Chapter 7

Chain reactions
&
Photochemical reactions
PHẢN ỨNG DÂY CHUYỀN VÀ PHẢN ỨNG QUANG HÓA

1
 Contents

1.Chain reactions

2. Photochemical reactions

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1.Chain reactions

3
Ex: H 2  Br2  2 HBr

ban đầu lan truyền

kết thúc

Bodenstein and Lind investigated (1907)

4
 Gốc tự do
Free radical/radical
• atoms, molecules, or ions with unpaired
electrons:

Br2  Br
. + Br
.
h/q

• Free radicals may have positive, negative,

or zero charge.
• these unpaired electrons cause radicals to
be highly chemically reactive.

5
 Chain reaction
Phản ứng dây chuyền là phản ứng có sự tham gia của các gốc tự do, bao gồm ba quá trình riêng
biệt:
• Chain reactions are reactions involving free
radicals, consist of three distinct processes:
(1) Initiation reactions result in increase in the
number of free radicals.
– formation of free radicals from stable species
– reactions of free radicals with stable species to form more free
radicals.

A1  R1 + R1

6
 Chain reaction
(cont.)
(2) Propagation reactions involving free radicals
in which the total number of free radicals
remains the same.
R1 + A2  B1 + R2
R2 + A1  B2 + R1
(3) Termination reactions result in decrease in the
number of free radicals.
R1 + R1  A1
R1 + reactor’s wall  …
R1 + inhibitor less active radical

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 Chain reaction
Classification: phân loại

 Unbranched chain reaction:

(a radical  a radical)
Không phân nhánh

 Branched chain reaction:

(a radical  2 or more radicals)

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a. Unbranched chain reaction
b. Branched chain reaction

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a. Regularly branched phân nhánh thường

b. Irregularly branched phân nhánh không đều

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 Động học của phản ứng không phân nhánh

Kinetics of unbranched chain reactions

số lượng gốc tự do đc tạo ra mỗi t mỗi thể tích

n0 : No. of radicals generated per time (s) per

volume (l) , assume =CONST
n : number of radicals in a volume at t (mol/l)
số lượng gốc tự do trong 1 thể tích V tại thời gian t

 : life-time of the radical (s) thời gian tồn tại của gốc tự do
After  (s), a radical can:
+=1
kết thúc`
Generate a new radical terminate
.100 (%) .100 (%)
tạo 1 gốc tự do mới

khả năng chuỗi Possibility of chain khả năngPossibility of chain

kết thúc
phát triển
development chuỗi` termination 11
Kinetics of unbranched chain reactions
dn n.  : Possibility of chain
 n0  termination
dt 
 : life-time of the radical

 .t
n0 .   
n 1  e  
  


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Kinetics of unbranched chain reactions
 .t
n0 .   
n 1  e  
  

Tại trạng thái ổn định
At steady state:
n0 .
n0 . nmax 
nmax  


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Kinetics of unbranched chain reactions
 .t
n0 .   
n 1  e  
  

 .t
n n0   
Reaction rate: R   1  e  
  
Tốc độ phản ứng

nmax n0
At steady state: R 
 
(constant)
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Kinetics of unbranched chain reactions

Reaction Rate

n0
Rmax 


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Kinetics of unbranched chain reactions

Actual
Reaction Rate

n0
Rmax 


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 ĐỘNG HỌC CỦA PHẢN ỨNG DÂY CHUYỀN PHÂN NHÁNH

Kinetics of branched chain reactions

After  (s), a radical can:

Generate a new radical terminate

.100 (%) .100 (%)
Possibility of chain Possibility of chain
development termination
phân nhánh

++=1 Branch
.100 (%)
Possibility of chain
branching 17
Kinetics of branched chain reactions

dn n. n.  : Possibility of chain

 n0   termination
dt  
 : Possibility of chain
branching

(   ). t
n0 .   
n 1  e  
    


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Kinetics of branched chain reactions
(   ). t
n0 .   
n 1  e  
    


->0
n0 .
nmax 
 

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Kinetics of branched chain reactions
(   ). t
n0 .   
n 1  e  
    


-<0 nmax   

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Kinetics of branched chain reactions
(   ).t
n n0   
Reaction rate: R  1  e


    

At steady nmax n0
->0 R 
state:   
(constant)
trạng thái không ổn định

-<0 No steady state đùng!!

