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Examples of bimolecular reactions

O3 + NO → NO2 + O2
k = 2.0×10-12 exp(-1400/T)
OH + HCHO → HO2 + CO + H2O,
k = 8.8×10-12 exp(25/T)

Three body reactions (or termolecular reactions):

Example 1: O + O + M → O2 + M
Example 2: OH + NO2 + M → HNO3 + M
Example 3: O + O2 + M → O3 + M (where M=usually N2 or O2 for
atmosphere)
1. The steady-state approximation
K
1 K
2
AK
B C
-
1
The intermediate, B, is reactive, in low concentrations throughout the
reaction, and d[B]/dt  0; k-1, k2 >> k1

d[B]
 k 1 [A] - k -1 [B] - k 2 [B]  0
dt

k 1 [A]  k -1 [B] + k 2 [B]


k1
[B ] s.s.  [A]
k -1 + k 2
d[C]
= k 2 [B ] s.s.  k 2 k 1 [A]
dt k -1 + k 2
2. The rate limiting step approximation.
K K2
1
A B C

If k2 >> k1 (first step is the RDS)

d[C]
 k 1 [A]
dt
Simple empirical rate law

The overall rate of a series of consecutive steps can be no faster


than the slowest step, the “rate limiting step”. The rate of product
production is just the rate of the slow step.

No steps in a mechanism after the rate-limiting step will appear in a


rate law.

The slowest step involve collision of two molecules


3. The pre-equilibrium approximation

K
1 K
2
AK
B C
-
1
Suppose that each time a B is formed, the probability of it returning to A
is much greater than that for conversion to C ie, k-1>>k2

[ B] k1
 K eqm 
[ A] k 1

[ B]  K eqm[ A]

d[C ]
 k 2 [ B]  k 2 K eqm [ A]
dt
CONSECUTIVE REACTIONS WITH A REVERSIBLE STEP
K
1
2 K
AK
B C
-
1

The rate laws

- d[A]
= k 1 [A] - k -1 [B]
dt

d[B]
= k 1 [A] - k -1 [B] - k 2 [B]
dt

d[C]
= k 2 [B]
dt
K
1 K
2
AK
B C
-
1
d[C]
= k 2 [B ] s.s.  k 2 k 1 [A] The steady-state solution
dt k -1 + k 2

Note that if k-1 >> k2,

d[C] k 2 k 1
 [A]  K eqmk2 [ A] The pre-equilibrium solution
dt k -1

If k2 >> k-1

d[C]
 k1 [A] The rate-limiting step solution
dt

The steady-state approximation is the most general.


In a chain reaction, the product of one reaction step is a
reactant in a subsequent step, which in turn produces
species that can take part in subsequent reaction steps.

Initiation

Propagation
Explosions
• Thermal explosion: a very rapid reaction arising from a rapid increase of
reaction rate with increasing temperature.

• Chain-branching explosion: occurs when the number of chain centres


grows exponentially.

• An example of both types of explosion is the following reaction


2H2(g) + O2(g) → 2H2O(g)
1. Initiation: H2 → H. + H.

2. Propagation H2 + .OH → H. + H2O kp

3. Branching: O2 + .H → O + .OH kb1


O + H2 → .OH + H. Kb2

4. Termination H. + Wall → ½ H2 kt1


H. + O2 + M → HO2. + M* kt2
Example (II): Branching Chain Reaction

Initiation : H 2   H   H 
spark

Branching : H  O 2  HO    O 
Branching :  O   H 2  HO   H 
• Analyzing the reaction of hydrogen and oxygen (see preceding
slide), show that an explosion occurs when the rate of chain
branching exceeds that of chain termination.

Method: 1. Set up the corresponding rate laws for the reaction


intermediate and then apply the steady-state approximation.
2. Identify the rapid increase in the concentration of H.
atoms.

d[ H . ]
 v init  k p [ .OH ][ H 2 ]  k b1 [ H . ][O2 ]  k[O ][ H 2 ]  k t 1 [ H . ]  k t 2 [ H . ][O2 ][ M ]
dt

d [ .OH ]
  k p [ .OH ][ H 2 ]  k b1 [ H . ][O2 ]  k b 2 [O ][ H 2 ]
dt

d [O ]
 k b1 [ H . ][O2 ]  k b 2 [O ][ H 2 ]
dt

Applying the steady-state approximation to .OH and O gives


 k p [ .OH ][H 2 ]  kb1[ H . ][O2 ]  kb 2 [O][H 2 ]  0

k b1 [ H . ][O2 ]  k b 2 [O ][ H 2 ]  0
kb1[ H . ][O2 ]
[O ] 
kb 2 [ H 2 ]

