Professional Documents
Culture Documents
Dr. B. R. Thorat
Department of Chemistry
Govt. of Maharashtra, I. Y. College, Jogeshwari (E),
Maharashtra 400060
29.10.2008
In interactions with matter, visible light primarily acts to set elevate electrons to higher
energy levels. White light may be separated into its spectral colors by dispersion in a prism.
Absorbance (A)
Negative logarithm to the base 10 of transmittance or logarithm to the base 10 of
reciprocal of transmittance
A = -log T = log (1/T) = log(I0/It)
When beam of light is incident on homogeneous medium, a portion of the incident light
(I0) is absorbed (Ia), some can be reflected (Ir) and remaining can be transmitted (It) with
net effect of intensities.
I0 = Ia + Ir + It
The amount of reflected radiations (Ir) is so small nearly 4%;
I 0 = Ia + I t
A l
A is absorbance and l
is path length of
solution
I0
dl
I-dI
It
-dI/I = k1 x dl
l
A = -log T
= log (1/T)
-dI/I = k1 dl
-ln I = k1 x l + C1 Put Put l = 0, therefore I = I0, Therefore -ln I0 = C1
- ln I = k1 x l - ln I0.
ln I0 - ln I = k1 x l.
T = I/I0
ln (I0/I) = k1 x l.
ln (1/T) = k1 x l
log (1/T) = k1/2.303x l
A = K1 x l
Ac
A is absorbance and c is
concentration of
solution
- dI/I = k2 x dc.
dI is small change in intensity of incident
radiation, negative sign indicates decrease in
intensity with increases concentration of solution
dc. k2 is proportionality constant
-dI/I = k2 dc
- ln I = k1 x c + C2 Put l = 0, therefore I = I0 & - ln I0 = C2
- ln I = k2 x c - ln I0
ln I0 - ln I = k2 x c
T = I/I0
ln (I0/I) = k2 x c
A = -log T
ln (1/T) = k2 x c
= log (1/T)
log (1/T) = k2/2.303x c
A = K2 x c
A (l x c)
A=Kxlxc
A=axlxc
A=xlxc
K = a, When c is in
gm/lit or ppm
Surface Interference,
Scattering, Reflection,
Fluorescence &
Phosphorescence, etc
Real Deviations
(conc.)
It should be less than
0.01M to avoid
intermolecular forces
Instrumental Deviations
Use monochromatic light,
Stray radiations (reflected
and refracted radiations),
Slit width, Monochromator
of instrument not gives light
of desired wavelength.
Chemical Deviations
Molecules or ions
undergoes dissociation,
association, fragmentation,
rearrangement, etc.
4 C6H5CH2OH
(C6H5CH2OH)4
(monomer)
2 (Cr2O7)
(Orange)
2-
+ OH2
(tetramer)
2 HCrO4
2-
2 H + 2 (CrO4)
(Yellow)
Chemical Deviations
Molecules or ions undergoes dissociation, association, fragmentation, reaarrangement, etc.
Instrumental error
Moderate to high selectivity: Often a wavelength can be found at which the analyte alone
absorbs. Furthermore, where overlapping absorption bands do occur, corrections based on
additional measurements at other wavelengths sometimes eliminate the need for a separation
step.
Good accuracy: The relative errors in concentration encountered with a typical
spectrophotometric or photometric procedure lie in the range from 1% to 5%. Such errors
can often be decreased.
Ease and convenience: Spectrophotometric and photometric measurements are easily and
rapidly performed with modern instruments. In addition, the methods lead themselves to
automation quite nicely.
A stable source of
radiant energy
cuvette
Sources
Movable
Movable
cuvette
The sample must therefore be placed in a transparent container to allow measurement. These
containers are called cuvettes.
Cuvettes are generally made from transparent plastic, glass, or quartz. Different cuvettes have
different optical properties.
Plastic cuvettes are increasingly popular because they do not shatter when dropped, and
because their low price makes them disposable. However, plastic cuvettes tend to have
considerable absorbance in the ultraviolet.
Performing measurements in the far ultraviolet (below ~250 nm) requires relatively
expensive (and relatively fragile) quartz cuvettes. Glass cuvettes are also opaque in the
ultraviolet; unlike plastic cuvettes, glass cuvettes are effectively identical in physical
appearance to quartz cuvettes.
Plastic cuvettes
Glass cuvettes
quartz
Detector
PMT
photodiode
CCD
Photometric titration
Principle of Photometric titration: The titration can be represented as