Physical

Chemistry

Reaction Kinetics (3)

Xuan Cheng
Xiamen University

1
 Physical Reaction Kinetics
Determination
Chemistry of the Rate Law
1. Half-life method

The rate law r  k[ A] [ B] [ L] (17.48)

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

2n 1  1
log10 t1 / 2  log10  (n  1) log10 [ A]o (17.49)
(n  1)k A

2n 1  1
log10 t1 / 2  log10  (1  n) log10 [ A]o (17.49)
(n  1)k A

2
 Physical Reaction Kinetics
Chemistry
半衰期法确定反应级数
用半衰期法求除一级反应以外的其它反应的级数。
2n 1  1 1
根据 n 级反应的半衰期通式：t1/ 2  (n  1)k A [ A]on1 取两个
不同起始浓度 [A]o ， [A]o’ 作实验，分别测定半衰期为
t '1/ 2
t1/2 和 ，因为同一反应，常数相同，所以：
n 1
t1 / 2 [ A]o '  ln(t1 / 2 / t '1 / 2 )
  n  1
t '1 / 2  [ A]o  ln([ A]o ' /[ A]o )

ln t1 / 2  ln K  (1  n) ln[ A]o

以 lnt1/2 ～ ln[A]o 作图从直线斜率求 n 值。从多个实验数据

用作图法求出的 n 值更加准确。
3
 Physical Reaction Kinetics
Chemistry
Determination of the Rate Law
2. Powell-plot method r  k[ A]n

  [ A] /[ A]o   k A[ A]on 1t (17.50)

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

ln
 A
  k At For n = 1 (17.13)
 A o

 1 n  1  (n  1) For n  1
ln    For n = 1 (17.51)
4
 Physical Reaction Kinetics
Determination
Chemistry of the Rate Law
 1 n  1  (n  1) For n  1
ln    For n = 1 (17.51)
For a given n, there is a fixed relation between  and  for every
reaction of order n.

Plot  versus log10 for commonly occurring values of n to give a

series of master curves. (Fig. 17.6)

The Powell-plot method requires the initial investment of time

needed to make the master plots.

Table 17.1 gives the data needed to make the master plots.

5
 Physical Reaction Kinetics
ChemistryDetermination of the Rate Law
3. Initial-rate method
The rate law r  k[ A] [ B] [ L] (17.48)

Measure r0 for two different initial concentrations [A]0,1 and [A]0,2

while keeping [B]0, [C]0, …fixed.

The ratio of initial rates for runs 1 and 2


[ A]0,2 
r0,2 / r0,1     can be found
 0,1 
[ A]

The orders ,… can be found similarly

6
 Physical Reaction Kinetics
ChemistryDetermination of the Rate Law
4. Isolation method
The rate law r  k[ A] [ B] [ L] (17.48)

Make initial concentrations of reactant A much less than the

concentrations of all other species
[B]0 >> [A]0, [C]0 >> [A]0, …
The rate law becomes

r  k[ A] [ B ]0 [ L]0  j[ A] where j  k[ B]0 [ L]0 (17.52)

Where j is essentially constant.

The reaction has the pseudo-order .
The orders ,… can be found similarly.
7
 Physical Reaction Kinetics
Chemistry
孤立法确定反应级数
孤立法类似于准级数法，它不能用来确定反应级
数，而只能使问题简化，然后用前面三种方法来确定反
应级数。
 
r  k[A] [B]

1. 使 [A]>>[B] r  k '[B] 先确定 β 值

2. 使 [B]>>[A] r  k ' '[A] 再确定 α 值

8
 Physical Reaction Kinetics
Chemistry
Rate Laws and Equilibrium Constants for
Elementary Reactions
Show that for a reaction that takes place in a sequence of steps, the
overall equilibrium constant is a product of ratios of the rate
constants for each step.
It is sufficient to consider a reasonably general but simple two-step
reaction sequence, such as
A B  C  D (second-order in each direction, k1, k-1)
C  E  F (first-order forwarded, second-order reverse, k2, k-2)
A B  D  E  F (overall)
 d [ A]   d [C ] 
    k1[ A][ B ]  k 1[C ][ D]    k 2 [C ]  k 2 [ E ][ F ]
 dt   dt 

9
 Physical Reaction Kinetics
Rate Laws
Chemistry and Equilibrium Constants for
Elementary Reactions
At equilibrium, all the reaction are individually at equilibrium,
and setting the net rates each equal to zero gives
 d [ A]   d [C ] 
    k1[ A][ B ]  k 1[C ][ D]    k 2 [C ]  k 2 [ E ][ F ]
 dt   dt 
[C ][ D] k1 [ E ][ F ] k 2
 