2kb1[ H . ][O2 ]
[ OH ] 
.
k p[ H 2 ]
Therefore, d[ H . ]
 v init  (2k b1 [O2 ]  k t 1  k t 2 [O2 ][ M ])[ H . ]
dt
we write kbranch = 2kb1[O2] and kterm = kt1 + kt2[O2][M], then
d[ H . ]
 v init  (k branch  k term )[ H . ]
dt
At low O2 concentrations, termination dominates branching, so kterm >
v init
kbranch. Then [ H . ]  (1  e ( kterm  kbranch ) t ) this solution corresponds
k term  kbranch

to steady combustion of hydrogen.

At high O2 concentrations, branching dominates termination, kbranch >


kterm. Then [ H . ]  v init
( e ( kbranch  kterm ) t  1)
 k term  kbranch

This is an explosive increase in the concentration of radicals!!!


The explosion limits of the H2 + O2
reaction
Example (I)

Initiation : Br 2    Br   Br 
heat or radiation

Propagation : Br   H 2  HBr  H 
H   Br2  HBr  Br 
Terminatio n : Br   Br   Br2
• Self-test 23.2 Calculate the variation in radical
composition when rates of branching and
termination are equal.
• Solution:
d[ H . ]
 v init  (k branch  k term )[ H . ]
dt

kbranch = 2kb1[O2] and kterm = kt1 + kt2[O2][M],

d[ H . ]
 vinit
dt
The integrated solution is [H.] = vinit t
Chain-Growth Polymerization
1. Only growth reaction adds repeating units one at a time to the chain

2. Monomer concentration decreases steadily throughout the reaction

3. High Molecular weight polymer is formed at once; polymer molecular


weight changes little throughout the reaction.

• Long reaction times give high yields but affect molecular weight little.

• Reaction mixture contains only monomer, high polymer, and about 10-8
part of growing chains.

Step-Growth Polymerization
1. Molecular weight increases steadily.

2. High molecular weight polymers are found at the end.

3. Long reaction time needs to synthesize high conversion and high molecular weight.
Polymers
What is a polymer?
Very Large molecules structures chain-like in
nature.
Poly mer
many repeat unit
repeat repeat repeat
unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
Ancient Polymer History
• Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk
Bulk or Commodity Polymers
Range of Polymers
Range of Polymers
• Another way of classifying polymers is in
terms of their form or function
Important Monomers
• Ethylene
• Propylene
• Vinyl chloride
• Styrene
The three basic types of reaction
step in a chain polymerization
(a) Initiation: I → R. + R. vi = ki[I]
M + R. → .M1 (fast)
(b) Propagation: M + .M1→ .M2
M + .M2→ .M3
░ vp = kp[M][.M]
M + .Mn-1→ .Mn
(c) Termination:
Mutual termination: .Mn + .Mm→ Mn+m
Disproportionation: .Mn + .Mm→ Mn + Mm
Chain transfer: M + .Mn→ Mn + .M
Chain Growth Polymerization
(1) Initiation
kd : Initiator decomposition rate constant
: 10-4 ~ 10-6 L/mole sec

Bond Energy = 46 kcal/mole


Heat (60ºC)
UV kd
AIBN Primary radical

Unstable radical

Ri  ki M I 
Chain Growth Polymerization

(2) Propagation (Repetition of similar reaction)

Rp  k p M M 

kp : 102 ~ 104 L/mole sec (much faster than step-growth polymerization)


Chain Growth Polymerization

(3) Termination

(a) Coupling or combination

Rt  2k k M M   2 Rt M 
2
Chain Growth Polymerization

(3) Termination
(b) Disproportionation

k td

k td

kt=ktc+ktd 106 ~ 108 L/mole sec

Rt  2k k M M   2 Rt M 
2
Chain Growth Polymerization
(4) Chain Transfer

Physical chain length

Monomer, Polymer, Solvent or Chain transfer agent

Kinetic chain length


• the net rate of change of radical concentration is calculated as
 d [.M ] 
   2 fk i [ I ]  2k t [.M ]2
 dt 
  production