Explosion!!

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Kinetics of branched chain reactions

0< <
Reaction Rate

0<<

 =0
(unbranched)

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 Explosion
Nikolay Nikolaevich Semenov (Russian, 1896-1986)
(1926) : reaction P + O2
Observed 02 explosive limits
tìm ra 2 giới hạn nổ của pứ p+ 02

Cyril Norman Hinshelwood (English, 1897-1967)

(1927): Reaction: H2O2
Observed 02 explosive limits.

The Nobel Prize in Chemistry 1956: Semenov and Hinshelwood:

"for their researches into the mechanism of chemical reactions"

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 Explosion of (O2+H2)
2 H2 + O2  2 H2O

From experimental observation

1st explosive limit 1: depend on container’s size and structure
2nd and 3rd explosive limits: do not depend on container’s size and structure.

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Explosion mechanism (H2+O2)
1 H2 + O2  .H + .HO2 initiation
2 .OH + H2  .H + H2O propagation
3 .H + O2  .OH + O branching
4 O + H2  .OH + .H branching
5 .H + O2 + M  .HO2 + M termination*
6 .H  wall termination
7 :O  wall termination
8 .OH  wall termination
9 .HO2 + H2  .H + H2O2 initiation *
10 2 .HO2  H2O2 + O2 termination
11 H2O2  2 .OH initiation

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1 H2 + O2  .H + .HO2 initiation
2 .OH + H2  .H + H2O propagation
3 .H + O2  .OH + O branching
4 O + H2  .OH + .H branching
5 .H + O2 + M  .HO2 + M termination*
6 .H  wall termination
7 :O  wall termination
8 .OH  wall termination 
9 .HO2 + H2  .H + H2O2 initiation *
10 2 .HO2  H2O2 + O2 termination
11 H2O2  2 .OH initiation

Below 1st limit: chiếm ưu thế

Terminations by interaction with the container’s wall predominate 
no explosion

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1 H2 + O2  .H + .HO2 initiation
2 .OH + H2  .H + H2O propagation
3 .H + O2  .OH + O branching
4 O + H2  .OH + .H branching
5 .H + O2 + M  .HO2 + M termination*
6 .H  wall termination
7 :O  wall termination 
8 .OH  wall termination
9 .HO2 + H2  .H + H2O2 initiation *
10 2 .HO2  H2O2 + O2 termination
11 H2O2  2 .OH initiation H.
H. H.
Between 1st limit and 2nd limit: H.
Branching steps (2), (3) and (4). H.

3 .H + O2  .OH + :O H. H. H.
2 .OH + H2  .H + H2O H.
4 :O + H2  .H + .OH
 explosion
2 .OH + H2  .H + H2O H.
+ ____________________
.H + O2 + 3 H2  3 .H + 2 H2O H. H.
H. 27
1 H2 + O2  .H + .HO2 initiation
2 .OH + H2  .H + H2O propagation
3 .H + O2  .OH + O branching
4 O + H2  .OH + .H branching
5 .H + O2 + M  .HO2 + M termination*
6 .H  wall termination
7 :O  wall termination

8 .OH  wall termination
9 .HO2 + H2  .H + H2O2 initiation *
10 2 .HO2  H2O2 + O2 termination
11 H2O2  2 .OH initiation

Between 2nd limit and 3rd limit:

10 .HO2  H2O2 + O2 termination

 No explosion

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1 H2 + O2  .H + .HO2 initiation
2 .OH + H2  .H + H2O propagation
3 .H + O2  .OH + O branching
4 O + H2  .OH + .H branching

