UNIT – 2

SPECTROSCOPY
It is the branch of science that deals with the study of interaction of electromagnetic
radiation with matter.
OR
Spectroscopy is the analysis of the electromagnetic radiation scattered, absorbed or emitted by molecules. It
deals with the transitions that an electron in a molecules undergoes between its energy levels upon absorption
of suitable radiation.

Electromagnetic Radiation
 Electromagnetic radiation consist of discrete packet of energy called as photons.
 A photon consists of an oscillating electric field (E) & an oscillating magnetic field (M)which is
perpendicular to each other.
Energy of photon: E = hν = h c / λ; where h= plank’s constant and ν = frequency.

Based on the energy, electromagnetic radiation has been divided into different regions. for example, The
region of electromagnetic spectrum that human beings cansee is called visible region or visible spectrum.

ELECTROMAGNETIC SPECTRUM

The electromagnetic spectrum is a collection of all of the types of electromagnetic radiation.

OR
Arrangement of all types of electromagnetic radiation in order of increasing/ decreasing frequency/
wavelength/ wavenumber
 ELECTROMAGNETIC SPECTRAL REGION
Spectral Region Wavelength Energy j/Mole Quantum Change
9 11
Ү- rays 100-1pm 10 to 10 Change in nuclear configuration
7 9
X- rays 10nm-100pm 10 to 10 Change in electron distribution
5 7
U.V.- visible 1000-10nm 10 to 10 Change in electron distribution
3 5
I.R. 100µm-1000pm 10 to 10 Change in configuration
1 3
Microwave 1cm-100µm 10 to 10 Change in orientation
-1 1
ESR 100cm-1cm 10 to 10 Change in spin
NMR 10m-100cm 10-3 to 10-1 Change in spin

ORIGIN OF ELECTRONIC SPECTRA

Consider two energy levels of an atoms/molecules. The one with lower energy is called ground
state energy (Eg) and the one with higher energy is called excited state energy levels (Ee).
ATOMIC & MOLECULAR SPECTRA
Atomic Spectra: Its arise due to transition on of an electron between the atomic energy levels.
Molecular Spectra: Its arise due to transition of an electron between the molecular energy levels.

Molecular Property
1. Electronic Energy Levels:
 At room temperature the molecules are in the lowest energy levels E0.
 When the molecules absorb UV-visible light from EMR, one of the outermost bond / lone
pair electron is promoted to higher energy state such as E1, E2, … En, etc is calledas electronic
transition:

ΔE = h ν = En - E0 where (n = 1, 2, 3, … etc.)
ΔE = 100-10000 kJ/mole.

2. Vibrational Energy Levels:

 The spacing between energy levels are relatively small i.e. 1 to 100 kJ/mole.e.g.
 When IR radiation is absorbed, molecules are excited from one vibrational
level to another or it vibrates with higher amplitude.
 The spacing between energy levels are even smaller than Electronic energy levels. i.e
ΔEvibrational < ΔEelectronic
3. Rotational Energy Levels:
 Energy level spacing 0.01-1 kJ/mole.
 The spacing between energy levels are even smaller than vibrational energy levels.
i.e ΔErotational < ΔEvibrational
 When IR radiation is absorbed, molecules are excited from one rotational level to
another or it vibrates with higher amplitude
Hence, ΔErotational < ΔEvibrational < ΔEelectronic
Thus, total energy of the molecule can be represented as follows
ΔE = ΔErotational + ΔEvibrational + ΔEelectronic

