Chapter II: Simple reactions kinetics Chapter II

Objectives

 To know how to establish the rate laws for the simple order of chemical
reactions (order from 0 to 3)

 To be able to integrate the simple expressions of the differential forms

 To understand the difference between the differential and integral forms

of the rate expressions

We will examine here the case of reactions being held only in one direction
(thus leading to exhaustion of the reagents, or for the minor reagent in the
stoichiometry) without to worry about their real mechanism.
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 Rate law: Writing, integration Chapter II
and verification
Order Zero : R  P
Rate (speed) does not depend on the concentration of reagents

Thus rate is maintained constant as long as there is remaining reagent.

Rate expression = k (k in mol.l-1.s-1)

-dC= k.dt => C0 is the initial concentration

C is its concentration at time t.
Half-life time t ½ : If we substitute n by 0 we get the
expression of t half-life time
At its half life a reagent has C= ½ C0
=> C0 - ½ C0 =kt ½ => t ½= C0/2k

We recall that this relation applied for n≠1 2

 Rate law: Writing, integration Chapter II
and verification
Verification of the Zero order : R  P
Rate is constant, the integrated rate law is an equation of a straight
line ;
Using different measured values of C at different time t
aR -> P
C0 -C

The plot of C as a function of time should be a straight line

for a reaction of zero order 3
 Rate law: Writing, integration and verification Chapter II

Order 1 : A -> P or also A+ B -> P (order by respect to B is zero)

𝑑𝐶
Rate expression => ⇒ − = 𝑑𝑡
𝐶

we got
CA0 is the initial concentration & CA is the concentration at time t.
Developing the last expression, we can easily
calculate the concentration of A at any time t
according to the relation

Half-life time t ½ :

At its half life a reagent has C=

½ C0
𝑳𝒏𝟐
=> t ½= 𝒌
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 Rate law: Writing, integration and verification Chapter II

Verification of the first order reaction : A  P

r= k[A]1 : r is decreasing with time since reactant concentration decreases aA -> P
Using different measured values of C at different time t 𝐿𝑛
𝐶
= 𝑎𝑘𝑡
 The plot of versus time t is a straight line with a positive slop k 𝐶

Or of LnCA versus time t is a straight line with a negative slop -k

LnCA
Slop= k

t
Slop= - k

t 5
 Rate law: Writing, integration Chapter II
Order 2 :
A -> P : r= k[A]2 =
𝒅[𝑨]
(I) A+ B -> P : (order 1 by respect to each reactant)
𝒅𝒕 𝒅[𝑨]
When [A]=[B] r= k[A][B]= k[A]2 = (I)
𝒅𝒕
𝒅[𝑨] 𝒅[𝑩]
2A -> P : r= k[A]2 = (II) When [A]≠[B] r= k[A][B] = = (III)
𝒅𝒕 𝒅𝒕
(elementary reaction since the order = stochiometric coefficient)
𝟏 𝒅[𝑨] 𝟏𝒅 𝑨
 r= k[A]2 = −
𝒅[𝑨]
=>
𝒅𝑨
− 𝟐 = 𝒌 𝒅𝒕  r= k[A]2 = − => − = 𝒌 𝒅𝒕
𝟐 𝒅𝒕 𝟐 𝑨𝟐
𝒅𝒕 𝑨 [𝑨] 𝒕
[𝑨]
𝒅[𝑨] 𝒕 𝒅[𝑨]
⇒− = 𝟐𝒌 𝒅𝒕
⇒− 𝟐
=𝒌 𝒅𝒕 (I) [𝑨]𝟐
[𝑨]𝟎 [𝑨] 𝟎
[𝑨]𝟎 𝟎

𝟏 [𝑨] 𝟏 𝟏 (II)
 ⇒
𝟏 [𝑨]
] = 𝒌𝒕]𝒕𝟎 ⇒
𝟏
-
𝟏
= 𝒌𝒕  ⇒ [𝑨]][𝑨]𝟎 = 𝟐𝒌𝒕]𝒕𝟎 ⇒ -
[𝑨] [𝑨]𝟎
= 𝟐𝒌𝒕
[𝑨] [𝑨]𝟎 [𝑨] [𝑨]𝟎

𝑨𝟎 𝟏
[A] =
𝑨𝟎 t ½= 𝑲𝒂
𝟏
aA ---> P
[A] = t ½=
𝟐𝑲𝒂
𝟏 𝒌[𝑨]𝟎 .𝒕 𝟏 𝟐𝒌[𝑨]𝟎 .𝒕

𝟏 𝟏
- = 𝒂𝒌𝒕
[𝑨] [𝑨]𝟎
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 Rate law: Writing, integration Chapter II
Order 2 : A + B -> P When [A]≠[B]
A + B -> P (order 1 by respect to each reactant)
𝒅[𝑨] 𝒅𝑩 𝒅𝒂 𝒅𝒙 𝒅𝒙
at t=0 a b r= k[A][B] = = (III)
𝒅𝒕 𝒅𝒕 𝒅𝒕 𝒅𝒕 𝒅𝒕
at t a-x b-x x
𝒅[𝑨] 𝒅𝒙 𝒅𝒙
 r= k[A][B] = k(a-x)(b-x)= − = => = 𝒌 𝒅𝒕
𝒅𝒕 𝒅𝒕 𝒂 𝒙 𝒃 𝒙

