LECTURE NOTE

by Prof. Kook Joe Shin

Professor Emeritus, Seoul National University
Chair Professor, UNIST
Textbook: D. W. Oxtoby, H. P. Gillis, and A. Campion,
“Principles of Modern Chemistry”, 7 th ed., Cengage, (2012)

UNIT V RATES OF CHEMICAL AND PHYSICAL PROCESSES

Chapter 18
Chemical Kinetics

1
Scanning tunneling microscope images of dibutyl sulfide adsorbed on a
single crystal gold surface at different temperatures, with corresponding
ball-and-stick models shown in the bottom row. The molecule occupies a
unique single site at 7 K, then samples the two lowest energy, nearly
equivalent sites at 13 K, and finally rotates freely at 25 K. 2
 halk Stick of
Powdered c Smaller
chalk
ce area
Larger surfa Slow
surface
area
Fast

3
 Ca 2+ ( aq)  CO 2 ( g )  2 Cl  ( aq)  H 2O(l )
CaCO3 ( s)  2 HCl( aq)  
 Rates of Chemical Reactions
 Rate depends on concentration

Fig. 18.1 Zn + H2SO4 (dilute) Zn + H2SO4 (conc) 4

 Rate also depends on physical forms

Fig. 18.2 Steel wool burning in O2

5
 Measuring Reaction rates

 Quenching Method ~ for slow reactions

Rapid cooling at low temperature, chemical analysis
 Absorption Spectroscopy
Real time measurement of amount of absorbed light by
a reactant at a particular wavelength
~ Proportional to concentration
 Average rate
Change in concentration / change in time ~ [A]/t
Depends on the selected time interval
Change in concentration
Average reaction rate 
Change in time
6
Ex. NO 2 ( g )  CO( g )  
 NO( g )  CO 2 ( g )

[NO] [NO]f  [NO]i

Average rate  
t t f  ti

50s [NO] (0.0160  0) mol L 1

average rate   3.2 10 4 mol L 1s  1
0s
t (50  0) s

100s [NO] (0.0249  0.0160) mol L 1

average rate   1.6 10 4 mol L 1s  1
50s
t (100  50) s

 Average rate depends on the time interval chosen

7
 [NO]t t  [NO]t d [NO]
instantaneous rate  lim 
t  0 t dt
d [NO 2 ] d [CO] d [NO] d [CO 2 ]
(instantaneous) rate    
dt dt dt dt
 initial rate ~ instantaneous rate at the beginning of reaction

In general,
a A  b B 
 cC  dD

1 d [A] 1 d [B] 1 d [C] 1 d [D]

rate    
a dt b dt c dt d dt

8
 instantaneous rate
d [NO]

dt

[NO]
average rate 
t
[NO]f  [NO]i

t f  ti

Fig. 18.3 Time dependence of the concentration of NO in the reaction,

NO 2 ( g )  CO( g )  
 NO( g )  CO 2 ( g ) 9
 Rate Laws
 Order of reaction
 Rate Law
~ Concentration dependence of rate
In general, aA  bB  
 products
1 d [A]
rate  k[A]n [B]m
a dt
k: rate constant (or rate coefficient)
n: reaction order with respect to A
m: reaction order w.r.t. B
n + m: overall reaction order
Ex. N2O5 (g)  2 NO2 (g) + ½ O2 (g)
Fig. 18.4 Rate of decomposition
rate law: rate = k [N2O5] of N2O5 at 25oC is proportional to
its concentration.
1st order reaction 10
 Integrated Rate Laws

 First-Order Reactions: A  products

d [A] dc
rate  k[A]  rate  kc
dt dt
c 1 t
c0 c dc  k 0 dt  ln c  ln c0  kt

c
ln  kt or c c0 e  kt
c0

 Half-life (t1/2): At t1/2, c = c0 /2 .

c  c0 / 2  ln 2 0.6931
 kt1/2 ln   ln    ln 2 t1/2  
c
 0 c
 0  k k
 independent of c0
11
Ex. N2O5 (g)  2 NO2 (g) + ½ O2 (g) rate = k [N2O5]

