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=
(6)
where
a
a
sv
k DR N
k DR N
K
+
=
' 4
' 4
0
, ' N is the Avagadros
number (per millimole), D is the sum of the diffusion
coefficients (mutual diffusion coefficient) of the
reactants and R is the reaction distance at which the
reaction proceeds, k
a
the activation energy controlled
rate constant. A plot of
1
sv
K against [Q]
1/3
becomes
linear with negative slope. Mutual diffusion
coefficient D becomes directly accessible from the
slope of the graph exemplified in Eq. (6) and K
sv
is
obtained at [Q] = 0 regardless of the relative
magnitudes of k
a
and k
d
(=4N
'
D R), irrespective of
quenching is diffusion limited or not.
Therefore according to Eq. (6) we need to
determine the values of
1
sv
K and [Q]
1/3
. Where K
sv
=
[(I
0
/I)-1]/[Q] and [Q] the quencher concentration
from 0.02 to 0.1 M. For efficient quenching processes
(concentration dependent) the value K
sv
is often
observed to increase with [Q]. Hence, the values of
K
sv
were determined at each quencher concentration
in all the solvents and the values of
1
sv
K are also
determined. Fig. 3 shows the plots of
1
sv
K against
[Q]
1/3
. From these figures we see that all the plots in
different solvents are almost linear and small
deviation may be due to experimental uncertainties.
Hence, the linear dependence of
1
sv
K on the one-third
power of quencher concentration within the error
limits is confirmed
10
. Then the least square fit value of
0
sv
K (S-V constant at [Q] =0) was obtained from the
intercept of the plot of
1
sv
K against [Q]
1/3
. Similarly,
mutual diffusion coefficients D were determined from
the slope of the Eq. (6) by least square fit method and
the values of
0
sv
K and D are presented in Table 2.
Using these values of
0
sv
K and D, the distance
parameter R
'
was determined and the values are
presented in the Table 2. In our case R
'
>R in all the
solvents and hence the values of k
a
cannot be
determined. According to J oshi et al.
21
the
bimolecular reactions are said to be diffusion limited
if the values of k
q
are greater than 4N
'
R
'
D. Hence the
values of 4N
'
R
'
D are calculated using the
experimentally determined values of R
'
and D of
Eq. (6) and are presented in the Table 2. In all
solvents the values of k
q
are greater than 4N
'
R
'
D,
which is an expected result for diffusion limited
reaction
21
(Table 2).
Here we made an attempt to compare the results
obtained for anthracene +aniline system with that of
anthracene +CCl
4
obtained by others
7,8
. The values of
K
sv
obtained for anthracene +aniline system are high
compared to anthracene +CCl
4
system. Further, for
anthracene +CCl
4
they have observed an increase in
K
sv
with increase in dielectric constant of the solvent.
Similar trend was observed for the present anthracene
+aniline system (for example for cyclohexane K
sv
=
4.534 m
-1
and for ethanenitrile K
sv
=10.204 m
-1
). This
effect of dielectric constant suggests the charge
INDIAN J PURE & APPL PHYS, VOL 42, SEPTEMBER 2004
652
transfer character in the excited complex. The high
value of K
sv
in polar solvent ethanenitrile compared to
non-polar solvents (benzene, toluene, heptane and
cyclohexane) can be explained by the greater charge
transfer character of the exciplex in the polar
solvent
22
.
From the ongoing discussion we conclude that
quenching reaction is diffusion limited and both static
and dynamic quenching processes are partly playing a
role in the quenching mechanism. Charge transfer
nature of the excited complex is observed in the
present work.
Acknowledgement
The authors are greateful to Prof. B G Mulimani,
Chairman, Department of Physics, Karnataka
University, Dharwad, for providing facilities to carry
out experiments.
References
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Fig. 3 Plots of
1
sv
K versus [Q]
1/3
in different solvents
Table 2 Values of
0
sv
K (steady state quenching constant at
[Q] =0), mutual diffusion coefficient D, distance parameter R
'
,
4N
'
DR
'
and quenching rate parameter k
q
Solvent
0
sv
K
(m
-1
)
D 10
-5
(cm
2
s
-1
)
R
'
() 4N
'
R
'
D 0
9
(m
-1
s
-1
)
k
q
10
9
(m
-1
s
-1
)
Benzene
Toluene
Heptane
Cyclohexane
Ethanenitrile
14.06
12.95
16.77
16.47
37.59
0.325
0.295
0.466
0.388
0.917
11.66
11.83
9.70
11.44
11.05
2.868
2.641
3.424
3.361
7.671
3.355
3.099
4.130
4.060
10.393