MODULE: 4-SPECTROSCOPY

INTRODUCTION
 Spectroscopy deals with the interaction of electromagnetic radiation with matter.
 It measure and interpret the absorption or emission of electromagnetic radiation that
occurs when the molecules, atoms or ions undergo transition from one energy level to
another.
ELECTROMAGNETIC RADIATION
 Electromagnetic radiation is the radiant energy that is propagated through free space
or through a material medium.
Characteristics:
 They show wave particle dual nature.
 They are associated with oscillating electric and magnetic fields perpendicular to each
other and also to the direction of propagation of energy.
 All kinds of electromagnetic radiation travel with the same velocity(c) in vacuum,
3×10⁸m/s.
 The frequency(υ) of a wave is related to wavelength(λ) and velocity(c) of light by
υ=c/λ
 Energy of radiation (E) is related to its frequency, wavelength, wave number(ῡ) by the
equations
E=hυ
=hc/λ
=hcῡ h=6.626×10ˉ³⁴ Js

ELECTROMAGNETIC SPECTRUM
 The orderly distribution of electromagnetic waves according to their frequencies (or
wavelengths) into different regions is called electromagnetic spectrum.
General features of spectroscopy
Energy levels in molecules
 The total energy of a molecule is the sum of translational, vibrational, rotational and
electronic energies. Out of these rotational, vibrational and electronic energies are
quantized.
 Rotational energy is the energy possessed by the molecule by virtue of rotation about
an axis passing through its centre of gravity. Rotational energy states are designated
by quantum number J. J=0, 1, 2, 3,…..
 Vibrational energy is the energy associated with the periodic displacement of the
atoms from their equilibrium positions. Vibrational energy states are designated by
quantum number υ. υ = 0, 1, 2…
 Electronic energy is the energy associated with the distribution of the electrons of the
molecule in its various energy states. Electronic energy levels are designated by
quantum no. ʽnʼ. n=1, 2, 3,…
 Within each electronic state there are a number of vibrational energy states and within
vibrational energy states there rotational energy levels.
 The order of energy difference ΔE is electronic> vibrational> rotational.
 The electronic, vibrational and rotational levels of a molecule are collectively called
molecular energy levels.

