QU0918 - Physical Chemistry II

Unit 2: Complex reactions. Kinetic treatment

1
 Complex reactions. Kinetic treatment

2.1. Reversible reactions

2.2. Parallel reactions
2.3. Consecutive reactions
2.4. General treatment of complex reactions
2.5. Steady-state approximation
2.6. Rate limiting step approximation
 Complex reactions. Kinetic treatment

Reaction mechanism: detailed description of all the elementary steps that take place
during the complex reaction.

- The rate of appearance or disappearance of species can be expressed as the sum of

the speeds at each elementary stage it is involved.

- In each elementary step, the molecularity matches the order of the reaction.

Any mechanism can be constructed from the following reactions:

- opposite reactions (Reversible or bidirectional)

- consecutive reactions
- Parallel or competing reactions.
2.1. Reversible reactions

k1
aA + bB + … mM + nN + …
k-1

a b
vd k1 A B
v vd vi
m n
vi k1M N

In the equilibrium vd vi v 0 a b
k1 A eq B eq k1M
m
eq N
n
eq

m n
k1 M eq N eq
KC a b
k1 A eq B eq
2.1. Reversible reactions

Reversible reactions of order one for direct and invers reaction

k1
A B t=0 [A]=[A]0 [B]=[B]0 t=t [A]=[A]0 –x [B]=[B]0 +x
k-1

d A d A0 x
v k1 A 0 x k 1 B0 x
dt dt
dx
k1 A 0 k 1 B0 k1 k 1 x
dt
a b
dx
x
dt

x t 1 x
dx ln t
Integrating: dt
0 x 0
2.1. Reversible reactions

Reversible reactions of order one for direct and invers reaction

x = [A]0 – [A] = [B] - [B]0

dx
v k1 A 0 k 1 B0 k1 k 1 x x
dt
a b
x t 1 x
dx ln t
Integrating: dt
0 x 0

𝑘1 𝐴 0 − 𝑘−1 𝐵 0 − 𝑘1 + 𝑘−1 𝐵 − 𝐵 0
𝛽𝑡 = 𝑙𝑛 =
𝑘1 𝐴 0 − 𝑘−1 𝐵 0

𝑘1 𝐴 0 − 𝑘−1 𝐵 0 − 𝑘1 𝐵 − 𝑘−1 𝐵 + 𝑘1 𝐵 0 + 𝑘−1 𝐵 0

𝑙𝑛
𝑘1 𝐴 0 − 𝑘−1 𝐵 0
−𝑘$ ( 𝐵 − 𝐵 % ) = −𝑘$ ( 𝐴 % − 𝐴)
𝑘$ 𝐴 % − 𝑘$ 𝐴 % + 𝑘$ 𝐴 − 𝑘&$ 𝐵
𝛽𝑡 = 𝑙𝑛 =
𝑘$ 𝐴 % − 𝑘&$ 𝐵 %
2.1. Reversible reactions

Reversible reactions of order one for direct and invers reaction

k1
A B t=0 [A]=[A]0 [B]=[B]0 t=t [A]=[A]0 –x [B]=[B]0 +x
k-1

𝑘$ 𝐴 % − 𝑘$ 𝐴 % + 𝑘$ 𝐴 − 𝑘&$ 𝐵 k1 A k B
𝛽𝑡 = 𝑙𝑛 ln 1 k1 k t
𝑘$ 𝐴 % − 𝑘&$ 𝐵 % 1
k1 A 0 k 1 B0
#! $ "#"! %
- 𝑘! − 𝑘"! 𝑡 = 𝑙𝑛
#! $ # "#"! % #

