UV visible spectroscopy

Electronic Transition

( σ → σ* )
Eg:- saturated alkanes

(n → s* )
Eg:- Oxygen , Nitrogen & Sulphur

(n → p*)
Eg:- Saturated aliphatic ketones

(p → p*)
Eg:- Conjugated Dienes / carbonyl compound

Chromophore

Auxochrome

An auxochrome is a group of atoms
attached to a chromophore which
modifies the ability of that chromophore
to absorb light

Also called as colour enhancing group
Eg:- NH2 , OH , NHR, OR

Spectral Shift

Bathochromic shift ( Red shift)

Hyperchromic effect

Hypochromic effect

Chromophore was considered a system
responsible for imparting colour to the compound..

I. Independent chromophore:-
single chromophore is
sufficient to import color to the
compound e.g. Azo group

II. Dependent chromophore: -
When more than one chromophore
is required to produce color.
e.g. acetone having one
ketone group is colorless

.

INSTRUMENTATION of UV/VISIBLE :-

Sources (UV and visible)

Tungsten / Halogen
Hollow Cathode Discharge Lamp
Deuterium Arc Lamp
Hydrogen discharge lamp
Mercury discharge lamp

MONOCHROMATORS-

1-Grating Monochromator:-
• Reflection grating
• Echellette Reflection Grating

2- Prism monochromators

CUVETTE (sample container)

Quartz or fused silica cuvettes are required

DETECTORS

The photomultiplier tube

The linear photodiode array

Charge-Coupled Devices (CCDs)

UV-Vis Spectrophotometers

  1. Single beam

2.Double beam

Beer-Lambert’s law

A = abc

A= Absorbance
a= Absorptivity
b= path length
c= Concentration of solution

Limitation of Beer-Lamberts
law

fluoresecence or
phosphorescence

scattering of light

stray light

non-monochromatic radiation

The linearity is limited by chemical
and
instrumental factors.

Hypsochromic Shift
( Blue shift)