Fig. 18.5 Decomposition of N2O5 Fig. 18.6 The same data as in Fig. 18.5
in a 1st order reaction gives a plotted in a [N2O5] vs. time. The half-life,
straight line with negative slope in t1/2, is the time it takes for the concentration
a plot of ln[N2O5] vs. time. to be reduced to half its initial value.
12
 Second-Order Reactions: A + A  products
1 dc
[A] c  rate  kc 2
2 dt
c 1 t 1 1
c0 c 2 dc  2k 0 dt   2kt
c c0

 Half-life (t1/2)
1 1 1
  2kt1/ 2 t1/ 2 
c0 / 2 c0 2kc0

Ex. 2 NO2(g)  2 NO(g) + O2(g)

1 d [NO 2 ]
rate  k[NO 2 ]2 Fig. 18.7 Decomposition of NO2 in a 2nd
2 dt order reaction gives a straight line with
positive slope in a plot of [NO2]–1 vs.
time. 13
 Zeroth-Order Reactions: A + A  products

On solid surface ~ rate depends on desorption rate of product !

dc
rate   kc 0  k
dt
c t
 dc  k dt
c0 0

 c c0  kt

 Half-life (t1/2)
c0
c0 / 2 c0  kt1/ 2 t1/ 2 
2k

Ex. N2O(g)  N2(g) + ½ O2(g) on the surface of hot Pt

14
 Reaction Mechanisms
 Elementary Reactions ( 단일단계반응 )

Order of reaction (반 응 차 수 ) = Molecularity (반 응 분 자 수 )

 Unimolecular Reaction, (1st-order): A  products

Ex) N2O5*(g)  NO2(g) + NO3(g), rate = k [N2O5*]

 Bimolecular Reaction, (2nd-order): A + A (or B)  products

Ex) NO(g) + O3(g)  NO2(g) + O2(g), rate = k [NO][O3]

 Termolecular Reaction, (3rd-order): A + B + C  products

Ex) I(g) + I(g) + Ar(g)  I2(g) + Ar(g), rate = k [I]2[Ar]

15
 Reaction Mechanisms

 Decomposition of overall reaction into a sequence

of elementary reactions

Overall reaction: A  B
Elementary reaction 1: A  C
Elementary reaction 2: C  D
Elementary reaction 3: D  B
Overall reaction = Sum of elementary reactions:
Intermediates: C, D
 Rate-determining step: Slowest step in the mechanism

16
 Kinetics and Chemical Equilibrium
k1
 
aA  bB   cC  dD
k 1

If both forward & backward reactions are elementary reactions,

Forward rate = k1[A]a[B]b
Backward rate = k–1[C]c[D]d

 Principle of detailed balance ( 미세균형원리 )

At equilibrium, forward rate = backward rate.
k1 ([A]eq)a([B]eq)b = k–1([C]eq)c([D]eq)d

 Mass action law ( 질량작용법칙 )

c d
k1 ([C]eq ) ([D]eq )
 a b
K eq
k 1 ([A]eq ) ([B]eq )

17
 Reaction Mechanisms and Rate
 When the reaction-determining step is the first one…
Ex. 2 NO2(g) + F2(g)  2 NO2F(g), rate = kobs[NO2][F2]
Reaction mechanism:
k1
 
NO2(g) + F2(g) k2
NO2F(g) + F(g) (slow)
 
NO2(g) + F(g) NO2F(g) (fast)
rate = k1[NO2][F2]  kobs = k1
 When the reaction-determining step is one or more fast steps…
 reaction order > 2
Ex. 2 NO + O2  2 NO2, rate = kobs[NO]2[O2]
Reaction mechanism
k
  1 
 k  
1
NO + NO   k2  N2O2 (fast equilibrium)
 k  
2
N 2O2 + O 2 2 NO2 (slow)

rate = k2K1[NO]2[O2]  kobs = k2K1 18

 Fractional Order (?)
Overall reaction: H2 + Br2  2 HBr

rate = kobs [H2][Br2]1/2  determined by experiment

Reaction mechanism:
k1

 
Br2 + M k 1 Br + Br + M (fast)
 k
2

Br + H2 HBr + H (slow)
k3
 
H + Br2 HBr + Br (fast)

rate = k2 [Br][H2]

rate
[Br]2/[Br 2] = k
K21(K
=1)k1/2
1 /[H 2]1/2
k-12][Br [Br] = (K1)1/2 [H2][Br2]1/2