Interaction of electromagnetic radiation with matter

 When a sample is irradiated, either the electric field component or magnetic field
component of radiation can interact with molecular system. This will result in
absorption of radiation of a particular frequency by the system.
 For absorption to occur, the energy of photon (hυ) must match the energy difference
(ΔE) between the quantized energy levels E₁ and E₂.
ΔE= E₂-E₁= hυ
OR
A molecule can absorb a particular frequency only if there exist within the molecule
an energy transition of magnitude ΔE=hυ
This is called Bohr condition for spectral transitions.
 When a beam is made to fall on sample, there will be a decrease in intensity
corresponding to that particular frequency being absorbed. The record of the
particular frequency or wavelength can be made with an instrument called
spectrometer and the resulting spectrum is called absorption spectrum.
 Molecule excite to higher energy states on absorbing radiation and when these return
to lower levels, they emit radiations of particular frequency satisfying Bohr condition.
The record of particular frequency emitted is made by using spectrometer and the
resulting spectrum is called emission spectrum.
 The absorption and emission spectrum are complementary to each other and provides
the same kind of information regarding molecular structure.
 The spectrum is a plot of some parameters like intensity or absorbance or %
transmittance against another parameters like wave length or wave number of light.
Born- Oppenheimer approximation
 According to Born- Oppenheimer approximation, the motion of the nuclei is so slow
compared to the speed of electrons. Therefore, motion of nuclei and electrons in a
molecule can be treated separately.
 In molecular spectroscopy, Born- Oppenheimer approximation means the electronic,
vibrational, and rotational energies are completely independent of each other such that
Total energy Eₜₒₜₐₗ= E (elec)+ E(vib) + E (rot)
 Change in total energy of a molecule ΔEₜₒₜₐₗ= ΔE(elec)+ ΔE( vib)+ ΔE(rot)
IR SPECTROSCOPY(VIBRATIONAL SPECTROSCOPY)
 Two types of fundamental vibrations are
i) Stretching vibrations – Movement along the bond axis such that interatomic
distance is increasing or decreasing.
ii) Bending vibrations- There occurs a change in bond angle.
 Absorption of quantum of radiation in the infra-red region having a frequency equal
to the characteristic frequency of vibration increases the amplitude of vibration and
raises the molecule to higher vibrational level. The spectra from such absorptions
causing vibrational transitions are called vibrational spectra or infrared spectra.
Selection Rules
 For a particular vibration to result in absorption if infrared radiation, the displacement
of atoms during that vibration must cause a change in dipole moment of the molecule.
 Symmetric diatomic molecules like H₂,Cl₂ etc are IR inactive molecules because the
bond stretching vibrations in them do not result in any change in dipole moment.
 Heteronuclear diatomic molecules like HCl and polyatomic molecules like H₂O, CO₂,
NH₃, CH₄ etc are IR active molecules because these molecules have vibrational
modes which are capable of changing dipole moment.
 As per the simple harmonic oscillator model, according to quantum mechanical
principles, the selection rule for vibrational transitions is “Only those vibrational
transitions are allowed in which the vibrational quantum number v changes by one
unit”.
For an allowed transition, Δυ= ±1, Δυ=+1 for absorption and Δυ= -1 for emission
 For anharmonic oscillators, the selection rule is Δυ= ±1, ±2, ±3,….
Fundamental bands and overtones
 The transition of one vibrational mode of a molecule between ground state(υ=0) and
first excited state (υ=1) involving absorption of one quantum of energy is called
fundamental transition. The frequency corresponding to fundamental transition is
called fundamental frequency and the corresponding signal in the spectrum is called
fundamental band.
 In addition to fundamental band in the IR spectrum, presence of signal at higher
frequencies can occur, these are called overtones.
 The transition υ=0 to υ=2 occurs at frequency about twice that of fundamental
transitions and are called first overtones. The transition υ=0 to υ= 3 occurs at
frequency about three times that of fundamental and are called second overtones.
 The intensity of signals are of the order fundamental> first overtone> second overton

NORMAL MODES OF VIBRATION OF MOLECULES

 A molecular vibration in which all atoms vibrate with the same frequency and pass
through their equilibrium positions simultaneously is called normal mode.
 A linear molecule has (3n-5) and non-linear molecule has (3n-6) normal modes of
vibration, where n = no. of atoms in the molecule.
 Different normal modes of vibration having same frequency is called degenerate.
CO₂
 Linear triatomic molecule. There are (3n-5)=4 normal modes of vibration.
a) Symmetric stretching- It involves no dipole moment change. Hence IR inactive.
b) Asymmetric stretching- IR active ,υ=2350cmˉ¹.
c) In- plane bending- IR active.
d) Out-of plane bending- IR active
 Bending vibrations are degenerate and υ=667cmˉ¹.
H₂O
  Non-linear triatomic molecule. There are(3n-6)= 3 normal modes of vibration.
a) Symmetric stretching- IR active, υ=3652cmˉ¹.
b) Asymmetric stretching- IR active, υ= 2530 cmˉ¹.
c) Symmetric bending- IR active, υ=1596 cmˉ¹.
Concept of group frequencies
 Bonds in a chemical group vibrate with frequencies which are independent on
remaining portion of the molecule. They show a characteristic frequency irrespective
of the molecule. Recording the spectra of a large number of organic compounds gives
data on characteristic absorptions of most functional groups. Such data can be used in
the identification of various groups present in an unknown organic compound.
 Eg: O-H
Free -3650-3600cmˉ¹
H-bonded- 3500- 3200cmˉˡ
Carboxylic acids- 3400-2400cmˉˡ
N-H- Primary and secondary amines and amides
Stretch-3500-3100cmˉ¹
Bend- 1640- 1550cmˉˡ
C-H
Alkanes- Stretch-3000-2850cmˉ¹
Alkenes- Stretch- 3100-3000cmˉˡ
Alkynes- Stretch- 3300cmˉ¹
C=C
Alkene- 1680-1600cmˉˡ
Aromatic- 1600 and 1475cmˉ¹