Energy level spacing in molecule

Types of Molecular Spectroscopy

S.No. Spectra Transitions Region Criteria

1 Rotational Between rotational Microwave Molecules must be
(Microwave) energy levels (1-100cm-1) permanent dipole
moment
2 Vibrational (Infrared) Between vibrational IR (500-4000cm-1) Dipole moment of
energy levels molecules must
change during
vibration
3 Electronic (U.V.- Between electronic Visible Presence of
visible) energy levels (12,500-25,000cm-1) chromophore in
U.V. (25,000-70,000cm-1) molecules
4 Raman Between vibrational Far and near IR Region Periodic change in
& rotational energy polarizability due
levels to vibrational and
rotational
transition
5 Nuclear Magnetic Between magnetic Radio frequency Spin quantum
Resonance (NMR) energy levels of nuclei number of nuclei
(l>0)
6 Electronic Spin Between magnetic Microwave Presence of
Resonance (ESR) energy levels of unpaired of
unpaired of electron electron
Electromagnetic Effect on Technique used Information obtained
radiation molecule
Radio frequency Nuclear and Nuclear Magnetic  Molecular structure
waves electron spin Resonance (NMR)  Purity of the sample,
transition and Electron  Chemical
Paramagnetic environment
Resonance
(EPR)
Microwaves Molecular Rotational  Force constant,
rotational spectroscopy  Bond length
Transition  Bond angle
 Isotope composition
Infrared radiation Vibrational IR  Functional group,
transition spectroscopy  force constant,
 bondlength
 bond angle,
 Isotope composition
 Quantitative analysis
Raman Vibrational IR and microwave  Chemical structure,
Spectroscopy transition spectroscopy  molecular interaction
UV-Visible Electronic UV-Visible  Qualitative &
Radiation transition spectroscopy quantitative information of
Matter
Mass Spectroscopy Ionisation process Mass  Physical, Chemical
spectrometer and structural properties
 Isotope composition

Application of molecular spectroscopy

a. Molecular spectroscopy used in structural investigation. With its help, we can determine
electronic energy levels, bonds lengths, bond angles, & strength of bonds.
b. It can also be used to monitor changing concentrations of reactant of product in kinetic
studies.
c. It is also the basis of our understanding of colour in the world around us.
d. Emission spectroscopy is used for the study of energetically excited reaction products.

Advantage of spectroscopy over classical method

a. Spectroscopy method require less time and less amount of sample.
b. Sample recovery is possible after spectroscopic analysis because sample is not chemically
affected.
c. The results obtained by this technique are reliable, reproducible and correct.
Mass spectroscopy is an exception here.
 INTERACTION OF EMR WITH MATTER:

The interaction of electromagnetic radiation with matter causes the atoms and molecules to
absorb energy and go to a higher energy state. Since this state is unstable, they need to emit
radiations to return to their normal states. This gives rise to emission and absorption spectra.

Absorption Spectroscopy measures the amount of light absorbed by a sample by this

process.

For atoms: Atomic Absorption Spectroscopy

For molecules: Molecular Absorption Spectroscopy

ELECTRONIC SPECTROSCOPY/ U.V. –VISIBLE SPECTROSCOPY

Principle: “ It involves the transition of electron(s) within a molecules or ions from a lower to a
higher electronic energy levels or vice-versa by the absorption or emission of radiations falling in
the UV- visible range of electronic spectrum.”

while electronic spectra in the visible range 12,500cm-1 – 25,000cm-1, those in the UV region
25,000cm-1 – 70,000cm-1.

 When a sample absorbs UV light, VALENCE ELECTRONS are promoted to higher energy
levels in accordance with the frequency of absorbed light.
 The UV spectrum of a compound gives information about its electronic structure. In other
words, a sample with pi electrons, with pi bonds, with lone pairs, with conjugation, will show
characteristic absorption of UV light.
  UV region is divided into
 Near UV (wavelength region nearer to the visible region, λ ~ 250 nm – 400 nm)
 Far UV region (wavelength region farther to the visible region, λ ~ 190 nm – 250 nm)
 Vacuum UV region (λ< 190 nm).
 Ordinary UV-Visible measurements are carried out from about 200nm to 800 nm.
Below 200nm, the measurements are done under vacuum to avoid absorbance signals
from air components like CO2. Therefore, region below 200 nm is called vacuum UV.