19
 Looks alike but different type of reaction

Overall reaction: H2 + I2  2 HI

rate = kobs [H2][I2]  determined by experiment

Reaction mechanism (Sullivan):

k1

 
k1
I2 + M I + I + M (fast) K1 = [I]2/[I2]
 k
2

I + I + H2 2 HI (slow)
rate = [H2][I]2 = k2K1[H2][I2]

cf. rate = k2(K1)1/2[H2][Br2]1/2

20
 The Steady-State Approximation
 Lindemann’s mechanism
k1
 
 
N2O5(g) + M(g) k 1 N2O5*(g) + M(g)
 k
2

N2O5*(g) NO3(g) + NO2(g)

Subsequent steps to form O2 and NO2 from NO3 occur rapidly and
do not affect the measured rate:
 k
3

NO3(g) + NO2(g) NO(g) + NO2(g) + O2(g) (fast)
 k
4

NO3(g) + NO(g) 2 NO2(g) (fast)

Net rate of change of [N2O5*]:

~ the steady-state concentration of [N2O5*] is unchanged throughout
*
d [N O
most of the5 ] course of the reaction
2
0 k1[N 2 O5 ][M]  k 1[N 2O*5 ][M]  k2 [N 2O*5 ]
dt
21
 k1[N 2 O5 ][M]
[N 2 O*5 ] 
k2  k 1[M]

The rate of the overall reaction: N2O5  2 NO2 + (1/2) O2

1 d [NO 2 ] k k [N O ][M]
rate  k2 [N 2O*5 ]  1 2 2 5
2 dt k2  k 1[M]

~ Two limiting cases

i) Low pressure (k2 >> k–1[M])

rate  k1[N2O5][M]  2nd-order reaction

ii) High pressure ( k2 << k-1 [M] )

[N2O5]  1st-order reaction

22
 Chain Reactions

~ Photochemical reactions, Free radicals, A-bomb

CH4(g) + F2(g)  

CH3F(g) + HF(g)


Initiation: CH4 + F2 CH3 + HF + F


Propagation: CH3 + F2 CH3F + F


Propagation: CH4 + F CH3 + HF


Termination: CH3 + F + M CH3F + M

Branching Chain Reactions:

 
H(g) + O2(g)  
 OH(g) + O(g)
O(g) + H2(g) OH(g) + H(g)

23
 Effect on Temperature on Reaction Rates
 Gas-Phase Reaction Rate Constants
 Arrhenius Law (1889)
Ea
k  Ae  Ea / RT
 ln k ln A 
RT

Fig.18.10 The temperature dependence

of the Maxwell-Boltzmann distribution of
Fig.18.9 An Arrhenius plot of ln k vs. 1/T. molecular energy plotted against the average
An extrapolation to 1/T = 0 gives the speed, u .
constant ln A from the intercept of this line.
24
 A: Pre-exponential factor
~ Collision frequency, Spatial conformation
Ea: Activation energy
~ Effective collision intensity for reaction to occur
~ A threshold energy for reaction
exp(Ea/RT)

~ Fraction of molecules exceeding the critical energy Ea

Rate constant at T1 vs. rate constant at T2

ln k1 = ln A – Ea/RT1 , ln k2 = ln A – Ea/RT2
k E  1 1
ln k1  ln k2 ln 1  a   
k2 R  T2 T1 

25
 The Reaction Coordinate and the Activated Complex

 Reaction coordinate (or path)

~ Along which reactants feel the lowest possible potential energy

A  B  [AB]*   products

[AB]*: Activated Complex (or Transition State)

~ Unstable complex at the saddle point
 Energy profile along the reaction coordinate for the reaction

NO2(g) + CO(g)  NO(g) + CO2(g)

 U = Ea,f – Ea,r: Change in internal energy of the chemical reaction

~ Thermodynamic quantity obtained from calorimetric measurements

 Ea,f, Ea,r: Activation energies for the forward and reverse reactions

~ Obtained from temperature dependence of rate constants

26
 Fig. 18.11 The energy profile along the
reaction coordinate for the reaction:
NO2 + CO  NO + CO2

 Ea > 0 always for elementary reactions

 There is always some energy barrier to surmount.