C=N Nitriles 2260-2240cmˉ¹

C=O Ketones 1725-1705cmˉˡ
Aldehydes 1740- 1720cmˉ¹

Fingerprint region
 The region 700-1400 cmˉˡ of IR spectrum is called fingerprint region. The pattern of
vibrations in this region is unique characteristic of each molecule.
 The frequencies of some of the stretching vibrations and most of the bending
vibrations fall in the fingerprint region. Similar molecules may show similar spectra
 outside the fingerprint region, but the band pattern is different in the fingerprint
region.
 Very helpful in establishing the identity of an unknown compound by comparing with
IR spectra of known compound.
Applications:
 Elucidation of structure-
If the IR spectrum of a compound shows an absorption band at a frequency which is
characteristic of a particular group, it indicates the presence of that group in that
compound.
 Detection of H- bonding-
The O-H group generally absorbs around 3600cmˉ¹. The presence of H-bonding ,
lengthens the bond, weakens it and lower the vibrational frequency.
UV-VISIBLE SPECTROSCOPY ( ELECTRONIC SPECTROSCOPY)
 Electronic spectroscopy involves the study of electronic transitions from lower to
higher quantized energy levels by absorbing energy in UV and visible regions.
Beer- Lambert’s law-
 When a beam of monochromatic radiation passes through a solution of an absorbing
substance, the rate of decrease of intensity of radiation with thickness of the solution
is directly proportional to the intensity of radiation and also to the concentration of
solution.
-dI/dx α Ic
I is the intensity of radiation and c the molar concentration of the solution
-dI/dx = kIc
dI/I = -kcdx
If Iₒ is the intensity of incident radiation and Iₓ the intensity of emergent radiation, x is
the thickness of medium, then on integration within the limits Iₓ and Iₒ
∫dI/I = -kc∫dx
ln Iₓ/Iₒ= -kcx
log Iₓ/Iₒ= -kcx/2.303
log Iₒ/Iₓ= kcx/2.303
log Iₒ/Iₓ= εcx
where k/2.303 =ε , called molar absorption coefficient or molar extinction
coefficient.
logIₒ/Iₓ=A, known as absorbance or optical density of the solution.
When Iₓ=(1/10 )Iₒ and c=1 mol Lˉˡ, then
ε=1/x
  Molar absorption coefficient is defined as the reciprocal of the thickness of 1 molar
solution which reduces the intensity of radiation to 1/10 th of its initial value.
 The ratio of the emergent intensity( Iₓ) to the incident intensity(Iₒ) is called
transmittance(T).
T=Iₓ/Iₒ
 A= - log T
Electronic spectra in polyatomic molecules
 Electrons are filled up in molecular orbitals in the increasing order of energy. The
Lowest energy electronic transition is caused by absorption of radiation from HOMO
to LUMO. In most of the organic and inorganic molecules, the HOMO is bonding(σ
or π) or non- bonding(n) where as LUMO is an antibonding (σ* or π*) .Electronic
transition by absorption of UV or visible radiation involves excitation of an electron
from bonding or non- bonding MO into one of the antibonding MOs.
 Six kinds of transitions are possible and the decreasing order of energy of excitation
are