Electronic Transitions:

The absorption of UV and visible light is through the transition of an electron in the molecule
from lower to a higher energy molecular orbital. The various electronic transitions observed
in organic compound are shown in Figure below:

Therefore, the order for the energy required for various transitions is
σ → σ* > n → σ* > π → π* > n → π*.
The possible electronic transitions are:

σ→ σ* transition:

• σ → σ* transition is a high energy process

 lies in the vacuum UV region.
 electron from σ orbital is excited to corresponding anti-bonding orbital σ*.
 Alkanes, wherein only σ → σ* transition is possible show absorption bands ~150 nm
wavelength e.g. Methane (CH4) has C-H bond only and can undergo σ → σ* transition and shows
absorbance maxima at 125 nm.
 π→ π* transition:
 π electron in a bonding orbital is excited to corresponding anti-bonding orbital π*.
 Compounds containing multiple bonds like alkenes, alkynes, carbonyl, nitriles,
aromatic compounds, etc undergo π → π* transitions.
 e.g. Alkenes generally absorb in the region 170 to 205 nm.
 In an aliphatic ketone, for example, the absorption band around 185 nm arises due to
the π → π* transition in the carbonyl group.
n → σ* transition:
 Saturated compounds containing atoms with lone pair of electrons like O, N, S and
halogens are capable of n → σ* transition.
 These transitions usually requires less energy than σ → σ* transitions.
 The number of organic functional groups with n → σ* peaks in UV region is small
(150-250 nm).
n → π* transition:
 An electron from non-bonding orbital is promoted to anti-bonding π* orbital.
 Compounds containing double bond involving hetero atoms (C=O, C≡N, N=O)
undergo such transitions.
 n → π* transitions require minimum energy and show absorption at longer
wavelength around 300 nm.

σ→ π* transition & π→ σ* transition

•These electronic transitions are forbidden transitions & are only theoretically possible.

Thus, n → π* & π → π* electronic transitions show absorption in region above 200 nm

which is accessible to UV-visible spectrophotometer.

When a molecule is subjected to UV range, a spectrum is obtained in spectrophotometer.

The spectrum consists of bands which are the plots between absorbed light and wavelength.
Through the study of these bands we can elucidate the molecular structure.

S.No. Organic Compound Transition Position of band & Remarks

1 Alkanes σ → σ* (150nm)
Require high energy, which do not lie in UV region)
2 Alkenes (simple) π → π* (170-190nm)
3 Saturated aliphatic n → π* (280nm) forbidden and hence of low intensity
ketones n → σ* (185nm) allowed and hence of high intensity
π → π* (160nm) allowed and hence of high intensity
4 Conjugated dienes π → π* (217nm) transition is of very low energy and is due to conjugation.

Allowed & Forbidden transitions

Allowed transitions: The transition with value of £max more than 104 are usually called allowed
transitions generally due to π → π* transitions.
Forbidden transitions: The transition with value of £max less than 104 are usually called forbidden
transitions generally due to n → π* transitions. Ex. Benzophenone, two types of transitions
 a. Allowed Transition 252nm, £max 20,000.
b. Forbidden Transition 325nm, £max 180.

Designation of UV Bands
R – Band: The bands due to n → π* transitions are called R-bands. They have low molar absorptivity
(£max < 100) and called forbidden bands.

K – Band: Such types of bands arise due to π → π* conjugated π system. These types of bands are
found in dienes , polyenes etc. £max is usually more than 104.

B – Band: This band characteristics of aromatic and hetroaromatic compounds representing π →

π* transition. The B-Band region from 250-255nm.

E – Band: This band characteristics of aromatic and hetroaromatic compounds. The E1 and E2
bands of benzene occur near 180-200nm respectively, with the £max value between 2000-14000

ABSORPTION LAW
Lambert – Beer’s Law
When a beam of monochromatic radiation is allowed to pass through a absorbing medium , the
rate of decease of intensity(-dl) with the thickness of absorbing medium(dx) is directly
proportional to the intensity of radiation(l) as well as to the concentration of the solution.
 A = acx
Also
A = £Cm X
where,
£ = molar absorptivity ; Cm = molar concentration Cm = C/ molar mass ; X = path length
Also
A = -log T
where
T = transmittance (T = I/I0)

Deviations from Beer-Lambert law:

i. High sample concentration: The Beer-Lambert law generally holds good only for dilute
solutions. At higher concentrations, the molecules come in close proximity thereby influencing their
electronic properties.

ii. Chemical reactions: If a molecule undergoes a chemical reaction and the spectroscopic
properties of the reacted and unreacted molecules differ, which result in the combined absorbance
from reacted and unreacted molecules. Thus the deviation from Beer-Lambert law is observed.

iii. Instrumental factors: As ε is a function of wavelength, Beer-Lambert law holds good only
for monochromatic light. Use of polychromatic radiation will result in deviation of Beer-Lambert’s
law.
TERMS USED IN UV / VISIBLE SPECTROSCOPY

CHROMOPHORE: The part of a molecule responsible for imparting colour, are called as
chromospheres.
OR
The functional groups containing multiple bonds capable of absorbing radiations above 200 nm
due to n → π* & π → π* transitions. e.g. NO2, N=O, C=O, C=N, C≡N, C=C, C=S, etc.

