21.

4 Reactions approaching equilibrium

(a) First-order reactions close to equilibrium
If [ B ]= 0, [ A] + [ B=
] [ A]0
→ B
k1 d [ A] at all times
= −k1 [ A] + k−1 [ B ] d [ A]
0
A ←
k−1 dt = − k1 [ A] + k −1 ([ A]0 − [ A] )
−k1 [ A] + k −1 [ B ] =
dt
k−1 + k1e −( k1 + k−1 )t − ( k1 + k −1 ) [ A] + k −1 [ A]0
[ A] = [ A]0 =
k1 + k−1  
1  d [ A] 
−  = dt
k1 + k −1  A − k −1 A 
 [ ] k + k [ ]0 
k−1
[ A]∞ = [ A]0  
k1 + k−1 1 −1


[ A]0 
k −1
[ B=
]∞ [ A]0 − [ A]∞  [ A] −
1 k1 + k −1
− ln  = t
k1 + k −1  A − k −1 A 
k1  [ ]0 k + k [ ]0 
= [ A]0  −1 
k1 + k−1
1

k −1 [ A] − k−1
[ A] − [ A]0
[ B ]∞ k1 =
k1 + k −1 [ A]0 k1 + k−1
= e −( k1 + k−1 )t
K≡ =
[ A]∞
k1 k1
k−1 [ A]0
k1 + k −1 k1 + k −1

=
[ A] k1
e −( k1 + k−1 )t
+ =
k −1 k1e −( k1 + k−1 )t + k −1
[ A]0 k1 + k −1 k1 + k −1 k1 + k −1
(2015) Chemical Kinetics by M Lim 1
21.4 Reactions approaching equilibrium
(a) First-order reactions close to equilibrium
If [ B ]=
0
0, [ A] + [ B=
] [ A]0 at all times
dx d [ A]
= −adt −k1 [ A] + k −1 [ B ] =
= − k1 [ A] + k −1 ([ A]0 − [ A] )
x−b dt
ln ( x − b ) − ln ( x0 − b ) =−adt − ( k1 + k −1 ) [ A] + k −1 [ A]0
=
 
x−b  d [ A] 
ln = −at   = dt
x0 − b k
 [ A] − k + k [ A]0 
 − 1 
x−b  1 −1 
= e − at 
[ A]0 
k −1
x0 − b  [ A] −
k1 + k −1
ln   = − ( k1 + k −1 ) t
x − b=( x0 − b ) e − at k
 [ A]0 − k + k [ A]0 
 −1 
 
b + ( x0 − b ) e − at
1 −1
x= [ A] k
k −1
[ A] − [ A]0 [ A] − k +−k1
a ( k1 + k −1 )
= k1 + k −1
= 0 1 −1
= e −( k1 + k−1 )t
k k1
k1 [ A]0 − −1 [ A]0
b= [ A]0 k1 + k −1 k1 + k −1
k1 + k −1
=
[ A] k1
e −( k1 + k−1 )t
+ =
k −1 k1e −( k1 + k−1 )t + k −1
[ A]0 k1 + k −1 k1 + k −1 k1 + k −1
(2015) Chemical Kinetics by M Lim 2
 21.4 Reactions approaching equilibrium
(a) First-order reactions close to equilibrium


k1
A ← →B
d [ A]
k−1
= −k1 [ A] + k −1 [ B ]
k −1 dt
[ A]∞ = [ A]0
k1 + k −1
[ B=
]∞ [ A]0 − [ A]∞ At equilibrium
d [ A]
=
k1
[ A]0 −k1 [ A]eq + k −1 [ B ]eq =
= 0
k1 + k −1 dt
[ B ]∞ k1 [ B ]eq k1
K≡ = ∴ = ≡K
[ A]∞ k −1 [ A]eq k−1

(2015) Chemical Kinetics by M Lim 3

A reaction taking place in a sequence of steps
Koverall = a product of Ks for each step

→
ka
ex, A + B ← C + D
[C ][ D ] = ka
k− a
[ A][ B ] k− a
→
kb
C ← E + F
[ E ][ F ] = kb
k− b
[C ] k − b
A+ B  D+E+F
[ D ][ E ][ F ] =ka kb
[ A][ B ] k− a k−b

