12/09/2022

A. Kinetics of irreversible reactions

• First-order reactions
• Second-order reactions
• Third-order reactions
• n-order reactions
• zero-order reactions

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1

A B

Rates of reactions can be determined by monitoring the change in

concentration of either reactants or products as a function of time t.
[A] = concentration of reactant A.
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A. KINETICS OF IRREVERSIBLE REACTIONS

1) First-order reactions
The order of a reaction is defined as the sum of the exponents in the rate law.
A → P
t=0 a 0
t a–x x

d [ A]
The rate equation: v=-
dt
ó

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3

C0 = a; Ct = a - x
dCt
- = k (a - x)
dt
t a- x
d (a - x)
Integration of the rate equation: = kdt; ò Û ò
a-x 0 a

- ln(a - x) = kt
1 a
k = ln
t a-x

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gure 2.5: Kinetics of first-order reactions. 12/09/2022

• The half lifetime t1/2 is the

time after which [A] has
dropped to 1/2 of its initial
value.

• The half lifetime for a

first-order reactions is
independent of the initial
concentration!

Kinetics of first-order reactions. 5

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me constant: The rate coefficient has the dimension of an inverse time. Thus,
Experimental determination of k
1
= (2.39)
• Plot of ln[A] vs. t gives a straight line with slope m = −k (see slide 5):

1
s dimension of time and is the time
Advantage: We doafter which
not need [A] has
to know droppedconcentration
the absolute to (= 36 of 8 %)
[A].of
initial value:
• Numerical fit of k to the exponential
− [A]decay
0
curve
[A]0
using the Marquardt-Levenberg non-
[A] = [A]
linear least-squares fitting = ≈
algorithm. This method (2.40)
= 0
2 718 is useful in particular for analyzing
experimental decay curves with a constant background term. Again, we do not need to
know the absolute concentration of [A].
1
alf lifetime: • The
Anybody who wants
half lifetime 1 2toisdothe
least-squares
time afterfitting
whichis urged to consult
[A] has dropped appropriate
to of literature
2 draw an
before doing the fitting! As the saying goes: With three parameters, you can
initial value (Fig. 2.5):
elephant. With a fourth parameter, you can make him walk.
£ ¡ ¢¤ − [A]0
A = 1 2 = [A]0 1 2
= (2.41) 6
2
6
− 1
1 2
= (2.42)
2
1 2 = ln 2 (2.43)
3

ln 2
1 2 = (2.44)
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Example 1. Typical problem of 1st order reaction

The decomposition of A is first order, and [A] is monitored. The following data are
recorded:
t / min 0 2 4 8
[A]/[M] 0.100 0.0905 0.0819 0.0670
Calculate k (What is the rate constant? k = 0.0499)
Calculate the half life (What is the half life? Half life = 13.89)
Calculate [A] when t = 5 min. (What is the concentration when t = 5 min?)
Calculate t when [A] = 0.0100. (Estimate the time required for 90% of A to
decompose.)

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Example 2.
After 14 days, a radioisotope has decayed 6.85 wt%. Determine rate
constant k, haft-lifetime t1/2 and calculate the time it was decayed 90 wt%
and 75 wt%.

Solution.

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Solution:

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• Put the reaction time at 90% is t90, remaining concentration is10%.

Therefore:

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Examples for the first order reaction:

1. N2 O → N2 + O

2. •C3H7 → •CH3 + C2H4

3. C12H22O11 + H2 O → C6H12O6 + C6H12O6

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A. KINETICS OF IRREVERSIBLE REACTIONS

2) Second-order reactions: different initial concentration

A + B → P
t=0 a b 0
t=t a−x b−x x

Substitution:
dx dC dC
W =+ = - A - B = k (a - x)(b - x)
dt dt dt

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Integration using partial fractions:

1 A B bA - xA + aB - xB bA + aB - x( A + B)
= + = =
(a - x)(b - x) a - x b - x (a - x)(b - x) (a - x)(b - x)

Left equation = 1 => (A + B) = 0 ó bA + aB = 1.

