Chemical Kinetics:

Rates and Mechanisms of

Chemical Reactions
C.P. Huang
University of Delaware
1

Content
1.
2.
3.
4.
5.
6.

Introduction
Reaction rate
Rate laws
Analysis of rate equations
Rate theories
Reaction mechanisms
1.
2.
3.

Complex
Catalysis
Chain

7. Reactions in solution
8. Reactions at interface
2

1. INTRODUCTION

Objectives

Chemical Kinetics: study of rates of chemical

reactions and mechanisms by which they occur
A reaction may be spontaneous but does not occur at
measurable rates

Why kinetics
How fast a reaction can take place?
What steps or pathways are involved in any chemical
reaction?
How complete is the chemical reaction?
What are the two major factors controlling the
outcome of chemical reactions?
Chemical thermodynamics
Chemical kinetics

2. REACTION RATE

Definition of reaction rate

Rate change in some variable per unit time
Rate

1/time

Reaction rate change in concentration per unit time;

M/s or mol/(L-s)
Rates are determined by monitoring concentration as
a function of time
Rates are negative for reactants and positive
quantities for products

Types of reaction rate

Instantaneous rate rate at a specific time
Average rate [A] over a specific time interval
Initial rate instantaneous rate at t = 0
Note: Rates and rate laws are not based on
stoichiometry!! They must be determined
experimentally.

Factors affecting reaction rate

Kinetics are very difficult to describe from first
principles
Structure, elements, behavior
Rate of reaction describes how fast reactants are
used up and products are formed
There are 4 basic factors that affect reaction rates
Nature of reactants
Effective concentrations
Temperature
Presence of catalysts
Number of steps

Nature of reactants: particle size

The degree of intimacy among particles obviously
depends on the physical nature of the particles.
Particles in the liquid state are closer than in the
solid state.
Likewise, particles in a finely divided solid will be
closer than in a chunk of the solid
In both situations, there is a larger surface area
available for the reaction to take place
This leads to an increase in rate.
The smaller the particles the faster the reaction rates

10

Nature of reactants: bonding

Ions react rapidly:
Ag+ + Cl- AgCl(s) Very fast
Reactions which involve bond breaking are slower:
NH4+ + OCN- OC(NH2)2
Redox reactions in solutions are slow
Transfer of electrons are faster than those of atoms.
Reactions between covalently bonded molecules are
slow:
2 HI(g)
H2(g) + I2(g)

11

Concentration
For every reaction the particles must come into
intimate contact with each other.
High concentrations by definition implies that
particles are closer together (than dilute
solutions).
So rate increases with concentration.
Surface area
larger surface area increases reaction
Mixing increases interaction
Need to minimized precipitation or colloid
formation

12

Temperature
Temperature affects rate by affecting the
number and energy of collisions
So an increase in temperature will have the
effect of increasing reaction rate

13

Reaction rates and stoichiometry

Rate has units of moles per liter per unit time
- M s-1, M h-1
Consider the hypothetical reaction
aA + bB cC + dD
1 [ A]
1 [ B ]
We can write
r

a t
b t
1 [C ] 1 [ D]

c t
d t

14

Example
At a given time, the rate of C2H4 reaction is 0.23
M/s. What are the rates of the other reaction
components?
C2H4(g) + 3 O2(g) 2 CO2(g) + 2 H2O(g)
0.23 M/s

15

3. RATE LAW

16

Rate law
Consider the following reaction
aA + bB products
Rate Law: equation describing the
relationship between the reaction rate and
concentration of a reactant or reactants
Rate = k[A]m[B]n
where k is called the rate constant

17

Concentration and rate

aA + bB cC + dD
General form of rate law:
rate = k[A]m[B]n
[A], [B] concentration, in M or P
k rate constant; units vary
m, n reaction orders
Reaction orders and, thus, rate laws must be
determined EXPERIMENTALLY!!!
Note: m a and n b
Overall order = sum of individual orders
18

Reaction order
Rate = k[A][B]0 m = 1 and n = 0
- reaction is first order in A and zero order in B
- overall order = 1 + 0 = 1
- usually written: Rate = k[A]
The values of the reaction order must be determined
experimentally; they cannot be found by looking at
the equation, i.e., the stoichiometry of the reaction