5 .H + O2 + M  .HO2 + M termination*
6 .H  wall termination
7 :O  wall termination
8 .OH  wall termination
9 .HO2 + H2  .H + H2O2 initiation *
10 2 .HO2  H2O2 + O2 termination
11 H2O2  2 .OH initiation

Above 3rd limit

(9), (10), (11) become important

 Explosion

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 Explosion types
Branched chain explosions:
Rapidly increase concentration of radical  increase ration rate  explosion

Thermal explosions:
(i) Exothermal reaction, phản ứng tỏa nhiệt
(ii) Heat are not transferred to the surroundings
(iii) Increasing temperature  increase reaction rate
High temperature fast reaction more heat generated

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Thermal explosion

Branched chain explosions

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32
Giới hạn nổ dưới (LEL): Nồng độ thấp nhất(phần trăm) của khí hoặc hơi trong không khí có khả năng
tạo ra tia lửa khi có nguồn đánh lửa = (thấp hơn giới hạn cháy (LFL)
Lower explosive limit (LEL): The lowest concentration
(percentage) of a gas or a vapor in air capable of producing a
flash of fire in presence of an ignition source = (lower
flammable limit (LFL)

Example:
At 200C the LEL of CH4 is 5.1% by volume.

If the atmosphere has less than 5.1% methane, an explosion

cannot occur even if a source of ignition is present.
When methane (CH4) concentration reaches 5.1% an
Safety explosion can occur if there is an ignition source.
LEL concentrations vary greatly between combustible gases.
first!!!
Upper explosive limit (UEL): Highest concentration (percentage) of a gas or a
vapor in air capable of producing a flash of fire in presence of an ignition source
(arc, flame, heat).

Example:
At 200C the UEL of CH4 is 15% by volume. 33
2. Photochemical reactions
study of chemical reactions that proceed with the
absorption of light by atoms or molecules

34
 Lambert – Beer law

cường độ sáng
I, I0: light intensity
I0 I
l
I
Transmission (or transmissivity) (T): T
I0

độ hấp thụ
I
Absorbance (optical density) (A/D): D   ln( )
I0
mật độ quang học
35
 Lambert – Beer law
I
ln T  ln   K .l  k .n.l
I0

l : thickness of the cell

K: absorption constant: K = k.n =.C
k: molecular absorption constant hằng số hấp thụ phân tử
n: number of molecules in a volume số phân tử trong 1 đv thể tích
: molar absorption constant hằng số hấp thụ mol`
C: concentration (mol/l) nồng độ

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 Lambert – Beer law
I
ln T  ln  k .n.l   .C.l
I0

 k .n.l  .C .l
I  I 0 .e  I 0 .e
Light absorption energy:
 .C .l
năng lượng hấp thụ
ánh sáng A  I 0  I  I 0 (1  e )
37
 Van t’ Hoff law
• 1841 (Draper): only absorbed light can lead
to chemical conversion.

• 1904 Van t’ Hoff (first law of photochemistry):

The amount of reactants photochemically
converted is in proportion to the energy of the
absorbed light energy (A) .
-dC = const.A.dt

38
 Reaction rate
dC  .C .l
-dC = const.A.dt   const.I 0 (1  e )
dt

Maclaurin series:

.C.l : small

dC dC
  k1.C   const.I 0 ( .C.l )
dt dt
1st order reaction 39
 Reaction rate
dC  .C .l
-dC = const.A.dt   const .I 0 (1  e )
dt

.C.l : large

e-.C.l = 0

dC dC
  k1   const.I 0
dt dt
Zero order reaction 40
 Kích thích quang hóa
Photochemical excitation
ánh sáng là dòng điện từ bao gồm các photon ( lượng tử)`
• Light is electromagnetic flow consisting of
photons (quantum).
• When molecules absorbed a photon of light,
its internal energy raised E1  E2.
khi các phân tử hấp phụ 1 photon của ánh sáng nội năng của chúng tăng.
E = E2 - E1 = h

