Complex Reactions

Chain Reactions - Process

Many reactions proceed via chain reaction
 Reaksi Konsekutif
 polymerisation
 explosion
 Peluruhan Radioaktif
…

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 First-order consecutive reactions.
First-order with two steps.
Consider the consecutive first-order reaction involving two stages:
k1 k2
A1 A2 A3 (1)

This mechanism can be described by the following set of rate expressions:

d [ A1 ] (2)
 k1[ A1 ]
dt

d [ A2 ]
 k1[ A1 ]  k2 [ A2 ] (3)
dt
d [ A3 ] (4)
 k2 [ A2 ]
dt

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The concentration of A1 is obtained after integration as
[ A1 ]  [ A1 ]0 e  k1t (5)

The concentration of A2 is computed from equation (3)

d [ A2 ]
 k 2 [ A2 ]  k1[ A1 ]0 e  k1t (6)
dt
Solving this equation, we obtain the time dependence of [A2]:

 k 2t k1[ A1 ]0  k1t
(7) [ A2 ]  [ A2 ]0 e  (e  e  k 2 t )
k 2  k1
If [A2]0=0 at t=0, then

k1[ A1 ]0  k1t
[ A2 ]  (e  e  k 2 t ) (8)
k 2  k1

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The concentration of A3 can be determined from conservation of mass:
[A1]0 = [A1] + [A2] + [A3] (9)
Hence we have

 k1t k1
[ A3 ]  [ A1 ]0 [1  e  (e  k1t  e  k 2t )]
k 2  k1 (10)

Simplifying this expression gives

k2  k1t k1
[ A3 ]  [ A1 ]0 [1  e  e  k 2t ]
k 2  k1 k 2  k1 (11)

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CH4003 Lecture Notes 16 (Erzeng Xue)

Complex Reactions

Chain Reactions - Rate Law

 Rate law of chain reaction
d [HBr] k[H 2 ][Br2 ]3/2
Example: overall reaction H2(g) + Br2(g)  2HBr(g) observed: 
dt [Br2 ]  k' [HBr]
elem step rate law
a. Initiation: Br2  2Br ra=ka[Br2]
b. Propagation: Br + H2  HBr + H rb=kb[Br][H2]
H + Br2  HBr + Br r’b=k’b[H][Br2]
c. Termination: Br + Br  Br2 rc=kc[Br][Br]=kc[Br]2
H + H  H2 (practically less important therefore neglected)
H + Br  HBr (practically less important therefore neglected)
d. Retardn (obsvd.) H + HBr  H2 + Br rd=kd[H][HBr]

HBr net rate: rHBr= rb+ r’b- rd or d[HBr]/dt=kb[Br][H2]+k’b[H][Br2]-kd[H][HBr]

Apply s.s.a. rH= rb- r’b- rd or d[H]/dt=kb[Br][H2]- k’b[H][Br2]-kd[H][HBr]=0
rBr= 2ra-rb+r’b-2rc +rd or d[Br]/dt=2ka[Br2]-kb[Br][H2]+k’b[H][Br2]-2 kc[Br]2 +kd[H][HBr]=0

d [HBr] 2kb k a / kc  [H 2 ][Br2 ]3/2

1/2
solve the above eqn’s we have 
dt [Br2 ]  k d / k'b [HBr]
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CH4003 Lecture Notes 16 (Erzeng Xue)

Complex Reactions

Chain Reactions - Rate Law

 Rate law of chain reaction
d [HBr] k[H 2 ][Br2 ]3/2
Example: overall reaction H2(g) + Br2(g)  2HBr(g) observed: 
dt [Br2 ]  k' [HBr]
elem step rate law
a. Initiation: Br2  2Br ra=ka[Br2]
b. Propagation: Br + H2  HBr + H rb=kb[Br][H2]
H + Br2  HBr + Br r’b=k’b[H][Br2]
c. Termination: Br + Br  Br2 rc=kc[Br][Br]=kc[Br]2
H + H  H2 (practically less important therefore neglected)
H + Br  HBr (practically less important therefore neglected)
d. Retardn (obsvd.) H + HBr  H2 + Br rd=kd[H][HBr]

HBr net rate: rHBr= rb+ r’b- rd or d[HBr]/dt=kb[Br][H2]+k’b[H][Br2]-kd[H][HBr]

Apply s.s.a. rH= rb- r’b- rd or d[H]/dt=kb[Br][H2]- k’b[H][Br2]-kd[H][HBr]=0
rBr= 2ra-rb+r’b-2rc +rd or d[Br]/dt=2ka[Br2]-kb[Br][H2]+k’b[H][Br2]-2 kc[Br]2 +kd[H][HBr]=0

d [HBr] 2kb k a / kc  [H 2 ][Br2 ]3/2

1/2
solve the above eqn’s we have 
dt [Br2 ]  k d / k'b [HBr]
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CH4003 Lecture Notes 16 (Erzeng Xue)