19

Rate law
m, n are called reaction orders - they indicate the
sensitivity of the rate to concentration changes of
each reactant
NOTE: the orders have nothing to do with the
stoichiometric coefficients in the balanced overall
equation
An exponent of 0 means the reaction is zero order in
that reactant - rate does not depend on the
concentration of that reactant

20

Rate Law
An exponent of 1, rate is directly proportional to the
concentration of that reactant
- if concentration is doubled, rate doubles
- reaction is first order in that reactant
An exponent of 2, rate is proportional to the square
of concentration of that reactant
if concentration is double, rate is quadrupled
reaction is second order in that reactant

The overall reaction order is the sum of all the orders

21

Reaction orders
For the reaction: A B, the rate law is:
rate = k[A]m
Order (m)

[A] by a factor of

Rate increases by

Zero (0)

2, 4, 15, , etc.

None

2
3
2
3

2X
3X
4X
9X
X

1st

(1)

2nd (2)

22

Example
2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g)
rate = k[NO]2[H2]
1.
2.
3.
4.
5.
6.

What is the order with respect to NO?

What is the order with respect to H2?
3
What is the overall order?

2
1

If [NO] is doubled, what is the effect on the reaction

rate?
quadrupled
If [H2] is halved, what is the effect on the reaction
rate?
halved
What are the units of k?
M-2-s-2
23

Example
PtCl2(NH3)2 + H2O PtCl(H2O)(NH3)2 + Cl-

Calculate the rate of reaction when the

concentration of PtCl2(NH3)2 is 2.0x10-2 M.
Rate = 9x10-3 (h-1) x 0.02 (M) = 1.8x10-5 (M-h-1)

What is the rate of Cl- production under

these conditions?
d[Cl]/dt = rate = 1.8x10-5 (M-h-1)
24

Example
2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g)
rate = k[NO]2[H2] k = 6.0 x 104 M-2s-1 @1000K

Calculate rate when [NO] = 0.025 M and [H2] = 0.015 M.

Rate = 6x10-4 (M-2-s-1)x0.025 M x 0.015 M
=225 (M-s-1)

25

Measurement of reaction rate

Rate may be measured in three ways
Average reaction rate: a measure of the change in
concentration with time
Instantaneous rate: rate of change of concentration
at any particular instant during the reaction
Initial rate: instantaneous rate at t = 0; that is, when
the reactants are first mixed

26

Measurements of reaction rate

C
C

C
Initial rates
nc

Instantaneous rate

nc

nt

C1
C2
C3
t

t1

t2

t3

Here nc is true order, with respect to concentration

and nt is order with respect to time.
When nt < nc, reaction is inhibitory and when nt >nc
reaction is autocatalytic.
27

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Time, s

[C4H9Cl], M

0.1000

50

0.0905

100

0.0820

150

0.0741

200

0.0671

300

0.0549

400

0.0448

500

0.0368

800

0.0200

10,000

In this reaction, the

concentration of butyl
chloride, C4H9Cl, is
measured at various
times.

28

Time, s

[C4H9Cl], M

Average rate, M/s

0.1000

50

0.0905

1.9E-4

100

0.0820

1.7E-4

150

0.0741

1.6E-4

200

0.0671

1.4E-4

300

0.0549

1.22E-4

400

0.0448

1.01E-4

500

0.0368

0.8E-4

800

0.0200

0.56E-4

10,000

29

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Initial rate

Instantaneous rate at 500 s

30

Determination of rate law

The method of initial rate
Measuring the initial rates as a function of the initial
concentrations
Avoids problems of reversible reactions
Initially there are no products so they cannot affect
the measured rate
This method is chosen to check the effect of a single
reactant on the rate

31

Bench-Top Reactors

32

Atlas Reactors

http://www.syrris.com/batch-products/atlas-parallel-system

33

Stopped-Flow Technique

http://www.hi-techsci.com/techniques/stoppedflow
34

Temperature Jump

http://www.hi-techsci.com/techniques/stoppedflow
35

Quench-Flow Technique

http://www.hi-techsci.com/techniques/stoppedflow

36

Summary of Experimental Methods

Method

Range of half-life, s

Conventional

102 108

Flow

10-3 - 102

Relaxation

10-10 -1

pressure jump

10-6 - 1

temperature jump

10-7 - 1

field pulse

10-10 10-3

shock tubes

10-9 10-3

Kinetic spectroscopy

10-15 10-10

37

4. ANALYSIS OF RATE LAW

38

Types of rate laws

Differential rate law or rate law: Shows how the
reaction rate changes with concentration
Integrated rate law: Shows how concentration
changes with time

