (the distance where reaction occurs)

R
[B]r 1 [B]
r
Rate of reaction 4R 2 J ( J : molar flux of B toward A)
d [B]r D [B]
From Fick' s first law J DB B
dr r R R
Rate of reaction 4R DB [B] for
all
A
4R DB [B]N A 4R DB N A [A][B]
DB DA DB D A is not stationary
d [P]
k d [A][B] 4R DN A [A][B] k d 4R DN A
dt
 Chapter 22: Reaction Dynamics
By using Stokes - Einstein equation;
kT kT
DA DB ( RA , RB ; hydrodynam ic radius, ; viscosity of medium)
6RA 6RB
8 RT
RA RB 12 R k d 4R DN A
3

22.3 The material balance equation

Generalize d diffusion equation : the diffusion equation including convection
[J] 2 [J] [J]
D 2 v
t x x
[J] 2 [J] [J]
Including chemical reaction D 2 v k r [J]; material balance equation
t x x
No convection ; [J] [J]e kr t [J] : for no reaction
n0 x 2 / 4 Dt
No reaction; [J] e
A(Dt )1/ 2
For general cases, we can solve the material balance equation numericall y!!
 Chapter 22: Reaction Dynamics
TRANSITION STATE THEORY
transition state theory (or activated complex theory, ACT), a theory of rate constants
for elementary bimolecular reactions.
transition state, the arrangement of atoms in an activated complex that must be
achieved in order for the products to form.

22.4 The Eyring equation

pC p
A B C K
p A pB
p J RT [ J ] RT
[C ]
K [A][B]
p
C P v k [C ] Our task!!
RT
v k r [A][B] kr k K
p
 Chapter 22: Reaction Dynamics
22.4(a) The rate of decay of the activated complex
transmission coefficient, , the constant of proportionality between the rate of passage
of the complex (k) through the transition state and the vibrational frequency along the
reaction coordinate (); k = .
22.4(b) The concentration of the activated complex
q J N q

K J,m e r E0 / RT K C e r E0 / RT where p 1 bar & r E0 E0 (C ) E0 (A) E0 (B)

A

J N A qA qB
1
Partition function for specific vibration which leads to product formation; q
1 e h / kT
1 kT
h kT q
h h
1 1
kT
kT
qC q where qC denotes the partition function for all the other modes of the complex.
h C

kT N q C r E0 / RT
K
( K ; K with one vibrational mode of C discarded)
A
K K e
h
qA qB
 Chapter 22: Reaction Dynamics
22.4(c) The rate constant
RT kT RT kT
kr k K K
K ; Eyring equation
p h p h C
For qC , we have to know the size, shape, and structure of activated complex very difficult!

22.4(d) The collision of structureless particles

Vm h RT
q 3

J Vm
J (2mJ kT )1/ 2 p
J

~ 2
2 IkT VmhcB
A B C (A B), q correspond s to rotatioal mode q 2 3

C
2I
C
C
m A mB
I r 2 , , mC m A mB
m A mB
3
kT RT N A 3A 3B 2 IkT r E0 / RT kT AB 2 IkT r E0 / RT
kr 2
e NA 2 e
h p CVm
C
3
h
1/ 2
8 kT
8kT 2 r E0 / RT
E / RT
k r
N Ae a

N A 2 r e r 2 , Ea r E0

 Chapter 22: Reaction Dynamics
22.4(e) Observation and manipulation of the activated complex
Na+I- decay

Photoreaction of IHOCO van der Waals complex

IHOCO HOCO resembles the activated complex of H + CO2[HOCO] HO+CO
 Chapter 22: Reaction Dynamics
22.5 Thermodynamic aspects
22.5(a) Activation parameters
Gibbs energy of activation , G RT ln K
kT RT G / RT G H TS is absorbed into S term S / R H / RT kT RT
kr e k Be e B
h p h p
r

ln k r
k r Ae Ea / RT Ea RT 2 Ea H 2 RT

T

k r e 2 Be S / R e Ea / RT
S / R S steric / R
A e Be 2
Pe

correlation analysis, a procedure in which ln K (=-rG/RT) is plotted against ln k

