UNIT-IV

MOLECULAR SPECTROSCOPY
In earlier days the structure and properties of organic compounds was determined by
chemical methods.But in modern days it is done by using physical methods known as spectro-
scopic methods.These are most suitable methods than the other physical and classical
chemical methods,by using these methods structure determination is possible in less time and
accurately.

Advantages of spectroscopic methods:-

1.The sample required for spectroscopic analysis is very less(1mg /2mg)

2.Highly sensitive methods.

3.Time requird for structure determination is very less (<1min)

4.Accurate results are obtained.

5.Sample recovery is possible and which is used for another time.
Some common spectroscopic methods are:
1)UV-Vissible spectroscopy -To know unsaturation &conjugation.
2)Infrared(IR)Spectroscopy -To know nature of the functional group.
3)Raman spectroscopy -To known bond lengths &bond energies.
4)Microwave spectroscopy -To know various rotation of molecules.
5)Proton magnetic Resonance spectroscopy(pmr)-To know different types of
protons 6)Mass spectros copy -To known molecular weight &molecular formula of
compounds. 7)Electron spin Resonance spectroscopy(ESR)-To know free radicals.
Electro Magnetic radiation -EMR:-
The radiation which pocess both electric and magnetic fields in right angles which are per-

pendicular to each other is called electromagnetic radiation.

[O In spectroscopic methods these EMR are used
Types of EMR's;

Wave length (z.) increases (x1)

(or)
Frequency (o)deereases (vL)
(or)
Energy (E)decreases (E↓)
(Electro magnetic spectrum)
Interaction of electromagnetic radiation with molecules:-
When EMR is passed through a molecule/compound,it absorbs light energy and
undergs some internal changes.due to absorption of energy electrons of molecules gets
excited.but thisl unstable state.In this state changes occurs in energy levels of molecule.The
difference in enel; of excited state and normal state is equal to the energy absorbed,by the
molecule /compound

h=planck's constant
γ=frequency

Depending upon the nature of EMR passed,The following changes occur in the molecules.

1.Translation motions 2.Rotations 3.Vibrations

4.Electronic Transitions 5.Magnetic energy changes
Spectrum:-
The arrangement of group of wavelenths |Frequencies of light is called spectrum.
 O spectrum is recorded by using spectrophotometer instrument.

Principle;-

Spectrum
(Devices in spectrophotometer)
ypes of molecular spectras:-

There are mainly two types of spectras.

(1)Absorption spectra:-The spectrum which consist the lines corresponds to the waverength

of absorbed light is called absorption spectrum.

O Absorption spectrum consist dark lines on bright background.

Ex:NMR,U.V,I.R …

Absorption spectra

(2)Emission spectra:-The spectrum which consist,the lines corresponds to the wavelengths

of emitted light is called emission spectrum.

O Emission Spectrum Consist bright lines on dark background.

Ex:Fluorescence,Phosphorescence
 ROTATIONAL SPECTKUSUUFT ML
Microwaves~ Sample
Principle:-
Sample Iradiated with microwave range (λ=0.1-30cm)of radiation brings about change,
in rotational energy levels of molecules is called rotational spectroscopy,
O Sample must be in gaseous (or)vapour state.
O Molecules should be with permenant (μ≠0)dipolemoment so Homo atomic molecules
canng show M.W spectra.
Ex:-H₂ ,O₂ ,Cl₂ ,N₂ ……
Rotational axis:-

The axis passes through the centre of the body /molecule around which the molecule
can take infinite number of rotations is called Rotational axis.Ex:Rotation of earth on its own
axis. Intensities of spectral lines :-
The pure rotational spectrum of a diatomic molecule consists of a series of equally
space lines corresponding to the transitions J=0→J=1,J=1→J=2,J=2→J=3.We
now esti. mate the relative intensities of these spectral lines.The important factor that
decides the intensity of lines will be the number of molecules present in each level.This
depends on the boltzmann factor and the degeneracy of the level which is (2J+1).
If NO is the no.of molecules in the J=0 level.The numbers in the jth leves is

Taking degeneracy into account,the number actually available in a state.

To find the value of'J'for which the populaticn is maximum,we have to set
dNJ/dJ=0. This leads to

That is the level nearest to this'J'value will have the maximum population.Hence trans
tion originating from the level having this 'J'value will have the maximum
intensity. Isotope effect in rotational spectra /Isotopic substitution :-
An atom when replaced by one ofit's isotopes,the interbond distance remains the
samed tl deinlegct o cha ge in th umtionmdeonetsofni te thiange,However,the mass of the
nucleus change

increase in mass of atom in the molecule-increases reduced mass (u).

