• 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 13-1
 • This reaction profile shows how the potential
energy of the reactants A and B change in the
course of a simple bimolecular reaction.
• The horizontal axis (called the reaction
coordinate) represents the course of the
individual reaction event.

SN2 Reaction
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-2
 • Transition state theory (also called activated complex theory)
pictures a reaction between A and B as proceeding through the
formation of an activated complex (C‡), in a rapid pre-equilibrium:
• For a gas phase reaction, p / p o
p p o
C‡ C‡
¢Ô
K 
‡
o o

A + B C ( p A / p )( pB / p ) p A pB
pC ‡ p oRT [ C ‡
] p o
p o
[ C ‡
]
Using pJ = RT[J], K ‡
  
p A pB RT [A]  RT [B] RT [A][B]

RT ‡
Therefore, [C ] 
‡
o
K [A][B]
p

• The activated complex falls apart by unimolecular decay into

products. ‡
k
C‡  P v  k ‡ [C ‡ ]
• The rate of product formation:
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-3
 RT ‡ k‡
[C ]  o K [A][B]
‡
C  P
‡
v  k ‡ [C ‡ ]
p
RT ‡ ‡
• It follows that v  k r [ A][ B] where k r  o k K
p
‡
• Now, our task is to calculate the unimolecular rate constant k
and the equilibrium constant, K ‡ .

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-4
 • The criterion for the activated complex turning into products is
that it pass through the transition state.
• If its vibration-like motion along the reaction coordinate occurs
with a frequency ‡, then the frequency with which the cluster of
atoms forming the complex approaches the transition state is
also ‡.
• However, not every oscillation along the reaction coordinate
takes the complex through the transition state.
• Therefore, we suppose that the rate of passage of the complex
through the transition state is proportional to the vibrational
frequency along the reaction coordinate:
k ‡   ‡ In many cases  = 1
where  is the transmission coefficient (dimensionless).
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-5
 i
 i
q  e
Ni e kT 
 
kT
N
 kT
 i
e
i i

• According to the statistical thermodynamics, the equilibrium

constant for the reaction,
 r E0
(qCo ,m / N A ) c (qDo ,m / N A ) d 
aA  bB  cC  dD K o a o b
e RT
(q A, m / N A ) (q B ,m / NA)

where rE0 is the difference in molar energies of the ground

o
q
states of the products and reactants. J ,m is the standard molar
partition function of species J.

• For the pre-equilibrium, A + B C¢Ô

qCo ‡ / N A 
E0
N A qCo ‡ 
E0
K‡  e RT
 e RT
where ΔE0  E0 (C‡ )  E0 (A)  E0 (B)
(q Ao / N A )(qBo / N A ) q Ao qBo

Note that since NA and qJ have the units of mol-1, K‡ is

dimensionless.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-6
• Assuming that a vibration of the activated complex (C‡) tips it
through the transition state, the partition function for this vibration
is: 1
q h ‡

1 e kT

where ‡ is its frequency (the same frequency that determine

k‡).
• This frequency is much lower than for an
ordinary molecular vibration and so the force
constant is very low.

• Provided h‡/kT << 1,

1 1 kT
q  

h ‡
 h ‡  h ‡
1 e kT 1  1   
 kT 
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-7
 RT ‡ ‡
v  k r [ A][ B] where k r  k K
po

• Therefore, we can write kT

q o
 q
C‡
h ‡ C‡

where qC denotes the partition function for all the other modes
‡

of the complex.
kT N A qCo‡ 
E0

• The constant K ‡ is therefore, K ‡  ‡ K ‡ K‡  o o

e RT

h q q
A B

‡
• K is a kind of equilibrium constant, but with one vibrational
mode of C‡ discarded.
• Now combining all the parts of the calculation into:
RT ‡ ‡ RT ‡ kT ‡ RT ‡
k r  o k K  o  K ‡
Set K c  o K
p p h ‡
p
kT ‡
kr   K c called the Eyring Equation
h
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-8
 ‡ RT ‡
Kc  o K
p
kT ‡
Eyring Equation kr   Kc N A qCo‡ 
E0
h K‡  e RT
o o
q q
A B

• In principle, the second-order rate constant for a bimolecular

reaction can be calculated by using the molecular parameters for
the reactants and the activated complex and the quantity κ.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-9
 • If we accept that K ‡ is an equilibrium constant (despite one
mode of C‡ discarded), we can express it in terms of a Gibbs
energy of activation (‡G ) through the definition,
‡G   RT ln K ‡