Therefore: A = − B
=> bA + a(− A) = 1 → (b − a)A = 1
=> A = 1/(b − a)
B = − 1/(b − a)
Therefore:

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è 1 é 1 1 ù
- dx = kdt
b - a êë a - x b - x úû b-x
ln
After integration: 1 b-x a-x
ln = kt + I
b-a a-x
1 b
Substitution t = 0, x = 0: I = ln
b-a a
1 a(b - x)
k= ln
t (b - a) b(a - x)
ó

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A. KINETICS OF IRREVERSIBLE REACTIONS

3) Second-order reactions: The same initial concentration
A + A → P
t=0 a a 0
t=t a−x a−x x
The reaction rate:
d (a - x)
W =- = k (a - x)(a - x) = k (a - x) 2
dt

Intergration: a- x t
d ( a - x)
- ò
a
(a - x) 2 ò0
= kdt
netics of second-order reactions 25
Initial value condition at t = 0

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igure 2.9: Kinetics of second-order reactions.
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The half lifetime for a

second-order reactions depends
on the initial concentration!

Kinetics of second-order reactions. 16

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alf lifetime: 8
£ ¡ ¢¤ [A]0
A 1 2 = (2.87)
2
y
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5.5. Réaction du deuxième ordre par rapport à A

Soit une réaction d'équation : A B C D

- d'ordre 2 par rapport au constituant A
- et d'ordre 0 par rapport aux autres constituants

Les définitions de la vitesse volumique v et de l'ordre conduisent à l'équation différentielle :

1 dA 2
. = k. A
α dt
dA Pour une réaction d'ordre 2 par rapport
Séparons les variables [A] et t : 2
= k dt à un réactif, k est donc homogène à
A l’inverse du produit d’un temps et d’une
concentration (L.mol-1.s-1).
[A] t t
dA
Intégrons entre 0 et t 2
= k dt k dt
[ A ]0 A 0 0
[A]
1 1 1 1 1 t
k t 0 k t
A (t) [ A ]0
A (t) A (0) A0 A (t)
1 1
d’où k t
A (t) A0

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Examples for second-order reaction:

- H2 + I2 → 2HI
- 2NOCl → 2NO + Cl2
- •CH3 + •CH3 → C2H6

Example 3: Consider the following reaction:

A + B ® C
Initial concentration [A] and B are 0.100M, rate constant k = 10-2 l/mol.s.
After 100 s, concentration of [A] is:
a) 0.91 M
b) 0.091 M.
c) 9.1 M
d) 0.0091 M

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A. KINETICS OF IRREVERSIBLE REACTIONS

4) Third-order reactions: The same initial concentration
A + A + A P
With C is the concentration of A:
dC
W =- = kC 3
dt
dC 1
Û - 3 = kdt Intergration: = kt + I
C 2C 2
ó

3
Þ t 1/ 2 = và k = C - 2 .t -1
2kC 0

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A. KINETICS OF IRREVERSIBLE REACTIONS

5) Third-order reactions: different initial concentration
A + B + C P
t=0 a b c
t=t a-x b-x c-x x

dx
The reaction rate: = k (a - x)(b - x)(c - x) ó
dt
Integration using partial fractions (skipped here): ……………..
we write this result in compact form as:

1 é a b c ù
kt = (b - c ) ln + ( c - a ) ln + ( a - b ) ln
(a - b)(b - c)(c - a) êë a-x b-x c - x úû
This expression is not so easy to memorize, but we may recast it in a simple way 20
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A. KINETICS OF IRREVERSIBLE REACTIONS

6) Third-order reactions: different initial concentration
2A + B P
t=0 a b c
t=t a-2x b-x x
The reaction rate: dx
= k (a - 2 x) 2 (b - x) ó
dt
Integration using partial fractions (skipped here): ……………..
we write this result in compact form as:

1 é 1 1ù 1 é b( a - 2 x ) ù
kt = ê - ú+ êln a(b - x) ú
(2b - a) ë a - 2 x a û (2b - a) 2 ë û

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A. KINETICS OF IRREVERSIBLE REACTIONS

7) Third-order reactions: different initial concentration
A + B + C P
t=0 a b c
t=t a-x b-x a-x x

dx
The reaction rate: = k (a - x) 2 (b - x) ó
dt

Integration using partial fractions (skipped here): ……………..

we write this result in compact form as:

1 é 1 1ù 1 é b( a - x ) ù
kt = ê - ú+ êln a(b - x) ú
(b - a) ë a - x a û (b - a) 2 ë û

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Examples for third-order reaction:

• O2 + 2NO → 2NO2.