 The last three transitions occur in the near UV and visible region and are generally
applicable in electronic spectroscopy.
 Saturated hydrocarbons which contain only single bonds and no lone pairs do not
show absorption in near UV and visible region. Compounds containing non- bonding
electrons show absorption in near- UV and visible region.
Terms of importance
a) λmax : The wavelength at which maximum absorption occurs.
b) Absorbance: A=log Iₒ/Iₓ
c) Molar absorption coefficient(ε): A=εcx. It is a measure of the intensity of absorption
for maximum absorption. The magnitude of ε is directly proportional to the
probability of a particular transition. The ε value at λmax is εmax.
d) Transmittance:
T=Iₓ/Iₒ

Nature of the spectrum

 Absorption of UV- Visible radiation induces electronic transitions as well as
vibrational and rotational transitions. Thus, an electronic transition produces a number
of bands which corresponds to vibrational and rotational transitions.
 Vibrational transitions produces coarse structure and rotational transitions produce
fine structure on the electronic spectra. This structure is visible for gaseous samples.
  In liquid or solid, the lines merge together and form a broad band.
Chromophores
 Chromophores are isolated functional groups which exhibits a characteristic peak in
the UV or visible region.
 They are generally groups having unsaturated centres or hetero atoms or both.
 Eg: -C=C-, -C≡C-, -C=O, -COOH,-NO₂, -N=N, -C≡N etc.
Auxochromes
 Auxochromes are functional groups that does not show absorbtion above 200nm, but
when present along chromophore, shift absorption to longer wavelength and increase
the intensity of absorption peak.
 Eg: -OH, -NH₂, -OR, -NHR, -NR₂,-SH,-SR etc
Shifts in absorption maximum and peak intensity
Four types of shifts are
a) Bathochromic shift( Red shift):
Shift of absorption maximum(λmax) to longer wavelength.
Eg: benzene shows a λmax of 255nm. Aniline(C₆H₅NH₂) shows λmax of 280nm.
b) Hypsochromic shift( Blue shift):
Shift of absorption maximum to shorter wave length.
Eg: aniline shows λmax of 280nm. Addition of acid to aniline gives anilinium ion
which shows λmax of 254nm.
c) Hyperchromic shift:
Shift of molar absorption coefficient (εmax ) to a higher value, showing an increase in
the intensity of absorption band. Bathochromic shift is often accompanied by
hyperchromic shift,
Eg: conversion of phenol to phenoxide ion shifts εmax from 6200cmˉ¹ to 9200cmˉ¹.

d) Hypochromic shift:
Shift of molar absorption coefficient (εmax) to a lower value, showing a decrease in
intensity of absorption band. Hypsochromic shift is accompanied by hypochromic
shift.
Eg: conversion of benzoic acid to benzoate ion shift εmax from 11600cmˉ¹ to
8700cmˉ¹.
APPLICATIONS OF ELECTRONIC SPECTROSCOPY
1. Organic chemistry:
a) Identification of compounds:
 The spectrum of each compound is the unique characteristics of its structure.
Comparison of spectrum of an unknown compound with the spectra of known
compound, make it possible to identify the compound.
b) Detection of functional groups:
Functional group containing unsaturated centres or heteroatoms show
characteristic absorption maximum in the UV- Visible spectroscopy.
Chromophores in unknown compound can be detected by comparison of its
spectrum with the known compounds.
c) Identification of geometrical isomers:
Trans isomers have generally higher λmax and εmax as compared to cis
compounds.
d) Study of conjugation:
Presence of conjugation shifts λmax to higher values. Greater the conjugation,
the higher will be the λmax.
2. Inorganic chemistry:
 Several co-ordination complexes show peaks in the UV-Visible region arising
from d-d transitions, charge transfer (CT) transitions etc.
 Electronic spectra provides information regarding nature and types of metal
ions and ligand present and also the types of interaction present in co-
ordination compounds.
3. Organic and inorganic qualitative analysis.
The expression for Beer- Lambert law is
LogIₒ/Iₓ= εcx
A= εcx
If we plot a graph between A and c we get a straight line which pass through the
origin.
To estimate the concentration of unknown solution, we prepare a series of standard
dilute solutions. Their absorbances (A) are measured using spectrophotometer. Then
we plot a graph between A and c. we get a linear plot which passes through the origin.
This curve is known as calibration curve. Then, the absorbance of unknown solution
is measured. The concentration corresponding to the measured absorbance of the
unknown solution is obtained from calibration curve.