𝟏 𝑾 𝒁 𝑾 𝒃 𝒙 𝒁(𝒂 𝒙) 𝑾𝒃 𝒁𝒂 𝒙(𝑾 𝒁)
Elementary reaction since Supposing that (𝒂 = (𝒂 + (𝒃 = = (𝒂 𝒙)(𝒃 𝒙)
𝒙)(𝒃 𝒙) 𝒙) 𝒙) (𝒂 𝒙)(𝒃 𝒙)
the order = stochiometric By similarity : Wb + Za=1 (I) & W+Z= 0 (II)
coefficient (I) ⇒ Wb= - Za +1 (II) ⇒ W= -Z
𝟏 𝟏 𝟏
(I) & (II) ⇒ 𝐖=𝒃 𝒂 &𝒁 = 𝒂 𝒃 = −𝒃 𝒂
𝒅𝒙 𝒅𝒂 𝒙 𝒅𝒃 𝒙
𝒂 𝒙 𝒃 𝒙
=− 𝒂 𝒙 𝒃 𝒙
=− 𝒂 𝒙 𝒃 𝒙
𝒙 𝒅𝒙 𝒙 𝒅𝒙 𝒙 𝒅𝒙 𝒕 (III)
∫𝟎 (𝒂 𝒙)(𝒃 𝒙)
= ∫𝟎 (𝒂 𝒙)(𝒃 𝒂)
− ∫𝟎 (𝒃 𝒂)(𝒃 𝒙)
=k ∫𝟎
𝒅𝒕

𝒙𝒅(𝒂 𝒙) 𝒙 𝒅(𝒃 𝒙) 𝒕
⇒ ∫𝟎 − ∫𝟎 = k∫𝟎 𝒅𝒕
(𝒂 𝒙)(𝒃 𝒂) (𝒃 𝒂)(𝒃 𝒙)
𝟏 𝟏
⇒− 𝑳𝒏 𝒂 − 𝒙 ]𝒙𝟎 + 𝑳𝒏 𝒃 − 𝒙 ]𝒙𝟎 = 𝒌𝒕
𝒃 𝒂 𝒃 𝒂 𝟏 𝒂(𝒃 𝒙)
𝟏 (𝒃 𝒙) 𝒂 ⇒ 𝑳𝒏 =kt
⇒ 𝑳𝒏 + 𝐋𝐧 = kt 𝒃 𝒂 𝒃(𝒂 𝒙)
𝒃 𝒂 (𝒂 𝒙) 𝒃 7
 Rate law: Writing, integration Chapter II
Order 2 :
𝑨𝟎
[A] = t ½=
𝟏
𝟏 𝟐𝒌[𝑨]𝟎 .𝒕 𝟐𝒌𝒂

Comparing the CA variations for reactions with order 1 and 2

We note that the
decrease in
First order concentration is 2nd order
slower for the case
of second order
reaction compared
to those of the first
order reaction

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 Rate law: Writing, integration Chapter II
Order 2 : A + mB -> P When [A]≠[B]

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 Rate law: Writing, integration Chapter II

Order 3 : A + B + C -> P (order 1 by respect to each reactant)

𝒅[𝑨] 𝒅𝑩 𝒅𝑪
r= k[A][B][C] = = (we will not treat the case where [A]≠[B] ≠[C])
𝒅𝒕 𝒅𝒕 𝒅𝒕
𝒅[𝑨]
When [A]=[B] =[C] => r= k[A]3 = If we substitute n by 3 we get
𝒅𝒕
the expression of the rate law
𝒅[𝑨] 𝒅𝑨
 r= k[A]3 = − => − = 𝒌 𝒅𝒕 of 3rd order reaction
𝒅𝒕 𝑨𝟑
[𝑨] 𝒕
𝒅[𝑨]
⇒− 𝟑
=𝒌 𝒅𝒕
[𝑨]𝟎 [𝑨] 𝟎
aA -> P
𝟏 [𝑨] 𝟏 𝟏
 ⇒ ] = 𝒌𝒕]𝒕𝟎 ⇒ - 𝟐 = 𝟐𝒌𝒕
𝟐 𝑨 𝟐 [𝑨]𝟎 𝑨 𝟐 [𝑨]𝟎 𝟏 𝟏
𝟑 - = 𝟐𝒂𝒌𝒕
t½= [𝑨 ] [𝑨]𝟎 𝟐
𝟐
𝟐𝒌[𝑨]𝟐𝟎

If we substitute n by 3 we get the

expression of t half-life time
𝟑
t½=
𝟐𝒌[𝑨]𝟐𝟎

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 Rate law: Writing, integration Chapter II

Order 3 : A + B + C -> P (order 1 by respect to each reactant)

𝒅[𝑨] 𝒅𝑩 𝒅𝑪
r= k[A][B][C] = =
𝒅𝒕 𝒅𝒕 𝒅𝒕
When [A]=[B] ≠[C]
A + B + C -> P
At t=0 a a c
At t a-x a-x c-x

𝒅[𝑨] 𝒅𝑪 𝒅𝒙
r= k[A]2[C] = k(a-x)2(c-x)= = =
𝒅𝒕 𝒅𝒕 𝒅𝒕

𝟏 𝒙(𝒄 𝒂) 𝒄(𝒂 𝒙) 𝟏 𝒙(𝒄 𝒂) 𝒄(𝒂 𝒙)

k.t= ; k=
(𝒄 𝒂) 𝒂(𝒂 𝒙) 𝒂(𝒄 𝒙) 𝒕.(𝒄 𝒂) 𝒂(𝒂 𝒙) 𝒂(𝒄 𝒙)

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Rate law and half-life time: Summary Chapter II

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Rate law and half-life time: Summary Chapter II

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