[ A][ B] k 1 [C ] k 2
The equilibrium constant of the overall reaction is therefore
[ D][ E ][ F ] [C ][ D][ E ][ F ] [C ][ D] [ E ][ F ] k1 k
Kc       2
[ A][ B] [ A][ B ][C ] [ A][ B ] [C ] k 1 k  2
kf
Kc  elementary reaction (17.53)*
kb
10
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
The Rate-Determining-Step Approximation
The reaction mechanism is assumed to consist of one or more
reversible reactions that stay close to equilibrium during most of the
reaction, followed by a relatively slow rate-determining step, which
in turn is followed by one or more rapid reactions.
The number of molecules that react in an elementary step
The molecularity of the elementary reaction

A  products unimolecular
A  B  products 2 A  products bimolecular

A  B  C  products 2 A  B  products 3 A  products

trimolecular (termolecular)
11
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
k1
For the consecutive unimolecular reactions A  k2
B  C
Suppose now that k 2  k1

Then whenever a B molecule is formed it decays rapidly into C.

e  k 2t  e  k1t k 2  k1  k 2

 k2  k t k1  k t 
[C ]  [ A]o 1  e 1  e 2  (17.41)
 k2  k1 k 2  k1 

reduces to 
[C ]  [ A]o 1  e  k1t 
The formation of C depends on only the smaller of the two rate constants
k1
A  B is called the rate-determining step of the reaction.
12
 Physical Reaction Kinetics
Chemistry
Reaction Mechanisms
The Steady-State Approximation
Assumes that during the major part of the reaction, the rates of
change of concentrations of all reaction intermediates are
negligibly small
Reactants

Concentration
d [ Intermediate]
0
dt

k1 k2 (17.35)
A  B  C
Products
 d [ B] 
   k1[ A]  k 2 [ B ]  0
 dt  Intermediates
k  d [C ]  Time
[ B]  1 [ A]    k 2 [ B ]  k1[ A]
k2  dt 
13
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
C is formed by a first-order decay of A, with a rate constant k1,
the rate constant of the slower, rate-determining step.
 d [C ] 
   k 2 [ B ]  k1[ A]
 dt 

 A   A o e k1t (17.38)

[C ]  k1[ A]0 0t e  k1t  (1  e  k1t )[ A]0


[C ]  [ A]o 1  e  k1t 
The same result as before, but obtained much
more quickly.
14
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Consider the following mechanism composed of unimolecular reactions

k1 k2 k3
A  B  C  D
     
k 1 k 2 k 3
D is rapidly formed
(the rate-determining step)from C
k 1  k 2 k3  k 2 k3  k  2

B  C is slower than B  A
A B remains close to equilibrium

BC is not in equilibrium

15
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Example 17.4
The rate law for the Br--catalyzed aqueous reaction
 Br 
 C6 H 5 N 2  2 H 2O
H  HNO2  C6 H 5 NH 2 

is observed to be r  k[ H  ][ HNO2 ][ Br  ] (17.55)

A proposed mechanism is
k
H   HNO2 
1
H 2 NO2 rapid equilib.
 
k 1

k2
HNO2  Br   ONBr  H 2O slow (17.56)
k
ONBr  C6 H 5 NH 2 
3
C6 H 5 N 2  H 2O  Br  fast

16
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Example 17.4
Deduce the rate law for this mechanism and relate the observed rate
constant k in (17.55) to the rate constants in the assumed mechanism
(17.56)
r  k[ H  ][ HNO2 ][ Br  ] (17.55)
k
(1) H   HNO2 
1
H 2 NO2 rapid equilib.
 
k 1
the rate-determining
k2
step (2) HNO2  Br   ONBr  H 2O slow (17.56)
k
(3) ONBr  C6 H 5 NH 2 
3
C6 H 5 N 2  H 2O  Br  fast

The formation of ONBr in (2) r  k 2 [ H 2 NO2 ][ Br  ] (17.57)