The change in mass not changes the bond length,with increase in μ the T also increase
 HM

&tu

16
l3 )16

ole

c¹²o¹⁶=1=μ (1)
cl³o¹⁶=l¹=p' _ (2)

cl²ol6

Heavier isotopic substituion in the molecule decreases 'B'due to increase

'I'. cl²o¹⁶→vj=BJ(J+1)cm-l

Cl³o¹⁶=vj=B'(J+1)cm-
Isotopic substitution decreases energy as well as wave numbers of rotational
energy levels.i.e.,energies of energy levels of cl³ol6 smaller than energies of energy levels
of cl²ol6. The effect of cl3 Isotope substitution on the rotational spectrum of diatomic
molecule cl²ol⁶
is
 rotational spectrum of diatomic molecule dotted lines —→ isoto.
cfusfnes d
ically s uti mole
e c c l
ermi n a t ion of b o n d lengt frigid diatomic molecules:
u bs d ia to m i

Ex: HCI Molecule

(C.G=Centre of Gravity )

r₁+r2=0——(1)
Rotation based on centre of gravity

mi=m₂?z ——(2)
Moment of Inertia of a diatomic molecule

I=mr²+m₂r2——(3)
I=m₁i.ri±m₂'2·Y2

=m₂Y₂·ri+m₁i:Y2 (from eg"(2)

∴I=rr2(m+m₂)——(4)
from(1),(2)equation

Yi+/2=r0 r₂(m₁+m₂)=m₁o
r=(o-
r₂)
m₂²₂=m₁(₀-
r₂)
m₂Y²=mro-mr₂
m₂Y₂+m₁Y₂=m₁o
m₁i=m₂Y₂ m₂²₂=m₁(₀-r₂)
 Solve the
1=Lrā
schrodinger's wave eauetien

J=spin quantum number

J=0,1,2,3 …
from planck's equation
E=hv

E=hc v

方 √ (01)c
E,=B/(J+1)Cm²
Energy levels:-
E,=BJ(J+1)Cm~
lfJ=0→E₀=B.0(0+1)=0Cm~
J=1→ε₁=B.1(1+1)=2 BCm~l
J=2→E₂=B.2(2+1)=6BCm- ¹
J=3→E₃=B.3(3+1)=12BCm~

T=6-
 ia7ni h
Energy dif.between two success the energy
△c= △V=2B(J+1)]Cm⁴(J=0,1,2,3…)
Distance between two adjacent lines in a rotation spectrum of diatomic molecule 2B Cm²¹

Important questions
1.What is moment of Inertia ?Give the classification of molecules based on this.
(LQ) 2.Give the selection rules of rotational spectroscopy.(SQ)
3.Explain how to determine bond iength of diatomic molecules.(LQ)
4.Explain effect of Isotope on rotational spectra.(SQ)

INFRA RED SPECTROSCOPY

(OR)
VIBRATIONAL SPECTROSCOPY
Radiation:Infrared radiation.

For organte molecules absorptlon energy is 625-4000cm²(or)2.5n-154(1u=10cm).

i.e.Middle IR range is
useful.
R ectrum

I p
When sample irradlatedwlthIR-range of radiation,ltb r i- gs about changes
vibrational levels of molecules.lte,molecule vibrates from one vib level to another due to
vibrations the bond lengths,bond angles in the molecules are altered.Those vibrations
this
change the dipolemoment of the molecules are detected by detector and information pass to
the recorder,and give a spectrum.
There are two type of molecular vibrations due to IR-radiation
1)Stretching vibrations 2)Bending vibrations
1.Stretching vibrations:-
In these vibrations the bond length of the molecules increases (or)decreases.These are
high energetic vibrations.

Ex:For a diatomic molecule

bond length=x
stretched vib
 For triatomic molecule

(Bond stretchings) (Symmetrical stretching) Asymmetrical (Stretching)

For a diatomic molecules only stretching vibrations are possible

2.Bending vibrations:-
This is also called Deformation of molecule.These vibrations taking place with change in Bond
angle of the molecule.These are low energetic vibrations.

Energy levels of simple harmonic oscillator:-

Ex:Diatomic molecule.

(spring)simple harmonie oscillator

The oscillator which takes in equal distance is called simple harmonic oscillator.

Frentoncw nf mnlartlla is in simple harmonic motion is qiven by Hook's Law.

 v=√F z:——(1)
m=Reduced mass

k =force constant

DIvide the equatlon (1)with 'C'(velocity of light)

y-=wave number
LIke other molecular energylevels,the vibrational energies also quantised.Vibrationa
enegles of systems are calculated by using schrodinger's wave equation
For a simple harmonic osclllator

V=Vib.quantum no.