• Using steady-state approximation (the rate of production of radicals


equals the termination rate) 1/ 2
 fk 
[.M ]   i  [ I ]1 / 2
 kt 
• The rate of polymerization 1/ 2
 fk 
vp = kp[.M][M] = kp[M]  i  [I ]1 / 2
 kt 
• The above equation states that the rate of polymerization is
proportional to the square root of the concentration of the initiator.
Chain Growth Polymerization

Kinetic Chain Length :


kinetic chain length υ of a radical chain polymerization is defined as the
average number of monomer molecules consumed (polymerized) per each
radical, which initiates a polymer chain.
Radical
ex) Monomer # 4000 1,2,3,4
Disproportionation

υ =4,000/4 =1,000
Determined by steps 1, 2, 3. (Initiation, propagation, and termination)
(No chain transfer)

Physical Chain Length :


This condition contains Step 1, 2, 3, 4.
Step-growth polymerization
Monomers for step-growth polymerization
• the polar repeat units in many step-growth polymers
result in strong intermolecular forces (e.g., hydrogen bonding)

• Lower-molecular-weight step-growth polymers often produce


stronger materials than higher-molecular-weight chain-growth
polymers
The Kinetics of
Step - Growth Polymerization
Flory investigated polyesterifications of the type;

A-A + B- B A - AB - B
use A’s and B’s to represent the monomer’s reactive functional groups

O O

HO - C - (CH2)n - C - OH + HO - (CH2)m - OH

O O

HO - C - (CH2)n - C - O - (CH2)m - OH + H2O

So here A-A is a diacid and B-B is a dialcohol (diol). One’s first guess would be
that this bimolecular reaction would be second order with a rate constant k2;

Reaction Rate   d  A  k2  AB


dt
The Kinetics of
Step - Growth Polymerization
Actually, experimental measurements show that the (overall) reaction is
actually third order (rate constant = k3) because the reaction is catalyzed by
acids (so one of the reacting components also acts as a catalyst). Hence;
d A k  A 2B
  3
dt

Note two important things. First, the rate of the reaction is described in terms
of the disappearance of one of the functional groups, in this case the A’s or
acids. (Because A’s only react with B’s and the stoichiometry is 1:1, we could
just as easily chosen the B’s to follow). Second, the quantities [A] and [B] are
the concentrations of functional groups, not monomers or molecules.
Stepwise polymerization
• The rate law can be expressed as
d[ A]
  k[ A]2
dt
• Assuming that the rate constant k is independent
of the chain length, then k remains constant
throughout the reaction.

[ A]0
[ A] 
1  kt[ A]0
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Catalysis
• We will briefly discuss three types of
catalysts. The type of catalyst depends on
the phase of the catalyst and the reacting
species.
– Homogeneous
– Heterogeneous
– Enzyme
Features of homogeneous catalysis
• A Catalyst is a substance that
accelerates a reaction but
undergoes no net chemical
change.

• Enzymes are biological


catalysts and are very specific.

• Homogeneous catalyst: a
catalyst in the same phase as
the reaction mixture.

• heterogeneous catalysts: a
catalyst exists in a different
phase from the reaction mixture.
Homogeneous Catalysis
• The catalyst and the reactants are in the same
phase
• e.g. Oxidation of SO2 (g) to SO3 (g)
2 SO2(g) + O2(g)  2 SO3 (g) SLOW
• Presence of NO (g), the following occurs.
NO (g) + O2 (g)  NO2 (g)
NO2 (g) + SO2 (g)  SO3 (g) + NO (g) FAST
• SO3 (g) is a potent acid rain gas
H2O (l) + SO3 (g)  H2SO4 (aq)
• Note the rate of NO2(g) oxidizing SO2(g) to
SO3(g) is faster than the direct oxidation.
• NOx(g) are produced from burning fossil
fuels such as gasoline, coal, oil!!
Example: Bromide-catalyzed decomposition of hydrogen peroxide:
2H2O2(aq) → 2H2O(l) + O2(g)
is believed to proceed through the following pre-equilibrium:

H3O+ + H2O2 ↔ H3O2+ + H2O


[ H 3O2 ]
K
[ H 2O2 ][ H 3O  ]

H3O2+ + Br- → HOBr + H2O v = k[H3O2+][Br-]

HOBr + H2O2 → H3O+ + O2 + Br- (fast)