39

First order
Log [A]

1 d[ A]
k (T ,I )[ A ]
A dt
1.0

[ A ] [ A ] o e k ( T ,I )t
k ( T ,I )
log[ A ] log[ A ] o
t
2.303

0.1

0.01

0.001

t
1

3
40

Second order

1 d[ A ]
k ( T )[ A ] 2
A dt

1
1

i k ( T )t
[A]
[ A ]0

[ A ]o A [B]o
ln B
[A]

[B]o

ln A
[ A ]o

B [B]o A [ A ]o k(T )t

41

Third order
1 d[ A ]
R
k(T )[ A ][B ][C ]
A dt

A B C 1
[ A ]o [B]o [C]o

1
1

2k(T )t
2
2
[A]
[ A ]o

42

Summary Rate Equations

Rate = k[A]n; [A] = concentration at time t, [Ao] = initial concentration, [X] =
product conc.
0 order

[A0]-[A] = kt, [X] = kt

1st order ln[A ] - ln[A] = kt,

0
2nd order

3rd order

k = M/s
ln[A0] - ln([Ao] - [X]) = kt

k = 1/s

k = M-1-s-1

k = M-2-s-1

43

Half-life
The half-life, t1/2, is defined as the time it takes for
the reactant concentration to drop to half its
initial value

Note: the half-life for a first order reaction does

not depend on the initial concentration
The value of the half-life is constant

44

Half-Life
Half-life
A =Aoe-t
= ln2/t1/2
If a rate half life is known,
fraction reacted or
remaining can be
calculated

(CH3)2N2(g) N2(g) + C2H6(g)

Time
Pressure (torr)
0
36.2
30
46.5
t
0

A
36.2
30 36.2(1-x)

B
0
36.2x

C
0
36.2x

46.5 = 36.2(1-x+2x)=36.2(1+x)=36.2+36.2x

Ct =Coe-kt

46.5-36.2 = 36.2x x = 0.285

kt0.5=ln(2)
to.5 = - [ln(2) t]/[ln(Ct/Co)]

A = 36.5(1-0.285) = 25.9

to.5 = - [ln(2) (30)]/[ln(25.9/36.5)]=62.1 (min)

45

t0.5
2t0.5
t0.53
t0.5

t0.5

t0.5

46

5. RATE THEORY

47

ARRHENIUS EQUATION
In 1885, Hood proposed the following
equation:
A'
logk B
T
In 1884, vants Hoff-Arrhenius
proposed the following equation:
d ln K c
E

dT
RT 2

Kc is the equilibrium constant

48

ARRHENIUS EQUATION
k1
k 1
A B

CD

k1[ A][ B] k 1[C ][ D]

Kc

k1 [C ][ D]

k 1 [ A][ B]

Ea
d ln k

dT
RT 2
Ea
ln k
C
RT

d ln k1
E
12 1
dt
RT
d ln k 1
E
12 1 E E1 E 1
dt
RT
d ln k1 d ln k 1 E

dt
dt
RT 2

C = constant

Activated state; X*

E2
E1
Final state
E=Ea

Initial state

49

Arrhenius Equation
Svante Arrhenius developed an equation for the
mathematical relationship between k and Ea.

A is the frequency factor, which represents the

number of effective collisions.
E

e RT : Boltzmann expression for the fraction of system

having energy in excess of the value, Ea, so that is
may be identified with the fraction of reactant
molecules that are activated complexes
a

50

Arrhenius Equation
Or
log k = log A Ea/(2.303 R) (1/T)
Slope = Ea/2.303 R = Ea/4.57 Cal

Y=mx+b

51

To find slope, m
Ln k

m=

k2
ln

k
1
1
1

T
T1

Ea/3R

1/T

52

Arrhenius Equation
This is Arrhenius Equation
Can be arranged in the form of a straight line

ln k = (-Ea/R)(1/T) + ln A
Plot ln k vs. 1/T slope = -Ea/R
Log [k]

