Sie sind auf Seite 1von 28

# Physical

Chemistry

Reaction
Kinetics (1)
Xuan Cheng
Xiamen University

1
Physical Reaction
Chemistry Kinetics
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: can’t answer (1) how to make them happen

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

2
Physical Reaction
Chemistry Kinetics
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
Chemistry Rate of Reaction Kinetics

## 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

## 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
Chemistry Rate of Reaction Kinetics

## 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
Chemistry Rate Laws Kinetics

## For many reactions

r = k [ A]α [ B ] β [ L ] λ (17.5)*

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

α , β , …λ : order or partial order

α +β + … +λ ≡ n : overall order

## The expression for r as a

function of concentrations at a
fixed temperature is called the
rate law. 6
Physical Reaction
Chemistry Reaction Orders Kinetics

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
Chemistry Kinetics
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
Reaction
Chemistry Mechanisms Kinetics
Reaction actually occurs
NO
2SO2 + O2 
→ 2 SO3

O2 + 2 NO → 2 NO2 (17.7)
intermediate
NO2 + SO2 → NO + SO3

reaction

## Step (b) NO2 + NO3 → NO + O2 + NO2 (17.8)

Step (c) NO + NO3 → 2NO2

9
Physical Reaction
ChemistryMeasurement of Reaction Kinetics

## The concentration of a reactantRates

or product as a function of time

## Cooling the sample

Chemical Method removing a catalyst
Diluting the mixture
At constant T Adding a species

the reaction

## Rapidly analyze chemical

Reaction vessels compositions of the mixture
10
Physical Reaction
Chemistry Kinetics

11
Physical Reaction
Measurement
Chemistry of Reaction Kinetics
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.

（ IR 、 UV-VIS 、 ESR 、 NMR 、 ESCA 等）

12
Physical Reaction
Chemistry Integration of Rate Laws Kinetics

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

Assumptions

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

13
Physical Reaction
ChemistryFirst-Order Reactions Kinetics

## 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]α [ B ] β [ L ] λ (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
ChemistryFirst-Order Reactions Kinetics

2
∫1 [ ][ ]
d A / A = − 2
ln ( [ A] 2 /[ A]1 ) = −k A (t 2 − 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
Chemistry Kinetics
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
Chemistry First-Order Reactions Kinetics

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

## t1 / 2 = 0.693 / k A Independent of [A]o

17
Physical Reaction
ChemistrySecond-Order Reactions Kinetics

(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
Chemistry Kinetics
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
Chemistry Second-Order Reactions Kinetics

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

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

20
Physical Reaction
Chemistry Kinetics
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
Chemistry Second-Order Reactions Kinetics

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
Chemistry Kinetics
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
Chemistry Second-Order Reactions Kinetics

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
Chemistry Third-Order Reactions Kinetics

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
Chemistry nth-Order Reaction Kinetics

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
Chemistry nth-Order Reaction Kinetics

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
Chemistry Kinetics
Homework
Page 591

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

28