The second step is the rate-determining step. Thus the production rate
of O2 can be expressed by the rate of the second step.
d [O2 ]
 k[ H 3O2 ][Br  ]
dt
The concentration of [H3O2+] can be solved
[H3O2+] = K[H2O2][H3O+]

d [O2 ]
Thus  Kk[ H 2O2 ][ H 3O  ][Br  ]
dt
The rate depends on the concentration of Br- and on the pH of the solution
(i.e. [H3O+]).
• Michaelis-Menten mechanism
E + S → ES k1
ES →E + S k2
ES →P + E k3
The rate of product formation:
d[ P ]
 k3 [ ES ]
dt
To get a solution for the above equation, one needs to know the
value of [ES]
d[ ES ]
 k1[ E ][ S ]  k2[ ES ]  k3[ ES ]
dt
Applying steady-state approximation
k1[ E ][ S ]  k2 [ ES ]  k3 [ ES ]  0

k1
[ ES ]  [ E ][ S ]
k2  k3
[ E ]0
Because [E]0 = [E] + [ES], and [S] ≈ [S]0 [ ES ] 
 k  k3  1
1   2 
 k1  [ S ]0
• Michaelis-Menten equation can be obtained by plug the value of
[ES] into the rate law of P:
dP k 3 [ E ]0

dt  k  k3  1
1   2 
 k1  [ S ]0
• Michaelis-Menten constant:
k2  k3
KM 
k1

KM can also be expressed as [E][S]/[ES].

• Analysis:
1. When [S]0 << KM, the rate of product formation is proportional to [S]0:
k1k 3
v [ S ]0 [ E ]0
k2  k3

2. When [S]0 >> KM, the rate of product formation reaches its maximum
value, which is independent of [S]0:
v = vmax = k3[E]0
v max
With the definition of KM and vmax, we get v
K
1 M
[ S ]0

The above Equation can be rearranged into:


1 1 K  1
   M 
v v max  v max  [ S ]0

Therefore, a straight line is expected with the slope of KM/vmax, and a y-


intercept at 1/vmax when plotting 1/v versus 1/[S]0. Such a plot is
called Lineweaver-Burk plot,
Enzymes Catalysis

Three principal features of enzyme-catalyzed reactions:

1. For a given initial concentration of substrate, [S]0, the initial rate


of product formation is proportional to the total concentration of
enzyme, [E]0.

2. For a given [E]0 and low values of [S]0, the rate of product
formation is proportional to [S]0.

3. For a given [E]0 and high values of [S]0, the rate of product
formation becomes independent of [S]0, reaching a maximum
value known as the maximum velocity, vmax.
ENZYME INHIBITION
Example: The enzyme carbonic anhydrase catalyses the hydration of CO2 in red
blood cells to give bicarbonate ion:
CO2 + H2O → HCO3- + H+
The following data were obtained for the reaction at pH = 7.1, 273.5K, and an
enzyme concentration of 2.3 nmol L-1.

[CO2]/(mmol L-1) 1.25 2.5 5.0 20.0


rate/(mol L-1 s-1) 2.78x10-5 5.00x10-5 8.33x10-5 1.67x10-4
Heterogeneous Catalysis
• The catalyst and the reactants are in
different phases
– adsorption the binding of molecules on a
surface.
• Adsorption on the surface occurs on active
sites
– Places where reacting molecules are
adsorbed and physically bond to the metal
surface.
• The hydrogenation of ethene (C2H4 (g)) to
ethane
C2H4 (g) + H2(g)  C2H6 (g)
• Reaction is energetically favourable
– rxnH = -136.98 kJ/mole of ethane.
• With a finely divided metal such as Ni (s),
Pt (s), or Pd(s), the reaction goes very
quickly .
• There are four main steps in the process
– the molecules approach the surface;
– H2 (g) and C2H4 (g) adsorb on the surface;
– H2 dissociates to form H(g) on the surface; the
adsorbed H atoms migrate to the adsorbed C2H4 and
react to form the product (C2H6) on the surface
– the product desorbs from the surface and diffuses
back to the gas phase
Simplified Model for Enzyme Catalysis

• E  enzyme; S  substrate; P  product


E + S  ES
ES P + E
rate = k [ES]
• The reaction rate depends directly on the
concentration of the substrate.
Enzyme Catalysis
• Enzymes - proteins (M > 10000 g/mol)
• High degree of specificity (i.e., they will
react with one substance and one
substance primarily
• Living cell > 3000 different enzymes
The Lock and Key
Hypothesis
• Enzymes are large, usually floppy
molecules. Being proteins, they are folded
into fixed configuration.
• According to Fischer, active site is rigid,
the substrate’s molecular structure exactly
fits the “lock” (hence, the “key”).
The Lock and Key (II)
Photochemical Reactions