Step (1) is near equilibrium. Equation (17.53) gives

17
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Example 17.4
kf
Kc  elementary reaction (17.53)*
kb

k1 [ H 2 NO2 ] k
K c,1   [ H 2 NO2 ]  1 [ H  ][ HNO2 ]
k 1 [ H  ][ HNO2 ] k 1

r  k 2 [ H 2 NO2 ][ Br  ] (17.57)

r  (k1k 2 / k 1 )[ H  ][ HNO2 ][ Br  ]

r  k[ H  ][ HNO2 ][ Br  ] (17.55)
k  (k1k 2 / k 1 )  K c,1k 2
Example 17.5
18
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
More examples in using the steady-state approximation
Account for the rate law for the decomposition of N2O5
2 N 2O5 ( g )  4 NO2 ( g )  O2 ( g ) r  k[ N 2O5 ]
on the basis of the following mechanism:
k
N 2O5 
a
NO2  NO3
k a'
NO2  NO3  N 2O5
k
NO2  NO3 
b
NO2  O2  NO
k
NO  N 2O5 
c
3NO2

First identify the intermediates NO and NO3

19
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
k
N 2O5 
a
NO2  NO3
k a'
NO2  NO3  N 2O5
k
NO2  NO3 
b
NO2  O2  NO
k
NO  N 2O5 
c
3NO2

d [ NO ]
 kb [ NO2 ][ NO3 ]  kc [ NO][ N 2O5 ]
dt

d [ NO3 ]
 ka [ N 2O5 ]  ka' [ NO2 ][ NO3 ]  kb [ NO2 ][ NO3 ]
dt

d [ N 2O5 ]
 k a [ N 2O5 ]  ka' [ NO2 ][ NO3 ]  kc [ NO][ N 2O5 ]
dt 20
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
According to the steady-state approximation, set both rates equal
to zero d [ NO ] d [ NO3 ]
0 0
dt dt
kb [ NO2 ][ NO3 ]  kc [ NO][ N 2O5 ]  0

k a [ N 2O5 ]  k a' [ NO2 ][ NO3 ]  kb [ NO2 ][ NO3 ]  0

k [ NO ][ N 2O5 ]
[ NO3 ]  c
kb [ NO2 ]
kc [ NO ][ N 2O5 ] ka [ N 2O5 ] k a kb
 [ NO3 ]  [ NO ] 
kb [ NO2 ] (ka'  kb ) [ NO2 ] kc (k a'  kb )
k k a kb [ N 2O5 ] ka [ N 2O5 ]
[ NO3 ]  c 
kb kc (k a'  kb ) [ NO2 ] (k a'  kb ) [ NO2 ]

21
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
k a kb
[ NO ] 
kc (k a'  kb )
kc k a kb [ N 2O5 ] ka [ N 2O5 ]
[ NO3 ]  
kb kc (k a  kb ) [ NO2 ] (k a'  kb ) [ NO2 ]
'

The net rate of change of concentration of N2O5 is

d [ N 2O5 ]
 ka [ N 2O5 ]  ka' [ NO2 ][ NO3 ]  kc [ NO][ N 2O5 ]
dt
d [ N 2O5 ] ka [ N 2O5 ] k a kb
 k a [ N 2O5 ]  ka' [ NO2 ]  kc [ N 2O5 ]
dt ' '
(k a  kb ) [ NO2 ] k c ( k a  kb )

d [ N 2O5 ]   k a k a'  k a kb  k a k a'  k a kb

 [ N
 2 5 O ]  [ N 2O5 ]
dt ' '
 ( k a  kb )  ( k a  kb )

22
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
d [ N 2O5 ] 2k k
  a b [ N 2O5 ]
dt k a'  kb

because [ N 2O5 ]  2

k a kb
r [ N 2O5 ]  k[ N 2O5 ]
k a'  kb

It follows that the reaction rate is

r  k[ N 2O5 ]

k a kb
where k
k a'  kb

23
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Pre-equilibria
From a simple sequence of consecutive reactions we now turn to a
slightly more complicated mechanism:
k k
A  B 
a
C 
b
P
'
ka

Where C denote the intermediate.

This scheme involves a pre-equilibrium, in which an intermediates
is in equilibrium with the reactants.
A pre-equilibrium arises when the rates of formation of the
intermediate and its decay back into reactants are much faster than
its rate of formation of products; thus, the condition is possible
when k’a>>kb but not when kb >>k’a. Because we assume that A, B,
and C are in equilibrium.
24
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Pre-equilibria
We can write: [C ] k
 Kc Kc  a
[ A][ B ] k a'