EA/2.303
= dlog K/d(1/T)

1.0

Ea < 5 kcal/mol: diffusion

control reaction
Ea > 5 kcal/mol; reactive
control

0.1

Diffusion
regime

Reaction
regime

0.01

0.001

1/T
1

53

Activation Energy, Ea
Energy barrier (hump) that must be overcome
for a chemical reaction to proceed
Activated complex or transition state
arrangement of atoms at the top of the barrier

54

Temperature Effects
Maxwell-Boltzmann Distribution

At higher temperatures, more molecules will have

adequate energy to react.
This increases the reaction rate.
55

Example
A reaction which rate constant doubles when
temperature is raised by 10oK from 300 oK. What is
its Ea value?
Given k310 = 2k300
or k1 = 2k0
Given k310 = 2k300
or k1 = 2k0
Ea

k
k
T1To
310)(300
(8.34) ln o 53594(J / mol)
ln 0
2k o
T o T1 k 1 (300 310)

56

Summary of A and Ea
Reaction

Ea(kJ/mol)

N2ON2+O
N2O5 2NO+O2
N2+ON+NO
OH+H22H2O+H

8x1011
6x1014
1x1011
1x1011

251
88
315
42

1st
1st
2nd
2nd

CO2+OH-HCO3- 1x1011

315

2nd

57

Example
It is given for a specific reaction, k =0.00123 /ms at
290oK and 0.0394/ms at 350oK. What is its Ea and k
at 308oK?
ln k 1 ln A

Ea
RT1

(350)(298)
0.0394
Ea
57811( J / mol) 57.8(kJ / mol)
(8.34 )
350

298
0
.
00123

E 1
k
1
ln 2 a

k1
R T2 T1
TT
k
E a 1 2 R ln 2
T2 T1
k1

ln k ln(0.00123 )

57811 1
1

8.70 0.578 5.94

8.324 308 298

k e 5.94 0.00263 2.63x10 3 (1/ ms)

58

Collision Theory
COLLISION THEORY: a reaction results when
reactant molecules, which are properly oriented and
have the appropriate energy, collide
The necessary energy is the activation energy, Ea

M. Silberberg

59

Molecular Orientation and Effective

Collisions
Not all collisions leads to a reaction
For effective collisions proper
orientation of the molecules must be
possible

60

Molecular Collisions

Before collision

Effective collision

Before collision
No-effective collision
61

Collision Theory
two identical gas molecules colliding with each other at a velocity,
v (molecules/cm3-s) [N.C. Leuis (1918) and Eyring (1935)]

v z AA e
z AA

E
RT

zAA = # collision/(s-cm3)

2 d 2 cn 2
2
c

molecules/(cm3-s)

8T
= average velocity of each molecule
m

m: mass of each molecules

k = Boltzmann constant

1
8 T
T
2d2n2
2n2 d2
2
m
m
1
E
m A mB 2 RT
2
v n A nB d AB 8T
e
dAB: average distance, sum of radii
m A mB

z AA

62

Collision Theory
1
2

v n A nB d

k = kNa (cm3/mol-s)

2
AB

m A mB RT
e
8T
m A mB

1
2

m
m

v
B
RT
k'
d 2AB 8T A
e
m A mB
n A nB

1
2

m
m

B
RT
k Na d 2AB 8T A
e
m A mB

1
2

m A mB
2
A Na d AB 8T
Z
m A mB

k BT e
2

E
RT

k PZe

RT

Z
T

63

Example
Estimate he rate constant for the decomposition of HI(g)
molecules at 321.4oC according to the collision theory.
Given for the HI(g) molecules the following prosperities:
2HI(g) = H2(g) +I2(g)
= 3.5 = 3.5x10-8 cm;
E = 44,000 cal/g-mol;
mA = mB = MHI = 128 g;
R = Na = 1.38x10-16x6.023x1023
= 8.3x107 (erg/oK-mol) = 1.98 (cal/oK-g-mol)
T = 273 + 321.4 = 594.6 oK

64

Example

1
2

2 44000 (8.34 x107 )(594.6 )

