Consecutive Reactions

(Pre-Equilibrium)
k2 k1
• A + B (AB) C …(1)
k-1

d [( AB )] steady state
 k 2 [ A][ B ]  k 1 [( AB)]  k1 [( AB)]  0 …(2)
dt
Pre-equilibrium is possible when k-1 >> k1, but not for k1 >> k-1
Assume: k2 and k-1 >> k1, then:
k 2 [ A][ B]  k 1 [( AB )] …(3)

and
k2
[( AB)]  [ A][ B ]  K [ A][ B] …(4)
k 1 1
 Consecutive Reactions
(Pre-Equilibrium)
…(5)
[( AB )]
• Since equilibrium constant K
[ A][ B]
k2
• Then [( AB)]  K [ A][ B] i.e. K 
k 1
d [C ] …(6)
• And   k1 [( AB)]  k1 K [ A][ B ]
dt

• i.e. 2nd order and k1K combined, is the 2nd order rate constant

• Another example of pre-equilibrium is the Michaelis-

Menten Mechanism for enzyme action

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 Consecutive Reactions
(Pre-Equilibrium)
Michaelis-Menten Mechanism for Enzyme Action
k2 k1
• E + S k-1 (ES) P + E …(7)

• E – enzyme, S – substrate, (ES) – enzyme substrate

complex, P – product molecule
d [ P]
 k1 [( ES )] Assume steady-state for [(ES)]
dt

d [( ES )] …(8)
 k 2 [ E ][ S ]  k 1 [( ES )]  k1 [( ES )]  0
dt
• Difficult to measure [E], but [E]o, the initial (= total)
enzyme concn is known (i.e. [E]o = [E] + [(ES)]) and
[E] = [E]o – [(ES)]. Substitute into eqn (8) to give:
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 Consecutive Reactions
(Pre-Equilibrium)
Michaelis-Menten Mechanism for Enzyme Action
k 2 ([ E ]o  [( ES )])[ S ]  k 1 [( ES )]  k1 [( ES )]  0 …(9)

k 2 [ E ]o [ S ]  k 2 [( ES )][S ]  k 1 [( ES )]  k1 [( ES )]  0 …(10)

k 2 [ E ]o [ S ]  [( ES )](k 2 [ S ]  k 1  k1 ) …(11)

k 2 [ E ]o [ S ] …(12)
[( ES )] 
( k 2 [ S ]  k 1  k1 )

d [ P] k1k2 [ E ]o [ S ]
• Now  k1[( ES )]  …(13)
dt (k2 [ S ]  k1  k1 )

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 Consecutive Reactions
(Pre-Equilibrium)
Michaelis-Menten Mechanism for Enzyme Action
• Eqn (13) divided through by k2 to give:
d [ P] k1[ E ]o [ S ] k1[ E ]o [ S ] …(14)
 
dt  k  k  [S ]  K M
 [ S ]  1 1 
 k2 
• Where KM is the Michaelis constant.
• Linear dependence on [E]o, complicated dependence on [S].
• Usually [S] >> KM and equation 14 becomes.
d [ P]
 k1[ E ]o …(15)
dt
• since all the enzyme is in the form ES, i.e. [ES] ~ [E]o

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 Consecutive Reactions
(Pre-Equilibrium)
Michaelis-Menten Mechanism for Enzyme Action
• make vmax  k1[ E ]o
• maximum velocity when all enzyme is complexed in the
form ES, i.e. when [E]o = [ES]
v [S ]
• Therefore: 
vmax [ S ]  K M

• More useful linear forms are:

1 KM 1 1 [S ] K M 1
  or   [S ]
v vmax [ S ] vmax v vmax vmax
y= m x + c y = c + m x
Where experimental data for v at varying [S] is required.
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 Consecutive Reactions
(Pre-Equilibrium)
Michaelis-Menten Mechanism for Enzyme Action
k1 [ E ] o [ S ]
• Recall: v  k1 [ ES ] 
K M  [S ]

k1 [ E ] o
• At low [S], KM >> [S] and: v  [S ] 1st order in [S]
KM

• At high [S], KM << [S] and: v  k1 [ E ]o zero order in [S]

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[S]
 CHAIN REACTIONS
• Reactive intermediates are usually atoms or radicals
• Three processes:
– (i) Initiation
– (ii) Propagation
– (iii) Termination

• e.g. thermal decomposition of acetaldehyde

CH CHO  CH + C H + CO
3 4 2 6

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 CHAIN REACTIONS
Thermal Decomposition of Acetaldehyde

ka
CH3CHO CH3 + CHO
kb
CH3 + CH3CHO CH4 + CH3CHO

kc
CH3CHO CO + CH3
kd
2 CH3 C2H6