KINETICS

Chemical kinetics looks at dynamics-details of process of how system
gets form one state to another and time required to do so - complex area
of study
Equilibrium thermodynamics - static viewpoint - interested only in initial
and final states of a system - can tell with precision the extent of reaction
kinetics - more crudely predicts rates of reaction
- explains rate in terms of reaction mechanism
- reaction mechanism describes relative positions of all microscopic
particles as f(time) whose motion is necessary for reaction to occur
Also look at theoretical models for predicting rxn rates based on
Arrhenius conclusion: most commonly observed relationship between
rate of rxn and T implies that there exists an energy barrier to progress
of rxn
- kinetic molecular theory & activated complex theory

Techniques to Study Kinetics (come up with mechanisms)
ultimately - conc as f(time)
1. pressure changes
- at least one component must be gas
2. spectroscopy
- use Beer's law A a c
- only one species must absorb at particular l
3. Electrochemical methods
- can monitor change in pH or conductivity of solution

4. Other more sophisticated methods

Assuming closed systems:
aA + bB  cC + dD

moles of i : ni = ni(t) = nio + i 
i = stoichiometric coef. - unitless - rcts, + pdts

dni =id

noi = constant

dni
d
 i
dt
dt
const. V 

 = extent of rxn = mol

dni /V  i d dci


dt
V dt dt

 i d dci
For const. V: rate ui =
= rate of species i

V dt

dt

Example: N2 + 3H2 = 2NH3
u = rate of reaction =

dc

1 d
2 1

V dt
dt
3

dc

dc

dc

rate of formation NH3 =

dc

H

2 1
dt
2

dc

NH

3

dt

N

1
1
2 u

u


u NH
N
H
dt
2
2 3
2
3

rate of disappearance N2= 
rate of disappearance H2= 

N

H

3
2 u

3
u


u NH
H
N
dt
2
2
2
3

NH

2
3 u

2
u


u H2
NH3
N
dt
3
2

u(t) = rate of rxn is related to concentrations of various chemical
species present at time
 t. This relationship called rate law.

which components of rxn are kinetically active, i.e. a
change in its concentration will alter the rate of rxn. or
included in rate law
Rate law often looks like following:
u = k[A]a[B]b
k = rate constant = f(T) c 
must be determined experimentally, cannot be deduced
from stoichiometry of rxn.
Example:
rate law
Br2 + I2 = 2BrI

d [ BrI ]

 k[ Br2 ][ I 2 ]
dt

Br2 + H2 = 2HBr

d[ HBr ]
k[ Br2 ]1/ 2[ H 2 ]

dt
1  k '[ HBr ] /[ Br2 ]

In general:

[A]a[B]b[D]d

a = order with respect to species A
b = order with respect to species B
d = order with respect to species D
(a+b+d) = overall order of rxn
a can be fraction, negative
For 1st rxn: order w.r.t. Br2 and I2 is 1, overall order =2
rate law happens to reflect rxn stoichiometry
For 2nd rxn: concept of order does not apply
rate law is complicated and rxn occurs by multistep process

If concentration of any kinetically active species is
nearly constant it can be incorporated into k and we get
pseudo nth order rxn. C = catalyst for instance:

d [ A]

 k AB C 
dt

(3rd order)

if [C]~ constant

d [ A]

 k ' AB 
dt

(pseudo 2nd order)

can use to determine the order (isolation method)

Co

Conc.

equilibrium

time

• to find rate of reaction at any time, measure change of
concentration with time at constant T
• rate at any time = slope of curve at that time
• easier to compare integrated rate expression

First Order Reactions
A  products

d [ A]
= k[A]
u(t) = 
dt
d[ A]
 kdt
[ A]
ln

[A]
 kt
[A]o
Plot ln[A] vs t

A + B  products

or

d[ A]  k t dt
 [ A]

[ A]o
0
[ A]

[A] = [A]oe-kt

slope = -k

Half-life: time required for half of the specified
reactant to disappear
t = t1/2 when [A] = [A]o/2
For first order reaction:

ln [ A]o / 2  kt 1
2
[ A]o

1
ln  kt1
2
2

ln 2

k

t 1  f (conc.)

