CHEMICAL REACTION

The Chemical Kinetics Aspects

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 Chemical Thermodynamics

Itt dea
dealss with
t tthe
e equ
equilibrium
b u position
pos t o o
of
the process : The relative stabilities of
Chemical products and reactants and their relative
concentrations at equilibrium (chemical
(chemical
P
Processes equilibrium))
equilibrium

Chemical Kinetics
It deals with the rate (how fast) of the
process and with the mechanisms (the
sequence of processes) by which the
process occurs.
occurs

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 Chemical Kinetics
Concept of Reaction Rates :

• In a chemical reaction, the concentration of the

reactants decreases and simultaneously the
concentration of the products increases.
• The concentrations, at first, change rapidly and then
more slowly approaching their equilibrium limiting
concentrations.
• As the reaction progress
progress, not only the concentration
of the reactants decrease, but the rate of change of
its concentration also decreases.

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 • Since the rate of change of concentration is not
constant, it is best expressed as a time derivative
∆C/
C/∆∆t, which gives the change of concentration per
unit time, at a particular instant.

Rate of ∆C dC
= lim =
reaction ∆t → 0 ∆t dt

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 A → B
C [[Beq]

A [Aeq]

t
Time dependence of concentration of reactants and
products in a chemical reaction
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For a reaction :

A→B
Rate of reactant
d[A]
=—
elimination
dt

Rate of product d[B]

formation =+
dt
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 The Rate Laws

A→B
The Differential Rate Law :
It shows how the rates of reaction depend on the concentration
of the participating chemical species. Assuming the reaction is a
simple first order:

d[A] d[B]
— = k [A] or + = k [B]
dt dt
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The Integrated Rate Law :
It is also useful in practice to show how the concentrations
(of the reactants or of the products) depend on time. This
information can be obtained from the differential rate laws
by integration.

d[A]
— = k [[A]]
dt

[A] = [A]o exp (-

(- kt
kt))
The integrated rate laws
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 A → A* → B
E A*
A Ea

progress
p g

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For a reaction :

A→B
The rate constant k :

k = A exp (- Ea/RT)
Arrhenius’s Equation

• The rate constant increases as the

temperature increases.
• A chemical
h i l reaction
ti proceeds
d faster
f t att
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 THE KINETICS OF THE MOST COMMON
CHEMICAL REACTIONS
In most chemical systems, chemical transformation
usually involve complex reactions , including :

1. Parallel Reactions

2. Consecutive Reactions

3. Reversible Reactions

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 1. PARALLEL REACTIONS

k1 d [A] = - k [A]
B1 Æ 1
dt
k2 d [A] = - k [A]
A B2 Æ dt
2

k3 d [A] = - k [A]
B3 Æ dt
3

Diff
Differential
ti l rate
t laws
l :
d [A] = - (k +k +k )[A]
1 2 3
dt
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 k1
B1
k2
A B2
k3
B3

Integrated rate laws :

- (k1+k2+k3) t
[A] = [A]o e
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 2. CONSECUTIVE REACTIONS

A → B → C
k1 k2

Differential rate laws :

d [A] = - k1[A]
dt

d [B] = + k1[A] - k2[B]

dt
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 Integrated rate laws for [A] :

d [A] = - k1[A]
dt

- k1t
[A] = [A]o e

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 Integrated rate laws for [B] :
- k1t
[A] = [A]o e

d [B] = + k1[A] - k2[B]

dt

d [B] = + k1[A]o e
- k1t
- k2[B]
dt
d [B] + k2[B] = + k1[A]o e
- k1t

dt
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 d [B] + k [B] = + k [A] e - k1t
2 1 o
dt
+ k2t
xe

d [B]e + k2t + k [B]e + k2t = + k [A] e(k2- k1)t

2 1 o
dt

d {[B]e
{[B]
+ k2t
} = + k1[A]o e
(k2- k1)t

dt

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 The only problem in solving [B] is just the integration of the last
equation under a condition at t = 0 → [B] =0.

+ k2t (k2- k1)t

d {[B]e } = + k1[A]o e dt

Substitution :
+ k2t
U = [B] e At t = 0 → U = 0
At t = t → U = U

∫dU = + k [A] ∫e 1 o
(k2- k1)t
dt

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 ∫dU = + k [A] ∫e
1 o
(k2- k1)t
dt

U t
k1[A]o (k2 – k1)t
U = e
k2 – k1
0 0

k1[A]o (k2 – k1)t

U-0 = (e - 1)
k2 - k1

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 Substitution : U = [B] e + k2t

+ k2t k1[[A]]o ((k2 – k1))t

[B] e = (e - 1)
k2 - k1

k1[A]o – k1t – k2t

[B] = (e - e )
k2 - k1

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 A → B → C
[X] [C]

[A]
t
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 3 REVERSIBLE REACTIONS
3.
Reversible reactions are characterized by a mixture of
both products and reactants at chemical equilibrium.

k1
A k2
B

Note that most acid

acid-base
base and complexation reactions
in natural waters are reversible reactions.

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 REVERSIBLE REACTIONS :

- ACID
ACID--BASE REACTIONS

- ADSORPTION
ADSORPTION--DESORPTION

- BIOCONCENTRATION - DEPURATION

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 k1
A k2
B

C B

A
t
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 k1
A k2
B
The total concentration of the chemicals :

CT = [A] + [B]

The differential rate laws :

d [A] = - k1[A] + k2[B]

dt
d [B] = - k2[B] + k1[A]
dt
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 d [[A]] = - k [[A]] + k ((C - [[A])
])
1 2 T
dt
d
[A] = - k1[A] + k2CT - k2[A]
dt
d
[A] + (k1+k2)[A] = k2CT
dt
(k1+k2)t
xe

d (k1+k2)t (k1+k2)t (k1+k2)t

[A]e + (k1+k2)[A]e = k2CTe
dt

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 d (k1+k2)t (k1+k2)t (k1+k2)t
[A]e + (k1+k2)[A]e = k2CTe
dt

d (k1+k2)t (k1+k2)t
{[A] e } = k2CT e
dt

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 d (k1+k2)t (k1+k2)t
{[A] e } = k2CT e
dt

∫d {[A] e (k1+k2)t
} = k2CT∫e
(k1+k2)t
dt

Substitution :
(k1+ k2)t
U = [A] e At t = 0 → U = 0
At t = t → U = U

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 U t

0
∫dU = k2CT ∫e
0
((k1+k2))t
dt
U t
k2 CT (k1+k2)t
U = e
0 k1+k2 0

k2 CT (k1+k2)t
U-0 = (e - 1)
k1+k2

k2 CT (k1+k2)t
U = (e - 1)
k1+k2
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 k2 CT (k1+k2)t
U = (e - 1)
k1+k2

(k1+ k2)t k2 CT (k1+k2)t

[A] e = (e - 1)
k1+k2

k2 CT - (k1+k2)t
[A] = (1 - e )
k1+k2

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 k2 CT - (k1+k2)t
[A] = (1 - e )
k1+k2

At chemical equilibrium (t Æ ~) :

k2 CT
[A] = CT = [A] + [B]
k1 + k2

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 k2 CT
[A] = CT = [A] + [B]
k1 + k2

(k1 + k2)[A] = k2([A] + [B])

k1[A] + k2[A] = k2[A] + k2[B]

[B] k1
= =K
[A] k2
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