AUXOCHROME
The functional groups attached to a chromophore which modifies the ability of the
chromophore to absorb light, altering the wavelength or intensity of absorption.
OR
The functional group with non-bonding electrons that does not absorb radiation in near UV
region but when attached to a chromophore alters the wavelength & intensity of absorption.
e.g. Benzene λmax = 255 nm
 Phenol λmax = 270 nm

Aniline λmax = 280 nm

ABSORPTION AND INTENSITY SHIFTS:

1. Bathochromic Shift (Red Shift)

• When absorption maxima (λmax) of a compound shifts to longer wavelength, it is known as
Bathochromic shift or red shift.
• The effect is due to presence of an Auxochrome or by the change of solvent. e.g. An
Auxochrome group like –OH, -OCH3 causes absorption of compound at longer wavelength.
• In alkaline medium, p-nitrophenol shows red shift. Because negatively charged oxygen
delocalizes more effectively than the unshared pair of electron.

2. Hypsochromic Shift (Blue Shift)

When absorption maxima (λmax) of a compound shifts to shorter wavelength, it is known as
hypsochromic shift or blue shift.
• The effect is due to presence of an group causes removal of conjugation or by the change of
solvent.
• Aniline shows blue shift in acidic medium, it loses conjugation.
 1. Hyperchromic Effect: When absorption intensity (ε) of a compound is increased, it is known as
hyperchromic shift. If Auxochrome introduces to the compound, the intensity of absorption increases
Increase in absorbance can be due to the induction effect of CH3 group present in 2-methyl pyridine
which result in the increase in the electron density as a consequence transition probability increases.

2. Hypochromic Effect:
When absorption intensity (ε) of a compound is decreased, it is known as hypochromic shift. The
decrease in the value of absorbance is due to hypochromic effect of methyl group which distorts the
chromophore by forcing the rings out of coplanarity resulting in the loss of conjugation.

 Factors causing shifts in UV-VIS spectroscopy:

1. Conjugation:
Conjugation brings about a bathochromic shift in the absorption bands. The higher the extent of
conjugation, the more is the bathochromic shift.
Increase in Conjugation decreases the energy differences between the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO. Therefore, the electronic
transition becomes possible even at lower energy (higher wavelength).
2. Auxochrome:
• Auxochromes are the chemical groups that result in a bathochromic shift when attached to a
chromophore.
• They exhibit bathochromism by extending conjugation through resonance.

• Solvents: The solvents used in any spectroscopic method should ideally be transparent (non-
absorbing) to the electromagnetic radiation being used.

 Polarity of solvents is an important factor in causing shifts in the absorption spectra.

 The two electronic transitions π → π* and n → π* respond differently to the changes in polarity.
 Polar solvents stabilize all the three molecular orbitals (n, π, and π*), albeit to different extents
(Figure).
 The non-bonding orbitals are stabilized most.
 π* more polar than π in polar molecules. hence, π * better stabilized than π in polar solvent
 π → π* transition undergoes bathochromic shift with increasing polarity of solvent
 Hydrogen bonding stabilizes n more than π* in polar solvents
 n → π* undergoes hypsochromic shift
 peak absorbance is reduced due to stabilization of nonbonding electrons

∆Eπ*

∆En

∆Eπ
 Nonbonding orbital stabilizes more than antibonding π orbital and
bonding π orbital as shown in the above figure. Following is the
order of decrease in energy of respective molecular orbital

∆Eπ < ∆Eπ* < ∆En

APPLICATIONS OF UV / VISIBLE SPECTROSCOPY

 Qualitative & Quantitative Analysis: It is used for characterizing

aromatic compound and conjugated olefins specially which absorbs
radiation in UV region.
 It can be used to find out molar concentration of the solute under study.
 Detection of impurities: It is one of the important method to
detect impurities in organic solvents.
 Study of Chemical kinetics
 Structure elucidation of organic compounds
 Quantitative analysis of pharmaceutical substances
 Determination of molecular weight using Beer’s law.