(proportional to -G /RT).
liner free energy relation (LFER), a linear relation obtained in correlation analysis;
reaction becomes thermodynamically more favorable.
 Chapter 22: Reaction Dynamics
22.5(b) Reactions between ions
kinetic salt effect, the effect of a change in ionic strength on the rate constant of a reaction.
d [P] a [ C
]c
C
k [C ] K C K K
dt aA aB [A][B] A B
d [P] k K k r0 k K when 1 k r0
k r [A][B] kr k r
dt K K
From Debye - Huckel limiting law (log z z- AI 1/ 2 , A 0.509 for aq. at 250 C),
log A AzA2 I 1/ 2 log B AzB2 I 1/ 2
log C A( z A z B ) 2 I 1/ 2

log k r log k r0 A z A2 z B2 ( z A z B ) 2 I 1/ 2
log k r0 2 AzA z B I 1/ 2

Exercise Example 22.3!

 Chapter 22: Reaction Dynamics
THE DYNAMICS OF MOLECULAR COLLISIONS
22.6 Reactive collisions
22.6(a) Experimental probes of reactive collisions
infrared chemiluminescence, a process in which vibrationally excited molecules emit
infrared radiation as they return to their ground states.
IR chemiluminescence

O+CSCO+S
 Chapter 22: Reaction Dynamics

laser-induced fluorescence (LIF), a technique in which a laser is used to excite a

product molecule from a specific vibrationrotation level and then the intensity of
fluorescence is monitored.
 Chapter 22: Reaction Dynamics
multiphoton ionization (MPI), a process in which the absorption of several photons by
a molecule results in ionization.
resonant multiphoton ionization (REMPI), a technique in which one or more photons
promote a molecule to an electronically excited state and then additional photons are
used to generate ions from the excited state.

A laser pulse excites electrons in a semiconductor

surface (10 layers C 60 on a Cu(111) substrate) which in
turn pass their energy to adsorbed molecules (NO).
REMPI measures the motion of the desorbed molecules.
 Chapter 22: Reaction Dynamics
reaction product imaging, a technique for the determination of the angular distribution
of products.

Reaction products detected in the Streamer Chamber when a 1.1-GeV-per-nucleon

beam of holmium-165 collided with a holmium-165 target at the Bevalac.
 Chapter 22: Reaction Dynamics
22.7 Potential energy surfaces
potential energy surface, the potential energy as a function of the relative positions of
all the atoms taking part in the reaction.

HA + HB-HC HA-HB + HC
 Chapter 22: Reaction Dynamics

saddle point, the highest point on a potential energy surface encountered along the
reaction coordinate.
HA + HB-HC HA-HB + HC
 Chapter 22: Reaction Dynamics

saddle point, the highest point on a potential energy surface encountered along the
reaction coordinate.
HA + HB-HC HA-HB + HC
 Chapter 22: Reaction Dynamics
Example of potential energy surfaces.

Ultrafast reaction dynamics of the

complete photo cycle of an
indolylfulgimide studied by absorption,
fluorescence and vibrational spectroscopy
 Chapter 22: Reaction Dynamics
22.8 Some results from experiments and calculations

HA + HB-HC
HA-HB + HC
Chapter 22: Reaction Dynamics
HA + HB-HC HA-HB + HC
 Chapter 22: Reaction Dynamics
22.8(a) The direction of attack and separation

300
 Chapter 22: Reaction Dynamics
22.8(b) Attractive and repulsive surfaces
attractive surface, a potential energy surface in which the saddle point occurs early on
the reaction coordinate.
repulsive surface, a potential energy surface in which the saddle point occurs late on
the reaction coordinate.

H + Cl2 HCl +Cl

attractive surface repulsive surface

 Chapter 22: Reaction Dynamics
22.8(c) Classical trajectories
direct mode process, a bimolecular process in which the switch of partners takes place
very rapidly.
complex mode process, a bimolecular process in which the activated complex survives
for an extended period.

direct mode process complex mode process