MOLECULAR

REACTION DYNAMICS
kinetics 3
 reaction dynamics
@ Recall:
= temperature dependence of reaction rates

Arrhenius equation Ea
k  Ae
Ea/RT
or ln k  ln A 
RT
= some - not Arrhenius - like
 whose activation energy Ea may be
defined:
 lnk 
Ea  RT 
2

 T  V  dlnk 
or Ea  R  
 d(1/T) 
 reaction dynamics
 Arrhenius equation

 pre-exponential factor A
= measure of the rate at which collisions occur

 product of A and the exponential eEa/RT

= the rate of successful collisions
 collision theory
 Collision Theory
basis:
= particles collide with a frequency calculated
from the kinetic theory of gases,
= reaction occurs if the collision is sufficiently
energetic
Gas - phase reaction :
- collision theory assumes that the reaction rate is
proportional to
 collision theory

(a) the frequency of reactant collision

(= frequency collision, Z)

(b) the probability that the collision is energetic

* effective collision - occur with a kinetic
energy along the direction of approach
of at least Ea
 frequency calculated from kinetic
theory of gases
* according to the Boltzmann distribution
= at a given T, the proportion of each
collisions is eEa/RT
 collision theory
 consider the gaseous reaction:
A + B  product

- the reaction rate is of the form :

if r = k[A][B] = rate = z e-Ea/RT
and z = k’[A][B] = (k/e-Ea/RT) [A][B]
= k eEa/RT[A][B]
= it becomes identical to the Arrhenius
equation
 collision theory
 conclusion:

= the Arrhenius temperature dependence of rate

coefficients reflects the number of encounters

that are sufficiently energetic to lead to reaction

@ the higher the temperature the greater the

proportion of vigorous encounters
 collision theory
 Basic calculations

* if zAB = the number of A and B collisions per unit

time per unit volume
 collision density or frequency

* then: the rate of change of the number of A

particles per unit volume is equal to zAB
multiplied by the proportion of collisions that
occur with a kinetic energy along the line of
approach in excess of some threshold value,
Ea’
 collision theory
 the rate of concentration (molar) change of A is
= rate law (r = z e-Ea/RT ) divided by the
Avogadro’s constant, NA
d[A]  
  zAB  eEa/RT
dt  NA 
 and, the collision frequency, zAB is given as,
æ 8kT ö1/2 2
=
z AB çs ÷ (NA ) [A][B]
è pm ø
where:  = collision cross-section
= (RA + RB)2
1/ = 1/mA + 1/mB
 collision theory
 from collision theory:
= rate of change in [A] per unit time
d[A] zAB f 

dt NA
where,
f = fraction of collision, f = eEa/RT
* therefore,
1/2
d[A]  8kT 
   NA [ A ][B ] e
Ea/RT

dt   
 by definition - a simple binary reaction,
d[A]
 ka [ A ][B ]
dt
collision theory
* then,
1/2
 8kT 
ka     
 NA e
Ea/RT

  
 form of the Arrhenius equation

* as long as the experimental T dependence

dominates the weak square root T
dependence of the pre-exponential
factor (A)
 collision theory
 From the general definition of activation energy -

 lnk 
Ea  RT 
2
  Ea' 21 RT
 T V

* shows that the activation energy is weakly

temperature dependent

* generally, Ea’ is much larger than ½RT

 1/2
 8kT 
collision theory ka      
NA e
Ea/RT

  
 calculated rate coefficients
* simplest method = use for  the values of non-
reactive collisions

 discrepancies between experimental and

calculated results vary:
(1) experimental values are smaller than the
calculated values -
* suggests:
- collision energy = not the only criterion for
reaction
- relative orientation of the colliding species is
important
collision theory
(2) experimental values are larger than the
calculated values -
* indicates:
- reaction occurs more quickly than the
particles collide
- distance of approach needed is quite
different
- cannot use  for non-reactive collision
 collision theory
 Steric requirement
- replacing  in the equation
1/2
 8kT 
ka   *   NA  e
Ea/RT

  
by * = called the reactive cross-section

 introduces the stearic factor, P

* = P
 collision theory
therefore,
1/2
 8kT 
ka   *    
NA e
Ea/RT

  

and
  8kT  
1/2

ka  P    NA  e 
Ea/RT

    