INFRA RED SPECTROSCOPY

Infrared Spectroscopy is the analysis of molecule interacting with infrared radiation.
This can be analysed in three ways by measuring absorption, emission and reflection.
When infrared radiation was absorbed by molecule, transition of electron from
vibrational ground state to vibrational excited state occurs. Hence, It is also called as
vibrational spectroscopy.
OR
Infrared spectroscopy involve the transition between the vibrational energy levels of a
molecules on the absorption of radiations falling in the spectral line range of 500 –
4000cm-1.

Principle of IR spectroscopy
The principle of IR Spectroscopy is related to the vibrational and rotational energy of a
molecule. when the frequency of the IR radiation is equal to the natural frequency of
vibration, the molecule absorb IR radiation. Absorption of IR radiation causes an
excitation of molecules from a lower to the higher vibrational level.
 IR region divided into three region

near IR region middle IR region far IR region

(12,000 – 4000cm-1) (4000 – 667cm-1) (667 – 50cm-1)

functional group IR region finger print IR region

(4000 – 1400cm-1) (1400 – 667cm-1)
Range of the IR spectrum
 Peaks that are found in the region 4000 cm−1 to 1400 cm−1 indicates the presence of
functional group in the molecule. This region is called as functional group region.
These peaks can be used to identify and determine the functional groups of an
unknown compound.
 Peaks that are found in the region 1400 cm−1 to 667 cm−1 are unique to each molecule,
and acts like a fingerprint, and thus this region is known as fingerprint region and is
used to compare the spectra of one compound to another.
 Thus IR spectra is the finger print of a molecule.
 Hooke’s law and frequency of vibration (IR Spectroscopy Principle)
The bonds are not static but vibrating in different ways. A vibrating bond can
therefore be considered a spring with its ends tethered to two atoms.

If the masses of the atoms are m1 and m2, the frequency of stretching vibration of the
diatomic molecule can be given by the Hooke’s law:

………………………………………………………………….(1)

where, ν is the frequency of vibration, k is the spring constant, and μ is the reduced
mass in Kg.
Where m1 and m2 is the mass of individual atom taken in gram N A is the Avogadro
number which is 6.023 x 1023 and M1 and M2 are the atomic mass Dividing equation 1 by
λ gives:

……………………………………………………………………(2)

The spring constant, k is the measure of the bond strength. The stronger the bond,
the higher the k, and consequently the higher is the frequency of vibration.
Compound K (dyne/cm) Bond length ( Å) Frequency (cm-1)

HCl 527667 1.274 2990

HBr 386800 1.41 2650
HI 290000 1.61 2310
CO 1860000 1.13 2170
NO 1550000 1.15 1904

These characteristic vibration frequency is called Natural frequency of vibration.

 When infrared radiation interact with molecule, then it causes the vibration between the
 atoms of the molecules
 Vibration between atoms of molecule occur when,
Applied infrared frequency = Natural frequency of vibration
Then, Absorption of IR radiation takes place and a peak is observed.
 Different functional groups absorb characteristic frequencies of IR radiation. Hence
gives the characteristic peak value.

Therefore, IR spectrum of a chemical substance is a finger print of a molecule
for its identification.

Criteria for a compound to absorb IR radiation

The two essential criteria’s for a molecule to be IR active are:
1. Correct wavelength of radiation
2. Change in dipole moment

1. Correct wavelength of radiation:

A molecule to absorb IR radiation, the natural frequency of vibrations of some part of a
molecule is the same as the frequency of incident radiation.

2. Change in dipole moment:

A molecular vibration is IR active i.e. it absorbs IR radiation if the vibration results in a
change in the dipole moment.
 All the homonuclear diatomic molecules such as H2, N2, O2, etc are IR inactive.
 All Heteronuclear diatomic are always IR active due to present of permanent dipole. This
is because atom in diatomic molecule have electronegative differences. E.g. Vibration of
carbon monoxide (C=O).