7
k' (3.5 x10 ) 88.3x10 594.6
e
128

1.70x10 10 e 37.4
8 2

9.72x10 27 (cm 3 / molecules s)

k =9.72x10-27
(cm3/moleculesx)(6.023x1023)(molecules/mol)
= 5.86x10-3 (cm3/mol-s)
=5.86x10-3x(1000)
=5.85x10-6 (L/mol-s)

65

Example
Collision of two water molecules at room temperature, 298 oK,
given:
d = 0.30 nm, T=298oK;
mA=mB=18(g-mol-1)/6.023x1023 =2.99x10-26 kg;
=1.38x10-23 J/oK

Z 0.3x10

9 2

81.38x10

23

298

26
2.99x10 / 6x10
2.37x10 10 (cm 3 / molecules s)
26 2

1
2

2.37x10 16 (m 3 / molecules s)

66

Example

Reaction

k
(cm3-molecules-1-s-1)

k
(L-mol-1-s-1)

CH4+OHCH3 + H2O

8.14x10-15

4.9x1012

CH3+O2 CH2O+OH

3.76x10-36

2.26x10-9

CH3O+O CH2O+OH

1.7x10-11

1.02x1016

k (L-mol-1-s-1) = 1000 x6.023x1023 k (cm3-molecules-1-s-1)

67

Transition State Theory

During a chemical reaction, reactants do not suddenly
convert to products
The formation of products is a continuous process of
bonding breaking and forming
At some point, a transitional species is formed containing
partial bonds
This species is called the transition state or activated
complex

68

Transition State Theory

The transition state is the configuration of atoms at the
maximum of the reaction energy diagram
The activation energy is therefore the energy needed to
reach the transition state
Note also that the transition state can go on to form
products or break apart to reform the reactants

rA

uA
R

b
uBC

rB

69

Transition State Theory

A + B = AB* C
r = [AB*]; (s-1); [AB*](molecules/cm3)
a *AB
*AB [ AB*]

K
a A aB A B [ A][ B]
*

*AB
r K *
[ A][ B ]
A B

K* e

G*

K = 1.38x10-16 erg/oK

RT

= 6.624x10-27 erg/s

70

Transiton Theory
T *AB

r
A B

S * / R H * / RT
e

T *AB S */ R

e
A
A B
T *AB S */ R H */ RT

e
r
e
A B

f e S */ R e H */ RT

TZe H */ RT

E =H*
71

Summary of Rate Theory

Rate Theory
Arrhenius
Collision
Activated
Complex
(Transition)

Equation
k Ae
1
2

k BT e

Ea

A term
RT

E
RT

T S * R H* RT
k
e
e

A
BT1/2

T S * R
e

Exponential
term
Ea
RT
Ea
RT
H *
RT

72

6. REACTION MECHANISMS

73

Reaction Mechanisms
Reactions occur in a series of elementary steps
collectively called a mechanism.
Determining the reaction mechanism is the overall goal
of kinetic studies.
One step, the rate-determining step (RDS), is much
slower than the other.
Usually, an intermediate (isolable) or a transition state
(non-isolable) is formed at some point during the
reaction.
molecularity the number of molecules that participate
in a reaction

74

Reaction Mechanism
MECHANISM: the step-by-step pathway by which a
reaction occurs
Each step is called an elementary step
NO2(g) + CO(g) NO(g) + CO2(g)
Mechanism:
NO2(g) + NO2(g) NO(g) + NO3(g)
NO3(g) + CO(g) NO2(g) + CO2(g)
NO3 is a reaction intermediate

75

Reaction Mechanism
The slow step is called the ratedetermining step (RDS) or rate-limiting
step (RLS)
A reaction can never occur faster than its
slowest step
Overall reaction = sum of all elementary
steps
The mechanism proposed must be
consistent with the rate law

76

Elementary Steps and Molecularity

Molecularity

Elementary Reaction

Rate Law

Unimolecular

A products

Rate = k[A]

Bimolecular

A + A products

Rate = k[A]2

Bimolecular

A + B products

Rate = k[A][B]

Trimolecular

A + A + A products

Rate = k[A]3

Trimolecular

A + A + products

Rate = k[A]2[B]

Trimolecular

A + B + C products

Rate = k[A][B][C]

Molecularity is the number of molecules reacting.