t1

2

2

Second Order Reactions
A  products

or

A + B  products

d [ A]
= k[A]2
u(t) = 
dt
[ A]
d[ A]  k t dt
d[ A]
 kdt
 [ A]2

2
[ A]o
0
[ A]


1 
 1


  kt
 [A] Ao 

1
1

[ A] Ao

1
1

 kt
[ A]  Ao

Plot 1/[A] vs t

 kt

slope = k

Half-life for Second Order Reaction
t = t1/2 when [A] = [A]o/2

2
1

[ A]o  Ao

t1

2

1

k  Ao

 kt 1

kt 1

2

2

1

[ A]o

t 1  f (initial conc.)
2

Second Order Reactions

d [ A]
d [ B]
u(t) = 

= k[A][B]
dt
dt

d[ A]
 kdt
AB

need to integrate but we have a problem
need to know how [B] varies with [A]
[A] = [A]o - /V and [B] = [B]o - /V
/V = [A]o-[A] so [B] = [B]o -[A]o+[A]

d[ A]
 kdt
ABo  Ao  A

method of partial fractions: for [B]o

[A]o

1
p
q
 
ABo  Ao  A A Bo  Ao  A
1 = p([B]o -[A]o+[A] ) + q[A] = p([B]o -[A]o) +(p+q)[A]
1= p([B]o -[A]o)

0 = p+q

1
p
Bo  Ao 

1
q
Bo  Ao 

 A

1

 A o  AB o   Ao   A
 A
d A
 d A
 
 
 A o  AB o   Ao   A o B o   Ao B o   Ao   A
 A




1
A
1
B o  Ao  A

ln

ln
 kt
Bo  Ao  Ao Bo  Ao 
Bo



1
Ao B o  Ao  A
1
Ao B 

ln
 kt 
ln
Bo  Ao 
Bo  Ao  ABo
ABo

Second Order Autocatalytic Reaction
AB

d
[
A
]
d
[
B
]
u(t) = 

= k[A][B]
dt
dt

d[ A]
 kdt
AB

[A] = [A]o - /V and [B] = [B]o + /V
/V = [A]o-[A] so [B] = [B]o + [A]o- [A]

d[ A]
 kdt
ABo  Ao  A

method of partial fractions: for [B]o

[A]o

1
p
q
 
ABo  Ao  A A Bo  Ao  A
1 = p([B]o +[A]o-[A] ) +q[A] = p([B]o +[A]o) - (p-q)[A]
1= p([B]o + [A]o) 0 = p-q

p=q

1
p
Bo  Ao 
 A

1

 A o  AB o   Ao   A

 A
d A
d A
 
 
 A o  AB o   Ao   A o B o   Ao B o   Ao   A
 A

Bo  Ao  A

1
A

ln

ln
 kt
Bo
Bo  Ao  Ao Bo  Ao 
1


1
AB o

ln
 kt
B o  Ao  Ao B


AB o  A B  kt
B 
e
Ao
o

o

• if no B is present initially, [B]o = 0, reaction will not
proceed - S shaped curve typical of autocatalytic rxns
and many growth processes (populations) autocatalytic
kinetics common in biochemical processes

Concentration

CB

o

[B]

if [B]o = 0, reaction will not proceed

time

Third order: lead to more complicated integrations

Determining the Rate Law
1. Take c vs. t , guess n, plot as discussed
1st order ln c vs. t straight line n=1
2nd order 1/c vs. t straight line n = 2
2. Isolation method:
log

d  A
a
b

 k  A B  D 
dt

d  A
 log k  a log  A  b log B    log D 
dt

- perform experiment at const. T where [B] and [D] are in excess

d  A
a
 k '  A
dt

where k' includes [B] and [D]

- can determine k' and a
- do for other components as well

2 ½. Method of Initial Rates
uo  k'
- measure rates at initial concentrations
- run experiment at series of initial concentration
rates plot log uo vs. log [A]o slope = a