Complex Reactions

Chain Reactions - Rate Law

 Rate law of chain reaction
d [HBr] k[H 2 ][Br2 ]3/2
Example: overall reaction H2(g) + Br2(g)  2HBr(g) observed: 
dt [Br2 ]  k' [HBr]
elem step rate law
a. Initiation: Br2  2Br ra=ka[Br2]
b. Propagation: Br + H2  HBr + H rb=kb[Br][H2]
H + Br2  HBr + Br r’b=k’b[H][Br2]
c. Termination: Br + Br  Br2 rc=kc[Br][Br]=kc[Br]2
H + H  H2 (practically less important therefore neglected)
H + Br  HBr (practically less important therefore neglected)
d. Retardn (obsvd.) H + HBr  H2 + Br rd=kd[H][HBr]

HBr net rate: rHBr= rb+ r’b- rd or d[HBr]/dt=kb[Br][H2]+k’b[H][Br2]-kd[H][HBr]

Apply s.s.a. rH= r b- r’b- rd or d[H]/dt=kb[Br][H2]- k’b[H][Br2]-kd[H][HBr]=0
rBr= 2ra-rb+r’b-2rc +rd or d[Br]/dt=2ka[Br2]-kb[Br][H2]+k’b[H][Br2]-2 kc[Br]2 +kd[H][HBr]=0

d [HBr] 2kb k a / kc  [H 2 ][Br2 ]3/2

1/2
solve the above eqn’s we have 
dt [Br2 ]  k d / k'b [HBr]
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Complex Reactions

Chain Reactions - Process

 Many reactions proceed via chain reaction
 polymerisation
 explosion
 …

 Elementary reaction steps in chain reactions

1. Initiation step - creation of chain carriers (radicals, ions, neutrons etc, which are capable of
propagating a chain) by vigorous collisions, photon absorption
E
R R (the dot here signifies the radical carrying unpaired electron)
2. Propagation step - attacking reactant molecules to generate new chain carriers
R + M  R + M
3. Termination step - two chain carriers combining resulting in the end of chain growth
R + M  R-M
There are also other reactions occur during chain reaction:
Retardation step - chain carriers attacking product molecules breaking them to reactant
R + R-M  R + M(leading to net reducing of the product formation rate)
Inhibition step - chain carriers being destroyed by reacting with wall or foreign matter
R + W  R-W (leading to net reducing of the number of chain carriers)
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Complex Reactions

Chain Reactions - Rate Law

 Rate law of chain reaction
d [HBr] k[H 2 ][Br2 ]3/2
Example: overall reaction H2(g) + Br2(g)  2HBr(g) observed: 
dt [Br2 ]  k' [HBr]
elem step rate law
a. Initiation: Br2  2Br ra=ka[Br2]
b. Propagation: Br + H2  HBr + H rb=kb[Br][H2]
H + Br2  HBr + Br r’b=k’b[H][Br2]
c. Termination: Br + Br  Br2 rc=kc[Br][Br]=kc[Br]2
H + H  H2 (practically less important therefore neglected)
H + Br  HBr (practically less important therefore neglected)
d. Retardn (obsvd.) H + HBr  H2 + Br rd=kd[H][HBr]

HBr net rate: rHBr= rb+ r’b- rd or d[HBr]/dt=kb[Br][H2]+k’b[H][Br2]-kd[H][HBr]

Apply s.s.a. rH= rb- r’b- rd or d[H]/dt=kb[Br][H2]- k’b[H][Br2]-kd[H][HBr]=0
rBr= 2ra-rb+r’b-2rc +rd or d[Br]/dt=2ka[Br2]-kb[Br][H2]+k’b[H][Br2]-2 kc[Br]2 +kd[H][HBr]=0

d [HBr] 2kb k a / kc  [H 2 ][Br2 ]3/2

1/2
solve the above eqn’s we have 
dt [Br2 ]  k d / k'b [HBr]
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Complex Reactions

