Ch.

III: Rate Law

Degeneration of the order A +B → M
At t=0 a b
-Case 1
At t a-x b-x x
Reagent in high excess,
At ∞ 0 0 b
Other reagent is the
limiting one
r = k (a - x) (b - x) r = k'(b - x)
• [A] >>> [B]; (a-x) ≈ a=Cte
k’ = k(a-x) =kapp

A reaction of order N become of order N-1

N-1 is also called observed order or apparent order or pseudo order

1- Diluted reactions in which the solvent is a reagent

2- One or several reagents (is or are) in high excess

This method is also called the method of OSTWALD

 Ch. III: Rate Law
-Case 2
Reactions where one of the reagents is regenerated like catalyst

r = k [isobutene] [H2O] [H+]

r = k' [isobutene] [H2O]

k’ = k[H+]= kapp
 Ch. III: Rate Law
Methods for the determination of the reaction order

rate law
Experimental information
Reaction order

• Rate Law tells us the instantaneous rate

as a function of concentration r = f(Conc)

• Integrated Rate Law tells us the concentration

as a function of time C= f(t)
 Ch. III: Rate Law
Methods for the determination of the reaction order
First method
1-Method based on the initial rate A+B→P

For only one reagent; ro depend of [A]0

[A]

r = k [A]α Ln r = Ln k + α Ln [A]
r0

We realize several experiments With different [A]0.For each experiment we find r0

[A]0 a b c d
ro = k [A]oα
t
r0 r01 r02 r03 r04

Ln ro = Ln k + α Ln [A]o

Plot Lnro versus Ln[A]0

 Ch. III: Rate Law First method
Methods for the determination of the reaction order
1-Method based on the initial rate
[A]
r0

r0 = k [A]0α[B]0β (Empirical rate law)

Ln r0 = Ln k + α Ln [A]0 + β Ln [B]0

Several reagents t

We apply this method to obtain series of initial rates

- Initial concentrations from one of the reagents

- We keep constant other reagents concentrations

We repeat the same procedure for each of others reagents

Total order of the reaction is the sum of partials orders
 Solution:
r0 = k [P4]0a[H2]0b (Empirical rate law)
a. (r0)1 = k [0.011]a[0.075]0b

(r0)2 = k [0.011]a[0.015]0b

(r0)3 = k [0.022]a[0.015]0b

To determine the order relative to P4 we consider experiments where [H2]0 is kept constant

𝒓𝟎𝟐 𝒌 (𝟎. 𝟎𝟏𝟏)𝒂 (𝟎. 𝟎𝟏𝟓)𝒃 𝟔. 𝟒. 𝟏𝟎−𝟒 𝒌 (𝟎. 𝟎𝟏𝟏)𝒂 (𝟎. 𝟎𝟏𝟓)𝒃
= 𝒂
⇒ −𝟒
=
𝒓𝟎𝟑 𝒌 (𝟎. 𝟎𝟐𝟐) (𝟎. 𝟎𝟏𝟓) 𝒃 𝟔. 𝟑𝟗. 𝟏𝟎 𝒌 (𝟎. 𝟎𝟐𝟐)𝒂 (𝟎. 𝟎𝟏𝟓)𝒃
=> 1 = ( ½ )a => a = 0
To determine the order by respect to H2 we consider experiments where [P4]0 is kept constant
𝒓𝟎𝟏 𝒌 (𝟎. 𝟎𝟏𝟏)à (𝟎. 𝟎𝟕𝟓)𝒃 𝟑. 𝟐. 𝟏𝟎−𝟒 𝒌 (𝟎. 𝟎𝟏𝟏)𝒂 (𝟎. 𝟎𝟎𝟕𝟓)𝒃
= ⇒ =
𝒓𝟎𝟐 𝒌 (𝟎. 𝟎𝟏𝟏)𝒂 (𝟎. 𝟎𝟏𝟓)𝒃 𝟔. 𝟒. 𝟏𝟎−𝟒 𝒌 (𝟎. 𝟎𝟏𝟏)𝒂 (𝟎. 𝟎𝟏𝟓)𝒃

=> ½ = ( ½ )b => b = 1
Or, knowing that the order zero by respect to P4
the rate law is written as r = k [H2]b
𝒓𝟎𝟏 𝒌 (𝟎. 𝟎𝟕𝟓)𝒃 𝟑. 𝟐. 𝟏𝟎−𝟒 𝒌 (𝟎. 𝟎𝟎𝟕𝟓)𝒃
= ⇒ =
𝒓𝟎𝟐 𝒌 (𝟎. 𝟎𝟏𝟓)𝒃 𝟔. 𝟒. 𝟏𝟎−𝟒 𝒌 (𝟎. 𝟎𝟏𝟓)𝒃

=> ½ = ( ½ )b => b = 1

b. Rate law is r = k [H2]

c. k1= (r0)1/[H2]01=3.2 .10-4/0.0075 = 4.266 10-2 s-1

k2= (r0)2/[H2]02= 6.4 .10-4/0.015 = 4.266 10-2 s-1 Average k = 4.2644 10-2 s-1

K3= (r0)3/[H2]03= 6.39 .10-4/0.015 = 4.26 10-2 s-1

 Ln r0 Ln P
5,88 0,4
5,7 0,03
5,48 -0,41
5,21 -0,99

PNO
r0 = k [NO]α[H2]b [H2]b= Cte & [NO]α= [
𝑹𝑻
]a
0,6
1
=> r0 = k’[PNO]α where k’= k[H2]b[ ]a 0,4 y = 2,0695x - 11,765
𝑹𝑻 0,2 R² = 0,9998
0
Linear form Ln r0 = Ln k’ + α Ln [PNO] -0,2 5 5,2 5,4 5,6 5,8 6

Ln r0
-0,4
-0,6

Plot Ln ro versus Ln[PNO] -0,8

-1

=> α = 2,0695 ≈
-1,2
2 Ln PNO