[] Example: unimolecular isomerization

ciclopropane Propene
time
2.1. Reversible reactions

Reversible reactions of order one for direct and invers reaction

k1
A B t=0 [A]=[A]0 [B]=0 t=t [A]=[A]0 –x [B]=x
k-1

d A d A0 x dx
v k1 A 0 x k 1x
dt dt dt
k1 xeq
In the equilibrium: v 0 0 k1 A 0 xeq k 1 xeq Kc
k 1 A0 xeq

k1 A 0 xeq dx dx k1 A 0 xeq
k 1
k1 A 0 x k 1x k1 A 0 x x
xeq dt dt xeq

dx k1 xeq A 0 x k1 x A 0 xeq dx k1 xeq A 0 k1 xeq x k1 x A 0 k1 xeq x

dt xeq xeq dt xeq

dx A 0 k1
xeq x
dt xeq
2.1. Reversible reactions

Reversible reactions of order one for direct and invers reaction

k1 dx A 0 k1
A B xeq x
k-1 dt xeq

integrating:
ln (xeq-x)
x dx A 0 k1 t
dt slope = -([A]0k1)/xeq
0 xeq x xeq 0

ln xeq

t
A 0 k1
ln xeq x ln xeq t
xeq

y = c + mx
 2.1. Reversible reactions

Reversible reactions of order one for direct and order two for invers reaction

k1
A B+C t=0 [A]=[A]0 [B]=[B]0 [C]=[C]0
k-1
t=t [A]=[A]0 –x [B ]=[B]0 +x [C ]=[C]0 +x

d A dx
v k1 A k 1 B C k1 A 0 x k 1 B0 x C 0 x
dt dt
dx
k1 A 0 k 1 B0C 0 k1 k 1 B0 k 1C 0 x k 1x 2
dt

a b g

dx 2 dx
x x 2
= dt
dt α + βx +γ x
 2.1. Reversible reactions

Reversible reactions of order one for direct and order two for invers reaction

k1
A B+C t=0 [A]=[A]0 [B]=[B]0 [C]=[C]0
k-1
t=t [A]=[A]0 –x [B ]=[B]0 +x [C ]=[C]0 +x

x x t t
dx
2
dt
x x
x 0 t 0
2
q q 4
x
2
ln qt 2 q
q ln
x q
2

Ex.
2.1. Reversible reactions

Examples of kinetics of reversible reactions

first order – first order

Ex. a-glucose <-> b-glucose

first order – second order

Ex. C4H9Br <-> C4H8 + HBr

second order – first order

Ex. H2+ C2H4 <-> C2H6

second order – second order

Ex. acid + alcohol <-> ester + water
 2.2. Parallel reactions

k1 P
d A k1 k 2 t
A v k1 A k2 A k1 k2 A A A 0e
dt
k2 Q

There is not a single way for the reaction to advance

dP k1 k 2 t P t
vP k1 A k1 A 0 e dP k1 A 0 e k1 k 2 t
dt
dt 0 0

k1 A 0 k1 k 2 t
P 1 e
k1 k2
P k1
In a similar way, for product Q:
Q k2
k2 A 0 k1 k 2 t
Q 1 e
k1 k2
2.2. Parallel reactions

If the reactions are reversible:

k1 P
eq P eq
k-1 K P
A k2
A eq
P eq K Peq
k-2 Q Q eq K Qeq
eq
Q eq
K Q
A eq Thermodynamic control

When the reverse reactions are negligible:

P k1
Kinetic control
Q k2
2.2. Parallel reactions

Parallel reactions with different order

k1 For the common reagent :

A P Q
k2
A B P R d A
v k1 A k2 A B k1 k 2 B A
dt
We should solve the system of differential equations for A and B

Usually we accept: A B

d A
v k A k k1 k2 B
dt
- Different experiments are carried out with different [B] in excess, and k is determined
- Representing k vs [B], k1 and k2 are obtained
 2.2. Parallel reactions
Concurrent reactions
Both elementary reactions and [P]0=0
A k1

P k1t k 2t
A A 0e B B 0e
B k2

Mass balance: A0 B0 A B P P

k1 t k 2t
P P A 0e B 0e

k1t k 2t
Applying logarithms: ln P P ln A 0 e B 0e

A representation of ln P P vs t does not give a straight line

2.2. Parallel reactions
Concurrent reactions

A k1 But, if k1 >>> k2, it will come a time when all the reagent A will
have consumed:
P