• R + R + M → RR + M

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A. KINETICS OF IRREVERSIBLE REACTIONS

8) n-order reactions: The same initial concentration
The rate equation: dC dC
- = kC n Û - n = kdt
dt C
Integration:
C t C t
dC
- ò n = ò kdt ® - ò C - n dC = ò kdt
C0
C 0 C0 0

1
®- C - n +1 C
C0 = kt Û 1 é 1 1 ù
- n +1 ®k = ê n -1 - n -1 ú
(n - 1)t ë C C0 û
2 n -1 - 1
® t 1/ 2 =
k (n - 1)C0n -1
® [k ] = C 1- nt -1

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A. KINETICS OF IRREVERSIBLE REACTIONS

9) Zero-order reactions: In a zero order reaction the rate does not depend on the
concentration of reactant. The decomposite reaction with solid catalysts, reaction rate is
independent with the reactant concentration.
Example:

dC

[A], M
The reaction rate: - = kC 0 = k
dt

ó – dC = kdt
After intergration: C = – kt + C0

t, min

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SUMMARY OF THE RATE LAWS

A + B à C

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5.7. Caractéristiques comparées des réactions

d’ordre 0, 1 et 2
Pour la réaction : A B C D

représentation
ordre p [A](t) t1/2 unité de k
linéarisée

[A]0
0 A0 k t A (t) A0 k t t 1/ 2 mol.L-1.s-1
2 k

αkt ln 2
1 A0e ln A ln A 0 k t t 1/ 2 = s-1
k

A0 1 1 1
2 k t t 1/ 2 L.mol-1.s-1
1 k t A0 A A0 k A0

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BÀI TẬP 1

Cho phản ứng:

2 NO + O2 ® 2 NO2
Biểu thức thực nghiệm của tốc độ phản ứng là:
v = k [NO]2[O2]
Phát biểu nào dưới đây là đúng:
a) Phản ứng bậc 1 đối với oxi và bậc 1 đối với NO
b) Phản ứng có bậc tổng quát là 3.
c) Khi giảm nồng độ NO hai lần, tốc độ phản ứng giảm 2 lần
d) Khi tăng nồng độ NO2 ba lần, tốc độ phản ứng tăng 3 lần
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BÀI TẬP 2

Nồng độ được dùng là nồng độ mol (đơn vị M tức mol/l), thời gian
tính bằng giây (s). Vậy, hãy cho biết đơn vị của hằng số tốc độ k
của từng phản ứng có bậc sau đây:

a) Bậc không; b) Bậc một;

c) Bậc hai; d) Bậc ba.

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BÀI TẬP 3

Phản ứng phân hủy dinitơ pentoxit N2O5 có giá trị hằng số tốc
độ k = 5.1x10-4 s-1 tại 45 0C.

2N2O5 (k) ® 4NO2 (k) + O2 (k)

a) Biết nồng độ đầu của N2O5 là 0.25 M, hỏi sau 3.2 phút,
nồng độ của nó là bao nhiêu?
b) Sau bao lâu nồng độ N2O5 giảm từ 0.25 M thành 0.15 M?
c) Sau bao lâu chuyển hóa hết 62% N2O5?

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BÀI TẬP 4

Phản ứng xà phòng hóa este metyl axetat trong dung dịch
kiềm:

CH3COOCH3 + NaOH ® CH3COONa + CH3OH

có phương trình động học u = k[CH3COOCH3][OH ], trong đó

hằng số tốc độ k = 0.137 mol-1 l s-1 ở 250C.
a) Biết nồng độ đầu của metyl axetat và của NaOH là 0.050
M. Hỏi sau bao nhiêu giây, 5% este bị xà phòng hóa ở
250C?
b) Nồng độ của NaOH là 0.015 M và axetat là 0.02 M, tính
thời gian để phản ứng hết 50% axetat.

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Exercise 5:
CH3COCH3 → C2H4 + H2 + CO
Experimentals records:
t, ph 0 6,5 13,0 19,9
p, N/m2 41589,6 54386,6 65050,4 74914,6
Determine n, k (V = const).

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