UV-Visible Spectroscopy

Undergraduate
 Interaction of light/EMR with matter
Electromagnetic radiationlight-is a form of energy whose behavior is described by the properties of both waves

and particles. Some properties of electromagnetic radiation, such as its refraction when it
passes from one medium
to another, are explained best by describing light asa wave. Other properties, such as absorption and emission, are

better described by treating light as a particle

Plane-polarized electromagnetic radiation showing the

oscillating electric field in red and the oscillating magnetic field

in blue. The radiation's amplitude, A, and its wavelength, A,

direction
of are shown.
propagation
The wavelength, lambda, is defined asthe distance between

magne successive maxima

For ultraviolet and visible electromagnetic radiation the

wavelength is usually expressed in nanometers (1 nm =10

When matter absorbs electromagnetic radiation it
undergoes a change in energy.

The interaction between matter and electromagnetic radiation is easiest to understand if we assume that
radiation consists of a beam of energetic particles called photons.

When a photon is absorbed by a sample it is "destroyed," and its energy acquired by the sample.

The energy of a photon, in joules, is related to its frequency, wavelength, and wavenumber by the following

equalities
 Increasing Frequency (v)
1024 1022 1020 1018 1016 1014 1012 1010 108 106 104 100 v (s1)
102

Y-rays X-rays Microwave FM AM Long radio waves

Radio waves

10-16 1014 10-12 10-10 10-3 :106 104 102 100 102 104 106 108 (nm)
-.
IncreasingWavelength 0)
Visible Spectrum
IypesofAtomic & Molecular Transitions
rays: nuclear
X-rays: core-level electrons
Ultraviolet(UV):valence electrons
Visible (Vis): valence electrons
Infrared (IR): molecular vibrations
Microwave: molecular roations; electron spin
400 500 600 700 Radio waves: nuclear spin

IncreasingWavelength ()in nm-

 Introduction to UV spectroscopy

Vibrational levels Absorption of ultraviolet and visible radiation leads to a change

V
ELECTRONIC EXCITEDSTATE in the analyte's electronic energy levels and, possibly, a change
in vibrational energy as well.

>Achange in vibrational energy without a changein electronic

energy levels occurs with the absorption of infrared radiation.

Vibrational levels
The energy difference is 125 to 650 kJ/mol

ELECTRONIC GROUND STATE

 Electronic energy level and transitions
-* b)
}Unoccupied
Slevels
n-
Energy

TT Occupied levels

In alkanes

In carbonyl compounds

Tt* In alkenes, carbonyl compounds,alkynes,

Increasing energy azo compounds,and so on

Inoxygen, nitrogen, sulfur, and

halogen compounds
In carbonyl compounds
 UV/Vis Spectra for Molecules and lons
The valence
o, pi

,
electrons

bonding,

antibonding,
in organic molecules

T, and non-bonding,
molecular orbitals

Four types oftransitions

The bonds, functional groups,
and polyatomic

n, molecular

are slightly higher

or molecules responsibie
orbitals

in
ions, such as CO,occupy quantized
(MOs). Unoccupied sigma antibonding,

energy.

between quantized energy levels account for most molecular UV/Vis spectra.

Transiton Waveength Range

sigma bonding,
s,

Sxamples
and pi

for these transitions.

<200 nm C-C, C-H
These transitions, the most important are nT*
and TTT* nm
160-260 H,0,CH,OH, CH,CI
These transitions involve important functional groups
nm
that are characteristic of many analytes and TT 200-500 C-C,C-0,C=N, C=C
because the wavelengths are easily accessible.
The bonds and functional groups that give rise to nT 250-600 nm
C-0,C-N, N=N, N=O
the absorption of ultraviolet and visible radiation

are called chromophores.

The valence
o, pi
UVVis Spectra for Molecules and
electrons in organic molecules

bonding,

antibonding,

Four types
T, and non-bonding,

T, molecular orbitals
and polyatomic ions, such as

n, molecular

are slightly higher

orbitals

in energy.
CO, occupy quantized
(MOs). Unoccupied
lons

sigma antibonding,

oftransitions between quantized energy levels account for most molecular UV/Vis spectra.
,
sigma bonding,
and pi

The bonds, functional groups, or molecules responsible

Transition Wavelength Range Examples
for these transitions.
<200 nm C-C,C-H
These transitions, the most important are n-T*
and TTTT* nm
160-260 H,0,CH,OH, CH,CI
These transitions involve important functional groups
that are characteristic of many analytes and 200-500 nm C-C,C-0, C-N, C=C
because the wavelengths are easily accessible.
T
The bonds and functional groups that give
the absorption of ultraviolet and visible radiation
rise to nT 250-600 nm
C-0,C-N,N=N,N=O

are called chromophores.