3. Half-life Method
nth order: 

d [ A]
=k[A]n for n > 2
dt

t1

2

Ao

a

(2(n-1) - 1)

k(n - 1)[A]on -1

Determining rate law: need 2 different [A]o at const. T (k is same)

(2(n-1) - 1)
t 1 Ao 1 k(n - 1)[A]n -1 1 [A]n -1 2 [A] 2 n 1
o
o
o
2





(n-1)
(2 - 1)
t 1 Ao 2
[A]on -1 1  [A]o 1 
2
k(n - 1)[A]on -1 2
solve for n knowing [A]o(1), t½ (1), [A]o(2), t½ (2) from experiments
rate law must be of form  d [ A] = k[A]n

dt

Reversible Reactions
- usually study reactions far from equilibrium where
reverse reaction is not important
A = B
AB
BA

k1, k-1
k1
k-1

d [ A] d [ B]

 k1[ A]
For forward rxn:
dt
dt
d [ A]
d [ B]
For reverse rxn:

 k1[ B]
dt
dt
For both rxns: d [ A]   d [ B]  k1[ A]  k1[ B]
dt
dt

[A] = [A]o - 1/V + 2/V and
[B] = [B]o+ 1/V - 2/V = [B]o+[A]o-[A]

assume [B]o= 0

d [ A]
= -k1[A] + k-1([B]o+[A]o-[A]) = -(k1+k-1)[A] + k-1[A]o
dt

t
d A
  dt

0
 A o k -1[A]o - (k 1  k -1 )[A]

 A

1
 A
ln k1Ao  (k1  k -1 ) A| A  t

o
(k1  k -1 )
 k Ao  (k  k ) A
1
-1
ln 1
  (k1  k -1 )t
 k1 Ao



Solve for [A]

 k e (k1  k -1 )t  k  A
 1
1 
o
1
 (k1  k -1 )t

 

 k1 Ao e
A 
 k1 Ao  
(k1  k -1 ) 
(k1  k -1 )

At eqm. t = 

k1Ao
Aeqm 
(k1  k -1 )



k

1

[B]eqm = [B]o + [A]o - [A] = [B] = [A]o-[A]eqm = Ao 1 
 (k  k ) 
1
-1 

Beqm
KC 
Aeqm

k

1
(k  k ) k
1 -1  1

k
k -1
1
(k  k )
1 -1
1

Another way to look at it:

d [ A] d [ B]

 k1[ A] eqm  k1[ B] eqm  0
dt
dt
Beqm k1
k1[ A]eqm  k1[B]eqm
KC 

Aeqm k -1

At eqm.

Effect of Temperature on Reaction Rate
- most common relationship is exponential one
- reaction rate increases by a factor of 2 or 3 for each 10o rise in T

expt'ly we see: plot of ln k vs. 1/T is linear

Ea
d ln k

dT
RT 2
integrate

Arrhenius eqn. - empirical relationship

 Ea
ln k 
 ln A
RT

or

k  Ae

 Ea
RT

Ea = activation energy f(T) - energy needed for rct to proceed to products

A = preexponential factor or frequency factor
A has units of k
1st order
k = s-1
2nd order
k = M-1s-1

The higher Ea, the stronger the T dependence of k

Ea = 0 means rate independent of T
Ea < 0 means rate

as T

will talk more about significance of A and Ea later

Elementary Reactions
- rxns that occur in a single step - only involve 1 or 2
molecules
- most rxns do not take place in a single collision but have
mechanisms that involve several elementary reactions
molecularity of rxn - # of particles involved in simple collisional
process for elementary rxn
- theoretical concept, whereas order is empirical
unimolecular - one that takes place w/o collision
- spontaneous disruption or transformation
- radioactive disintegration
- absorption of radiation to give energy
bimolecular - 2 molecules collide

Rate law of elementary rxn based on chemical rxn alone:
unimolecular:

aA  P

bimolecular: aA + bB  P

1 d A
d P
a
 k A  u 
a dt
dt
1 d A
a
b

 k A B
a dt

only dependent on reactants & their stoichiometric coef.
reaction mechanism - theory that has been devised to
explain currently known experimental facts, such as
overall stoichiometry, dependence of rxn rate on conc., T,
P, or other variables
- major goal of kinetics is to determine mechanisms of
complex rxns.
- several mechanisms may be consistent with data

