Ch.

III: Rate Law

Objective

Concentrations effect
- Define the order
- Introduce the concept of degeneration of the order.
- Establish various methods for the order determination of reaction

Temperature effect
- Introduce and interpret the Arrhenius equation
 Ch. III: Rate Law
a A + b B + ... → m M + n N + etc

r = − dnA/dt , or r = + dnM/dt

For the elementary reaction and

According to the law of VAN'T HOFF

r= kexp [A] [A] [A]... [B] [B] [B]... etc.

a times b times

r= kexp [A]a [B]b... etc. σ = a + b + ... etc

 Ch. III: Rate Law

Elementary reaction:

Total order is also the molecular order

Partial orders are also the stoichiometric coefficients

The experiment shows that we can never have reactions

with global order higher than 3

No elementary reaction:
r = kexp [A]α [B]β... etc.
α ≠ a, β ≠ b,... Where
a, b .. are the stochiometric coefficients
a , b.. are the partial orders
 Ch. III: Rate Law
-Case 2
Reactions where one of the reagents is regenerated

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

r = k' [isobutene] [H2O]

 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 reaction in which the solvent is a reagent

2- One or 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
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 A + B → P
1-Method based on the initial rate
[A]
r0

r = k [A]α[B]β (Empirical rate law)

Ln r = Ln k + α Ln [A] + β Ln [B]

Several reagents t

We apply this method to obtain series of initial rates

- Initial concentrations from one of the reagents

- We keep constant others reagents concentrations

We repeat the same procedure for each of others reagents

Total order of the reaction is the sum of partials orders
 Ch. III: Rate Law 2nd method
Methods for the determination of the reaction order
𝒅(𝒂 − 𝒙ሻ
2- Differential Method 𝒓= = 𝒌 (𝒂 − 𝒙ሻ𝒏
𝒅𝒕
r1 k (a-x1)n
r2 k (a-x2)n
… …
ri k (a-xi)n

r = k [A]n

Ln r = Ln k + n Ln [A]
2nd method
 Ch. III: Rate Law Thirst method
Methods for the determination of the reaction order
3- Integral method
• Each rate law led by integration to a different relation
C = f (C0, t)
3.1- Graphic method
-Transforming the integrated expression into
a form of the equation of a line
-Plot the points in a graph and check that they
are well aligned

3.2- Numerical method :

- calculating K for each point
- making sure that these values are appreciably constant
 Ch. III: Rate Law Thirst method
Methods for the determination of the reaction order
3- Integral method
[A] = [A]0e-kt
3-1- Graphical method
CH3NC → CH3CN

This is indicative of a first order reaction

 Ch. III: Rate Law Thirst method
Methods for the determination of the reaction order
3- Integral method
3-1- Graphical method CH3NC → CH3CN

We try to see whether the value of t1/2 remains constant

t1/2 = (ln 2) / k
 Ch. III: Rate Law Thirst method
Methods for the determination of the reaction order
3- Integral method
3-1- Graphical method 2 NO2 → 2 NO + O2
 Ch. III: Rate Law Thirst method
Methods for the determination of the reaction order
3- Integral method
3-2- Numerical method

We calculate the reaction constant by supposing that

the reaction is successively of order 1, 2 and 3

C2H5NH2 → C2H4 + NH3

Order 1 Order 2 Order 3

𝟏 𝟏 𝟏 𝟏 𝟏 𝟏
𝐤=
𝟏
𝐋𝐧
[𝑨]
k= ( - ሻ k= ( - 𝟐ሻ
𝒕 [𝑨]𝟎 𝒕 [𝑨] [𝑨]𝟎 𝟐𝒕 𝑨 𝟐 [𝑨]𝟎
 C2H5NH2 → C2H4 + NH3

t P (Torr) α 102 k1 (min -1) 103 k2 (min -1 Torr-1) 104 k3 (min-1 ·Torr-2)

0 55 0 -- -- --
1 60 0,090 9,53 1,82 0,35
2 64 0,163 8,95 1,78 0,36
4 72 0,309 9,24 2,03 0,45
8 84 0,527 9,37 2,54 0,72
10 80 0,618 9,62 2,04 0,97
20 102 0,854 9,63 5,34 3,82
30 107 0,945 9,70 10,51 18,5
40 108,5 0,972 9,01 16,21 55,5
t 110 - - - -
 Ch. III: Rate Law Fourth method
Methods for the determination of the reaction order
4- Method consisting on the reaction t1/2 determination
2 ( n −1) − 1 𝐿𝑛𝑡1 = 𝐿𝑛𝐶𝑡𝑒 + (1 − 𝑛ሻ𝐿𝑛𝑎 n≠ 1
t1/2 =
(n − 1)ka ( n −1) 2

We plot the graph log t½ versus log a

This gives a slope as –(n-1) from where we can deduce n

CH3COCH3 → C2H6 + CO
P (mm Hg) 98 192 230 296 362
t1/2 = (ln 2) / k
t1/2 86 78 85 80 77

t½ is independent of the pressure and is almost= 81 s

and k = 0,0085 s-1
 Methods for the determination of the reaction order Fourth method
0,105