* shows three contributions to the rate

coefficient
 collision theory
@ three (3) contributions to the rate coefficient:

(1) steric factor, P = which take care of the local

properties of the reaction

(2) transport factor = which governs - how often

the particle come together

(3) energy criterion

 collision theory
 the theory would be very well if we could calculate
the steric factor

- in some cases we can:

example: reaction K + Br2  KBr + Br

P = 4.8  “anomalously” large reaction

cross-section,
* = 4.8 

* proposed that the reaction proceeds by a

harpoon mechanism
 collision theory
 harpoon mechanism model
- imagine K atoms approaching the Br2 molecule
- when close enough, an electron flips

neutral molecules  2 ions are formed
* three (3) energy contributions
(for the process: K + Br2  KBr + Br )
(1) ionization energy of K
(2) electron affinity energy of Br2
(3) coulombic interaction energy between ions
- product formation
 collision theory
Diffusion-controlled reactions (reactions in
solution)

* reactions in solution occur differently than in the

gaseous phase

= particles travel through the solvent particle

 encounter frequency is much less than in a
gas

= however, since particles migrate slowly

collision theory
= however, since particles migrate slowly
 two (2) particles encountering each other
will stay near each other much longer

therefore, increased chances of reaction

- but activation energy of the reaction is much more

complicated
 because the pair is surrounded by solvent

How diffusion affects the rate of reaction

 collision theory
 consider the reaction  encounter pair AB
 kd ‘  A + B
A + B  kd  AB 
k P
= 2nd order in reactants A and B

rate of formation :
d[A]
 kd [ A ][B ]
dt
 collision theory
 the encounter pair

(1) can break up without reaction:

AB  A + B d[AB]
  kd ' [ AB ]
dt
(2) can go on to form the product:
AB  P d[AB]
  k [ AB ]
dt
* the steady-state concentration of AB
d[AB]
 kd [ A ][B ]  kd ' [ AB ]  k [ AB ]  0
dt
 collision theory
 solving for [AB],

 kd 
[AB]   [ A ][B ]
 k d ' k 

the overall rate law for the formation of products:

d[P]
 k [ AB ]  k eff [ A ][B ]
dt
kk
keff 
d
where
k d ' k
 collision theory
 Two (2) limiting cases
Case I: rate of break up of the pair = slower than
the rate product formation
 kd’ << k
kk
thus, keff 
d

k
* with this limit:
- the rate of reaction is governed by the rate at
which the reactant particles diffuse
through the medium
= called: diffusion-controlled limit
and the reaction is diffusion controlled
collision theory
Case II: substantial activation energy is involved
in the reaction of A and B
 k << kd
thus, kk
keff 
d

kd ' K = equilibrium constant

* with this limit:
- the reaction rate depends on the accumulation
of energy in the encounter pair - due to
its interaction with the surrounding
solvent
= called: activation-controlled reaction
collision theory
 Diffusion and Reaction (diffusion of B towards A)
= rate of a diffusion-controlled reaction can
be calculated by considering the rate at
which the reactants diffuse together
Consider: stationary particle
A in a solvent containing
B particles
- - imaginary sphere of
radius r surrounds
particle A
- - particles B outside this
sphere
 D=DA +DB

Reaction occurs at R*
 collision theory
 from Fick’s first law of diffusion,
= the flux is proportional to the concentration
gradient (towards A)

 d[B] 
* J (flow) = 4r2 J = 4r2DBNA  
 dr 

where, DB = diffusion coefficient of B

 collision theory
 two information needed:
(1) when r is infinite
= the conc. of B is the same as the bulk conc.
(2) the flow through a shell is the same whatever
the radius
= no reaction occurs until A and B touch

* thus, under steady-state conditions,

J = is a constant independent of r
so,
 collision theory
suppose R* = critical distance
= reactants touch and reaction occurs with the
destruction of B