Consecutive Elementary Reactions
239U

239Np

23.5 min

AB

k1

BC

k2

A  Ao e

 k1t

239Pu

2.35 day

d A
 k1 A
dt
d B
 k1 A  k2 B
dt

dC
 k2 B
dt

d B 
 k1 Ao e k1t  
k 2 B
dt

k1
B  
e  k1t  e  k 2t Ao
k 2  k1
[C] = [A]o –[A] – [B]

(good luck)

assuming [B]o = 0

if [B]o & [C]o = 0


1
 k1t
 k 2t 
C   Ao 1 
k2e  k1e 
 k1  k2

must integrate:


1
 k1t
 k 2t 
C   Ao 1 
k2e  k1e 
 k1  k2

[A]o
[C]
[A]
Conc.

[B]
eqm.
time

Can calculate time at which [B] = max by setting d B   0
dt

Parallel 1st Order Reactions
AU
AV
AW

d A

 k1 A  k2 A  k3 A  k1  k2  k3 A  k A
dt

ln [ A]  kt
[ A]o

[A] = [A]oe-kt

d U 
 k1 A  k1 Ao e kt
dt
U 

- k1
k1
- kt
Ao e  Ao
d U    k1 Ao e dt  [U] - Uo 

k
k
U 
0
o

t

 kt

k1
[U]  Uo  1 - e-kt Ao
k

k2
[V]  Vo 
1 - e-kt Ao
k

k3
If [U]o = [V]o = [W]o = 0
[W]  Wo 
1 - e-kt Ao
k
[W] k 3
[V] k 2


and
U  k1
U  k1
[A]o
[U]
eqm.
Conc.

[V]
[W]
[A]
time

products are in a constant ratio to each other
dependent on time, [A]o and k's.

Steady State Approximation
A = Bk1, k-1
BC
k2
d A
 k1 A  k1 B
dt

d B
 k1 A  k1 B  k2 B
dt
d C 
 k2 B
dt

steady state approximation - assumes that the conc. of
all rxn intermediates (B) remain constant thruout exp't.
- usually intermediates are very reactive & thus are
present in small conc.

d B
 k1 A  k1 B  k2 B
dt
k1 A
B 
k1  k2 

d B 
0
dt
d C  k1k 2  A

k 1  k 2 
dt

 k1
  k1k2 A
d A
k1k1 A
d C 
 k1 A 
 k1 A
 1 

k1  k2 
dt
dt
 k1  k2   k1  k2 

A  Ao e

k1k 2
  k  k t
1
2

Eqm. approximation: if A & B are in eqm.
k1 Beqm
KC 

k1 Aeqm

k1 A
B 
k1  k2 

k1  A
B  
k 1

(2)

from (1)

when k2 << k-1 both [B] agree
- which says B forms A much faster than it forms C

If k2 << k-1 rate determining step (slow step) is k2

d C  k1k 2 A
d A

 k 2 K C A  k 2 B   
dt
k 1
dt

Chain Reactions
-rxn where intermediates are produced which generate
more intermediates thus propagating the rxn.
3 main rxn types:
1. initiation - unimolecular or bimolecular (can be
photoinitiated)
2. chain propagation - often bimolecular - one
intermediate and one substrate - intermediate is
product
3. termination - converts chain propagating
intermediates to stable molecules
4. inhibition - rxn where product is destroyed, i.e. is rct
(intermediate is destroyed & no new one produced)

Example:

Ethane decomposition

C2H6  C2H4 + H2

C2H6
CH3. + C2H6
C2H5.
H. + C2H6
H. + C2H5

 2CH3.
k1
 CH4 + C2H5.
 C2H4 + H.
 H2 + C2H5.
 C2H6
k5

methane is a byproduct

initiation
k2 initiation
k3 propagation
k4 propagation
termination

d C2 H 6 
 -k1[C2H6 ] - k2[CH3][C2H6] -k4[H][C2H6] +k5[C2H5][H]
dt

1. d H   k3[C2H5] -k4[H][C2H6] -k5[C2H5][H] =0
dt
d CH 3 
 2k1[C2H6] - k2[CH3][C2H6] = 0
2.
dt