In writing these equations, we are presuming that the rate of

reaction of C to form P is too slow to affect the maintenance of the
pre-equilibrium (see the following example). The rate of formation
of P may now be written:
d [ P]
 kb [C ]  kb K c [ A][ B ]
dt
This rate law has the form of a second-order rate law with a
composite rate constant: d [ P] k a kb
 k[ A][ B] where k  kb K c  '
dt ka
25
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Pre-equilibria
Example: Analyzing a pre-equilibrium
Repeat the pre-equilibrium calculation but without ignoring the
fact that C is slowly leaking away as it forms P.
The net rates of change of P and C are ka kb
A  B  C  P
d [ P] '
 kb [C ] ka
dt
d [C ] k a [ A][ B ]
 ka [ A][ B]  k a' [C ]  kb [C ]  0 [C ] 
dt k a'  kb

d [ P]
 k[ A][ B ]
dt k a kb
where k
k a'  kb

26
 Physical Reaction Kinetics
Chemistry Reaction Mechanisms
Pre-equilibria

d [ P] k a kb
 k[ A][ B] where k
dt k a'  kb

When the rate constant for the decay of C into products is much
smaller than that for its decay into reactants k  k '
b a

d [ P] k a kb
 k[ A][ B] where k  k K
b c 
dt k a'

27
 Physical Reaction Kinetics
Chemistry
Homework
Page 592 Page 593

Prob. 17.28 Prob. 17.39

Prob. 17.29 Prob. 17.52
Prob. 17.33

28
 Physical
Chemistry

速率决定步骤

在连续反应中，如果有某步很慢，该步的
速率基本上等于整个反应的速率，则该慢步
骤称为速率决定步骤，简称速决步或速控步。
利用速决步近似，可以使复杂反应的动力学
方程推导步骤简化。

29
 Physical

速率决定步骤
Chemistry

例 1.A  B  C  D  E
慢 快 快

r  k1[A][B]
慢步骤后面的快步骤可以不考虑
。
例 2. A B  C  D  E  F
快 慢 快 快
只需用平衡态近似法求出第 1 ， 2 步的速率。
虽然第二步是速决步，但中间产物 C 的浓度
要从第一步快平衡求。
30
 Physical
Chemistry
稳态近似
从反应机理导出速率方程必须作适当近似
，稳态近似是方法之一。

假定反应进行一段时间后，体系基本上处
于稳态，这时，各中间产物的浓度可认为保持
不变，这种近似处理的方法称为稳态近似，一
般活泼的中间产物可以采用稳态近似。

31
 Physical
氢与碘的反应
Chemistry

H 2  I 2  2HI 总包反应
1 d[HI]
r  k[H 2 ][I 2 ] 实验测定的速率方程
2 dt
反应机理：
(1) II22  M  22II  M
M 快平衡
(2) H 2  2I  2HI 慢
1 d[HI]
 k2 [H 2 ][I]2
2 dt
分别用稳态近似和平衡假设来求中间产物 [I]
的表达式，并比较两种方法的适用范围。
32
 Physical
Chemistry
用稳态近似法求碘原子浓度
1 d[I]
 k1 [I2 ][M]-k-1 [I]2 [M]-k2 [H 2 ][I]2  0 反应机理：
2 dt (1) II22  M  2I
2 I MM 快平衡
(2) H 2  2I  2HI 慢
k1[I 2 ][M]
[I]2 
k1[M]  2k2 [H 2 ]
k1 k2 [H 2 ][I 2 ][M]
r  k2 [H 2 ][I]2 
k1 [M]  2k2 [H 2 ]

因为 (1) 是快平衡， k-1 很大； (2) 是慢反应， k2 很小，

分母中略去 2k2[H2] 项，得： k1k2
r [H 2 ][I 2 ]  k[H 2 ][I 2 ]
k1

与实验测定的速率方程一致。
33
 Physical
Chemistry
用平衡假设法求碘原子浓度
反应 (1) 达到平衡时： 反应机理：
(1) II22 M 2 IMM
M 2I 快平衡
k1 [I 2 ][M]  k-1 [I]2 [M] (2) H 2  2I 
 2HI 慢

k1
[I] 
2
[I 2 ]
k1
k1 k2
r  k2 [H 2 ][I] 2
[H 2 ][I 2 ]  k[H 2 ][I 2 ]
k1
显然这个方法简单，但这个方法只适用于
快平衡下面是慢反应的机理 , 即 k-1>>k2 。
34
 Physical
Chemistry
稳态近似法与平衡态近似法的比较

稳态近似法 — 优点：所得最终动力学方程中包含了复合
反应中的全部动力学参数 (
优缺点
如 k1 ， k-1, k2) 缺点：所得动力学方程的形式复杂
平衡态近似法 —缺点：所得最终动力学方程中只有一个
动力学参数 (k2) ，而且包
含在 k2Kc 的乘积中
优点：所得动力学方程的
形式简单