MOLECULAR VIBRATIONS:
There are 2 types of vibrations:
 Stretching vibrations
 Bending vibrations

1. Stretching vibrations:
 Vibration or oscillation along the line of bond.
 There occurs a change in bond length.
 Occurs at higher energy: 4000-1250 cm-1.
 It is of 2 types:
a) Symmetrical stretching
b) Asymmetrical stretching

A. Symmetrical stretching: 2 bonds increase or decrease in length simultaneously.

B. Asymmetrical stretching: in this, one bond length is increased and other is decreased.
2. Bending vibrations
• Vibration or oscillation are not along the line of bond
• These are also called as deformations
• In this, bond angle is altered
• Occurs at low energy: 1400-666 cm-1
• These are of 2 types:
a) In plane bending: scissoring, rocking
b) Out plane bending: wagging, twisting

a) In plane bending
 Scissoring: This is an in plane blending in which 2 atoms approach each other and bond angles
decreases.
 Rocking: Movement of atoms take place in the same direction.

b) Out plane bending

 Wagging: 2 atoms move to one side of the plane. They move up and down the plane.

c) Out plane bending

 Wagging: 2 atoms move to one side of the plane. They move up and down the plane.
 Twisting: One atom moves above the plane and another atom moves below the plane.

Diagram showing different molecular vibrations in IR spectroscopy

 Types of Vibrations Frequency (cm-1)
Alkane C-C stretching 1200
C-H stretching 3000-2840
-CH2 bending 1465
-CH3 bending 1375
-CH2 rocking 720
Alkenes C=C stretching 1650
=C-H stretching 3095-3010
=C-H bending 1000-650
Alkynes C≡C stretching 2100
≡C-H stretching 3300
≡C-H bending 700-600
Aromatic C=C stretching 1600, 1500, 1450
=C-H stretching 3040-3010
=C-H bending Below 900
C=O stretching Amide 1680
Carboxylic acid 1710
Ketone 1715
Aldehyde 1725
Ester 1735
Acid chloride 1800
Anhydride 1760 (I), 1810 (II)
C-O Stretching 1300-1000
O-H Alcohol, phenol
Free 3600
H-bonded 3400-3200
Carboxylic acid 3400-2400
Amine -N-H stretching 3440 (as), 3350 (s)
-N-H bending 1650-1580
C-N stretching 1350-1000
Amide -N-H stretching 3370 (as), 3150 (s)
-N-H bending 1650-1560
Nitriles C≡N 2250
Imines C=N 1690-1640
Nitro group (NO2) N=O 1550 (as), 1350 (s)
Alkyl halide (C-X) C-F 1350
C-Cl 750
C-Br, C-I <660
 Number of fundamental vibrations:

For a linear molecule = 3n -5 , where n is the number of atoms.

For a non-linear molecule = 3n -6
Example
CO2 (linear molecule)
n = 3, no of fundamental vibrations = 3n -5 = (3 x 3) -5 = 4 H2O (nonlinear molecule)
n = 3, no of fundamental vibrations = 3n -6 = (3 x 3) -6 = 3
CH4 (nonlinear molecule)
n = 5, no of fundamental vibrations = 3n -6 = (3 x 5) -6 = 9

Vibrational modes of CO2

Fig. Vibrational mode of CO2

 The symmetric stretch does not result in a change of the initially zero dipole moment, so it is IR-
inactive.
 The asymmetric stretch does result in a change in dipole moment so it is IR active.
 The bend also results in a change in dipole moment so it too is IR-active.

To sum up, carbon dioxide has 3 IR-active vibrational modes.

 Interpretation of an IR spectra

FUNCTIONAL GROUP REGION (4000-1500 cm-1):

1. The most common application of IR spectroscopy is perhaps to identify the functional groups.
2. This is possible because different functional groups vibrate at different frequencies
allowing their identification.
3. Region from 4000-1500 cm-1 in an IR spectrum is useful for identification of functional groups,

The wavenumbers for some of the stretching mode vibration in molecule in Table:

FINGER PRINT REGION (1500-600 cm-1):

 The region below 1500 cm-1 (1500-667 cm-1) is known as finger print region.
 It contains number of vibrations caused by bending and stretching vibrations.
 This region shows a number of vibrations which makes it complex.
 However each organic group has its own unique absorption pattern in this region.
 The molecules containing same functional groups show similar absorption above 1500 cm -
but if the molecules are different, then the spectra differ in finger print region. On the other
hand if along with high frequency region (above 1500 cm-1), the finger print region also
 matches, the two molecules are of same compound.
 This region thus provides confirmation of identity of molecules.
 No two compounds except enantiomers can have similar IR spectra.
Example: Consider the example of propane -1-ol and propane-2-ol

Both spectra are quite similar in the functional group region, but their absorption patterns in the
fingerprint region are completely different.