 Rates of elementary reactions increase with increasing temperature
 “Negative activation energy” possible for overall reactions
 rates of overall reactions decrease with increasing temperature
27
Ex) 2 NO + O2  2 NO2 , rate = kobs[NO]2[O2]
Reaction mechanism:
k
  1
 k 
NO + NO 1
N 2O2 (fast equilibrium)
k
  2 
 k  2
N 2O2 + O 2 2 NO2 (slow)

rate = k2K1[NO]2[O2]  kobs = k2K1

k2 is for elementary reaction  increases with increasing T

K1 is an equilibrium constant
 Could decrease with increasing T for exothermic reaction!

28
 Molecular Theories of Elementary Reactions
Collision Theory
 Rate of collisions between a particular A molecule with other
A molecules in a gas:
NA N  RT
Z1  2  d 2u 4 A d 2 (9.26)
V V M

NA kTN 
Z1  2  d 2u 4 c B  A  (18.7)
V m  V 
5 109 s  1 (for N 2 at 1 atm and 298 K)

 Collision cross section,  c  d 2 :  hard sphere cross section

~ Geometric cross section of a sphere that represents
the “size” of a molecule
 Total rate of collisions between A molecules with B molecules in a gas
per unit volume:
8kBT  N A   N B  Reduced mass,
Z AB  c
  V   V   mA mB /(mA  mB )
29
Fig. 9.20,18.12 A collision cylinder. Molecule A sweeps out a cylinder
of volume (  d 2u ) per second, where d = (dA + dB)/2. It will collide with
all of the B molecules whose centers lie within the cylinder.
30
 Derivation of an expression for the bimolecular rate constant kAB

1) Macroscopic second-order rate law: Rate = kr (NA/V)(NB/V) = ZAB

kr  r u
 ( r : reaction cross section)

2) Defining an energy-dependent reaction cross section,  r(), to

account for the fact that only those collisions that meet a specific
energy criterion will lead to the reaction.
3) Find the threshold energy for reaction and determine the functional
dependence of  r() on .
4) Using the Maxwell-Boltzmann distribution, f(), integrating the
energy-dependent reaction probability over all possible relative
kinetic energies weighted by that distribution. 1/ 2
 N  N   N  N   2   N  N 
Rate kr  A   B   r ( )u  A   B   r ( )    A   B 
 V  V   V  V      V  V 
31
   2 
1/ 2
 N  N 
Total rate   r ( )   f ( ) d    A   B 
0     V  V 
 
 1/ 2
 2 
Rate constant: kr  r ( )   f ( )d  (18.9)
0   
Maxwell-Boltzmann distribution:
3/ 2
 m 
f (u ) 4   u 2 exp(  mu 2 / 2kBT ) (18.10)
 2 k T
B 

Substitutions:   u 2 / 2, u 2 2 /  , du d  /(2  )1/ 2

Relate f (u )du to f ( ) d  :
3/ 2
   2 d
f (u )du 4   exp(  / k BT )
 2 k T
B   (2  )1/ 2
3/ 2
  
2    1/ 2 exp(  / kBT ) d   f ( ) d 
  kBT 

32
 3/ 2  1/ 2
 1   2 
 kr 2 
 k
 B  T
 
0
 r ( )  
  
 1/ 2 exp(  / kBT )d 
1/ 2 
(18.11)
 8   1 
     r ( ) exp(  / kBT ) d 
  kBT  k T
 B 0

 Assert that only the relative velocity directed along the line of
centers, vAB, is effective in activating reaction.