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (NMR)

 NMR is a spectroscopic technique based on the absorption of electromagnetic
radiation in the radiofrequency region by nucleus of non- zero spin quantum number
I.
  Energies of certain nuclei get splitted in the presence of magnetic field. Absorption of
radiofrequency radiation cause transition between these magnetically induced energy
levels.
Basic principles
 The nuclei of many isotopes have spin angular momentum (I) characterized by spin
quantum number I.
 The spin quantum number can be determined from mass number and atomic number.
Mass no. Atomic no. Spin quantum no. I
Odd Odd or even Half integer
Even Even zero
Even Odd Integer
 Nuclei with non- zero spin quantum number can give NMR spectra.
 The spinning of such nuclei produces a magnetic field. It act as magnetic dipole.
 In the presence of an external MF, the degenerate spin states split into (2I+1)
different energy levels. The allowed spin states is given by magnetic quantum no. mI.
mI= -I, (-I+1),….., (I-1), I.
 The magnitude of the magnetic dipole is expressed in terms of nuclear magnetic
moment μ. It is proportional to spin angular momentum.
μ=γI
γ is the gyromagnetic ratio of the nucleus.
γ=gN( e/2mp)
gN is the nuclear g- factor. e is the charge of proton. Mp is the mass of proton.
Therefore, μ = gN(e/2mp)I
Nuclear magnetic resonance
 In an external field B₀, the magnetic moment interacts with the field. The energy of
the nucleus is given by
E= -γ B₀ MI h/2π
Substituting the value of γ and putting eh/4πmp = βN,nuclear magneton.
E= -gN βN B₀ MI
The separation between the energy levels is given by
|ΔE| = |gN|βNB₀|ΔMI|
When ΔMI=1
ΔE = |gN|βNB₀
 Absorption of radio frequency energy results in transition between nuclear magnetic
energy levels that corresponds with the separation between energy levels. This
phenomenon is called NMR resonance.
  The selection rule is ΔMI = ±1
 The frequency of radiation that corresponds to the transition is called resonance
frequency.
υ=ΔE/h = |gN|βNB₀
h
 The frequency of radiation depends on strength of applied magnetic field.
PROTON NMR SPECTROSCOPY
 Proton has I value=1/2
There are (2I+1) = 2 allowed spin states. The magnetic moment are aligned either
parallel (MI=+1/2, lower energy) or anti- parallel (MI= -1/2, higher energy) with the
applied field.

 When frequency of radiation become equal to frequency of separation of the two spin
states, absorption takes place and a NMR signal is obtained.
 In NMR experiments, the magnetic field (B₀) is kept constant and frequency is varied
( frequency sweep method) or frequency is maintained constant and magnetic field is
varied ( field sweep method).

CHEMICAL SHIFT
Electron Shielding and de-shielding
 When a compound is placed in a MF, the surrounding electrons also generate a MF
called induced MF or secondary MF.
 The induced MF may reinforce or oppose the applied MF.
 If induced MF opposes the applied field, then effective field experienced by the
proton decreases. Thus, protons are said to be shielded. Greater MF is required by
protons for flipping to higher state. Thus, proton absorbs upfield.
 If induced MF supports the applied MF, the effective field experienced by the proton
increases. Thus, protons are said to be deshielded. Deshielded protons absorbs
downfield. They require smaller field to flip.
 Protons in different chemical environments have different shielding and deshielding
effects.
 Protons in the identical chemical environment are said to be chemically equivalent
and they will produce only one peak in NMR spectra.
 The difference in the absorption position of a particular proton from that of a
reference proton is called chemical shift of that proton.
 The most commonly used reference compound is Tetramethyl silane (TMS). Its
protons are more shielded than almost all organic protons. It give a sharp intense
peak.
 Chemical shift value on δ- scale is given by
δ= BRef – Bsample x 10⁶ ( field sweep)
Bref
Frequency sweep:

 For protons of most compounds the chemical shift varies from 0 to 10 ppm. The
chemical shift of TMS proton is take as zero.

