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Quenching:
A quenching process is defined as one which competes with the spontaneous emission
process and thereby shortens the lifetime of the emitting molecule. These quenching reactions
are energy transfer or electron transfer processes. Quenching may be classified into three
types.They are,
A* + A A + A + heat
2. Impurity quenching: In impurity quenching the excited molecule loses its energy as
heat by collision with the molecule of impurity present in the system.
A* + Q A + Q + heat
3. Solvent quenching: In solvent quenching the excited molecule A* loses its energy as
heat by collision with the solvent molecule.
A* + S A + S + heat
Initially the normal molecule A goes to an excited state by the absorption of incident
A A* Rate= Ia
radiation.
The rate of formation of A* depends upon the intensity of incident radiation(I a).In the
absence of any quenching molecule the excited molecule A* is deactivated by the following
three processes
Where [A*]o is the concentration of the excited molecule A* in the absence of quenching
molecule.
Stern-Volmer equation Stern-Volmer equation is the kinetic pattern which accounts for
the quenching of the excited donor by the acceptor.
Under steady illumination, according to steady state approximation the rate of formation of
an excited molecule A* is equal to its rate of deactivation and the concentration of A*
remains constant.
=0
i.e., Ia = kf[ +
=[
[
(1)
fo=kf[A*]o /Ia
(2)
A* + Q A + Q Rate=kq[A*][Q]
=[
[ (
3)
0f kf k +k + K ISC + k q [Q]
= X f IC
f k f + k IC + K ISC kf
= 1+
(5)
This eqn is Stern-Volmer eqn and k SV is called Stern-Volmer constant. Ksv is the ratio of
bimolecular quenching constant to unimolecular decay constant and has the dimension of
litre/mole.It implies a competition between the two decay pathways and has the character of
the equilibrium constant.
Calculation of Ksv
The actual life time of the fluorescence molecule in the absence of bimolecular quenching ()
ksv = kq .
The value of is measured experimentally, the ratio of Ksv/ gives the rate constant k q for
the bimolecular quenching step. For efficient quencher Ksv=102-103 l mol-1 and =10-8S,then
This value of kq is almost equal to collision frequency (or encounter frequency). This shows
the quenching step is a diffusion controlled process.
The rate constant for quenching Kq can also be calculated from the condition of 50%
quenching. If [Q]1/2 is the concentration of the quencher when the solution is half quenched
Fron eqn 5
=1+
This eqn shows that the Ksv = reciprocal of [Q] 1/2, half-quenching concerntration or half
value concerntration Ch.