(2015) Chemical Kinetics by M Lim 4

 (b) Relaxation methods for fast reaction
Return of a system to equilibrium
d ln K ∆ r H o
Suddenly change K: T jump =
→ B
A ←
k1 dT RT 2
k−1 p jump

−( k1 + k−1 )t 1 x ≡ [ A]e − [ A] = [ B ] − [ B ]e
x = x0e , relaxation time: τ =
k1 + k −1 d [ A]
=− ( −k1 [ A] + k −1 [ B ])
dx
=−
dt dt
=k1 ([ A]e − x ) − k −1 ([ B ]e + x )

x − ( k1 + k −1 ) x + k1 [ A]e − k −1 [ B ]e
=
 → B+C
kf
A ←
kr
{k [ A]
1 e
0}
− k −1 [ B ]e =
 [ B ]e 
k f + k r ([ B ]e + [C ]e )
1 k1
= =
K = 
τ  k −1 [ A]e 
dx
 → C+D = − ( k1 + k −1 ) x
k
A + B ←
f

kr
 dt
∴x = x0e −( k1 + k−1 )t
1
= kf
τ
([ A] + [ B ] ) + k ([C ] + [ D ] )
e e r e e

(2015) Chemical Kinetics by M Lim 5

 (b) Relaxation methods for fast reaction
Ex 21.4 When Kw=1.008×10−14 at 298K, τ=37 µs and pH = 7.
What is kf and kr for H2O ↔ H+ + OH− ?


k1
H 2O ←
k2
→
 H +
( aq ) + O H −
( aq ) ,
1
τ
=
e
(
k1 + k2  H +  + OH − 
e
)
 H +
k1   e    OH −
 Kw
= e
= M ≡ K = 1.81 × 10−16 M , k1 = k2 K s −1
k2 [ H 2O]e 55.6

τ
1
( )
k1 + k2  H +  + OH −  =
=
e e
k2 K + k2 ( Kw + Kw = ) (
k2 K + 2 K w )
1 −1 −1
k= = × 11

( )
1.4 10 M s
τ K + 2 Kw
2

= K 2.4 × 10−5 s −1
k1 k2=

(2015) Chemical Kinetics by M Lim 6

 21.5 The T dependence of reaction rate
• Arrhenius equation (an empirical observation)
− Ea RT
k = Ae =
ln k ln A −
Ea
RT
A: pre-exponential factor (frequency factor)
Ea : activation energy (Emin that Rs must have to form Ps)

Ea
=
ln k ln A −
RT
d ln k Ea d ln k Ea
= or = −
dT RT 2 d (1 T ) R
• Non-Arrhenius: Ea(T) (we can still define Ea)
d ln k d ln k High Ea:
Ea ≡ RT 2
=
−R
dT d (1 T ) stronger T-dependence of k
(2015) Chemical Kinetics by M Lim 7
(2015) Chemical Kinetics by M Lim 8
 21.5(b) The interpretation of the parameters
Ex 21.5 Determining the
Arrhenius parameters.
− Ea RT
Slope = −Ea/R = −22.7 k = Ae Activation complex
Intercept = ln A = 27.7
(transition state)

22.7 × (8.314 JK −1mol −1 ) × 103 K

Ea = reaction coordinate
= 189 kJ mol −1
= = 1.1 × 1012 M −1s −1
A e 27.7
(2015) Chemical Kinetics by M Lim 9
 Review 21-2

k1
A ← →B
k−1

k1
K=
k −1
−( k1 + k−1 )t 1
x x=
0e , relaxation time: τ
k1 + k −1

− Ea RT
k = Ae
d ln k d ln k
Ea ≡ RT =
−R
2

dT d (1 T )

(2015) Chemical Kinetics by M Lim 10

 21.6 Elementary reactions
(Real reactions at the molecular level)

Molecularity:
# of molecules coming together to react in elementary reaction

Unimolecular (1, 1st-order)

ex, cyclopropane → propane
Bimolecular (2, 2nd order)
ex, CH3I + CH3CH2O- → CH3CH2OCH3 + I-
Termolecular (3, third-order; rare)