77

Steady-state Approach
When reaction mechanism has several steps of
comparable rates, the rate-limiting step is often not
obvious. There are intermediates in some steps.
SSA: a method used to derive a rate law based on the
assumption that one intermediate is consumed as
quickly as it is generated.
2 N2O5 4NO2 + O2

N2O5 NO2 + NO3

NO3 + NO2 NO+ NO2 + O2
NO3 + NO 2NO

(1)
(2)
(3)

78

2N2O5 4NO + O2
N2O5

k1
k-1

NO2 + NO3

NO3 + NO
NO3 + NO

k2
k3

NO + NO2 + O2
2NO

d [ NO ]
k 2 [ NO3 ][ NO ] k3 [ NO3 ][ NO ] 0
dt

k 2 [ NO3 ][ NO2 ]
[ NO ]
k3 [ NO3 ]
d [ NO3 ]
k1[ N 2O5 ] k 2 [ NO3 ][ NO2 ] k3 [ NO3 ][ NO ] k 1[ NO2 ][ NO3 ] 0
dt

[ NO3 ]

k1[ N 2O5 ]
k 2 [ NO3 ][ NO2 ] k3[ NO3 ][ NO ] k 1[ NO2 ][ NO3 ]

79

[ NO3 ]

k1[ N 2O5 ]
k 2 [ NO2 ] k3 [ NO] k 1[ NO2 ]

k1[ N 2O5 ]
k
(k 2 k 1 )[ NO2 ] k3 2 [ NO2 ]
k3

k1[ N 2O5 ]
(2k 2 k 1 )[ NO2 ]

d [O2 ]
k 2 [ NO3 ][ NO2 ]
dt
k k k [ N O ][ NO2 ]
1 2 3 2 5
(2k 2 k 1 )[ NO2 ]

k1k 2 k3 [ N 2O5 ]
k '[ N 2O5 ]
(2k 2 k 1 )
80

Catalysis
Catalyst increases the rate of a reaction without being
consumed or changing chemically
Accomplishes this by lowering the activation energy by
changing the reaction mechanism.
Heterogeneous vs. homogeneous catalysis
Examples:
Catalytic converter
Enzymes in the body
Ozone depletion

81

Catalysis
Reaction rates are also affected by catalysts
Catalyst: a substance that increases the rate
of a reaction without being consumed in the
reaction
Catalysts work by providing alternative
pathways that have lower activation energies
A catalyst may be homogeneous or
heterogeneous
Homogeneous: catalyst and reactants are in
the same phase
82

Energy

Ea

Uncatalyzed
pathway
Catalyzed
pathway

Ea

products

E
Reactants

Reaction process

83

 Heterogeneous: catalyst in a different phase

Typically: a solid in a liquid
An important example: catalytic converters in
automobile
- convert pollutants to CO2 H2O, O2, N2
- usually Pt, Pd, V2O5, Cr2O3, CuO
Cars must use unleaded fuels lead poisons the
catalytic bed
84

Enzyme Kinetics
Michaelis-Menten mechanism for enzyme kinetics is:

85

Catalytic efficiency,
= kcat/KM
= k2/[(k-1+k2)/k1]
max, = k1; if k2 >>k-1
k1 = rate of formation of ES
Diffusion limit ~ 108 109 M-1-s-1
For enzyme sized molecules at room
temperature
Decomposition of hydrogen peroxide
= 4x108 M-1-s-1

Turnover number or catalytic constant

= number of catalytic cycles performed by the activate
Site in a given time intervals divided by the duration of that

86

Lineweaver Burk Plot

1 KM 1
1

v vmax S S

vmax [ S ]
v
K M [S ]

S K M
v

vmax

S
vmax

v/[S]

[S]/v

1/v

v vmax
v

S K M K M

1/vmax

KM/vmax

1/KM
vmax/KM
KM/vmax

1/vmax
1/[S]

[S]

v
87

Hypothetical

KM = 20

Vmax = 2

88

Enzyme Inhibition
Reversible: enzyme activity can be regenerated by
removing the inhibitors.
Irreversible: complete loss of enzyme activity after
a period of time