• Many reactions are initiated by the


absorption of light.
• Stark-Einstein Law – one photon is absorbed
by each molecule responsible for the primary
photochemical process.

vI  I
I = Intensity of the absorbed radiation
Copyright © 2010 R. R. 63
Dickerson & Z.Q. Li
Primary Quantum Yield

• Define the primary quantum yield, 

# of primary products

# of photons absorbed
Copyright © 2010 R. R. 65
Dickerson & Z.Q. Li
What happens after a chemical species absorbs light?

The primary step of a photolysis reaction is:

X + hv→X*

X* an electronically excited state of molecule X.

X* subsequently undergo either physical or chemical processes:

Physical processes:
Fluorescence X* →X + hv
Collisional deactivation X* + M →X + M

Chemical processes:
Dissociation X* →Y + Z
Isomerization X* →X’
Direct reaction X* + Y →Z1 + Z2
Intramolecular rearrangement X* →Y
Ionization X* →X+ + e
Decay mechanism of excited singlet state
• Absorption: S + hvi → S* vabs = Iabs

• Fluorescence: S* → S + hvi vf = kf[S*]

• Internal conversion: S* → S vIC = kIC[S*]

• Intersystem crossing: S* → T* vISC = kISC[S*]

S* is an excited singlet state, and T* is an excited triplet state.


d [ S *]
The rate of decay = - kf[S*] - kIC[S*] - kISC[S*]
dt

• When the incident light is turn off, the excited state decays exponentially:

t / 0 with
[ S*]t  [ S*]0 e 0 
1
k f  k IC  k ISC
• If the incident light intensity is high and the absorbance
of the sample is low, we may invoke the steady-state
approximation for [S*]:
Iabs - kf[S*] - kIC[S*] - kISC[S*] = 0
Consequently,
Iabs = kf[S*] - kIC[S*] - kISC[S*]
The expression for the quantum yield of fluorescence
becomes:
vf kf
f  
I abs k f  k IC  k ISC

• The above equation can be applied to calculate the


fluorescence rate constant.
Quenching
• The presence of a quencher, Q, opens an additional channel for
deactivation of S*
S* + Q → S + Q
vQ = kQ[Q][S*]

Now the steady-state approximation for [S*] gives:


Iabs - kf[S*] - kIC[S*] - kISC[S*] - kQ[Q][S*] = 0

The fluorescence quantum yield in the presence of quencher


becomes
kf

k f  k IC  k ISC  kQ [Q ]

• The ratio of Φ/ Φf is then given by


f
 1   o kQ [Q]

• Therefore a plot of the left-hand side of the above equation against
[Q] should produce a straight line with the slope τ0kQ. Such a plot is
called Stern-Volmer plot. (fluorescence intensity and life time)
Photochemistry of the simplest carboxylic acid

H°(kcal/mol)
HCOOH + hn → CO + H2O 6.3
→ CO2 + H2 -3.5
→ HCO + OH 96.8
→ HCOO + H 106.1
→ H + COOH 91.1

CO(n→p*)
S1←S0
s(193nm)=0.8x10-19 cm2
Ephoton(193nm)=148 kcal/mol
Formic acid (FA)
(trans)
H. Su et al., J. Chem. Phys. 113, 1891 (2000).
Photochemistry of FA in gas phase

IR emissions

HCO(2A´)+OH(2P)

H2O+CO

H2+CO2
t-HCOOH

[CO]/[CO2] ≈ 11

H. Su et al., J. Chem. Phys. 113, 1891 (2000).


Photosensitization

• Transfer of excitation energy from one


molecule (the photosensitizer) to
another nonabsorbing species during a
collision..
254 nm
Hg  Hg 
Hg  H 2  Hg  2H 

Hg  H 2  HgH  H 
Photochemical experimental setup

UV atmosphere dopant
beam vacuum gas
pH2
crystal

FTIR
beam

optical
radiation
substrate
shield
pH2
gas
FA 193 nm photolysis products in solid pH2

monomer
P=3.5 mW CO monomer CO2
0.3 3
20 Hz
15 min
[FA]i = 18 ppm
vdw
0.2 clusters 2
log10(I0/I)

HOCO

CO-HCOOH
radicals

CO-H2O
0.1 HCO 1

after

before
0.0 0

1840 1850 1860 2140 2150 2160 2342 2344 2346 2348

wavenumber / cm-1