B k2 ln P P ln B 0 k 2t

- From the linear portion of the representation we will obtain k2 and [B]0

k 2t
- Having k2 and [B]0, [B] can be calculated at any time: B B 0e

A0 B0 A B P P A P P B

k1t
A A 0e Representing ln [A] vs t we will obtain k1 and [A]0

approximate method: it depends on k1/k2 and on [A]0 and [B]0

2.3. Consecutive reactions

k1 k2
A B C

d A dB dC
k1 A k1 A k2 B k2 B
dt dt dt

dB k1 A 0 k1 t k 2t
A A 0e k1t
dt
k1 A 0 e k1t
k2 B B e e
k2 k1

A0 A B C C A0 A B

1 k1t k 2t
C A0 1 k2e k1e
k1 k2
2.3. Consecutive reactions

k1 k2
A B C

k1 A 0
B e k1 t
e k 2t
¿tBmax?, ¿[B]max?
k2 k1

1 k1
t Bmax ln
k1 k 2 k2
dB
0
dt

k2

max k1 k1 k 2
B A0
k2
2.4. General treatment of the complex reactions
Let’s consider the overall reaction: A + 4B → D + E

Where the proposed

reaction mechanism is:

- The mechanism of the reaction must justify the stoichiometry of the overall reaction

- The sum of all stages must give the overall reaction

- Each pair of reversible reactions only counts as the direct reaction
- Each stage can be multiplied by a factor, called stoichiometric number

A+B→C (x2)
2C→A+D 2A+4B+2C→2C+A+D+E A + 4B → D + E
2B→E
2.4. General treatment of the complex reactions

In order to obtain the rate equation, the differential equations are proposed for the
variation with time of the concentration of all species:

- The resolution of the system of differential equations is performed using numerical

algorithms.
 2.5. Steady-State approximation
The concentration of intermediate is small, because they are generally very highly
reactive species

k1 A 0 k1 t k 2t
A k1
B k2
C B e e
k2 k1
k1 A 0 k1t k 2t
The high reactivity of the intermediate results in k2>>k1 B e e
k2
- If k2 is large, the second exponential approach to zero

- If k1 is small, the first exponential will be close to 1 during long time

k1 A 0
B
k2

- After some initial period, provided that we do not get too close to the end of the
reaction:
dB
0
dt
2.5. Steady-State approximation
Means that, after a time, the concentration of all intermediates were approximately
constant and much smaller than the reactants and reaction products

Let’s consider the following overall reaction: A+B→Z

Proposed Mechanism:

k1

A B X
k 1

k2
X Z

We can get the rate equation if we apply the steady-state approximation to the
intermediate species X
 2.5. Steady-State approximation

Let’s consider the following overall reaction: A+B→Z

Proposed Mechanism: Raised the reaction rate from

the appearance of the product:
k1

A B X
k 1

k2
X Z

Using the steady-state approximation for X:

Substituting in the expression for the velocity:

 2.5. Steady-State approximation
Let’s consider the following overall reaction: 3A+2B→2C+2D

Proposed mechanism: A k1 2 X
X B k2 Y C
Y A k3 D
the appearance of the product:

Using the steady-state approximation for intermediates:

2.5. Steady-State approximation
Let’s consider the following overall reaction: 3A+2B→2C+2D

Proposed mechanism: A k1 2 X
X B k2 Y C
Y A k3 D
Substituting in the expressions of speed:

But as the reaction rate expressed in terms of these species is:

 2.6. Rate limiting step (rds) approximation
In mechanisms with consecutive steps, if one of these is much slower than the
others, the overall reaction speed match the speed of the slowest step, called
limiting step.

Let’s consider the following overall reaction: A+B→Z

k1

Proposed mechanism: A B X equilibrium

k 1

k2
X Z slow
 2.6. Rate limiting step (rds) approximation
Let’s consider the following overall reaction: A+B→Z
k1

Proposed mechanism: A B X equilibrium

k 1

k2
X Z slow

Rate-determining step: Steady-state approximation:

if k2<<k-1
if k2>>k-1

k 2 K c [ A][ B] 𝑣 = 𝑘1 ! 𝐴" ! 𝐵 "

k1
Kc
k1