[CH3 ] = 2k1/k2

d C2 H 5 
 k2[CH3][C2H6]-k3[C2H5]+k4[H][C2H6]-k5[C2H5][H]=0
3.
dt

1+3 k2[CH3][C2H6]-2k5[C2H5][H]=0

Plug in for [CH3]

2k1[C2H6]=2k5[C2H5][H]
From (1)

k3 C2 H 5 
H  
k 4 [C2 H 6 ]  k5 [C2 H 5 ]

2k1 C2 H 6  k1 C2 H 6 k 4 [C2 H 6 ]  k5 [C2 H 5 ]
C2 H 5  

2k5 H 
k3 k5 C2 H 5 
rearrange

C2 H 5  
k

k3k5[C2H5]2 - k1k5[C2H6][C2H5] - k1k4[C2H6]2 = 0

k1k5 [C2 H 6 ] 

k1k5 

k1k5[C2 H 6 ]2  4k1k3k4 k5[C2 H 6 ]2
2k 3 k 5

k1k5 2  4k1k3k4 k5 2 H  
2k3 k5

 k[C2 H 6 ]

k3 k C2 H 6 
 k'
k 4 [C2 H 6 ]  k5 k[C2 H 6 ]

d C2 H 6 
k 3k[C 2 H 6 ][C 2 H 6 ]
k 2 2k 1
 -k 1[C 2 H 6 ] [C 2 H 6 ] - k 4
 k 5 k' k[C 2 H 6 ]
dt
k2
k 4 [C 2 H 6 ]  k 5 k[C 2 H 6 ]

d C2 H 6 
=k”[C2H6]
dt

first order

Fluorescence Exp’t and Steady State Approximation
tris(2,2’-bipyridine) ruthenium +2 = R+2
R+2 + h  R+2*
R+2*  R+2

absorption (rate: Iabs)
fluorescence

R+2* + Fe+3  R+3 + Fe+2

 

 

quenching (rate constant:kq)



d R 2*
 I abs  k s R  2*  k q R  2* Fe 3  0
dt

R   k
 2*

I abs
3

k
Fe
s
q

Intensity of fluorescence a [R+2*]

I o intensity when no quencher present ([Fe+3]=0)
=
intensity when quencher present
I
Io
I abs / k s


3
I I abs / k s  kq [ Fe ]

k s  kq [ Fe3 ]
ks

kq
Io
 1  [ Fe3 ]
I
ks

Io
=
I

intensity when no quencher present ([Fe+3]=0)
intensity when quencher present

Io
I abs / k s


3
I I abs / k s  kq [ Fe ]

kq
Io
 1  [ Fe3 ]
I
ks

k s  kq [ Fe3 ]
ks

Unimolecular Reaction
(Lindemann-Hinshelwood Mechanism)
- unimolecular rxns seen as complicated rxn involving
multistep mechanism
- collisions are bimolecular, how can a rxn be first order
- from expt’l data, it has been seen that rate laws are often
1st order at high concentrations, but 2nd order at low
concentrations – look at Lindemann-Hinshelwood
Mechanism tp help explain this
Lindemann-Hinshelwood Mechanism
1. A + A  A* + A
k1
activation
2. A* + A  A + A
k-1
deactivation
3. A*  P______
k2
spontaneous decay- unimolecular
A  P
k
overall rxn

step 1: excitation due to collision, A's translational
kinetic E or with an inert molecule N2 or Ar
step 2: loss of energy due to collision of A* with A
step 3: truly unimolecular rxn.
assume steady state approximation

d A *
 k1[A ]2 - k -1[ A*]A - k 2 [A*]  0
dt
2
k1[A ]2


d
P
k
k
[A
]
A * 
0
 k 2 [A*]  1 2
- k -1A  k 2
k [ A]  k
dt
-1

2 limiting cases:

2

neither 1st or 2nd order

1. low P: fewer collisions, A* has time to decompose k2>>k-1[A]
uB = k1[A]2 second order
2. high P - more collisions [A] large k-1[A]>>k2
d P 
k1k 2  A first order (3rd step rate determining)
u 
dt

k 1

Homogeneous Catalysis (same phase)
catalyst - changes rate of desired reaction
- changes mechanism to one with lower Ea
enzymes - biological catalysts - read about MichaelisMenten rxn.
homogeneous catalyst - catalyst in same phase as rxn mixture
heterogeneous catalyst - catalyst in different phase,
i.e. solid in gaseous rxn.

Gas Phase Catalysis
2SO2 + O2  2SO3
slow
termolecular rxn needs to take place in order to occur
2NO + O2  2NO2
fast
termolecular rxn with NO well known
NO2 + SO2  NO + SO3
bimolecular
NO2 oxidizes SO2 in low Ea bimolecular process
In general: uncatalyzed A + B  P slow uP=k [A][B]
C = catalyst

catalyzed

k1

A + C  X fast

if k2>>k1

k2

X + B  P + C fast uP=k1[A][C]
catalyzed rxns often found expt'ly to be 1st order w.r.t. [catalyst]
we spoke of autocatalysis - product accelerates rxn.

Michaelis-Menten mechanism
-enzyme catalyzed reaction
Substrate = S products = P enzyme = E ES = intermediate
k1

d P
 k2 ES 
dt

k2

E + S = ES  P + E
k-1

d ES 
 k1E S   k1[ ES ]  k2 [ ES ]  0
dt

Steady-state approximation

k1 E S 
ES  
k1  k2

[E]o = [E] + [ES]
[S]o = [S] + [ES]

negligible

only a little enzyme is added so [S] >> [E]

k1 E o  ES S o
ES  
k1  k2

ES   k E  S    k S  ES 
1

o

k1  k2


k1S o  k1 E o S o 
 
ES 1 
k1  k2
 k1  k2 

o

1

o

k1  k2


k1 E o S o  
k1  k2
ES  


k1  k2  k1  k2  k1S o 

k1 E o S o 
ES  
k1  k2  k1 S o
k1k2 S o E o
d P
Since [S] = [S]o ~ const.

 k E o
 k2 ES 
k1  k2  k1 S o
dt
Rate varies linearly with enzyme conc.
k2 S o
k
K M  S o
d P  k2 S o E o

dt
K M  S o

KM 

k1  k2
k1

Michaelis const. mol/L

k2 S o
k
K M  S o

d P
 k[ E ]o
dt

rate of formation of product 1st order w.r.t. enzyme not so with substrate
when [S]o >> KM  k= k2

d P
 k2[ E ]o  umax
dt

0 order in S: so much substrate, rate is constant

- rate of formation of products is maximum

- maximum velocity of enzymolysis
- S forces eqm. to right so only dependent on P formation
when KM >> [S]o

[S]o low  reaction rate a [S]o and [E]o

d P  k2 S o E o

dt
KM

d P k2 S o E o
umax
u


dt
K M  S o 1  K M

S 

rearrange

o

1

u

1  KM

S 

umax

o

1

umax

KM
umax[ S ]o

Lineweaver-Burk plot: 1/u vs 1/[S]o  straight line
slope=KM/umax

y intercept =1/umax

x intercept = -1/KM

kcat = # substrate molecules converted to product per unit
time when enzyme is fully saturated with substrate
= umax/[E]o = k2 catalytic constant of enzyme

Theoretcial models for describing how chem rxns occur
1. Activated Complex Theory or Transition State Theory
- whether or not rxn occurs determined by movement of atomic
nuclei on a multidimensional potential energy surface
- valleys or holes = energy minima = stable molecular species
- heights or saddle points or cols = energy barrier to rxn
- rate = concentration of activated species x frequency with which
they pass over addle point
- need statistical mechanics to determine [activated species]

