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Reaction Mechanisms:

Reaction mechanism is a collection of elementary (one step)

reactions that would add up to result in the overall reaction.
Generally elementary (simple) reactions are bimolecular
Complex Reaction Mechanisms and unimolecular, rarely are termolecular.
Chapter 36
Experimentally determined rate law does not conform with
the stoichiometric coefficients of reactions, in general;
unless the mechanism itself is simple. Therein lies the need
to propose a mechanism for the reaction.

A valid reaction mechanism must be consistent with the

experimental rate law.

For example; Proposed mechanism:

Rate Law is of the ‘form’; R  k[ N 2O5 ]

The form of the rate law signals that the reaction involves
Reaction rate law can be written as;
multiple steps (a ‘complex’ mechanism).

Mechanisms involve many single step reactions (sum of -

them is the overall reaction), creation of intermediates
(allowing use of steady state approximation) and equilibria.

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Invoking SSA for NO and NO3.

[NO] =

Pre-equilibrium Approximation:
A useful concept for reactions that can proceed via an
equilibrium involving an intermediate I.
(1)

and rate=
(2)
Viola!!

Upon rearrangement

Substituting for [I]

in rate expression

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Reaction Experiment Lindeman Theory – Unimolecular Reactions:

R=
Mechanism: Pre-equilibrium
The energy necessary to overcome the activation energy
is achieved by collisions with any molecule (M) and M
can very well be A itself. Two steps involved.
Decay of intermediate In gas phase the reaction constants are concentration,
(i.e. pressure (total)) dependent.

In solution it is not concentration dependent, due to the

fact that the particle concentration is nearly constant in
solution phase.

Lindeman Theory – Unimolecular Reactions: Lindeman Theory – Uni-molecular Reactions:

The energy necessary to overcome the activation energy

In general
is achieved by collisions with any molecule M and M
(solutions/
can very well be an A. Two steps are involved, formation
gases);
of A* (activated reactant not an activated complex) and
decomposition of A* to form products.
For M=A
The pre-
equilibrium
step.

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Reaction rate =
For k-1[A]>>k2 For k-1[A]<<k2
Applying SSA to A*.
uni bi

True for [A] large.



Reaction rate =

For the general case - Lindeman Theory :

Reactions in
solutions or gases at
high pressure -
k-1[A] >>0 .
uni

[M] ~ constant
kapp = kuni is not
with
[A] large simplistic.

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Catalysis
Upon rearrangement; Reaction progress: Energy diagram
Increasing reaction rates
Part of Ea – energy required to
amounts
overcome to increasing
repulsive forces amongreaction
rate constants.
electron clouds of reacting
kuni molecules.

Ea One strategy would be to

>E’a lower E’a. Thereby increase the
E’a fraction of molecules with
Low T
<E’a energy > E’a.
[M]

Catalysis – a mechanism
S-C complex
Reactant = S

Reaction rate;

Applying SSA to SC;

Catalyst remain unchanged after the reaction, it changes

the reaction mechanism by combining with reactant(s)/
intermediates and therefore changes the reaction coordinate.

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Determining reaction
parameters k2 and Km;  Substituting for [S] and [C] in
[SC] =
Intial rate method. and rearranging ;

Substituting for [SC];

Conservation of
matter: @ t = 0, where R = R0

Simplifies to;

yields;

yields; Starting with;

(1) For [C]0 << [S]0 For [S]0 >> [C]0

experimental
conditions

(b) and also if [S]0 > Km

(a) and also if [S]0 < Km

k2
R0  [C]0 [S]0
Km
[R]0 linear to [S]0 . At large [S]0, R0 =k2[C]0

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alternatively Again,

(1) For [C]0 << [S]0

invert

(b) if [S]0 >> Km



Reciprocal plot
[R]0 reaches a limiting value and zero order w.r.t. [S] .

Michaelis-Menten Enzyme Kinetics

using;

(2) For [C]0 >> [S]0

enzyme
(a) if [C]0 < Km (b) if [C]0 > Km substrate
k2
R0  [C]0 [S]0 R0  k2 [S]0
Km
[R]0 linear to [C]0 & [S]0 . [R]0 linear to [S]0 .

