Physical

Chemistry

Reaction Kinetics
(1)
Xuan Cheng
Xiamen University

1
 Physical Reaction Kinetics
Chemistry
Reaction Kinetics
For example
 r G o / kJ  mol 1
1 3
N 2 ( g )  H 2 ( g )  NH 3 ( g ) -16.63
2 2
1
H 2 ( g )  O2 ( g )  H 2O(l ) -237.19
2

Thermodynamics: spontaneous reactions (possible to take place)

Thermodynamics: can’t answer (1) how to make them happen

(2) how fast they will take place (3) the reaction mechanism

2
 Physical Reaction Kinetics
Chemistry
Reaction Kinetics
Chemical Kinetics
1 3
2
N 2 ( g )  H 2 ( g )  NH 3 ( g )
2
T, P, catalyst
1
H 2 ( g )  O2 ( g )  H 2O(l ) T, catalyst
2

Chemical Kinetics:
The study of the rates and mechanisms of chemical reactions
A reacting system is not in equilibrium

3
 Physical Reaction Kinetics
Chemistry Rate of Reaction
Consider the homogeneous reaction (occurs entirely in one phase)
aA  bB    eE  fF   (17.1)

dn A / dt a 1 dn A 1 dnB
 
dnB / dt b a dt b dt

The rate of conversion J

1 dn A 1 dnB 1 dnE 1 dnF

J     (17.2)
a dt b dt e dt f dt

At equilibrium, J = 0
4
 Physical Reaction Kinetics
Chemistry Rate of Reaction
The rate of reaction r

J 1  1 dn A 
r     (17.3)
V V  a dt 

At constant V

1 d [ A] 1 d [ B] 1 d[ E ] 1 d[F ]
r     (17.4)*
a dt b dt e dt f dt

mol dm-3 s-1

mol cm-3 s-1
5
 Physical Reaction Kinetics
Chemistry Rate Laws
For many reactions

r  k  A  B    L  (17.5)*

k: rate constant (rate coefficient), k = f (T, P)

, , : order or partial order

+ +  +  n : overall order

The expression for r as a function of

concentrations at a fixed temperature is
called the rate law.
6
 Physical Reaction Kinetics
Chemistry Reaction Orders
r  ko Zero-order

r  k  A First-order

r  k  A 2 r  k  A B  Second-order

r  k  A  B 
2 r  k  A B  2 Third-order

r  k  A B  2 Negative First-order

r  k  A B 1 / 2 1.5-order


r  k  A B  / 1   B 1 / 2  No simple order
7
 Physical Reaction Kinetics
Chemistry
Rate Laws

Reaction Rate Law

k  H 2  Br2 1 / 2
H 2  Br2  2 HBr r
1  j HBr  / Br2 

H 2  I 2  2 HI r  k  H 2  I 2 

2 N 2O5  4 NO2  O2 r  k  N 2O5 

CH 3CHO  CH 4  CO r  k  CH 3CHO  3 / 2

8
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms Reaction actually occurs
NO
2SO2  O2 
 2 SO3

O2  2 NO  2 NO2 (17.7)
intermediate
NO2  SO2  NO  SO3

2 N 2O5  4 NO2  O2 Elementary

reaction

Step (a) N 2O5  NO2  NO3

Step (b) NO2  NO3  NO  O2  NO2 (17.8)

Step (c) NO  NO3  2NO2

9
 Physical Reaction Kinetics
Chemistry
Measurement of Reaction Rates
The concentration of a reactant or product as a function of time
Cooling the sample
Chemical Method removing a catalyst
Diluting the mixture
At constant T Adding a species

At intervals Slows down or stop

the reaction

Rapidly analyze chemical

Reaction vessels compositions of the mixture
10
 Physical Reaction Kinetics
Chemistry
反应速率的测定方法

化学方法

不同时刻取出一定量反应物，设法
用骤冷、冲稀、加阻化剂、除去催化剂等方法
使反应立即停止，然后进行化学分析。

11
 Physical Reaction Kinetics
Chemistry
Measurement of Reaction Rates
Physical Method More accurate and less tedious

Measures a physical property of the reaction system as a

function of time. This allows the reaction to be followed
continuously as it proceeds.

物理方法
用各种物理性质测定方法（旋光、折
射率、电导率、电动势、粘度等）或现代谱仪
（ IR 、 UV-VIS 、 ESR 、 NMR 、 ESCA 等）
监测与浓度有定量关系的物理量的变化，从而
求得浓度变化。物理方法有可能做原位反应。
12
 Physical Reaction Kinetics
Chemistry Integration of Rate Laws
1 d [ A] 1 d [ B] 1 d[ E ] 1 d[F ]
r     (17.4)*
a dt b dt e dt f dt

Integrate it to find [A] as a function of time: [A] = g(t)

Assumptions

(a) The reaction is carried out at constant temperature (k is constant)

(b) The volume is constant (r is given by (17.4))

(c) The reaction is “irreversible” (ko is very large)