Chain Reactions - Polymerisation

 Monomer - the individual molecule unit in a polymer
 Type I polymerisation - Chain polymerisation
 An activated monomer attacks another monomer, links to it, then likes another
monomer, so on…, leading the chain growth eventually to polymer.
initiator chain-carrier rate law  is the yield of Ix to xR
Initiation: Ix  xR (usually r.d.s.) ri=ki[I] d [M ]
R + M  M1 (fast)  x ki [I]
dt
Propagation: M + M1  (MM1)  M2 (fast)
M + M2  (MM2)  M3 (fast)
………………………
M + Mn-1  (MMn-1)  Mn rp=kp[M][M] (ri is the r.d.s.)
Termination: Mn + Mm  (MnMm)  Mm+n rt=kt[M]2
1/ 2
d [M]  x ki [I] 
Apply s.s.a. to [M] formed  x ri  2rp  x ki [I]-2kt [M]2  0  [M]   
dt  2 k t 
The rate of propagation 1/ 2
d [M] d [M]  x ki 
or the rate of M consumption  rp  k p [M][M ] i.e.  k p   [I]1/2[M]
or the rate of chain growth dt dt  2k t 
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Complex Reactions

Chain Reactions - Polymerisation

 Type II polymerisation - Stepwise polymerisation
A specific section of molecule A reacts with a specific section of molecule B forming chain
(a-A-a’) + (b’-B-b) {a -A-(a’b’)-B-b}
H2N(CH2)6NH2 + HOOC(CH2)4COOH  H2N(CH2)6NHOC(CH2)4COOH + H2O (1)
 H-HN(CH2)6NHOC(CH2)4CO-OH …
 H-[HN(CH2)6NHOC(CH2)4CO]n-OH (n)
Note: If a small molecule is dropped as a result of reaction, like a H2O dropped in rxn (1), this type of
reaction is called condensation reaction. Protein molecules are formed in this way.
 The rate law for the overall reaction of this type is the same as its elementary step
involving one H- containing unit & one -OH containing unit, which is the 2nd order

d [A] [A]0
 k[A][-OH]  k[A] 2 or [A] 
dt 1  kt[A]0
the conversion of B (-OH containing substance) at time t is
[A]0  [A] kt[A]0
XB  
[A]0 1  kt[A]0
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Complex Reactions

Photochemical Reactions
 Photochemical reaction
The reaction that is initiated by the absorption of light (photons)
 Characterisation of photon absorption - quantum yield
A reactant molecule after absorbing a photon becomes excited. The excitation may lead
to product formation or may be lost (e.g. in form of heat emission)
 The number of specific primary products (e.g. a radical, photon-excited molecule, or an ion)
formed by absorption of each photon, is called primary quantum yield, 
 The number of reactant molecules that react as a result of each photon absorbed is call
overall quantum yield, F
E.g. HI + hv  H + I primary quantum yield  =2 (one H and one I)
H + HI  H2 + I
2I I2 overall quantum yield F =2 (two HI molecules reacted)

Note: Many chain reactions are initiated by photochemical reaction. Because of chain reaction
overall quantum yield can be very large, e.g. F = 104

The quantum yield of a photochemical reaction depends on the wavelength of light used
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Complex Reactions

Photochemical Reactions
 Wave-length selectivity of photochemical reaction
 A light with a specific wave length may only excite a specific type of molecule
 Quantum yield of a photochemical rxn may vary with light (wave-length) used
 Isotope separation (photochemical reaction Application)
 Different isotope species - different mass - different frequencies required to match
their vibration-rotational energys
508 nm light
e.g. I36Cl + I37Cl I36Cl + I37Cl* (only 37Cl molecules are excited)
C6H5Br + I37Cl*  C6H537Cl + IBr
 Photosensitisation (photochemical reaction Application)
 Reactant molecule A may not be activated in a photochemical reaction because it
does not absorb light, but A may be activated by the presence of another molecule
B which can be excited by absorbing light, then transfer some of its energy to A.
254 nm light
e.g. Hg + H2 Hg* + H2 (Hg is, but H2 is not excited by 254nm light)
Hg* + H2  Hg + 2H* & Hg* + H2  HgH + H*
CO H2
H* HCO HCHO + H*
2HCO  HCHO + CO
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Complex Reactions

Chain Reactions - Explosion

 Type I Explosion: Chain-branching explosion
Chain-branching - During propagation step of a chain reaction one attack by a
chain carrier can produce more than one new chain carriers
Chain-branching explosion
When chain-branching occurs the number carriers increases exponentially
the rate of reaction may cascade into explosion
Example: 2H2(g) + O2(g)  2H2O(g)

Initiation: H2 + O2  O2H + H

Propagation: H2 + O2H  OH + H2O (non-branching)

H2 + OH  H + H2O (non-branching)

O2 + H  O + OH (branching) Lead to explosion

O + H2  OH + H (branching)

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Complex Reactions

Explosion Reactions
 Type II Explosion: Thermal explosion
A rapid increase of the rate of exothermic reaction with temperature
Strictly speaking thermal explosion is not caused by multiple production of chain carriers
 Must be exothermic reaction
 Must be in a confined space and within short time
DH  T r  DH  T r DH …
 A combination of chain-branching reaction with heat accumulation can occur
simultaneously

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