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Physical

Chemistry

Reaction
Kinetics (1)
Xuan Cheng
Xiamen University

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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: 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
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

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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

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
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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
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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
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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

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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

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

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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

At intervals Slows down or stop


the reaction

Rapidly analyze chemical


Reaction vessels compositions of the mixture
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Physical Reaction
Chemistry Kinetics
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。

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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.

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。
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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

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)

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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

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Physical Reaction
ChemistryFirst-Order Reactions Kinetics

2
∫1 [ ][ ]
d A / A = − 2
∫1 k Adt
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.
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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
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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

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

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


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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

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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]

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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

Second-order reaction with {t}

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


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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
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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 )

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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
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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
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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)

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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

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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
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Physical Reaction
Chemistry Kinetics
Homework
Page 591

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

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