13
 Physical Reaction Kinetics
Chemistry First-Order Reactions
Suppose the reaction aA  P is first-order with r  k  A
1 d [ A] 1 d [ B] 1 d[ E ] 1 d[F ]
r     (17.4)*
a dt b dt e dt f dt

r  k  A  B    L  (17.5)*

1 d  A
r  k  A (17.10)
a dt

define k A  ak d  A / dt  k A  A (17.11)

d  A / A   k Adt

1 d  A / A   1 k Adt
2 2

14
 Physical Reaction Kinetics
Chemistry First-Order Reactions
2
1 d  A /  A   2
1 k Adt
ln   A 2 / A1   k A (t2  t1 ) (17.12)

if  A1   Ao  at t1  0 and  A 2   A at t 2  t

ln
 A
  k At (17.13)
 A o
Integrated rate law
 A   A o e k At (17.14)*
1 d  A
r  k  A (17.10)
a dt
The concentration of A (and r) decreases exponentially with
time for a first-order reaction.
15
 Physical Reaction Kinetics
Chemistry
First-Order Reactions
 A   A o e k At (17.14)*
ln A  ln A o  k At
 A  e  k At
 A o ln A o / A  k At
[A]/[A]o

t Ln[A] t
First-order reaction: [A]/[A]o vs t First-order reaction: ln[A] vs t
16
 Physical Reaction Kinetics
Chemistry First-Order Reactions
Half-life: t1 / 2 The time needed for [A] to drop to half its value
A useful indication for the chemical reaction
rate
t  t1 / 2 [ A]  1 / 2[ A]o

ln
 A
  k At (17.13)
 A o
1 / 2[ A]o
ln   k At1 / 2 ln 1 / 2  k At1 / 2
[ A]o

k At1 / 2  ln 2  0.693 First-order reaction (17.15)*

t1 / 2  0.693 / k A Independent of [A]o

17
 Physical Reaction Kinetics
Chemistry Second-Order Reactions
(1) AB
 P r  k 2 [A][B]

(2) 2A 
 P r  k 2 [A]2

1 d  A
r  k  A 2 (17.10)
a dt

define k A  ak d  A / dt  k A  A
2
(17.11)

d  A
 k A  A 2
dt

1
2
1 d  A  k A 12 dt
 A 2

18
 Physical Reaction Kinetics
Chemistry
Second-Order Reactions
1
2
1 d  A   k A 12 dt
 A 2

1 1 1 1
   k A (t 2  t1 )   k At (17.16)
 A1  A 2  A  A o

 A o
 A  k A  ak (17.17)
1  k At  A o

A plot of 1/[A] versus t gives a strait line of slope kA

if 2
r  k  A

19
 Physical Reaction Kinetics
Chemistry Second-Order Reactions
1 1 1 1
  k At   k At
 A  A o  A  A o (17.16)

Half-life: t1 / 2
{[A]-1}
t  t1 / 2 [ A]  1 / 2[ A]o

1
t1 / 2 
[ A]o k A

Second-order reaction with {t}

r = k[A]2 Second-order reaction: 1/[A] vs t

20
 Physical Reaction Kinetics
Chemistry
Second-Order Reactions
ln 2
t1 / 2  First-order reaction with r = k[A]
kA

1
t1 / 2  Second-order reaction with r = k[A]2
[ A]o k A

aA  bB  products r  k  A B 

1 d  A
  k  A B  (17.18)
a dt

Three variables
21
 Physical Reaction Kinetics
Chemistry Second-Order Reactions
d  A
A  B  products   k  A B 
dt
t0  A o  Bo 0

t t  A o  x  Bo  x x

d  A d  A dx
 k  A B   k   A o  x    B  o  x  
dt dt dt

dx
 k   A o  x    B  o  x  x=0 when t=0
dt

dx x dx
 kdt 0  0t kdt
  A o  x    B o  x    A o  x    B  o  x 

22
 Physical Reaction Kinetics
Chemistry
Second-Order Reactions
x dx
0  0t kdt  kt
  A o  x    B o  x 

x dx 1 x 1 1 
0  0   dx
  A o  x    B o  x   B o   A o    A o  x    B o  x  
1    A o    B  o 
 ln   ln 
 B o   A o    A o  x 
 
  B  o  x 


1    A o    B  o 
ln   ln   kt
 B  o   A o    A o  x 

  B  o  x 
 

1   B  / B  o   A   A o  x
ln   kt (17.22)’
 B  o   A o   A / A o   B   Bo  x
23
 Physical Reaction Kinetics
Chemistry Second-Order Reactions
x dx x dx
If [A]o=[B]o 0  0  0t kdt  kt
  A o  x    B o  x    A o  x  2

x dx 1 1
0    kt
2  A  x  A
  A o  x  o o

1 1
  kt (17.23)’
 A  A o
Half-life: t1 / 2

t  t1 / 2 [ A]  1 / 2[ A]o

1
t1 / 2 
k  A o
24
 Physical Reaction Kinetics
Chemistry Third-Order Reactions
d  A d  A d  A d  A
 ak  A
3
  ak  A  B 
2
 ak  A B 
2   ak  A B  C 
dt dt dt dt

(Problems 17.17 and 17.24)

d  A 1 1
  k Adt   2k At
 A 3  A 2
 
A o2

 A o
 A 
1  2kt Ao 
2 1/ 2 (17.24)

25
 Physical Reaction Kinetics
Chemistry nth-Order Reaction
Consider d  A
  k A  A n (17.25)
dt

2d A    k 2 dt
Integration gives 1 A 1 (17.26)
 A
n

 
(1  n) A on 1 
 A n 1   A on 1 For n  1 (17.27)
  k At
 n 1

1 n
  A 
 
  A   1   A on 1 (n  1)k At For n  1 (17.28)
 o

26
 Physical Reaction Kinetics
Chemistry nth-Order Reaction
Half-life: t1 / 2 t  t1 / 2 [ A]  1 / 2[ A]o

2 n 1  1
t1 / 2  For n  1 (17.29)
(n  1) 
A on 1 k A

2d A    k 2 dt
1 A 1 (17.26)
n
 A
ln 2
 A   A o e  k At t1 / 2 
kA
For n = 1 (17.30)

 A o
 A o   A  k At t1 / 2  For n = 0
2k A
27
 Physical Reaction Kinetics
Chemistry
Homework
Page 591

Prob. 17.5
Prob. 17.6
Prob. 17.8
Prob. 17.10

28