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UV-VIS Molecular

Spectroscopy
Chapter 13-14
From 190 to 900 nm!

Reflection and Scattering


Losses

LAMBERT-BEER LAW
Psolution
P
T

Psolvent
P0

Power of
radiation after
passing
through the
solvent
Power of radiation
after passing
through the
sample solution

A log T log
P0
A abc kc
a absorptivity
b pathlength
c concentration

Absorption Variables

Beers law and


mixtures

Each analyte present in the solution


absorbs light!
The magnitude of the absorption depends
on its
A total = A1+A2++An
A total = 1bc1+2bc2++nbcn
If 1 = 2 = n then simultaneous
determination is impossible
Need ns where s are different to solve
the mixture

Assumptions

Ingle and Crouch, Spectrochemical Analysis

Deviations from Beers


Law

I r ( 2 1 ) 2

I 0 ( 2 1 ) 2

Successful at low analyte concentrations (0.01M)!


High concentrations of other species may also affec

Chemical Equilibria
Consider the equilibrium:

A+C

AC

If is different for A and AC then the absorbance


depends on the equilibrium.
[A] and [AC] depend on [A]total.
A plot of absorbance vs. [A]total will not be linear.

Instrumental deviation
with polychromatic
radiation

Effects of Stray Light


PS stray light
T

P PS
P0 PS

A log T
P PS

A log
P0 PS
A abc kc

PS
100
P0

Instrument Noise

Effects of Signal-to-Noise

1
0.9

Bad at High T

0.8

TRANSMISSION

0.7
0.6
0.5
0.4
0.3
0.2

Bad at Low T

0.1
0

10

% RELATIVE CONCENTRATION UNCERTAINTIES

11

Components of
instrumentation:

Sources
Sample Containers
Monochromators
Detectors

Components of
instrumentation:

Sources: Agron,

Xenon, Deuteriun, or

Tungsten lamps

Sample Containers: Quartz,


Borosilicate, Plastic

Monochromators: Quarts prisms and


all gratings

Detectors: Pohotomultipliers

Sources
Deuterium and hydrogen lamps (160
375 nm)

D2 + Ee D2* D + D + h
Excited deuterium
molecule with fixed
quantized energy

Dissociated into
two deuterium
atoms with
different kinetic
energies

Ee = ED2* = ED + ED + hv

Ee is the electrical energy absorbed by the molecule. ED2* is the


energy of D2*, ED and ED are kinetic energy of the two deuteriu

Sources
Tungsten lamps (350-2500 nm)
Blackbody type , temperature
dependent
Why add I2 in the lamps?
W + I2 WI2

Low limit: 350 nm


1)Low density
2)Glass envelope

General Instrument Designs


Single beam

Requires a stabilized voltage supply

General Instrument Designs


Double Beam: Space resolved

Need two detectors

General Instrument Designs


Double Beam: Time resolved

Double Beam Instruments

1.Compensate for all but the most short term fluctua


radiant output of the source
2.Compensate drift in transducer and amplifier

3.Compensate for wide variations in source intensity


wavelength

Multi-channel Design

Molar absorptivities
= 8.7 x 10 19 P A
A: cross section of molecule in cm 2 (~10-15)
P: Probability of the electronic transition (01)

P>0.1-1 allowable transitions


P<0.01 forbidden transitions

Molecular Absorption
habsorption 10-8 sec)
heat (relaxation process)
M* A+B+C (photochemical
decomposition)

Visible Absorption Spectra

The absorption of UV-visible


radiation generally results from
excitation of bonding electrons.
can be used for quantitative and
qualitative analysis

Molecular orbital is the nonlocalized


fields between atoms that are occupied
by bonding electrons. (when two atom
orbitals combine, either a low-energy
bonding molecular orbital or a high
energy antibonding molecular orbital
results.)
Sigma ( ) orbital
The molecular orbital associated with
single bonds in organic compounds
Pi ( ) orbital
The molecular orbital associated with
parallel overlap of atomic P orbital.
n electrons
No bonding electrons

Molecular Transitions
for UV-Visible Absorptions

What electrons can we use for


these transitions?

MO
Diagram for
Formaldehy
de
(CH2O)
H

H
=

=
n=

Singlet vs. triplet

In these diagrams, one electron has been excited


(promoted) from the n to * energy levels (nonbonding to anti-bonding).
One is a Singlet excited state, the other is a Triplet.

Type of Transitions

*
High energy required, vacuum UV range
CH4: = 125 nm

n *
Saturated compounds, CH3OH etc ( =
150 - 250 nm)

n * and *
Mostly used! = 200 - 700 nm

Examples of
UV-Visible Absorptions

LOW!

UV-Visible Absorption Chromophores

Effects of solvents

Blue shift (n- *) (Hypsocromic shift)

Increasing polarity of solvent better solvation of


electron pairs (n level has lower E)
peak shifts to the blue (more energetic)
30 nm (hydrogen bond energy)

Red shift (n- * and *) (Bathochromic


shift)

Increasing polarity of solvent, then increase the


attractive polarization forces between solvent and
absorber, thus decreases the energy of the
unexcited and excited states with the later
greater
peaks shift to the red
5 nm

UV-Visible Absorption Chromophores

Typical UV Absorption Spectra


Chromophores?

Effects of Multiple
Chromophores

The effects of substitution


Auxochrome
function
group

Auxochrome is a functional group that does not absorb in


has the effect of shifting chromophore peaks to longer wa
As increasing their intensity.

Now solvents are your


container

They need to be transparent and do


not erase the fine structure arising
from the vibrational effects

Polar solvents gener


tend to cause this
problem

Same solvent must b


Used when compari
absorption spectra f
identification purpo

Summary of transitions for


organic molecules

* transition in vacuum UV (single


bonds)
n * saturated compounds with nonbonding electrons
~ 150-250 nm
~ 100-3000 ( not strong)
n *, * requires unsaturated
functional groups (eq. double bonds) most
commonly used, energy good range for
UV/Vis
~ 200 - 700 nm
n * : ~ 10-100
*: ~ 1000 10,000

List of common chromophores


and their transitions

Organic Compounds

Most organic spectra are complex


Electronic and vibration transitions superimposed
Absorption bands usually broad
Detailed theoretical analysis not possible, but semi-quantitative or qualitative
analysis of types of bonds is possible.
Effects of solvent & molecular details complicate comparison

Rule of thumb for


conjugation
If greater then one single bond apart
- are relatively additive (hyperchromic shift)
- constant
CH3CH2CH2CH=CH2

max= 184

max = ~10,000

CH2=CHCH2CH2CH=CH2

max=185

max = ~20,000

If conjugated
- shifts to higher s (red shift)

H2C=CHCH=CH2

max=217 max = ~21,000

Spectral nomenclature
of shifts

What about
inorganics?

Common anions n * nitrate (313 nm), carbonate (217 nm)

Most transition-metal ions absorb in the UV/Vis region.

In the lanthanide and actinide series the absorption process


results from electronic transitions of 4f and 5f electrons.

For the first and second transition metal series the


absorption process results from transitions of 3d and 4d
electrons.

The bands are often broad.


The position of the maxima are strongly influenced by the chemical
environment.
The metal forms a complex with other stuff, called ligands. The
presence of the ligands splits the d-orbital energies.

Transition metal ions

Charge-TransferAbsorption
A charge-transfer complex consists of an
electron-donor group bonded to an
electron acceptor. When this product
absorbs radiation, an electron from the
donor is transferred to an orbital that is
largely associated with the acceptor.
1)
2)

Large molar absorptivity (max >10,000)


Many organic and inorganic complexes