89

Competitive Inhibition
E+S
+

k1
k-1

k2
ES E + P

EI

k3

KM

E I K
I
EI

I
KI

E S k1 k2
ES
k1

E+Q

k-3

d [ ES ]
k1[ E ][ S ] k 1[ ES ] k 2 [ ES ] 0
dt
d [ EI ]
k3 [ E ][ I ] k 3[ EI ] k 4 [ EI ] 0
dt

Eo [ E ] [ ES ] [ EI ]
Eo [ E ]

[ E ][ S ] [ E ][ I ]

KM
KI

[S ] [I ]
Eo [ E ]1

K
K
M
I

[E]

Eo
[S ] [ I ]
1

KM KI
90

1/v

[I]

d [ P]
k 2 [ ES ]
dt

KM [I ]

1
vmax K I

d [ P]
[ E ][ S ]
k2
dt
KM

1/vmax
[S]

d [ P] k 2
Eo
[S ]

[
S
]
[
I
]
dt
KM 1

KM KI

d [ P]

dt

k 2 Eo [ S ]

[I ]
K M 1
[ S ]

KI

vmax k 2 Eo

1
1
KM

v vmax vmax

vmax [ S ]
v
[I ]

[ S ]
K M 1
KI

[I ] 1
1

K I [S ]

Inhibitor is replaced
from the active sites
by substrate at high [S]
91

Non-competitive inhabitation
Inhibitor binds to some other binding sites;
Inhibitor combines with both free E and ES
2 possible mechanisms:
Ternary complex is a dead-end complex and does
not breakdown to yield products
Ternary complex breaks down at a slow rate than he
ES complex
KM
ES E + P
+

E+S
+
I

KI
EI + S

KM

KI
EIS E + P

92

E+S
+

k1
k-1

1/v
k2
ES E + P
+
I

KI
EI + S

k3
k-3

KI

[S ]

K M 1
K
M

EIS E + P

v k 2 [ ES ]

1/vmax-app

[S ]
v
KM

vmax 1 [ S ] [ I ] [ I ][ S ]
KM K I K IKM

1
vmax app

1
vmax

[I ]

vmax K I

1/vmax-app

Vmax=k2E0
v
vmax

1/(vmaxKI)

Henri-Michaelis-Menton Eq

[S ]
[I ]
[S ]

[ S ]1
K M 1
K
K
M
I

1/[S]

1/vmax
[I]

93

Uncompetitive inhibition
No binding site for inhibitor until substrate is bound to
the enzyme, so only ternary complex is possible

94

Uncompetitive Inhibition
KM
E+S
ES E + P
+

1/v

KM
vmax

KI
EIS E + Q

[I ]
1
vmax K I

v k 2 [ ES ]
[S ]
v
KM

vmax 1 [ S ] [ I ][ S ]
KM K IKM

1/[S]

1
1
[I ]

v' vmax K I
1/v

Vmax=k2E0

1 1 [ I ]
1 KM 1

v vmax [ S ] vmax K I

1/KI
1/vmax
[I]

95

E nS ES n P
K

[ ES n ]
[ E ][ S ]n

Yield

Eo [ E ] K [ E ][ S ]n
[E]

Hill eq.

[ ES n ]
K [ E ][ S ]n
Y

[ E ] [ ES n ] [ E ] K [ E ][ S ]n

Y
K [ S ]n
1 Y

KEo [ S ]n
1 K [ S ]n

n: Hill coefficient

Y
log
n log[S ] log K
1
Y

v k 2 [ ES ]

[ ES ]

Eo
1 K [ S ]n

k 2 E o K [ S ]n
v k 2 [ ES n ]
1 K [ S ]n
1
1
K

n
v vmax [ S ] vmax

Eo [ E ] [ ES ]
96

97

Chain Reactiosn
Chain reactions usually involve free radicals
H2+Br2=2HBr
The experimental rate law is
1
2

d [ HBr ] k '[ H 2 ][ Br2 ]

[ HBr ]
dt
1 k''
[ Br2 ]

98

Initiation

Br2 Br Br

Propagation

ka

kb
Br H 2
HBr H

kc
H Br2
HBr Br

Inhibition

Termination

kd
H HBr
H 2 Br

ke
Br Br
Br2

99

100

101

C2H6 = C2H4 + H2

102

103

The Lindemann Mechanism

N2O5 = NO2 + NO3.