: light’s frequency
c: light speed
: light’s wavelength
 = c/

41
 Photochemical excitation

1 photon interacts with 1 molecule

Energy of 1 photon: h
Energy of 1 mol photon : h.N0
hN 0C 2,857.10 3
E  hN 0   , kcal / mol
 (cm)  (cm)

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 Photochemical equivalent law
(2nd law of photochemistry)
mỗi photon bị hấp thụ gây ra sự thay đổi phân tử
• “Each of the absorbed photons causes a
molecular change”.
số lượng photon bị hấp thụ trong một đơn vị thời gian
– Number of absorbed photons in a unit of time:
A
na 
h
– Number of converted molecules under the light by
the first interaction (theory):
A
n p  na 
h

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 Photochemical equivalent law

N0 photon = 1 Einstein
N0 : Avogadro number

1 Einstein  change 1 mole of molecules.

1 einstein thay đổi 1 mol của phân tử

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 năng suất lượng tử

Quantum yield ()

lý thuyết

Theory: np = na
Real: np  na

np np
 
na A / h

Quantum yield (): ratio of converted

molecules to the absorbed photons.
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 Quantum yield ()
np np A
  n p   .na   .
na A / h h

 Reaction rate:


dn dn p
dt

dt
 .
dna
dt
 .
A
h
 .
I0
h

1  e  knl 


dC
dt
 .
103 I 0
hN 0

1 e Cl

46
 
dC
dt
 .
103 I0
hN0

1  e  Cl 

Rate of photochemical reactions:

• Proportional to the incident light intensity
I0 tỉ lệ thuận với cường độ ánh sáng tới
• Increased with increasing concentrations
of reactant and environmental thickness l.
ngược lại
• Inversely proportional to the frequency of
light 
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quantum yield
(năng suất lượng tử)
 < 1 ???
 > 1 ???
 = 1 ???
48
2 steps of photochemical reactions
Primary step:
• Light interacts directly molecules, atoms ->
unstable species:
M + h  M* or:
• Light dissociates molecules into atoms, radicals:
AB + h  A. + B. or:
• Light ionizes molecules/atoms:
M + h  M+ + e
Secondary step (reaction in dark): Active
species, which generated in the primary step,
react with other molecules without light
absorption. 49
2 steps of photochemical reactions
• Quantum yield of primary step  = 1
• Overall quantum yield   1
hiệu ứng lồng
• Cage effect: active species interact with
solvents.  small .
Light Light Quantum yield
Reaction absorption wavelength
compound (A)

Cl2 + H2 = 2HCl Cl2 3030- 104 – 106

5000
Br2 + H2 = 2HBr Br2 5000- 0,2
5780
50
4 groups of photochemical reactions

Group  Examples
1 1 O2 + Cl2  O2Cl2
H2S  H2 + S (in C6H14)
2 <1 H2S  H2 + S (in H2O)
(0,2=0,3)
3 >1 2HBr  H2 + Br2 (2)

4 >>1 Cl2 + H2 = 2HCl (104 – 106)

51
 Determination of quantum yield
n p phân tử đã phản ứng

na số photon bị hấp thụ
• np: Reacted molecules: np = nbegin – nend

• na: number of absorbed photon: n  A

a
h
cường độ sáng • A: light intensity (erg/s)
• h: Plank constant (6,62.10-27 erg.s) hằng số plank
tần số ánh sáng • : light frequency (1/s, Hz) = c/
• c: light speed (3.108 m/s)
bước sóng •  : light wavelength (m)
52
 Photochemical reactions vs.
non-photo chemical reactions

H2 + Br2 = 2HBr
0.5
k .CH 2 .CBr Without light
R1  2
CHBr T= 200 – 300oC
1  k '.
CBr 2
0.5
k .CH 2 .I
R2  With light, at room
CHBr
1  k '. temperature
CBr 2
53