Chemical Kinetics:

Rates and Mechanisms of

Chemical Reactions

C.P. Huang
University of Delaware

1
 Content

1. Introduction
2. Reaction rate
3. Rate laws
4. Analysis of rate equations
5. Rate theories
6. Reaction mechanisms
1. Complex
2. Catalysis
3. Chain
7. Reactions in solution
8. Reactions at interface
2
1. INTRODUCTION

3
 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

4
 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

5
2. REACTION RATE

6
 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

7
 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.

8
 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

9
 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
• We can write 1 [ A] 1 [ B ]
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, ½, etc. None
2 2X
1st (1)
3 3X
2 4X
2nd (2) 3 9X
½ ¼X

22
 Example
2 NO(g) + 2 H2(g) → N2(g) + 2 H2O(g)
rate = k[NO]2[H2]

1. What is the order with respect to NO? 2

2. What is the order with respect to H2? 1
3. What is the overall order? 3
4. If [NO] is doubled, what is the effect on the reaction
rate? quadrupled
5. If [H2] is halved, what is the effect on the reaction
rate? halved
6. 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 Instantaneous rate

nc nc
C1 nt
C2
C3

t t
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 In this reaction, the

0 0.1000 concentration of butyl
50 0.0905 chloride, C4H9Cl, is
100 0.0820 measured at various
150 0.0741 times.
200 0.0671
300 0.0549
400 0.0448
500 0.0368
800 0.0200
10,000 0

28
Time, s [C4H9Cl], M Average rate, M/s

0 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 0

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]
R  k (T ,I )[ A ]
ν A dt
1.0
[ A ]  [ A ] o e  k ( T ,I )t

0.1
k ( T ,I )
log[ A ]  log[ A ] o  t
2.303
0.01

0.001 t
1 2 3

40
 Second order

1 d[ A ]
R   k ( T )[ A ] 2
 A dt
1 1
  ν i k ( T )t
[A] [ A ]0

  [ A ]o   A [B]o    [B]o 
ln B   ln  A    B [B]o   A [ A ]o k(T )t
 [A]   [ A ]o 

41
 Third order

1 d[ A ]
R  k(T )[ A ][B ][C ]
 A dt

 A  B  C  1 1 1
2
 2
 2k(T )t
[A] [ A ]o
[ A ]o  [B]o  [C]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 k = M/s

1st order ln[A ] - ln[A] = kt, ln[A0] - ln([Ao] - [X]) = kt k = 1/s

0

2nd order
k = M-1-s-1

3rd order 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 (CH3)2N2(g)  N2(g) + C2H6(g)
– A =Aoe-t Time Pressure (torr)
0 36.2
–  = ln2/t1/2 30 46.5
– If a rate half life is known,
t A B C
fraction reacted or 0 36.2 0 0
remaining can be 30 36.2(1-x) 36.2x 36.2x

calculated
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, vant’s Hoff-Arrhenius
proposed the following equation:
d ln K c E

dT RT 2
Kc is the equilibrium constant
48
 ARRHENIUS’ EQUATION
A  B 
k1

k 1
CD d ln k Ea

k1[ A][ B]  k 1[C ][ D] dT RT 2
k1 [C ][ D] Ea
Kc  
k 1 [ A][ B]
ln k   C C = constant
RT
d ln k1 E
 12 1 Activated state; X*
dt RT
E2
d ln k 1 E
 12  1 E  E1  E 1 E1
dt RT
Final state
d ln k1 d ln k 1 E E=Ea
 
dt dt RT 2 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
a

• 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
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

Ea/3R
 k2 
 k 
ln  
 1 
m=  1 1 

T  
 2 T1 

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]

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

Ea < 5 kcal/mol: diffusion

0.1 Diffusion
control reaction regime
Reaction
regime

Ea > 5 kcal/mol; reactive 0.01

control
0.001 1/T
1 2 3 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

T1To k 310)(300 k
Ea  ln 0  (8.34) ln o  53594(J / mol)
T o  T1 k 1 (300  310) 2k o

56
 Summary of A and Ea

Reaction A Ea(kJ/mol)

N2ON2+O 8x1011 251 1st

N2O5 2NO+O2 6x1014 88 1st
N2+ON+NO 1x1011 315 2nd
OH+H22H2O+H 1x1011 42 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?