 Protons in the same chemical environment absorbs at the same field strength.
 Eg: NMR Spectrum of ethanol (CH₃- CH₂- OH) under low resolution.
There are three peaks corresponding to three groups of protons. Proton of –OH , -CH₂
and -CH₃ group. The –OH proton is shielded to lesser extend due to high
electronegativity of O atom. So, OH proton absorbs at low field strength. Number of
signals is equal to number of types of equivalent protons.
SPIN-SPIN COUPLING
 When NMR experiment is carried out at high resolution, the signals may get splitted
into multiplet, ie, doublet, triplet, quartet etc.
 This is due to the interaction of spins of one set of protons with another set through
the bonding electrons.
 General rules for determining spectra-
- Equivalent protons do not give rise to observable splitting.
- If the number of neighbouring protons is n, then the signal is splitted into (n+1)
lines. This is called (n+1) rule.
- If nA and nX are number of equivalent protons of set A and X, and if their spin
couple with another set M containing nM protons , then the signal of M split into
(nA+1)(nX +1) lines. This is the advanced (n+1) rule.
- The relative intensities of peaks is given by coefficient of binomial expansion
(1+x)ⁿ. The coefficients are given by pascal’s triangle.
 - The midpoint of the multiplet represent the chemical shift.
NMR spectrum of ethyl bromide(CH₃-CH₂-Br)
 There are two sets of protons- CH₃(methyl) and -CH₂( methylene).
 For methylene (CH₂) protons there are four equal probable combinations of spin
orientations of which two are equivalent.

 The combination which is aligned with the field causes deshielding of methyl protons
and the combination aligned opposite to the field causes shielding of methyl protons.
The two equivalent combinations at the centre do not affect the methyl protons. Thus
CH₃ signal is split into triplet of intensity 1:2:1
 For methyl (CH₃)protons there are eight equally probable orientations of spin
orientations which include 2 sets of three equivalent combinations.

 These spin orientations of CH₃ have similar effect on proton of CH₂ group. The CH₂
group split into a quartet with intensity 1:3:3:1.
NMR SPECTRA OF SOME SIMPLE COMPOUNDS
1. Acetone or propanone( CH₃-CO-CH₃)
 The six protons have identical chemical environments. They are chemically
equivalent and show the same chemical shift.
 A single peak around δ=2.1 ppm is obtained.

2. Dimethyl ether or methoxymethane (CH₃-O-CH₃)

 The six protons have identical chemical environments. They are chemically
equivalent and show same chemical shift.
 A single peak around δ= 3.2 ppm is obtained.

3. Ethanol (CH₃-CH₂-OH)
  Extra pure alcohol under high resolution show three sets of signals.
 A triplet at δ=1.15 for methyl protons due to their coupling with -CH₂ protons.
 A quartet of doublet at 3.6 δ for CH₂ protons due to their coupling with methyl
(CH₃) protons and the hydroxyl (OH)proton.
 A triplet for the hydroxyl protons at 4.8 δ due to the coupling with CH₂ protons.

4. Propanal (CH₃- CH₂- CHO)

 Under high resolution, propanal shows three sets of signals.
 A triplet at 1.0 δ for CH₃ protons due to their coupling with CH₂ protons.
 A quartet of doublets at 2.2 δ for CH₂ protons due to their coupling with CH₃ and
CHO protons.
 A triplet for CHO proton around 9.8 δ due to their coupling with CH₂ protons.