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Michaelis-Menten Enzyme Kinetics Michaelis-Menten rate law

Enzymes are reaction specific catalysts. For [E]0 << [S]0; Rate =

Km= Michaelis-Menten constant

and also if [S]0 >> Km above equation simplifies to,

Mechanism
The reaction rate plateau is at k2[E]0

Lineweaver-Burk Equation Determination of Km

With Rmax known,

evaluate Rmax/2
substitute in

invert Km?

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Determination of Km Photochemistry – physical processes

With Rmax known, Photochemistry deals with the chemical and physical
evaluate Rmax/2 changes of molecules following absorption of photons
substitute in in the visible/UV region.
Following the absorption of photons molecules undergo
electronic and vibrational and rotational (rotational in
k 2 [S]0 [E]0 R [S] gas phase ) excitation (photoexcitation).
R0   max 0
[S]0  K m [S]0  K m h
A   A*  A( radiatively ) physical
Rmax Rmax [S]@Rmax /2
 A( non  radiatively ) processes
2 [S]@Rmax / 2  K m
[S]@Rmax /2  K m  2[S]@Rmax / 2 Photoproducts
K m  [S]@Rmax /2 A * =excited molecule

h
Photo-excitation; A  P I0 I 010 l [ A]

Rate of A undergoing photo excitation; d[A]

= -k[A] Monochromatic beam
dt
I0
P I abs  I 0  I 010 l [ A]
I 010 l [ A]
h
 = molar absorptivity

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d [A]
  I abs
dt
Keeping I0 a constant and l = 1, substitute for Iabs;
Setting [A] low,
d [A]
  I 0 ( 2.303) [ A] First order loss
 l [ A] dt
 I abs  I 0 (1  10 )


d [A]
  I 0 ( 2.303) [ A] 2
dt Jablonski Diagram 7
(2’) 4
In terms of number of molecules; A = # molecules of A, (paths)
3 5
12’ (2’) 3 F
8
12456 P 9
 ka
4, 8 ISC T  S
6
1
7 IC S1S0
2, 5, 9 VR
A = absorption cross section.

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Jablonski Diagram shows the electronic states of a

molecule and the photo-physical transformations between
them in an energy diagram.

The energy states are grouped horizontally by their spin

multiplicity.

Non-radiative transitions are shown by wavy arrows and

radiative transitions by straight arrows.

The vibrational ground state of each electronic state is

indicated by heavy lines.

Kinetics of photo-physical processes

* Quenching: Excited molecules can lose its energy by way
of collisions with other molecules (quenchers) and thereby
relax non-radiatively. This must be considered another
kinetic process.

Kasha’s rule: Photon emission (fluorescence or

phosphorescence) occurs only from the lowest-energy
excited electronic state of a molecule.

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[S1] = [P]
Applying SSA to S1.
quencher q introduced

d [S1 ]
kq  ka [ S0 ]  ( k f  kic  k iscS  kq [Q])[ S1 ]
dt

Define

SSA
[S0] = [A]

Fluorescence yield: f

 kf Parallel reactions (elementary)

kic
S1 kisc

kq[Q]

Florescence

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Fluorescence yield: f

1. invert

2. substitute

# photons emitted as fluorescence


1 1 1 1 k f  kic  kisc  kq [Q]
# photons absorbed  
I f ka [S]0 k f  f ka [S]0 kf

Stern-Volmer Plot

If k f  kic and kisc

kq
with no quenching, we get pure flourescence I 0f slope 
kf
1 1
0
  I 0f  ka [S]0
I f ka [S]0

:Q present and
kf dominating

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[S1]
Measurement of f
time
Excite molecules with a short pulse of photons, monitor
decay afterwards.

Creates S1 species, with excitation turned off monitor the time

fluorescence decay of S1.
For S1;


1 1
ln[ S1 ]  ln[ S1 ]0  t  ln[ I f ]  ln[ I f ]0  t
f f

Plot
If conditions are such that k f  kic and kisc
1 1
f  
k f  kic  kisc  kq [Q] k f  k q [Q ] slope  kq
intercept  k f

kq
SVE  slope 
kf

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