Ea  (350)(298)   0.0394 
ln k 1  ln A  Ea   (8.34 )   57811( J / mol)  57.8(kJ / mol)
RT1  350  298   0 . 00123 

57811  1 1 
k E  1 1 ln k  ln(0.00123 )      8.70  0.578  5.94
ln 2  a    8.324  308 298 
k1 R  T2 T1 

 TT  k 
k  e 5.94  0.00263  2.63x10 3 (1/ ms)
E a   1 2 R ln 2 
 T2  T1   k1 

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

59
M. Silberberg
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)]

E

v  z AA e RT
zAA = # collision/(s-cm3)

1
z AA  2 d 2 cn 2 molecules/(cm3-s)
2
8κT
c = average velocity of each molecule
πm
m: mass of each molecules
k = Boltzmann constant

1 8 T T
z AA  2d2n2  2n2 d2
2 m m
1

2  m A  mB  2  RT
E
v  n A nB d AB 8T  e dAB: average distance, sum of radii 62
 m A mB 
 Collision Theory
1

 m A  mB   RT
2 E
v  n A nB d 2
AB 8T  e
k = k’Na (cm3/mol-s)  m A mB 
1

v  m  m  
2E
k'   d 2AB 8T A B
 e
RT
n A nB  m A mB 
1

 m  m  2

E
k  Na d 2AB 8T A B
 e
RT

 m A mB  E

1
k  PZe RT
2  m A  mB  2

A  Na d AB 8T  Z
 m A mB 
1 E
 Z
k  BT e 2 RT B
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 Å = 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

  2    44000 (8.34 x107 )(594.6 )

k'  (3.5 x10 ) 88.3x10 594.6
2
8 2 7
 e
  128  
 1.70x10 10 e  37.4
 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) 65
=5.85x10-6 (L/mol-s)
 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

81.38x10 298
1
  23  2

Z   0.3x10  
9 2 
 
  2.99x10  / 6x10
 26 2
 26
 

 2.37x10 16 (m 3 / molecules  s)

 2.37x10 10 (cm 3 / molecules  s)

66
 Example

Reaction k’ k
(cm3-molecules-1-s-1) (L-mol-1-s-1)
CH4+OHCH3 + 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 = 1.38x10-16 erg/oK
 G*
K*  e RT

T  = 6.624x10-27 erg/s

70
 Transiton Theory

T   *AB    S * / R   H * / RT 
r   e
   A B 

T   *AB  S */ R 
A  e
   A B 

T   *AB  S */ R   H */ RT
r  e e
   A B 
T
 f  e S */ R e  H */ RT

 TZe  H */ RT E =H*

71
 Summary of Rate Theory

Rate Theory Equation A term Exponential

term
Arrhenius 
Ea
A Ea
k  Ae RT
RT
Collision 1

E
BT1/2 Ea
k  BT e
2 RT
RT
Activated T  S * R  H* RT T  S * R H *
k e e e
Complex   RT
(Transition)

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 rate-

determining 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 (1)

NO3 + NO2  NO+ NO2 + O2 (2)
NO3 + NO  2NO (3)

