Application of Ultraviolet/Visible Molecular Absorption Spectros

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Application of

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

Electronic molecular energy levels


 Anti-bonding



 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

Ligand Field Theory

"Effect of ligand field on


d-orbital energies."
Absorption by Elements of the
First and Second Transition Series
Ligand Field
Theory
Absorption
spectra of some
transition-metal
ions
Absorption by Elements of the
First and Second Transition Series

Ligand Field Theory

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

then A1 = (D1*c1 + E1*c2)*b

A2 = (D2*c1 + E2*c2)*b
Solution of Binary Mixture
solve for c2
A2/b = (D2*c1 + E2*c2)

A2/b - D2*c1 = E2*c2

E2*c2 = A2/b - D2*c1

c2 = (A2/(b*E2) - (D2*c1)/E2
Solution of Binary Mixture
then
A1 = (D1*c1 + E1((A2/(b*E2)-(D2*c1)/E2))*b

A1/b = (D1*c1 + E1((A2/(b*E2)(D2*c1)/E2))

A1/b = (c1(D1 - D2*(E1/E2))+(E1/E2)*(A2/b))

A1/b - (A2/b)*(E1/E2) = c1(D1-D2*(E1/E2))


Solution of Binary Mixture
thus
(A1/b - (A2/b)*(E1/E2))
c1 = -------------------------------
(D1 - D2*(E1/E2))

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

Typical photometric titration curves. Molar absorptivities of the


substance titrated, the product, and the titrant are given by
s, p, and t, respectively
Photo-acoustic Spectroscopy
Block diagram
of a single-
beam photo-
acoustic
spectrometer
with digital
data
processing
Photo-acoustic Spectroscopy

Photo-acoustic spectra
of smears of blood and
blood components

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