 Effect of substituent on absorption
1. to lower energy or
Bathochromic shift (red shift)-a shift
longer wavelength.
2. Hypsochromic shift (blue shift)-a shift to higher energy or shorter wavelength.

3. Hyperchromic effect -an increase in intensity.

4. Hypochromic effect-a decrease in intensity.

 Effect of conjugation
Compound Amax nm Ema

203 8.000

CH-CH 244 12.000

CH-O 244 15,000

250 18.000

295 27,000
CH-CH (trans)
Effect of auxochromic substituent

Compound Amaxnm Ema

203 8.000

-OH 6.200
210

-o@Na 235 9,400

226 13,000

NH2 230 8,600

In ethanol or water
 UV absorption by metal ion
Many transition metal ions, such as Cu2tand Co*, form colorful solutions because the metal ion absorbs

visible light.

The transitions giving rise to this absorption are valence electrons in the metal ion's d-orbitals.

>For a free metal ion, the five d-orbitals are of equal energy.

In the presence of acomplexing ligand or solvent molecule, however, the d-orbitals split into two or more

groups that differ in energy.

>For example, in an octahedral complex of Cu(HO)2* the six water molecules perturb the d-orbitals into

two groups, as shown in Figure. d2 day2

The resulting d-d transitions for transition metal ions are relatively weak.

hv

Splitting of the d-orbitals in an octahedral field. dxy dxz dyz

 UV absorption by metal complexes
A more important source of UVNis absorption for inorganic metal-igand complexes is charge transfer, in which

absorption of a photon produces an excited state in which there is transfer of an electron from the metal, M, to
the ligand, L.
M-L +v (M'-L)*
Charge-transfer absorption is important because it produces very large absorbances.

One important example of a charge-transfer complex is that of o-phenanthroline with Fe2*, the UVVis spectrum
for which is shown in Figure.

Charge-transfer absorption in which an electron moves from the ligand to the metal also is possible.
 UV absorption by metal atom
The energy of ultraviolet and visible electromagnetic radiation is sufficient to cause a change in an atom's valence

electron configuration.

Absorption of a photon is accompanied by the excitation of an electron from a lower-energy atomic orbital to an
orbital of higher energy.

Not all possible transitions between atomic orbitals are allowed. 40

Forsodium the only allowed transitions are those in which 5s
there is a change of #1 in the orbital quantum number (); 4p

330.3
3d
thus transitions froms-p orbitals are allowed, and 4AS
1140.4 330.2
818.3

transitions from s dorbitals

are forbidden. 1138.3
819.5

3p
589.6 589.0
 Transmittance and Absorbance
As light passes through a sample, its power decreasesassome of it is absorbed.

This attenuation of radiation is described quantitatively by two separate, but related terms: transmittance and

absorbance.

T2P
(a) Schematic diagram showing the attenuation of
(a)

radiation passing through a sample; Po is the radiant Po

power from the source and Pr is the radiant power

transmitted by the sample.

(b) Schematic diagram showing how we redefine

P0 as the radiant power transmitted by the blank.
Po
 Recording 00:41:39

Principle of UV (absorption) spectroscopy

Beer-Lambert Law
When monochromatic electromagnetic radiation passes through an infinitesimally thin layer of sample of thickness

dx, it experiences a decrease in its power of dP

The fractional decrease in power is proportional to the sample's thickness and the analyte's concentration, C; thus

aCds

where Pis the power incident on the thin layer of sample, and a is a proportionality constant. Integrating the
equation

Converting the In into log and after substitution

In abc
A -abC A= EbC
where a is the analyte's absorptivity with units of cm1 conc-1. If weexpress Po P- P-dP PT
the concentration using molarity, then we replace a with the molar
absorptivity, e, which has units of cm-1 M-1 X=0 X=b
dx