78
 2N2O5 4NO + O2
k1
N2O5 NO2 + NO3
k-1
k2
NO3 + NO NO + NO2 + O2
k3
NO3 + NO 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

k1[ N 2O5 ]
[ NO3 ] 
k 2 [ NO3 ][ NO2 ]  k3[ NO3 ][ NO ]  k 1[ NO2 ][ NO3 ]
79
 k1[ N 2O5 ]
[ NO3 ] 
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 ]
r  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
Uncatalyzed
Ea 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
 vmax [ S ]
Lineweaver Burk Plot v
K M  [S ]

v vmax v
S   K M S   
1 KM 1
 
1  S  K M K M
v vmax S  S  v vmax vmax
[S]/v v/[S]
1/v
1/vmax
KM/vmax
1/KM
vmax/KM
KM/vmax
1/vmax
[S] v
1/[S]
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
k1 k2
E S   k1  k2  KM
E+S ES  E + P ES  k1
+ k-1
I E I   K
KI EI  I

k3
EI E+Q
k-3 Eo  [ E ]  [ ES ]  [ EI ]
[ E ][ S ] [ E ][ I ]
d [ ES ] Eo  [ E ]  
 k1[ E ][ S ]  k 1[ ES ]  k 2 [ ES ]  0 KM KI
dt
 [S ] [I ] 
d [ EI ] Eo  [ E ]1   
 k3 [ E ][ I ]  k 3[ EI ]  k 4 [ EI ]  0  K M K I 
dt
Eo
[E] 
[S ] [ I ]
1 
KM KI
90
 1/v

d [ P] [I]
 k 2 [ ES ]
dt
KM  [I ] 
1  
d [ P] [ E ][ S ] vmax  K I 
 k2
dt KM
1/vmax
[S]
d [ P] k 2 Eo
 [S ]
dt KM 1 [ S ]

[ I ]
1 1 KM  [I ]  1
KM KI   1  
d [ P] k 2 Eo [ S ]
v vmax vmax  K I  [S ]
v 
dt  [I ] 
K M 1   [ S ]
 KI  Inhibitor is replaced
vmax  k 2 Eo vmax [ S ]
from the active sites
v by substrate at high [S]
 [I ] 

K M 1   [ S ] 
 KI  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
E+S ES  E + P
+ +
I I
KI KI
KM
EI + S EIS  E + P 92
 1/v
k1 k2
E+S ES  E + P
+ k-1 +
I I
KI KI
k3  [S ] 
K M 1  
EI + S EIS  E + P  K M 
k-3

v  k 2 [ ES ] 1/vmax-app

1 1 [I ] 1/[S]
[S ]  
v KM vmax  app vmax vmax K I

vmax 1  [ S ]  [ I ]  [ I ][ S ] 1/vmax-app
KM K I K IKM

Vmax=k2E0
1/(vmaxKI)
Henri-Michaelis-Menton Eq
v [S ]

vmax  [S ]   [I ] 
K M 1    [ S ]1  
 K M   K I  1/vmax 93
[I]
Uncompetitive inhibition
No binding site for inhibitor until substrate is bound to
the enzyme, so only ternary complex is possible

94
 1/v
Uncompetitive Inhibition
KM
E+S ES  E + P
+
I
KI KM
EIS  E + Q vmax
1  [I ] 
v  k 2 [ ES ] 1  
vmax  K I 

1/[S]
[S ] 1 1 [I ]
 
v KM v' vmax K I

vmax 1  [ S ]  [ I ][ S ] 1/v’
KM K IKM

Vmax=k2E0
1/KI
1 KM 1
 
1 1  [ I ] 
 
v vmax [ S ] vmax  K I 
1/vmax
95
[I]
 E  nS  ES n P Eo  [ E ]  K [ E ][ S ]n
[ ES n ]
K
[ E ][ S ]n Eo
Hill eq. [E] 
Yield 1  K [ S ]n
[ ES n ] K [ E ][ S ]n
Y 
[ E ]  [ ES n ] [ E ]  K [ E ][ S ]n [ ES ] 
KEo [ S ]n
1  K [ S ]n
Y n: Hill coefficient
 K [ S ]n
1 Y
k 2 E o K [ S ]n
 Y  v  k 2 [ ES n ] 
log

  n log[S ]  log K 1  K [ S ]n
 1 Y 

1 1 K
v  k 2 [ ES ]  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
d [ HBr ] k '[ H 2 ][ Br2 ]
2


dt [ HBr ]
1 k''
[ Br2 ]