Fig. 18.13 Impact parameter b

33
 Velocity of A relative to B, vA
 Distance between centers of A and B in contact, d
 Impact parameter, b:
~ Distance between parallel lines passing through the
centers of A and B
 Component of the velocity directed along the line of centers, vAB

vAB = vA cos and sin = b/d

sin2 + cos2 = 1  cos = [(d2 – b2)/d2]1/2
vAB = vA 2[(d2 – b2)/d2]1/2
  12 v

 AB = A (d2 – b2)/d2 (18.12)

34
Impact parameter and reaction
Head-on collision, b = 0 (probability of reaction = 1)
No reaction as b increases (probability of reaction = 0)
The largest value of b for reaction to occur, b0
  
b02  1  a  d 2
  

a : Energy associated with b0

~ Specific energy that corresponds to the largest impact parameter
that leads to reaction.
~ Smaller values of a do not lead to reaction

35
 Multiply both sides by  and identify  r ( )  b0 and  c  d :
2 2

 a 
 r ( )  c  1  (18.13)
  

  r ( )  0 for all values of    a

 Physically unacceptable

  r ( ) 0 for   a

  r ( )  0 for all values of    a

Saturation at  r ( )  c ( d 2 )

 Every collision leads to reaction!

Fig. 18.14 Reactive cross section r()
vs. relative translational energy .

36
 1/2
 8   1 
kr      r ( ) exp(  / kBT )d  (18.11)
  k T
B   kBT  0

 a 
 r ( )  c  1  (18.13)
  
 
 a 
 r ( ) exp(  / kBT )d   c   1 
0 0 
  exp(   / kBT ) d 

( kBT ) c exp(   / kBT )
1/ 2
 8   1 
 
2
 kr     Bk T  c exp(  a / kBT )
  kBT  k T
 B  (18.14)
1/ 2
 8k T 
 c  B 
  
exp(  a / kBT )  A  T exp( E / RT )
a

 Temperature dependent rate constant in terms of molecular parameters

37
 Steric factor, P
~ Orientation of reacting molecules affects the pre-exponential factor

Fig. 18.15 The steric effect on the reaction probability.

38
  Transition State Theory ( 전이상태이론 , 轉移狀態理論 )

~ Activated Complex Theory

~ Gas and solution phase reactions
~ Formation of an activated complex (intermediate product) while
passing through the transition state along the reaction coordinate

Fig. 18.11 The energy profile along the

reaction coordinate for the reaction:
NO2 + CO  NO + CO2
39
 Eyring formula for the rate constant:

kBT †
kr  K
h

 : Transmission coefficient
~ Measures the probability that the system will proceed
through the transition state

kBT/h: Rate at which the activated complex dissociates

to form products
~ 5 1012 s–1 at 300 K
K : Equilibrium constant involving the activated complex

40
 Thermodynamic formulation of transition state theory

Substitute exp(  G † / RT ) for K †

kBT kBT
kr  exp( G / RT ) 
†
exp( H † / RT ) exp(S † / R)
h h

Compare to the Arrhenius equation:

kr  A exp( Ea / RT )

kBT
A   Ea  G † H †  T S †
h

41
 Michael Polanyi Henry Eyring
(HUN/UK,1891-1976) (US,1901-1981)

42
 Isotope Effects in Chemical Kinetics
 Kinetic isotope effect:
~ Isotopic substitution affects the rates of chemical reactions.
~ Primary effect for the isotope involved in a bond
Secondary effect for the isotope involved in an adjacent bond
~ Assume that zero-point energies of the relevant vibration are
identical for both isotopes in the activated complex
~ Zero-point energy of the heavier isotope is less than that of the
lighter one in the reactants producing an increase in activation
energies and a decrease in reaction rates.
Ea,H E  12 h CH
C–H bond: kH(T), (Evib,CH =hCH = 36 kJ mol–1 )
Ea,D E  12 h CD
C–D bond: kD(T), (Evib,CD =hCD = 25 kJ mol–1 )
43
 kH (T ) A exp( Ea,H / RT ) exp[( E  12 h CH / RT )
 
kD (T ) A exp(  Ea,D / RT ) exp[(  E  12 h CD / RT )
exp  12 h CH  h CD  / RT 8.33 at 300 K
E: Energy difference between PE min of reactants and PE max of ACT

Fig. 18.16 Energy profile along a

C–H bond reaction coordinate
showing the origin of the primary
kinetic isotope effect. The zero-point
vibrational energy of the C–D bond
is less than that of the C–H bond,
which leads to an increase in the
activation energy Ea for reactions
that involve breaking C–D bonds.