• All the ‡X in this section are standard thermodynamic

quantities ( ‡ X o ), but we shall omit the standard state sign to
avoid overburdening the notation.
• Then, the rate constant becomes:
Δ ‡G
kT ‡ kT RT ‡ kT RT 
kr   Kc   o
K  o
e RT
h h p h p
Δ ‡G
‡ 
 K e RT

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-10
 Δ ‡G
kT RT 
kr   o
e RT
h p
• By the definition, G = H – TS, the Gibbs energy of activation can
be divided into an entropy of activation and an enthalpy of
activation.
Δ ‡G  Δ ‡ H  TΔ ‡ S
Δ ‡G Δ ‡ H TΔ ‡ S Δ‡ H Δ‡S
kT RT  kT RT  kT RT 
kr   o
e RT
 o
e RT
 o
e RT
e R
h p h p h p
• When the quantity  is absorbed into the entropy term,
we obtain: Δ‡S Δ‡ H
 kT RT
k r  Be R
e RT
where B 
h po
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-11
 Δ‡S Δ‡ H
 kT RT
k r  Be R
e RT
where B 
h po
• Using the formal definition of activation energy,
 d ln k r   d ln k r 
Ea  RT     R 
2

 dT   d 1 / T  
after some calculation we
find that:

• For reactions of the type, A  B  P

In the gas phase, E a  Δ ‡ H  2 RT
In solution, E a  Δ ‡ H  RT See page 796 of 11th Ed.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-12
 Δ‡S Δ‡ H
 kT RT
k r  Be R
e RT
where B 
h po
• For a gas phase reaction, Δ ‡ H  E a  2 RT
Δ‡S E  2 RT Δ‡S Ea 2 RT
 a 
k r  Be R
e RT
 Be R
e RT
e RT

Δ‡S Ea

k r  e 2 Be R
e RT

• Therefore, the pre-exponential factor of the Arrhenius equation

can be identified as:
Δ‡S
A  e 2 Be R

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-13
 Δ‡S
A  e 2 Be R

• The entropy of activation is negative because two reactant

species come together to form one species (the activated
complex).
• Hence, the negative value of ‡S reflects the occurrence of the
collisions.
• Furthermore, collisions with well-defined relative orientations
correspond to an even greater reduction of entropy.
• Indeed, we can identify that additional reduction in entropy
(‡Ssteric), as the origin of the steric factor of collision theory,
Δ ‡ S steric
Pe R

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-14
 Δ ‡ S steric
Pe R

• The more complex the steric requirements of the encounter, the

more negative the value of ‡Ssteric.  the smaller value of P

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-15
 Δ ‡G
 r G o   RT ln K kT RT 
kr   o
e RT
h p

rG o Δ ‡G
ln K   ln k r  
RT RT
• Using correlation analysis in which ln K is
plotted against ln k, in many cases the
correlation is linear.
• This signifies that as the reaction
becomes thermodynamically more
favorable, its rate constant increases.

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-16
• For reactions in solution, the statistical approach of the
transition state theory is very complicated to apply because the
solvent plays a role in the activated complex.
• However, the thermodynamic version makes it relatively simple
to discuss reactions in solution.
• For a reaction in solution, in the thermodynamic approach, the
rate law can be combined with the thermodynamic equilibrium
constant:
d[P]
Rate law: C‡  P  k ‡ [C ‡ ]
dt
 C [C‡ ]c o
aC ‡  C [C‡ ]c o [C‡ ]c o
Equilibrium constant: K 
‡ ‡
   K
aA aB  A [A]   B [B]  A B [A][B] [A][B]
C ‡

where K is the ratio of activity coefficients, K     .

A B
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-17
 d[P] [C‡ ]c o
 k ‡ [C ‡ ] K  K
dt [A][B]

d[P] K [A][B]
• The combined equation is:  k‡
dt K c o

d[P] k ‡K
 k r [A][B] and kr 
dt K c o
o
k
• If r is the rate constant when the activity coefficients are 1,
we can write:
K  1 k ‡K
kr 
‡
k K K c o k ro
kr  o
o
kr 
c K

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-18
• At low concentrations the activity coefficients can be expressed
in terms of the ionic strength (I) of the solution by using the
Debye-Hückel limiting law:

log  J   Az J2 I
where A = 0.509 in aqueous solution at 298
o
K. C
k
• Because k r  r and K   ,
‡

K   A B

log k r  log k ro  log K   log k ro  log  C‡  log  A  log  B 


 log k ro  A z A2  z B2  ( z A  z B ) 2  I

log k r  log k ro  2Az A z B I

• Note that the charge numbers of A and B are zA and zB, so the
charge number of the activated complex is zA + zB.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-19
 1 2  bi 
I   zi  o 
2 i b 

• I is the dimensionless ionic strength of the solution, and bi is

its molality.
• Ionic strength is a function expressing the effect of the charge
of the ions in a solution.
• The summation is used for all the ions present in the solution,
and not only for those involved in the reaction.

ex) The ionic strength of an M2X3 solution of molality b (not bi).