Factor effecting vibrational frequency:

1. Bond order: Bond order affects the position of absorption bands. Higher the bond order larger is the
band frequency

2. Electronic Effects: Resonance and Inductive:

(a) Inductive Effect

 (b) Resonance Effect: As the molecule have -electron leading to conjugation results in the
delocalization of electron over 3-4 atoms or even more. This
(such as C=O). This can result in the decrease in vibrational frequency.

(c) weakens the multiple bond

3. Hydrogen Bonding:
 The presence of hydrogen bonding changes the position and shape of an infrared absorption band.
 Stronger the hydrogen bonding, greater is the absorption shift from the normal values which result
in red shift in IR spectra.

 The two types of hydrogen bonding (intramolecular and intermolecular) can be differentiated by
the use of infrared spectroscopy.
 WOODWARD FIESER RULE
 Application for conjugated diene
 Application to conjugated carbonyl compound

1. Type of conjugated dienes

2. Type of double bond characteristic

Endocyclic Double Bond
Any double bond where both the carbon is a part of ring or
cyclic structure concerned called endocyclic double bond.

Exocyclic Double bond:

Any double bond where only one
of carbon is a part of ring or the
concerned cyclic structure is called
endocyclic double bond.

3. Alkyl group or Ring residue:

Carbon atom of the ring system or functional
group connected to the carbon of conjugated
diene moiety of the molecule.
 Application of IR
 Qualitative Analysis: Main application of IR spectroscopy is compound identification and
molecular structure.
 Determination of Purity of a sample.
 Studying progress of the reaction
 Identification of functional group
 Distinguish between inter and intra molecular H bonding: IR spectra of the compound at different
concentration are recorded with increase in concentration, the absorption band due to inter
molecular H-bonding increases while that due to intra molecular H- bonding remains unchanged.
 Structural information: IR spectra provides valuable information regarding molecular symmetry,
dipole moments, bond strength, characteristic absorption etc.
 Analysis of petroleum hydrocarbons oils and greese content.

NMR Spectroscopy
The technique of spectroscopy involves the interaction of radio – frequency region light with
magnetic field of nucleus & external magnetic field. Radiofrequency region 4 to 900 MHz
Any charge particle generated the magnetic moment along the axis of spin. So that such nuclei
which have non- zero value of I (I = nuclear spin quantum no.) act like tiny magnet when such a
nucleus (proton) is place in external magnetic field.
Then its magnetic moment can be ling in two ways: (i) α – State (ii) β – State

Frequency of the radiation to flip the spin state of proton can be determine as –

frequency of radiation magnetic field strength

Gyromagnetic constant
 NMR Active Nuclei
1. If number of proton and number of neutron are odd then compound are NMR active.
2. If number of proton even and number of neutron are odd then compound are NMR active.
3. If number of proton odd and number of neutron are even then compound are NMR active.
4. If number of proton and number of Neutron are even then compound are NMR inactive.

Instrumentation of NMR & Principle

 Instrumentation of Nuclear Magnetic Resonance
(NMR) Spectroscopy

1. Sample holder
Glass tube with 8.5 cm long, 0.3 cm in diameter.
2. Permanent magnet
It provides a homogeneous magnetic field at 60-100 MHz
3. Magnetic coils
These coils induce a magnetic field when current flows through them
4. Sweep generator
To produce an equal amount of magnetic field pass through the sample
5. Radio frequency transmitter
A radio transmitter coil transmitter that produces a short powerful pulse of radio waves
6. Radio frequency receiver
A radio receiver coil that detects radio frequencies emitted as nuclei relax to a lower energy level
7. Read out systems
A computer that analyses and records the data.