2. Kinetic molecular theory
- calculate # of molecular collisions per unit volume per time and fraction of
those collisions whose energy exceeds some threshold energy
- atoms treated as rigid spheres - if collision betw. 2 spheres has enough
energy will react to form products
- does not deal with how large threshold energy must be or effectiveness of a
collision as a function of relative molecular orientation

Kinetic Model of Gases
3 assumptions
1. gas consists of molecules of mass m in ceaseless
random motion
2. size of molecules negligible dmol << ave. distance
traveled between collisions – treated as rigid spheres
3. they undergo perfectly elastic collisions (total
translational kinetic energy is conserved: no energy
transferred to rotational or vibrational modes

Look at volume swept out by sphere of radius d
dB
dB

where d = (dA+dB)/2

d
dA= diam of molecule A

dA

dB= diam of molecule B
dB

• assume center of one A molecule is at center of cylinder
• when the center of a B molecule is within this volume, A & B collide
• a collision occurs when the distance betw. centers becomes as
small as d

B molecule at rest, A molecule moves thru volume

2
Volume swept out per unit time = d crel

crel 
crel

= m3/s

relative mean speed – mean speed with which one molecule
approaches another

 8k BT 

 
  

1

2

m A mB

m A  mB

= reduced mass

s = d2 = collision cross-section = m2
kB =R/NA = 1.38 x 10-23 J/K

NA = Avogadro’s #

nB = moles B

If there are (nBNA/V) B molecules per unit volume then the # of
collisions of one A molecule with the B molecules in this V is given
by the collision frequency, z

P
molecules
 nB N A 
z  s crel 

  s crel
k BT
s
 V 

If there is not one, but (nANA/V) A molecules in this volume then
the # of collisions betw. A and B molecules is given by the
collision frequency, ZAB
1

Z AB

 8k BT  2 2
molecules2
 nB N A  n A N A 
 N A AB  
 s crel 

  s 
3

m
s
 V  V 


2

For a single gas molecule A = B

Z AA


1  8k BT
 s
2   mA

 2

Z AA  10 34

1

 2

 N A2 A2


mA
mA


2m A
2

# of collisions of A with other A molecules
in this volume. The ½ is included so as
not to count each collision twice

collisoins/m3s for typical gas at std. conditions

How can we relate to rate laws?
u = k2[A][B]

A + B  P

Only a fraction of collisions successful, f
- energy must exceed a minimum value E > Ea

 8k BT  2 2
d A
 N A AB    N A
fs 
dt
  
1

rate of rxn. = fZAB=

 8k BT  2
d A
 N A AB 

 fs 
dt
  
1

Experimentally we found:
1

 8k BT  2
 N A
k 2  fs 
  

d A

 k2 AB
dt

According to Arrhenius

k2  Ae

Ea

RT

Ea = activation energy
A = preexponential factor
There exists a threshold energy below which rexn will
not proceed. For most rxns E >>kBT
The fraction of molecules with E > Ethreshold is given by
Boltzmann distribution

prob. that molecules in E  E th

prob. that molecules in any E

1  E k BT
E k BT e dE
th

1  E k BT
0 k BT e dE

E

e


k BT

E

e

 Eth

Eth

k BT

 Eth
e k BT

 e k BT
0   1

0

 Eth

f = fraction of molecules with E > Eth =
1

e

k BT

e

 Eth N A

1

 8k BT 
 8k BT  2
 N A  k 2  s 
 N Ae  Eth N A / RT
k 2  fs 
  
  
?