98
  
Initiation Br2  Br  Br
ka

Propagation Br   H 2 
kb
HBr  H 

H   Br2 
kc
HBr  Br 

Inhibition H   HBr 

kd
H 2 Br 

Termination Br   Br  
ke
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
dN
Total flux at r from B: RB  4r D A 2 A
dr
1
N A at r=(rA+rB) is 0
 N 1A
RB  dr
r2
 4D A  d N 1A
( rA  rB ) 0

RB  4 (rA  rB ) DA N 1
A

RE1  4 DA  DB rA  rB N 1A N B1

4N a ( DA  DB )(rA  r B )
k diff  L-mol-1-s-1
1000 108
 Reactions in Solution


T k est
 k diff
D diff
exp( )  1
6r (T )
z A zBe2

2TN a (rA  rB ) 2 
 (rA  rB )T
k diff
3000 (T )rA rB

8 RT
k diff 
3000 (T )

8(8.31x107 )(298)
k diff   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; AS
• Becomes adsorbed onto the surface: A+SAS
• Reacted at the surface: ASPS
• Desorbed from the surface: PS—P+S
• Transported back to the bulk:
P Bulk

110
 Adsorption isotherms
(Langmuir)
A+ S = AS; K N 1AS
pV = nRT K 1 1
n/V =P/RT N ANB

1 1 N 1A = n/V =NaP/RT
N S =(1-) N T
bP
N 1
AS =N 1

1  bP
T

K = RT/(1-)NaP
N a K K 7.34 x10 21 K

T 1 b   (atm 1 )
K RT T T
1 N a P
111
 Adsorption Isotherm
(Fruendlich)
fi P
   f i i  
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 = 
  aP m

  T (b' P)T 112

 Maximum Adsorption Rate
1

A+SAS  T  2
RS1    SN 1A
1  2m A 
 8T  2
RE1     S2 N 1A N S1 RS1  k S SN 1A
  
mS m A 1
  mS
mS  m A  T  2
k s   
 2   S2   A2  S2  2m A 
S = Total surface area of spheres in 1 cm3 1
 T  2  T
S  ( 4rS2 ) N S1 k s    pe
 2m A 
N 1
S = total number of spheres in 1 cm3 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
16
k s     8.15 x10 9 (cm3  molecules 1  cm  2  s 1 )
 2 xx100 
 8.15 x10 9 x(10 3 ) x(6.023 x10 23 )( L / mol )(1 / cm 2 )(1 / s )
 4.91x10 12 ( L / mol )(1 / cm 2 )(1 / s )

1
 T  2
k s   
 2m A 
114
 Langmuir-Hinshelwood
A  S  AS ; K A bA PAbB P B
R  ks
B  S  BS ; K B (bA PA  bB PB ) 2
AS  BS  P  S ; k s R  ks
bA PAbB P B
 ks
bA PA
 ks '
PA
2
(bB PB ) (bB PB ) PB
R  k s [ AS ][ BS ]
bBPB > bAPA
bA PAbB P B bA PAbB P B
R  ks R  ks  k s, PA PB
(1  bA PA  bB PB ) 2 1
bA PAbB P B bB P B ' PB bBPB , bAPA <1
R  ks 2
 ks  ks
(bA PA ) bA PA PA

bBPB <bAPA 115

 Eley-Ridel Equation

A  S  AS ; K1
B  AS  C  S ; k s

bA PA
R  k s [b][ AS ]  k s PB
1  bA PA

bA PA b P
R  ks PB  k s A A PB  k s' PB
1  bA PA PA

bB PA
R  ks PB  ksbAPA PB  ks' PA PB
1 bA PA
116