Thus, when r = R*, [B]r = 0

therefore substituting into equation,
The following expression for the flow of B towards A
is obtained,
J = 4RB*NA[B]

* flow: average number of B particles per unit time

passing through any spherical surface centered
on any A
 collision theory
 the rate of the diffusion-controlled reaction is equal
to the average flow of B particles to all the A
particles in the sample

* if the bulk concentration of A is [A]

- the number of A in the sample of volume V
= NA[A]V
so, the global flow of all B to all A is equal to

JNA[A]V = 4R*DBNA2 [A][B]V

= this is the flow in terms of the numbers of B

 collision theory
 it is unrealistic to suppose that all A are stationary
= replace DB by D = DA + DB
Then,
the rate of change of concentration of AB is:
d[AB]
 4R *DNA [ A ][B ]
dt
* by comparison with the rate law expression,
kd = 4R*DNA

d[AB]
= kd [ A ][B ]
dt
 collision theory
 incorporating the Stokes-Einstein relation for each
particle
kT kT
DA  DB 
6R A 6RB
where RA and RB are effective hydrodynamic radii

= since this relation is an approximation, little extra

error is introduced if we write,
RA = RB = ½R*
this leads us to:
8kTN 8RT From kd = 4R*DNA
kd  
A

3 3
 collision theory
 this approximation shows that
8kTN 8RT
kd  
A

* the rate constant is : 3 3

- independent of the identities of the

reactants

- dependent only on the temperature and

the viscosity of the solvent
activated complex theory
 Activated Complex Theory (ACT)

 the advantage over Collision Theory :

- a quantity corresponding to the steric factor
(P) appears automatically

* ACT: attempts to identify the principal features


governs the size of the rate reaction

a model of the events that take place during the
reaction
 activate complex theory
 reaction profile

* consider the reaction: A + B  products

 generally features: how the energy of the

reactants change in the course of a simple
bimolecular reaction

* potential energy rises to a maximum then falls

down forming the products
activate complex theory
 activate complex theory
 ACT :
= pictures a reaction between A and B - through
the formation of an activated complex, C‡
A + B = C‡
* this activated complex falls apart by
unimolecular decay to form the products
C‡  k‡  P
@ rate = k‡[ C‡]
 problems: (1) find k‡
(2) concentration of C‡
 activate complex theory
 activated complex concentration
= proportional to the concentration of the reactants
C‡  [A][B] C‡ = K‡[A][B]
* therefore,
d[P]
 rate  keff [ A ][B ]
dt
where keff = k‡K‡

? how do we calculate for these two constant ?

 activate complex theory
 Rate of decay of the activated complex

* activated complex  forms products if it

passes the transition state

* the rate of passage of the complex through the

transition state
 the vibrational frequency along the reaction
coordinate (rate of decay of transition state)
or
k‡ = 
 activate complex theory
 concentration of the activated complex
- to determine the activated complex conc.
= assume: a pre-equilibrium between
reactants and the complex,
A + B = C‡
pC

KP 
pA pB
if pX = RT[X]

C   K RT A B 

P
 activate complex theory
 by comparison: K‡ = RT Kp
* from equilibrium constant discussion - defined
0
pC NA qC ΔE RT

*

KP  KP  0 0 e
0

pA pB qA qB
(equilibrium constant from structural data)
Eo* = molar energy separation between zero-
point levels to C‡ and A + B
qXo = standard molar partition functions

Eo* = Eo(C‡)  Eo(A) + Eo(B)

 activate complex theory
 let us look at the partition function of the activated
complex
- partition function for vibration
1
q  vibration frequency
1 e
h
kT

* if the force constant is low

(because oscillations correspond to the
complex falling apart)

hn << 1
kT
activate complex theory
= so the exponential may be expanded and the
partition functions becomes,

