DERIVATIVE SPECTROSCOPY

In Chemistry, Analytical methods based on

measurements of UV or visible light absorption
belong to the most popular and most often used in
laboratory practices.
Its Commercially available apparatuses are cheap
and easy for operation. Spectroscopy procedures
usually are not time and labor-consuming. The
economical aspects of UV-Vis techniques is worth
emphasizing as it is easily accessible and is a basic
equipment available in all laboratories.
The main disadvantage and limitation of the
spectroscopy is its low selectivity.

One of the simplest method for increasing a selectivity is

derivitisation of spectra. this operation allows us to
remove spectral interferences and as a consequence, leads
to the increase selectivity of assay.

Historically, the beginning of derivative spectroscopy is

dated on 1953 when the first analogue spectroscopy was
build by Singleton and Cooler.

But the fast development of this technique started in

70-s of twentieth century, when new generation of
spectroscopy controlled by computers were constructed.

So what is Derivative Spectroscopy?...

1
DERIVATIVE SPECTROSCOPY:
Derivative spectroscopy involves the conversion of a normal
spectra to its first, second or higher derivative spectra. The
normal spectrum is known as fundamental, zero order or D0
spectra.
The first derivative spectrum (D1) is a plot of the rate of change
of absorbance with wavelength against wavelength, i.e. plot of
A/ vs. .
The second derivative spectrum is a plot of 2A/ 2 vs. .
Not only can the first and second derivative of the absorbance
spectrum be obtained, but up to the fourth derivative is possible.
However, as the differentiation order increases, the noise
increases as well, and if a lower derivative is fine, going to
higher derivatives is a waste of time and effort.

The next slide will show how mathematically the

derivatives are graphed

2
 45

The absorption spectrum of methylene blue (D) and its fourth derivative (DIV)

46

3
 47

Fig. 2.18 Dynamics of

absorption spectra change:
(a) KMnO4 and (b) KNO3 in
dependence on
the order of derivative

48

4
49