Elementary bimolecular → 2nd-order kinetics

2nd-order kinetics → the reaction might be complex

(2015) Chemical Kinetics by M Lim 11

 21.7 Consecutive elementary reactions
A → I → P
k k a b

d [ A]
= −ka [ A]
dt If [=I ]0 [ = P ]0 0
d [I ] [ P ] + [ I ] + [ A] =
[ A]0 ka = 10kb
= ka [ A] − kb [ I ]
dt
[ A] = [ A]0 e − kat
d [ P]
= kb [ I ] ka [ A]0 − kat
dt = [I ]
kb − k a
( e − e − kb t )

[ P ] = [ A]0 − [ I ] − [ A]
 k a e − kb t − k b e − k a t 
= [ A]0  1 + 
 k b − k a 

(2015) Chemical Kinetics by M Lim 12

 21.7 Consecutive elementary reactions
A → I → P
k k a b

Ex 21.6 At what time will I be present in the

greatest concentration?

ka [ A]0 ka = 10kb
=[I ]
kb − k a
(e − ka t
−e − kb t
)
d [I ] ka [ A]0
dt
=
−
kb − k a
(
ka e − kat − kb e − kbt =
0 )
ka e − kat = kb e − kbt
ka
= e( a b )
k −k t

kb
1 ka
∴ tmax = ln
k a − kb kb
(2015) Chemical Kinetics by M Lim 13
21.7(b) The steady-state approximation
A  → I  → P d [I ]
ka kb

≈0 eg , ka << kb
dt
d [I ]
= ka [ A] − kb [ I ] ≈ 0
dt
ka
∴[ I ] = [ A]
kb
ka kb = 20ka
[I ] ≈ [ A]0 e− kat
kb
d [ P]
= k= b [I ] ka [ A]
dt
ka
[I ] ≈ [ A]0 e − kat = ka [ A]0 e − ka t
kb
d [I ]
dt
= −
ka 2
kb
[ A]0 e − kat [ P ] ≈ (1 − e− k t ) [ A]0
a

d [I ]

0 for ka kb
dt (2015) Chemical Kinetics by M Lim 14
 21.7(c) The rate-determining step
If kb >> ka , A 
ka
→ I 
kb
→ P [ A] = [ A]0 e − k t a

e − kbt << e − ka t , kb − ka ≈ kb ka [ A]0 − k t

=[I ] ( e − e−k t )
kb − k a
a b

ka [ A]0
[I ]
kb − k a
(e − ka t
− e − kb t )
=
 k a e − kb t − k b e − k a t 
[ P ] [ A]0  1 + 
 kb − k a 
ka [ A]0
≈
kb
(e ) ≈ 0
− ka t

 k a e − kb t − k b e − k a t 
[ P] [ A]0  1 + 
 k b − k a 
 − k b e − ka t 
≈ [ A]0  1 + 
 k b 
[ A]0 (1 − e − k t ) : depends on only the smaller of the two rate constant
a

rate determining step (RDS)

RDS may also stem from the low concentration of crucial R
and need not correspond to the step with the highest Ea
(2015) Chemical Kinetics by M Lim 15
 21.7(d) Pre-equilibria
→ ka
A + B ← I → P
kb
k− a

When k − a >> =
kb , K =
[ I] ka
[ A][ B ] k− a
d [ P]
= k= b [I ] kb K [ A][ B ]
dt
 k a kb 
= k [ A][ B ]  k ≡ 
 k −a 

(2015) Chemical Kinetics by M Lim 16

Ex 21.8 Without ignoring the kb.
→
ka
A + B ← I → P
kb
k− a

d [I ]
= ka [ A][ B ] − k− a [ I ] − kb [ I ] ≈ 0
dt
ka [ A][ B ]
[I ] ≈
k − a + kb
d [ P] kb ka [ A][ B ]
= k= b [I ] ≡ k [ A][ B ]
dt k − a + kb
kb k a
kr =
k − a + kb
k a kb
When k− a >> kb , k ≡
k− a
(2015) Chemical Kinetics by M Lim 17
 21.7(e) Kinetic and thermodynamic
control of reaction
Kinetic control: (before it reaches equilibrium)
If A + B 
k1
→ P1
A + B 
k2
→ P2
Rate of formation of P1 = k1 [ A][ B ]
Rate of formation of P2 = k2 [ A][ B ]

∴
[ P1 ] k1
=
[ P2 ] k2

Thermodynamic control: (when it is allowed to reach equilibrium)

the ratio is determined by the standard Gibbs energies

(2015) Chemical Kinetics by M Lim 18