k1 >> k-2 [N2O5]

Rate k2[N2O5]2
k1 << k-2 [N2O5]

104

(16)

Large M

105

7. Elementary Reaction in Solution

Solvent effect
Physical transfer
Chemical effect

106

Reactions in Solution
Upper limit for bimolecular steps of solution reaction.
Solutes behave like spheres undergoing Brown motion in
a viscous fluid and shows that the number of encounter
per cm3 per second is:

R 4 DA DB rA rB N N
1
E

1
A

1
B

dN 1A
J DA
dx
107

Reactions in Solution
1
A

dN
Total flux at r from B: RB 4r D A
dr
1
N A at r=(rA+rB) is 0
2

RB

( rA rB )

dr
r2

4D A

N 1A

d N 1A

RB 4 (rA rB ) DA N

1
A

RE1 4 DA DB rA rB N 1A N B1
k diff

4N a ( DA DB )(rA r B )

1000

L-mol-1-s-1
108

Reactions in Solution
T
D
6r (T )
k diff

2TN a (rA rB ) 2

3000 (T )rA rB

k diff

est
diff

k diff

exp( ) 1

z A zBe2

(rA rB )T

8 RT

3000 (T )

k diff

8(8.31x107 )(298)

6.4 x108 ( L / mol s)

3000(0.01)
109

8. REACTION AT INTERFACES

Mechanisms of surface reactions

Transport from the bulk to the interface; AS
Becomes adsorbed onto the surface: A+SAS
Reacted at the surface: ASPS
Desorbed from the surface: PSP+S
Transported back to the bulk:
P Bulk

110

Adsorption isotherms
(Langmuir)
A+ S = AS; K
pV = nRT
n/V =P/RT

N
N

1
S =(1-)

1
AS

=N

N 1AS
K 1 1
N ANB
1
T

1
T

K = RT/(1-)NaP

T 1
K
1 N a P

N 1A = n/V =NaP/RT

bP

1 bP
N a K K 7.34 x10 21 K
b

(atm 1 )
RT
T
T
111

Adsorption Isotherm
(Fruendlich)
f i i

fi P
1 bi P

f() = exp()
= fraction of sites with energy of adsorption e between 0 and d.

f( b( ) P

d
1 f( b( ) P
0
Let Eads =

T (b' P)T

aP

112

Maximum Adsorption Rate

1

A+SAS
1

T
S2 N 1A N S1
RE1

mS m A
mS
mS m A

2 S2 A2 S2

T
SN 1A
RS1
2m A

RS1 k S SN 1A

k s
2m A

S = Total surface area of spheres in 1 cm3

S ( 4rS2 ) N S1
N

1
S

= total number of spheres in 1 cm3

T 2 T
pe
k s
2m A
113

Example
Calculate the rate constant for the adsorption of a
metal ion, with molecular weight of 100 g at room
temperature, 298 oK.
1

1.4 x10 x 298 2

8.15 x10 9 (cm3 molecules 1 cm 2 s 1 )
k s
2 xx100
8.15 x10 9 x(10 3 ) x(6.023 x10 23 )( L / mol )(1 / cm 2 )(1 / s )
16

4.91x10 12 ( L / mol )(1 / cm 2 )(1 / s )

k s
2m A

114

Langmuir-Hinshelwood
A S AS ; K A
B S BS ; K B

bA PAbB P B
R ks
(bA PA bB PB ) 2

AS BS P S ; k s
R k s [ AS ][ BS ]

bA PAbB P B
bA PA
PA
ks
ks '
R ks
2
(bB PB )
(bB PB )
PB

bBPB > bAPA

bA PAbB P B
R ks
(1 bA PA bB PB ) 2
bA PAbB P B
bB P B
' PB
R ks
ks
ks
2
(bA PA )
bA PA
PA

bBPB <bAPA

bA PAbB P B
R ks
k s, PA PB
1
bBPB , bAPA <1
115

Eley-Ridel Equation
A S AS ; K1
B AS C S ; k s
R k s [b][ AS ] k s

R ks

bA PA
PB
1 bA PA

bA PA
b P
PB k s A A PB k s' PB
PA
1 bA PA

bB PA
R ks
PB ksbAPA PB ks' PA PB
1 bA PA
116