2

Ea = EthNA

= Ae-Ea/RT
1

 8k BT  2
 N A
A  s 
  

Arrhenius assumes A not f(T) here
shows slight dependence

RT

Arrhenius found

E
d ln k
 a2
dT
RT

If A ~ constant

1


 8k B  2
 Eth N A 1
 sN A 
ln k 
 ln T  ln 
RT
2
  


Ea
d ln k Eth N A 1



2
dT
RT
2T RT 2

Ea = EthNA + ½RT

if Ea >> ½ RT can neglect

Then Ea = EthNA
1

 8k BT  2
 N A
A  s 
  

Arrhenius assumes A not f(T) here
shows slight dependence

Steric Effects
- experimental values of A often much less than theoretical
- orientation of molecules may be a factor in rxn

CH3I (g) + Rb(g)
Rb

H
H

H
C

I

(not good)

H

C

I Rb

(good)

Instead of s use s* reactive cross-section s* = sp
p = steric factor p << 1

- calculate A experimentally, difference due to p
p = Aexptl/Ath
takes into account collision geometry

Activated Complex Theory
- look at reaction in terms of potential energy of rcts and
pdts & progress of rxn (reaction coordinate)
- formulate reaction rate in terms of properties of rcts &
activated complex for that reaction
- apply statistical mechanics to reactants & activated
complexes
Partition function for molecule: q 

 Ei / k B T
e

i

- probability that molecule will exist in any one of its
possible energy states i a q (q is unitless)
q gives indication of the average # of states that are
thermally accessible to a molecule at temperature T

Can write partition function in terms of partition functions of
vibration, rotation, translation, electronic

q = qvqrqtqe

A B  C





C
C
 DE / RT
K 
e


qA,m / N A qB,m / N A 
AB

qC,m / N A

o

qom = standard molar partition function

DEo = difference in ground state of
products & reactants
= Eo(C) - Eo(A) – Eo(B)

Derivation of Rate Equation with Activated Complex Theory
Rate of rxn. = # of activated complexes passing over top of
potential energy barrier per second

=

C

x average frequency with which complex moves to

product side, k

C

Potential E

transition state

A  B  C  P
bimolecular

unimolecular decay

assume rcts in eqm with C 
A+B
P
rxn coordinate

 

dP
uk C 
dt

transition state – certain energetic configuration of maximum
potential energy

K


C C 

 

AB

where

Experimentally

k  

K 

q

d P
 k2 AB
dt

P   1bar

RT
 k2  k K
P

 = frequency of vibration of

C

 = transmission coef. = success of vibration to
push complex thru transition state ~ 0.5 - 1

qC ,m / N A

A, m

P

RT

d P

 RT
AB
k K

dt
P

RT
C  K AB  
P

C 



/ NA q


B ,m

/ NA

e

 DEo / RT

N A qC ,m
q



A, m B , m

q

e

 DEo / RT

C

Complex moves to products when a vibration
pushes it thru transition state

Look at partition function of vibration

h
1
kB T

If

qv  1  e

h / kB T

1

then

2


h 1 h
h
h / kB T
and
e
1
 
  ... 1 
kB T 2  kB T 
kB T
k BT
qv 
qC   qr qt qe
Then qC   qv qC 
where
hu

qC

where

kB T 

qC
h

K 

Then write

A C  ,m


A, m B ,
m

N q
q

q

kB T 
K 
K
h

e  DEo / RT
has one vibrational mode missing

RT
kB T RT 
k2  k K   
 K
P
h P

k BT RT 
k2  
K

h P

Eyring eqn.

Thermodynamics of Activated Complex Theory
- look at Gibbs Energy, Enthalpy & Entropy of activation

D G   RT ln K 

k BT RT DG / RT
k2  
e

h P

K   e  D G / RT

D G  D H  TD S
where

eqm const without vibrational mode of C#

D S / R  D H / RT

k2  Be

k BT RT
B 
h P

e

Assume ~1

D S / R  D H / RT

k2  Be

e

k BT RT
B 
h P



kB R
D
S
D
H
2
ln k 2  ln   ln T 

hP
R
RT

d ln k 2 2 D H
 
dT
T RT 2

Ea
d ln k2

dT
RT 2

Arrhenius found

Ea  D H  2 RT
D S / R 2  Ea / RT

k2  Be

A  Be

ee

D S / R 2

e

experimentally
preexpoential factor

k 2  Ae  Ea / RT

A 
D S  R ln hAP / Rk BT e  R ln   2
B

D H  Ea  2 RT

k BT RT
B
h P

2 2

DG  D H  TD S

A = preexponential factor

For bimolecular collision 2 molecules form complex

D S  0