0,1

4- Method consisting
0,095

0,09 (t ½)2≈ 5,4 s

on the reaction t1/2 0,085

determination 0,08

0,075

0,07

0,065

0,06

0,055

0,05

0,045

0,04

0,035

0,03

0,025

0,02
(t ½)3≈ 6.4 s
0,015 (t ½)1≈ 3,1 s
0,01

0,005

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Methods for the determination of the reaction order Fourth method
4- Method consisting on the reaction t1/2 determination
t½
First order
t ½ cte 2 ( n −1) − 1
t1/2 =
(n − 1)ka ( n −1)
Slop= 1-n

Ln (a)
t½

𝐿𝑛𝑡1 = 𝐿𝑛𝐶𝑡𝑒 + (1 − 𝑛ሻ𝐿𝑛𝑎

2 Slop= 1-n

Ln (a)
 Ch. III: Rate Law Fifth method
Methods for the determination of the reaction order
5- Method based on the variation of the reaction time

Order Zero One Two Three

t1/2 a / 2k Ln2 / k 1 / ak 3 / 2a2k

t3/4 3a / 4k 1.38 / k 3 / ak 15/ 2a2k

t3/4/ t1/2 3/2 2 3 5

t1/2/ t3/4 2/3 1/2 1/3 1/5

 Ch. III: Rate Law Fifth method
At t ¾ [A]= ¼[A]0
Order Zero One Two Three
t3/4 3a / 4k 1.38 / k 3 / ak 15/ 2a2k

Order 0: [A]0- [A]= kt => ¾[A]0 =kt¾

[𝐴]0
Order 1: 𝐿𝑛 = 𝑘𝑡
[𝐴]

1 1 4 1
Order 2: − = 𝑘𝑡 => − = 𝑘𝑡3
𝐴 𝐴0 𝐴0 𝐴0 4

1 1 1𝟔 1
Order 3: 2
− 2 = 2𝑘𝑡 => 𝟐
− 2 = 2𝑘𝑡3
𝐴 𝐴0 [𝑨]𝟎 𝐴0 4
 Ch. III: Rate Law Sixth method
Methods for the determination of the reaction order
6—Method of the degeneration of the order
6-a- OSTWALD method

-We use an excess of all reagents except the reagent j

-We follow by kinetic measurements

-Then determine the order of the reagent j

-Then we do the same for the second reagent and so on

 Ch. III: Rate Law Sixth method
Methods for the determination of the reaction order
6—Method of the degeneration of the order
6-b-Method of constants initials partials concentrations

r = k Σ (ai – xj)ni (aj – xj)nj= K(aj – xj )nj

The constant terms are: ai and xj K: apparent constant

The variable terms are: r and aj

The graphical representation of the following equation:

Log r = log K + nj log ( aj – xj )

 Ch. III: Rate Law
Influence of the temperature on the rate constant

v = kT ƒ ([A]a, [B]ß,...).
kT doesn‘t depend of the time and of the
concentrations,

but only of the temperature T (no catalyzed reaction

or with is the catalyst is kept unchanged

A- ARRHENIUS equation (1889)

kT = A e-Ea/RT Ln kT = B – C/T d ( Lnk T ) C

= 2
dT T
VAN’T HOFF
d ( LnK T ) H
=
dT RT 2
 Ch. III: Rate Law
A- ARRHENIUS equation (1889) kT = A e-Ea/RT

LnKT = LnA – Ea/RT

 Ch. III: Rate Law
A- ARRHENIUS equation (1889) kT = A e-Ea/RT
NO + ClNO2 → NO2 + ClNO

LnKT = LnA – Ea/RT

Ea= 28,1 kJ mol-1

The pre-exponential factor is:Ln A = 27,15
or A= 6,1 1011 cm3mol-1s-1
 Ch. III: Rate Law
A- ARRHENIUS equation (1889) kT = A e-Ea/RT

→ 
H = E a − E a
 Ch. III: Rate Law
A- ARRHENIUS equation (1889) k = A e-Ea/RT

-T increase, Ea/RT decrease, eEa/RT decrease,

e-Ea/RT increase
Thus k is an increasing function of the temperature

-T → 0, Ea/RT → ∞, and 1/eEa/RT = e-Ea/RT → 0

-T → ∞, e-Ea/RT as 1/eEa/RT → 1. In this case, kT → A

Thus the curve kT = ƒ(T) admits an asymptote when the

temperature tends towards the infinity.
Consider that I as the inflection point.
 Ch. III: Rate Law
A- ARRHENIUS equation (1889) k = A e-Ea/RT
a A + b B m M + n N
→
k
m
[ M ]eq n
[ N ]eq d H

= = KT ( LnK T ) =
k
a
[ A] [ B]
eq
b
eq dT RT 2
→ → 
→  H E− E
d
(Ln  ) = ( Ln k ) − ( Ln k ) = 2 = 2
k d d
dT k dT dT RT RT
→ 
d → Ea d  Ea
( Ln k ) = and ( Ln k ) =
dT RT 2 dT RT 2
 Ch. III: Rate Law
A- ARRHENIUS equation (1889) kT = A e-Ea/RT

ki= A e-(Ea/R)(2R/Ea) = A e-2 with k < ki