3 2
M 2 X 3  2 M (aq)  3 X (aq) I
1
2
   b
2  3 2  3   2) 2 o
b
18  12 b b
  15
2 bo bo
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-20
 log k r  log k ro  2Az A z B I
• This expression shows that the rate constant of a reaction
between ions varies with the ionic strength of the solution.
( called kinetic salt effect).
• For reactant ions with a same sign, the
addition of inert ions results in an increase
of the rate constant.
• Conversely, for reactant ions with the
opposite sign, the addition of inert ions
results in an decrease of the rate constant.
• If one of reactants is neutral, no kinetic salt
effect.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-21
The rate constant for the base (OH−) hydrolysis of [CoBr(NH3)5]2+
varies with ionic strength as tabulated below. What can be
deduced about the charge of the activated complex in the rate-
determining stage?

k2
log k r  log k  2Az A z B I
o log  2Az A z B I
r k 2o

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-22
 kr
log o
 2Az A z B I  2  0.509  z A z B I  1.018  z A z B I
kr
• The slope of the (least squares)
straight line is −2.04, indicating that
zAzB = −2.
• Because zA = −1 for the OH− ion, if
that ion is involved in the formation
of the activated complex, then the
charge number of the second ion is
+2.
• This analysis suggests that
[CoBr(NH3)5]2+ participates in the
formation of the activated complex.
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-23
 • Next Reading: 21D Dynamics of molecular collisions

• Problem Set

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

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-24
 E a  Δ ‡ H  2 RT

Δ‡ S Δ‡ H
kRT 2
 kR Δ‡ S Δ‡ H
kr  e R
e RT
and ln k r  ln o  2 ln T  
hp o
hp R RT
d ln k r E
  a2
dT RT
d ln k r Ea 2 Δ‡ H
 2
 
dT RT T RT 2
Multiplying RT2, Ea  2 RT  Δ‡ H

E a  Δ ‡ H  2 RT in the gas phase

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-25
 Ea  Δ‡ H  RT

• For a reaction in solution, [ C ‡

] / c o
[C ‡ o
]c
K 
‡
o o

A + B C¢Ô ([ A] / c )([ B ] / c ) [ A][ B ]
1 ‡
Therefore, [C‡ ]  o
K [ A ][ B]
c

For the product formation, k‡

C  P
‡
v  k ‡ [C ‡ ]

• It follows that v  kr [ A][ B ] 1 ‡ ‡

where k r  o
k K
c
kT N A qCo‡ 
E0
k  
‡ ‡
and K‡  ‡ K ‡ where K ‡  e RT
h o o
q q
A B

1 ‡ kT kT ‡
kr   K ‡
  K
c o
h ‡
hc o

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-26
 Ea  Δ‡ H  RT
1 ‡ kT kT 1 ‡
k r  o  K 
‡
K
c h ‡
h c o

Δ‡G
Because  G   RT ln K , K ‡  e
‡ ‡ 
RT

Δ‡G
kT 1 ‡ kT 1 
kr   o
K  o
e RT
h c h c
Δ ‡G  Δ ‡ H  TΔ ‡ S
Δ‡G Δ‡ H TΔ‡ S Δ‡ H Δ‡ S
kT 1 kT 1 kT 1
 
kr   o

e RT
o
e  RT
o
e e RT R
h c h c h c
• When the quantity  is absorbed into the entropy term,
we obtain: kT 1 RT R
Δ‡ H Δ‡ S
kr  o
e e
h c
Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-27
 Ea  Δ‡ H  RT

Δ‡ S Δ‡ H
kT  k Δ‡ S Δ‡ H
kr  e R
e RT and ln k r  ln o  ln T  
hc o
hc R RT
d ln k r E
  a2
dT RT
d ln k r Ea 1 Δ‡ H
 2
 
dT RT T RT 2
Multiplying RT2, Ea  RT  Δ‡ H

Ea  Δ‡ H  RT in solution

Prof. Yo-Sep Min Physical Chemistry II, Fall 2017 Lecture 13-28