Spectroscopy

Fundamentals of Molecular Spectroscopy by

C. N. Banwell /

Any book on spectroscopy

Spectroscopy
Violet: 400 - 420 nm

Indigo: 420 - 440 nm

Blue: 440 - 490 nm

Green: 490 - 570 nm

Yellow: 570 - 585 nm

Orange: 585 - 620 nm

Red: 620 - 780 nm

 Color

Carotene

Hemoglobin
 Color of Coordination Complexes
d
Color of Coordination Complexes: Gem
d
stone

Ruby : Al2O3 with chromium

impurity
Electromagnetic Spectrum
 Beer Lamberts Law

Law: When a monochromatic light is passed through a solution the decrease

In intensity of light with the thickness of the solution is directly proportional to
the intensity of the incident light and the concentration of the solution.

A is absorbance A=xcxl
From atom to molecules
d
Electronic Transitions
 d
Absorption spectra: Number, Position & Intensity

Absorption
Absorption
[Ru(bpy)3]2+ [Ni(H2O)6]2+
104
10

~14 000 25 000 50 000

200 400 700

UV visible visible UV

nm (wavelength)
cm-1 (frequency)

UV = higher energy transitions - between ligand orbitals

visible = lower energy transitions - between d-orbitals of transition metals
- between metal and ligand orbitals
 d

Chromo- Compound Excitation

max, Solvent
phores nm
C=C Ethene to * 171 hexane

CC 1-Hexyne to * 180 hexane

n to
* 290 Hexane
C=O Ethanal to * 180 hexane

n to * 275 Ethanol
N=O Nitromethane to * 200 ethanol

C-X X=Br Methylbromide n to

* 205 Hexane
X=I Methyliodide n to * 255 hexane
 Terminology for Absorption Shifts

Nature of Shift Descriptive Term

Bathochromic
To Longer Wavelength
(Red Shift)
Hypsochromic
To Shorter Wavelength
(Blue Shift)

To Greater Absorbance Hyperchromic

To Lower Absorbance Hypochromic

Effect of Conjugation and solvent
 Effect of Conjugation
d
Color of Coordination Complexes
Splitting d-orbitals
Color in Coordination Complexes

Selection Rules

1. Transitions are
permitted only between
states of same spin
multiplicity i. e. s = 0

2. Only those transitions

are allowed where l = 1
(Laporte Selection Rule)

1. Symmetry is not perfect due to vibration

2. Mixing of d-orbital away from pure ionic bond
 d

Color in Coordination Complexes

d-d transition Charge transfer (CT)
Presence of d-electron Presence of d-electron is not
Laporte forbidden essential. It may occur in d0/d10
systems.
Extinction Coefficient ( 5-200 l
M-1cm-1) Laporte allowed
Not useful in Extinction Coefficient ( 1000-
spectrophotometric estimation 35000 l M-1cm-1)
Very much useful in
spectrophotometric estimation
 Infra-red Spectroscopy

Range : 400 cm-1 - 4000 cm-1

Sample: gas, liquid or solid
Functional Found in Range
group
C=O Aldehyde and 1700-40 cm-1
ketones, Carboxilic
acid
CN Nitriles 2200-80 cm-1

NH amines 3300-3500
cm-1
OH Alcohols 3200-
3400cm-1
CO 2140 cm-1

M-CO Less than

2100 cm-1
C=N Schiff Base 1660cm-1
d

Functional group region

Fingerprint Region
d

CO Stretching CH2 Stretching CH2 Stretching

Symmetric Anti-symmetric

CH2: Scissoring CH2: Rocking CH2: Wagging

-acid ligand
 Hookes Law : Elasticity of chemical bond

req

Energy

E2

E1

Internuclear distance

F = - (k x) Oscillation frequency = 1/2 (k/)

Variation of stretching frequency

Compound CO (cm1)
CO 2143
Ti(CO)62 1748
V(CO)61 1859
Cr(CO)6 2000
Mn(CO)6+ 2100
Fe(CO)62+ 2204
Fe(CO)5 2022, 2000
 Atomic Absorption Spectra -AAS

Atomic Absorption Spectroscopy (AAS) is used principally for the

quantitative determination of metal elements in aqueous and solid
samples from a wide range of fields including
medicine, food and geology. The technique is an
Australian invention ~1950s and since then has become well
established in laboratories around the world.
The essential theory and principles of AAS as well
as its applications and limitations for chemical analysis are important.
This unit concentrates on atomic absorption based on flames.
Flame AAS is widely used, simple, effective and relatively low cost.
Note that this section is written primarily around flame AAS.
ATOMS
Origin of atomic spectra
From molecule to atom

Flame atomization
process
Temp 2100-2800o C
AAS Instrument
Atomic absorption spectra Molecular absorption spectra

1- The outer most electrons occupy The outer most electrons occupy ,
one of the atomic orbitals and have its or n electronic energy in the ground
energy levels [K, L, M, N, ...... .state
s, s,p s,p,d s,p,d,f ]
Upon excitation electrons are- 2 Upon excitation electrons
promoted to any permissible higher raised to * or * energy.
atomic energy levels levels
Since there are no bonds there are-3 Since there are bonds, there are
no vibrational or rotational energy vibrational and rotational energy levels
levels in either the ground or excited in both the ground and excited states
. state
The analytical wavelength is the- 4 .The analytical wavelength is the max
resonance wavelength of the analyte
. The spectra are sharp form- 5 The spectra are in the form
of broad due to the presence
of very close, superimposed
and unresolved vibrational and
rotational energy levels in the
the excited state.