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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)
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
d[C]
k 1 [A]
dt
Simple empirical rate law
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
- 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
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
Initiation
Propagation
Explosions
• Thermal explosion: a very rapid reaction arising from a rapid increase of
reaction rate with increasing temperature.
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.
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
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
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
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
• 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.
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
Unstable radical
Ri ki M I
Chain Growth Polymerization
Rp k p M M
(3) Termination
Rt 2k k M M 2 Rt M
2
Chain Growth Polymerization
(3) Termination
(b) Disproportionation
k td
k td
Rt 2k k M M 2 Rt M
2
Chain Growth Polymerization
(4) Chain Transfer
υ =4,000/4 =1,000
Determined by steps 1, 2, 3. (Initiation, propagation, and termination)
(No chain transfer)
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
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;
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.
• 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:
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
• 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
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.
vI I
I = Intensity of the absorbed radiation
Copyright © 2010 R. R. 63
Dickerson & Z.Q. Li
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?
X + hv→X*
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
• 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
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
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