Working principle
Working principle of nuclear magnetic resonance (NMR) is based on the spins of atomic nuclei.
Nuclei with an odd mass or odd atomic number have "nuclear spin" (in a similar fashion to the
spin of electrons). Since a nucleus is a charged particle in motion, it will develop a magnetic field.
When the nuclei with non-zero spins placed in a strong magnetic field with respect to the applied
magnetic field with the supply of appropriate energy, these nuclei flip to a higher energy state
from lower energy state. The energy difference between the two states depends on the applied
field. The energy absorbed during this transition is a function of nucleus type and its chemical
environment in the molecule. The magnetic field is increased and the excitation or “flipping” of
nuclei from one orientation to another is detected as an induced voltage resulting from the
absorption of energy from the radio frequency field. The free induction decay, which is in time
domain gives its equivalent frequency domain signal on Fourier transformation. The area under
a peak is proportional to the number of nuclei “flipping” and by observing the field strength at
which protons absorb energy, one can know about the structure of a molecule.

Equivalent & Non-Equivalent Protons

The proton which is having a same environment and all protons give single peaks is called
equivalent proton. The proton which is having a different environment and all protons give
different peaks is called non-equivalent proton.
 Chemical shift (shielding and Deshielding Effect)
The position of signal in NMR represented in terms of chemical shift. Chemical shift represent the distance
Between two NMR signal.

OR

It is the separation between peak of the reference standard (TMS) & any other peak in an NMR spectrum.
Its represented by δ & express in term ppm.

 small value of chemical shift : shielded proton

 large value of chemical shift : deshielded proton
Formula
 S.No. compound Formula δ value
1 CycloPropane 0.2
2 10 Alkane CH3-CH3 0.9
3 20 Alkane CH3-CH2-CH3 1.3
4 30 Alkane 1.5

5 Allylic CH2=CH-CH3 1.7

6 Benzylic C6H5-CH3 2.2 to 3.0
7 Amino R-NH2 1 to 5
8 Hydroxil R-OH 1 to 5.5
9 Phenolic C6H5-OH 6 to 8
10 Alcohols CH3-OH 3.5 to 4.5
11 Ester CH3-O-R 3.5 to 4.5
12 Vinylic CH2=CH2 4.5 to 6
13 Acetyenic CH≡CH 2 to 3
14 Acids CH3COOH 10 to 12
15 Enolic H2C=CH-OH 15 to 17

Environmental Effect
a. Chemical shift effect
b. Spin – Spin Coupling

Chemical Shift (No. of Signal)

Chemical shift tells the number of signal present in a molecules.

Shielding and Deshielding Effect

If the induced field oppose the applied magnetic field. Then proton said to be shielded & this
effect is called shielding effect.
If the induced field reinforced the applied field the proton feels a higher strength & thus such
proton said to be deshielded and this effect is called deshielded effect.
Shielding shift of absorption: up field to get effective filed strength necessary absorption.
Deshielding shift of absorption: down field to get effective field strength necessary for
absorption.

Measurement of Signals
Why we use TMS as reference?
 It is chemically inert, miscible with large range of solvent.
 Its 12 proton are all magnetically equivalent so give only one signal.
 Highly volatile & can be easily removed to get back sample.
 It does not take part in intermolecular association with sample.
 Factor influencing the chemical shift

1. Electronegativity: - The proton is said to be deshielded if its attached with an

electronegative atom/group. Greater the electronegativity of atoms greater is the
deshielding caused to proton. if the deshielding more, then δ – value more

2. Anisotropic Effect (space effect): It has been found that in unsaturated compounds
shielding or deshielding depends upon the manner in which pi electrons circulate under
influence of applied filed. the effect are diamagnetic (oppose to the field) in certain
directions and paramagnetic (align with the filed ) in other , so these effects are called
Anisotropic effects

Alkenes:

Alkynes:
3. Hydrogen bonding:

Inter molecular H – bonding increasing the Deshielding effect. So increasing H – bonding

increases the δ – value.

Application of NMR Spectroscopy

1. To identify the molecular structure of its nature
2. To identify the purity and composition of sample
3. To identify the proton environment
4. To identify the moisture analysis
5. The percentage of Hydrogen in the Compound can be determined
6. Type and number of proton and Carbon
7. In medical field; MRI, Tumors etc;