44
 Molecular Beams
~ Gas-phase reactions, large and expensive instrument
~ Two molecular beams cross in a vacuum chamber
~ Molecular beam of narrow range of velocity selected by velocity
selector (Fig. 9.13)
~ Excite or fracture product molecules by laser gun
~ Study vibrational and rotational states of product molecules

Fig. 18.17 A crossed molecular

beam experiment for the reaction
K + HBr  KBr + H.
45
 Reactions in Solution
“Cage” effect: reactant surrounded by solvent molecules
 Two-step sequence reaction:
k
A  B   AB, AB  k
 1  2
products Rate k2 [AB]
k 1

d [AB] k1[A][B]
k1[A][B]  k 1[AB]  k2 [AB] 0  [AB] 
dt k 1  k2
k k [A][B]
Rate k2 [AB]  1 2
k 1  k2
(1) Activation-energy-controlled reaction
kk
k2  k 1 , Rate  1 2 [A][B] k2 K1[A][B]
k 1
~ Slow second step implies a large activation energy

(2) Diffusion-controlled reaction

k2 k 1 , Rate k1[A][B]

~ k1 is limited by the rate at which the reactants encounter

46
one another by diffusion
 Diffusion

 Einstein’s theory of Brownian motion (1905)

r 
2
6 Dt D : diffusion coefficient

r : diffusive displacement (actually, root mean square value)

 Smoluchowski’s model (1916) for diffusion-controlled reactions

Diffusion-controlled rate constant:
kd 4 R* DN A

where R* = rA + rB and D = DA + DB.

47
 Catalysis
 Catalyst
~ A substance that takes part in a chemical reaction and speeds
up the rate but undergoes no permanent chemical change itself

Fig. 18.18 (a) Decomposition of H2O2 to H2O and O2 catalyzed by a very

small amount of transition metal oxide. (b) The water evolves as steam
because of the heat given off in the reaction. 48
 Catalysts provide alternative pathways for reaction by lowering
the activation energy Ea.

Fig. 18.19 A catalyst speeds up

the reaction by reducing the
activation energy. Both the
uncatalyzed (red) and catalyzed
(blue) reaction coordinates are
shown.

49
 Homogeneous catalysis
Ag ( aq ) 
Tl (aq) + 2 Ce (aq)    
+ 4+  Tl3+(aq) + 2 Ce3+(aq)
k
 1 
Ag   Ce 4   Ag 2  Ce3 (fast)
k 1
k
Tl  Ag 2  
2
Tl2  Ag  (slow)
k
Tl2  Ce 4  
3
Tl3  Ce3 (fast)
 Heterogeneous catalysis
Ex 1) C2H4(g) + H2(g)  Pt
( s
)
 C2H6(g)

Ex 2) Catalytic converter to reduce the emission of pollutants

in the exhaust streams of automobile engines
 *
Oxidation: CO, CxHy, O2 CO2, H2O
 *
Reduction: NO, NO2 N 2, O 2
*
Pt and *Rh deposited on a fine honeycomb mesh of alumina (Al2O3)
Can be poisoned by Pb  unleaded fuel must be used
50
Fig. 18.20 The reaction H2 + C2H4 is catalyzed on the surface of platinum
by promoting the dissociation of H2 to H atoms, which can then add to C2H4
stepwise to give ethane. 51
Fig. 18.21 (a) A catalytic converter used to reduce car pollution and (b) its inside.

52
 Enzyme Catalysis

 Enzyme ( 효소 , 酵素 ): A catalyst for a reaction in living organism with

selectivity, a protein binding a substrate in a small region (active site)
 Substrate ( 기질 , 基質 ): A reactant in a biochemical reaction, a small
organic molecule, a small region of much larger molecule such as
a proton or a nucleic acid
 Glycolysis: Oxidation of glucose to CO2 and H2O in a series of

metabolic reactions
 Hydrolysis of urea catalyzed by the enzyme urease
H 3O  (aq )  (NH 2 ) 2CO( aq)  H 2O(l )  Urease
   2 NH 4 ( aq)  HCO 3 ( aq)

53
 Enzyme Kinetics
 Classification of enzymes
1) Oxidoreductase – Redox reaction
2) Transferase – Functional group transfer reaction
3) Hydrolase – Hydrolysis reaction
4) Lyase – Addition to carbon-carbon double bond
5) Isomerase – isomerization reaction
6) Ligase – bond-forming reaction

 Many enzymes require cofactors to carry out their catalytic functions.

