Application of Ultraviolet/Visible Molecular Absorption Spectros
Application of Ultraviolet/Visible Molecular Absorption Spectros
Application of Ultraviolet/Visible Molecular Absorption Spectros
Ultraviolet/Visible
Molecular
Absorption Spectroscopy
Absorption - Relaxation
Absorbing Species
M + h -----> M* -----> M + heat
Types of Transitions
Three types of transitions
1. , , and n electrons
2. d & f electrons
3. charge transfer electrons
Types of Transitions
Electron distribution in sigma and pi
molecular orbitals
Types of Transitions
Types of molecular orbitals in
formaldehyde
Absorbing Species Containing
, , and n Electrons
Anti-bonding
n
n Nonbonding
Bonding
Bonding
Types of Transitions
-----> * vacuum UV
UV Spectra
Ultraviolet
spectra for
typical organic
compounds
Visible Spectra
Ultraviolet
absorption spectra
for 1,2,4,5-tetrazine
(a.) in the vapor
phase, (b.) in
hexane solution, and
(c.) in aqueous
solution
Types of Transitions
n -----> *
normally below
200 nm
Some Examples of
Absorption Due to
n -> * transitions
Types of Transitions
n -----> * 200-700 nm
low (10 -> 100)
Types of Transitions
Absorption
Characteristics of
Some Common
Chromophores
Types of Transitions
Effect of Multichromophores on Absorption
Types of Transitions
Absorption Characteristics of Aromatic Compounds
Types of Transitions
2. d & f electrons
3. charge transfer electrons
Absorption by Elements of the
First and Second Transition Series
Ligand Field Theory
Electron-density distribution in the five d-orbitals
Absorption by Elements of the
First and Second Transition Series
Effect of Ligands on
Absorption Maxima
Associated with d ->
d transitions
Charge-Transfer Absorption
max > 10,000
Solvents for UV-Visible Regions
Analysis of Mixtures of
Absorbing Substances
Selection of Wavelength
Absorption spectrum
of a two-component
mixture
Analysis of Mixtures of
Absorbing Substances
Solution of Binary Mixture
"Schematic representation of the
absorption spectra of solutions containing
(1) c1 moles per liter of substance 1
(2) c2 moles per liter of substance 2
(3) c1 moles per liter of substance 1 and c2
moles per liter of substance 2."
Solution of Binary Mixture
Wavelength 1
Am,1 = a1,1*b*c1 + a2,1*b*c2
Am,1 = (a1,1*c1 + a2,1*c2)*b
Wavelength 2
Am,2 = a1,2*b*c1 + a2,2*b*c2
Am,2 = (a1,2*c1 + a2,2*c2)*b
Solution of Binary Mixture
let A1 = Am,1 A2 = Am,2
D1 = a1,1 D2 = a1,2
E1 = a2,1 E2 = a2,2
A2 = (D2*c1 + E2*c2)*b
Solution of Binary Mixture
solve for c2
A2/b = (D2*c1 + E2*c2)
c2 = (A2/(b*E2) - (D2*c1)/E2
Solution of Binary Mixture
then
A1 = (D1*c1 + E1((A2/(b*E2)-(D2*c1)/E2))*b
and
C2 = (A2/(E2*b) - (D2*c1)/E2
Method of Standard Addition
Al c s Vs
cx = ---------------
(A2 - Al )Vx
HP8452a Spectrometer
"Time-Based Scan Reports"
"Time-Based Scan Reports"
Solution of Binary Mixture
Photometric Titrations
Photo-acoustic spectra
of smears of blood and
blood components