11 (Chemical Kinetics)

-
-
1

11.1 (Rate of reaction)

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[C] [D]

[C] [D]
[A] [B]

[A] [B]
A+B
C+D t
A+B
C+D t
(A B)
( )
(C D)

3

 A D t

A+B
C+D
R

= - d[A]
=
- d[B]
dt
dt

R
= d[C]
=
d[D]
dt
dt
C+D
A + 2B
R = - d[A] = -1 d[B] = d[C] = d[D]
dt 2 dt
dt
dt
1
4

2N2O5 (aq) 4NO2 (aq) + O2 (g)

2.33

1.35

 (Rate) 2
-
-

=

AB

m
Rate = [A]500- [A]0 = 0 - 1.7 mol/L = 0.0034 molL-1sec-1
500-0
500 sec
8

AB

Rate 200 sec = [A]200-[A]0 = 0.4-1.0

m
200
200-0

mol/L = - 0.003 molL-1sec-1

sec

11.2
1
1. (The collision Theory)

O3 + NO O2 + NO2

-
-

Effective collision =>

(Activation Energy)

Ineffective collision =>
10



Maxwell-Boltzman
Maxwell-Boltzman
T ..

Ea T

Ea


11

2. -
(The activated complex Theory
and transition state theory)

(activated complex)

12

Ea,rEa

Activated
complex

Ea,r

Ea

Ea,p Ea

Ea,p

H < 0
rxn

Rxn. Ea,r< Ea,p activated complex rxn

()
13

Rxn. Ea,r> Ea,p activated complex rxn

()
Activated
complex
Ea,r

Ea

Ea,p

H > 0
rxn

14

11.2
A + B
C+D

- A
- B
- A B

15



r = k[A]m[B]n
m+n = 1
r

k
(First order reaction)
A A
m+n = 2
B B

m A
(Second order reaction)
n B
m+n

16

 A + B

[A]
[B]

(mol/L)
(mol/L)
1
0.5
0.5
2
0.5
1.0
3
1.0
1.0
1.
2.
3.

C

(mol/L.s)
0.02
0.08
0.16

17

11.3
1.

18

2.

CaCO3 + HCl

CaCl2 + CO2

1 M HCl

3 M HCl

6 M HCl

19

http://jchemed.chem.wisc.edu/JCESoft/CCA/CCA3/MAIN
/CLOCKRX/PAGE1.HTM

20

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Chemical kinetics surface area

3.

21

4.

22

5.

E
E
Ea

Ea

23


1. =>

2N2O (g)

2N2 (g) + O2 (g)

Ea = 240 kJ/mol
T = 600 C
2N2O (g)

Cl2

2N2 (g) + O2 (g)

Ea < 240 kJ/mol

T < 600 C
24

2. =>

2 N 2 O (g ) Au 2 N 2 (g ) + O 2 (g )

Homogeneous catalyst
Cl Cl

(Intermediate)

Cl

N2O + Cl

ClO + ClO

N2 + ClO

Cl2 + O2

25

Heterogeneous catalyst
N N
N N
O O

N N
N N
O O Au

Au
N
N N
N
O O Au

OO

Au

Au

N-O

26

Catalytic Converter

metal oxide
Cr2O3, CuO, ZnO,
Pt, Pd

CnH2n+2

O2

CO + H2O
CO2

Catalytic
converter

2 NO

N2 + O2

Catalytic
converter
27

11.4

+[Product]
t

[Product]
[Reactant]

-[Reactant]
t
t

28

29


A
B
[A]

R = k[A]o

R = k[A]1

R = k[A]2

30

R = k[A]o

Slope = k
R = k[A]1

R = k[A]2
R
[A]

[A]2
31

 (Zero order reaction)

W
NH (g)
1/2 N (g) + 3/2 H (g)
3

d[ NH 3 ]

k[ NH 3 ] o k
dt

[A]t = [A]o - kt
(First order reaction)


N2O5(g) 2NO2 (g) + 1/2 O2 (g)
32

d[ N 2 O5 ]

k[ N 2 O5 ]1
dt

[A ]t
ln
kt
[A ]o

[ A ]o
kt
log

[A] t 2.303

(half life)
[A] = [A]o t = t1/2
t1 / 2

0.693
k

33

 (Second order reaction)

C4H6 (g) C8H12 (g)

d[C 4 H 6 ]

k[C 4 H 6 ]2
dt

1
1

kt
[A ] t [A ]o
34

Frequency factor
k AeE a / RT

Take natural log ( ln)

E
ln k ln A a
RT

E
k
ln 2 a
k1
R

1
1

T2 T1

R = 8.314 J.mol-1.K-1

35