• Ch.

21 Molecular Reaction Dynamics

A. Collision Theory
B. Diffusion-Controlled Reactions
C. Transition State Theory
D. The Dynamics of Molecular Collisions
E. Electron Transfer in Homogeneous System
F. Processes at electrodes

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-1
 • Reactant molecules in solution have to jostle their way through
the solvent, so their encounter frequency is considerably less
than in gas.
• However, because a molecule in solution also migrates only
slowly away from a location, two reactant molecules that
encounter each other stay near each other for much longer than
in a gas.
• The lingering of one molecule near another due to the presence
of solvent molecules is called the cage effect.
• For the activation energy of a reaction in solution, we need to
consider the energy of the entire local assembly of reactant and
solvent molecules.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-2
 • Suppose that the rate of formation of an encounter pair AB is
first-order in each of the reactants A and B:
A  B  AB v  k d [A][B]

• As you shall see later, kd is determined by the diffusional

characteristics of A and B.
• The encounter pair can break up without reaction or it can go on
to form products P.
AB  A  B v  k d' [AB] and AB  P v  k a [AB]

Applying the QSSA,

d[AB] k d [A][B]
 k d [A][B]  k d' [AB]  k a [AB]  0 [AB] 
dt k d'  k a
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-3
 AB  P v  k a [AB]

• The rate of formation of products is therefore:

d [P] k d [A][B]
 k a [AB]  k a '
dt kd  ka
d [P] ka kd
 k 2 [A][B] and k 2 
dt k d'  k a

A  B  AB v  k d [A][B]

AB  A  B v  k d' [AB]

AB  P v  k a [AB]

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-4
 d [P] ka kd
 k 2 [A][B] and k 2 
dt k d'  k a

• If the rate of separation of the encounter pair is much slower

than the rate of product formation,
k d'  k a
ka kd
The effective rate constant is: k2   kd
ka

• In this limit, the reaction is diffusion-controlled.

 The rate of reaction is governed by the rate at which the
reactant molecules diffuse through the solvent.
Ex) Radical and atom recombination reactions are often diffusion-
controlled due to the low activation energy.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-5
 d [P] ka kd
 k 2 [A][B] and k 2 
dt k d'  k a

• When the activation energy of the reaction AB  P is large,

k d'  k a

ka kd kd
The effective rate constant is: k 2   ka K where K 
k d' k d'

• In this limit, the reaction is activation-controlled.

 The reaction proceeds at the rate at which energy
accumulates in the encounter pair from the surrounding solvent.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-6
 • For diffusion-controlled reactions,
d [P]
 k d [A][B] Cf) A  B  AB v  k d [A][B]
dt

• The rate of a diffusion-controlled reaction is calculated by

considering the rate at which the reactant to diffuse together.
• The rate constant for a reaction, in which the two reactant
molecules react if they come within a distance R* (See
Justification 21B.1), is:
k d  4R * DN A

where D is the sum of the diffusion coefficients of the two

reactant species in the solution. DD D A B

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-7
 k d  4R * DN A D  D A  DB

• As shown in Chapter 19, the diffusion coefficient is related to

the hydrodynamic radius by the Stokes-Einstein relation:
kT kT
D 
f 6a

• For the molecules A and B, of which the hydrodynamic radii are

RA and RB, respectively, in a medium of viscosity :
kT kT
DA  and DB 
R*
6RA 6RB
kT
• Assume that RA = RB= ½ R*, DA  DB 
3R *
RA RB
2kT 8 RT
k d  4R * DN A  4R * N 
3R * 3
A

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-8
 8RT
kd  R: gas constant.
3

• In this approximate expression, the kd is independent of the

identities of the reactants, and depends only on T and the
viscosity of the solvent.
• For example, the rate constant for the recombination of I atoms
in hexane ( = 0.326 cP) at 298 K is:

8 RT 8  8.31 J/K  mol (298K )

kd    2 . 0  10 7
m 3
/mol  s
3  2
3  0.326  10  0.1 kg/m  s 
This well agrees to the experimental value (1.3107 m3/mol·s).

Recall that 1 P  0.1 kg/m  s and 1 J  1 kg  m /s

2 2

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-9
• When both diffusion and convection occur, the generalized
diffusion equation (Chapter 19) is:
c  2c c
 D 2 v
t x x

• The concentration of particles may change as a result of

chemical reaction.
 For a further refinement of diffusion equation, the
concentration change by the reaction should treated.

[J ]  2 [J] [J ]

 D 2 v
t   x
x   

Diffusion Convection Reaction

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-10
• Consider a small volume element in a chemical reactor (or
biological cell).
• During some time interval, the total change of the number of
particles of some species J must satisfy the following material
balance equation.

 Net change of   Number   Number 

number of J in the   Number  

Number  
 formed by   dissappeared by
 
 entering   
leaving     
 volume element     reaction  reaction 

Accumulation In Out Generation

[J ]  2 [J] [J ]

D v
t x 2
x
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-11
 [J ]  2 [J] [J ]
D v
t x 2
x
• The reactant molecules (J) are formed or disappears due to
chemical reaction when they flow through the volume element.
• If the reaction is pseudofirst-order, then the net rate of change of
[J] is:
[J ]
 k[J]
t
• Therefore, the overall rate of change of [J] is:

[J ]  2 [J] [J ] (For a pseudofirst-order)

D  v  k [ J ]
t  x 2
x 
      Reaction
Diffusion Convection
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-12
 [J ]  2 [J] [J ]
D  v 
 k[J ]

t  
2
x    x Reaction
Diffusion Convection

• This is called the material balance equation.

• If k is large, then [J] will decline rapidly.
• If D is large, then the decline can be replenished as J diffuses
rapidly into the region.
• The convection term (e.g., caused by stirring) can sweep
material either into or out of the region according to the signs of v
and the concentration gradient (∂[J]/ ∂x).

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-13
 • The material balance equation is a second-order partial
differential equation and is far from easy to solve in general.
• As a special case, consider an unstirred reaction vessel (i.e., no
convection motion). [J ]  2 [J]
D  k[J]
t x 2

• If the solution of this equation in the absence of reaction (i.e., k

= 0) is [J], then the solution in the presence of reaction (k>0) is
[J]*. 
x2
 kt n0 e 4 Dt
[J ]*  [J ]e where [J ] 
x
A Dt
(See Problem 21B.1)
• Note that [J] is the solution for a system in which initially a layer
of n0NA molecules is spread over a plane of area A.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-14
 x2

 kt n0 e 4 Dt
[J ]*  [J ]e where [J ] 
A Dt

• This solution reveals that the

concentration of J decreases more rapidly
than that (gray lines) in the absence of
reaction.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-15
 • Next Reading: 21C Transition state theory

• Problem Set

21A.2b; 21A.5b; 21B.2b; 21B.4b; 21C.2b; 21C.6b;

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 12-16