1 kt
q 
h
1   1   ....  h

 RT 
thus,

qC 

kT
h
qC 

where q = partition function for all other

modes in the complex
activate complex theory
if that is the case then
kT
K  xK
‡

h 0
NA pC  ΔE RT

*

where K  RT 0 0 e
0

pA pB
* a kind of equilibrium constant with one
vibrational mode of C‡ discarded

* rate constant
keff = k‡K‡ =   kT K
giving  h 
 kT K
keff =     Eyring Equation
h
κ is the transmission coefficient
 activate complex theory
Collision of structureless particles
@ consider A and B as two structureless particles
- collide = to give an activated complex
 if J = A and B particles = structureless atoms
- the only contributions to the partition functions
are the translational term the of molar partition
function of J; q

q =V
q
m

l
J 3
J
where
h RT
lJ =
q
and Vm =
(kT2p mJ)
1/2 q
p
activate complex theory
 activated complex = a diatomic cluster
mass  mC‡ = mA + mB

has one vibrational mode
= corresponds to the motion along the reaction
coordinate, therefore does not appear in qc
 thus the molar partition function of the activated
complex is given as q
q 2IkT V m
q c± = 2 x 3 ±
lC
activate complex theory
@ for diatomic molecule of bond length r
moment of inertia, I = r2 ( µ = mAmB/(mA + mB))
then,  kT  RT  NA Λ3A ΛB3  2IkT   ΔE RT
keff     o  3 0  2  e
0

 h  p  ΛC Vm   


 kT   Λ A ΛB  2IkT   ΔE RT
keff    NA   2  e 0

 h   ΛC    

1/2
 8kT  2  ΔE RT
keff  NA   r e
0

  
identifying r2 as * or the reactive
Cross-section
activate complex theory
 partition functions
= calculated from
 spectroscopic information about their
energy levels
 approximate expressions

 difficulty with the Eyring equation:

= calculation of the partition function of the
activated complex
- make assumptions about its size, shape
and structure
activate complex theory
 Thermodynamic Aspects
 accepting K as equilibrium constant

express in terms of Gibbs energy of activation
G‡ =  RT ln K
since, G = H  TS
‡S = entropy of activation, and
‡H = enthalpy of activation

G‡ = ‡H  T‡S

activate complex theory
 G, H, and S of activation
= used to report experimental reaction rates

encountered when relationship between
equilibrium constants and values of
reaction are explored using correlation analysis
* in which, plot ln  against ln k

many cases = correlation is linear:
 that is as the reaction becomes
thermodynamically favorable its rate
constant increases
 activate complex theory
substituting G‡ = ‡H  T‡S into keff equation
 is absorbed into the entropy term
‡
Δ S
‡
Δ H kT RT
keff  Be R e RT where B x o
h p
- expressing this equation in the Arrhenius form
2  lnk 
Ea  RT 
 T  V gives
‡H = Ea  2RT for bimolecular gas-phase
reaction
‡H = Ea  RT for unimolecular reaction in
either phase
for reaction in solution
 activate complex theory
 then,
keff can be written in the Arrhenius form
Ea
keff  Ae RT

* for a bimolecular gas-phase reaction

A
and Δ S  R  ln  2 

‡
ΔSR
A e e2 ‡

 B 
 activate complex theory
 using ACT - thermodynamic version
- makes it simple to look at reactions between
ions (in solution)
A + B = C‡
C‡  Product
* in the thermodynamic approach - rate law
d[P] ‡ ‡
 k [ C ] d[P]  k2 A B 
dt dt
* with thermodynamic equilibrium constant
aC  C  ‡

 K  K
‡

K   or C   A B
‡

aA aB  [A][B]  Kγ
 activate complex theory
then
d[P]
 k2 A B 
dt
where K Expressing rate constant
k2  k
‡
In terms of thermodynamic
K constants
when a = 1,

o
k = rate constant
2 
o
k Kk
2
‡

that is o
k
k2 
2

K
 activate complex theory
 at low concentration a can be expressed in terms of
ionic strength
- using D-H limiting law log  j   Azj I
2

then, o

log k2  log k2  A z  z  z A  zB  I
2
A
2
B
2

log k2  log k2  2AzA zB I
o

 kinetic salt effect

A = 0.509 in aqueous solution at 298 K

 activate complex theory
* variation of the rate constant with ionic strength
thank you!

jose s. solis, ph.d.

i.s. martinez, ph.d.
institute of chemistry
university of the philippines
diliman, quezon city