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Chemistry
1
Physical Reaction Kinetics
Determination
Chemistry of the Rate Law
1. Half-life method
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]on1 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
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.
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)
[ A]0,2
r0,2 / r0,1 can be found
0,1
[ A]
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
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 ] [ 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
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
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
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
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
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 ]
'
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
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
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
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
k1[M] 2k2 [H 2 ]
k1 k2 [H 2 ][I 2 ][M]
r k2 [H 2 ][I]2
k1 [M] 2k2 [H 2 ]
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 IMM
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 ]
k1
k1 k2
r k2 [H 2 ][I] 2
[H 2 ][I 2 ] k[H 2 ][I 2 ]
k1
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