~ Metal ions
(Fe2+/Fe3+ in cytochromes, catalyzing electron-transfer reactions)
~ Small organic molecules called coenzymes (ex. Vitamins)

54
 Michaelis-Menten mechanism
~ Well-known enzyme-catalyzed reaction model for reaction kinetics
k1
 
E  S  ES  k
2
EP
k 1

E: free enzyme, S: substrate, P: final product

ES: complex of substrate bound to the active site of enzyme
 Mass conservation

[ET] = [E] + [ES] , [ET]: Total concentration of enzyme

 Steady-state approximation
d [ES] d [E]
 0  k1[E][S]  (k 1  k2 )[ES]
dt dt
 k1 [E T ]  [ES][S]  ( k 1  k2 )[ES]

k1[E T ][S] [E ][S] k 1  k2

[ES]   T Km  : Michaelis constant
k 1  k2   k1[S] K m  [S] k1

55
 Rate of formation of product
d [P] k [E ][S]
k2 [ES]  2 T Michaelis-Menten equation
dt K m  [S]

Fig. 18.23 Michaelis-Menten plot of

the dependence of the rate of an
enzyme-catalyzed reaction on the
concentration of the substrate,
showing saturation behavior as
[S]  .

 Maximum rate, Vmax k2 [E T ]

d [P] V [S]
k2 [ES]  max 
 V
max as [S] becomes very large
dt K m  [S]
56
 Determination of Km:
 V  
K m [ S ]   max   1  
 [S] when dP/dt = Vmax/2
  dP / dt  

 Turnover number, kcat

~ Number of substrate molecules converted into product
per enzyme molecule per second
Vmax
kcat k2 
ET
 Catalytic efficiency for low substrate concentration

When k2 >> k–1[S],

Km = k2/k1 (≡kcat/k1) and the 1st step is rate-determining:

d [P] k 
k1[E][S]  cat  [E][S]
dt  Km 
Maximum rate of the 1st step is the rate of E-S encounter  diffusion-limited

57
 Lineweaver-Burk equation
1  K  1  1
 m   
d [P] / dt  Vmax   [S]  Vmax

Fig. 18.24 The Lineweaver-Burk linear plot used to determine

parameters Km and Vmax.
58
 Temperature dependence of enzyme-catalyzed reactions
~ Rate increases , doubled every 10oC
~ Fall off above 50-60oC due to unfolding and degrading of
3D structures of protein

Fig. 18.25 Plot of the activity of an enzyme

vs. temperature. The increase in rate at
low temperatures is described by the
Arrhenius equation whereas the falloff in
rate at higher temperatures is due to loss
of structure necessary for function.

59
 Mechanisms of Enzyme-Catalyzed Reactions

~ High degree of specificity of enzyme-catalyzed reactions

 ‘Lock-and-key’ mechanism
Binding of substrates (the key) effected through molecular
recognition by the active site of enzymes (the lock)

Lock and key mechanism

60
 Induced fit hypothesis
Binding of the substrate by the active site is cooperative.

Fig.18.26 The enzyme hexokinase showing (a) the active site before binding
substrate and (b) binding of glucose accompanied by global structural changes
that brings the two domains together and closes off the active site.
61
 Thermodynamics of enzyme-catalyzed reactions

~ Interplay between the destabilization of ES complex and

the stabilization of the transition state EX

Fig. 18.27 (a) Free-energy profile for the uncatalyzed conversion of substrate
to product. (b) Energy profile for the enzyme-catalyzed reaction that shows the
preferential stabilization of the enzyme transition-state complex with respect to
the enzyme substrate complex. 62