E=-
((+3)αcm¹N=0.4.23…)
V=O→E₀=÷Toscilation(Zero vib-level)
V=1>&₁=2Toscillation(Fist vib-level)
V=2→E₂=号 Doscilation(Secound vib-level)
V=3→e₂=2Gosilation(Thard vib-level)

Inter atomic distance

Vibrational energy level of simple hormonic oscillator
Energy levels of Anharmonic Oscillator:-
"The oscllator which donot takes equal distances is called Anharmonic oscillator.“
Inter nuclear distance(r)
 e ot impl ey
Re a l m olec u l s do n f ollo w laws of s harmonic motion h donot ob H ook's La
internuclea r sep a rati on In real molecules sim le compression e elayngations are p erfectly
a t all
astic,
hut lons.The
for longerenergy
compressions and elongations
of real molecule theyofdeviate.experimentally
as a function it isisobserved
internuclear separations given by that the
morse
molecule is stretched beyond 10%of it's bond length,the molecule dissociates into atoms

Energy E=Da[I-ep{o(e-)]] (1)

a=constant
r=Distance between nucleus

Teg =equilibrium distance

Sub.equation(1)in schrodinger wave equation and solve it.We get equation four Anharmonic
oscillator

xe=Anharmonicity constant

xe=0.001(0<xe<<1)

Energy levels:
 Selectlon rules for Anharmonic osclllator(1)μ≠0,(2)△v=±1,±2,±3..

Er:(1)

AE=0(1-2x)Cm-l
Selection rules:-

1.Molecule should be with permenant (or)Induced dlpole moment.i.e μ≠0(or)

Ex:H₂molecule. :Rinactive
All Homo atomic molecule(H₂ ,Cl₂ ,O₂ ,N₂…)are IR inactive
Hetero atomic molecules dipole moment change with vibration so they are IR
active. (2)△V=±1 △V:Diff b/w vibrational quantum number.
Force constant(K):
Force constant (K)is the measure of elasticity (or)strength of the bond.

Object with mass 'm'is hanging to the spring and pull downward takes
simple'hormonic oscillations.In this process the Restoring force of the object taking the object to
original position. (Force responsible for taking back of object is called Restoring force).

compressed
Normal Stretched state
state
state

equilibrium position
F=Restoring force

F=ma α-x X=Displacement

F=-k x
k=Force constant

HooksLaw D=右 √

k=4π²C²v²μ
K=force constant.It glves strength of the bond (spring)

ōa k
 Force constant is directly proportional to the vib.frequency.l.e molecules
witi large force constant value high frequency radiation.
Ex:-

chH chcH
Fe=o-1kFocm² c=o=17k4↓5cm D=o=1715cm
kJ↓
Due to +I effect of -CHʒgroup the C=0 bond is weakend and value of K is
decreases. Therefore absorption frequency also decreases.

Bonzamide Phenyl acetate

-1

c=o=1693cm De=o=1730cm'

Oxygen is more E.N than Nitrogen.So for oxygen there is less chance to donate eO
pair.due to thin C=0 absorption frequency is more.
Force constant values of some molecules are given in the below table.

Molecules force constant (k) vibration(cm

(Nm

HF 966 4138.5
HCl 516 2990.6
HBr 412 2649.7
HI 314 2309.5
CO 1902 2169.7
NO 1595 1904.0
ICL 238 384.2

grees of freedom for polyatomic molecules:-

In 3D-space for a molecule total number of degrees of freedom =3N
N =No.of atoms in a molecule.
out of 3N-degrees of freedom the trans lattonal degrees offreedoms are three (for
both linear &Non -linear)
0 For a linear molecule rotational degrees of freedoms are two (3N-3-2
 Fora non-inear molecutle rotational degrees offreedoms are three =(3N-3-3)
·Fundamental vibrations of 'N'atoms molecules

For linear molecule=3N-5 -

6
Fun :=
v=1 and the band appeared by this transition is known

Over tones :-
The transitions between v=0. v=2,3,4.......results overtones with weak intensity.
i.e.transitions from ground state to higher vibrational levels.
Hot bands:-
The bands due to vibrational transitions such as v=1 →v=2,v=2 →v=3……..in
presence of high temperature only are called hot bands.
Selection Rules:-

1.Molecules should pocess a permenant dipole moment.

μ≠0 (∵μ=Dipole moment)

Ex:HCl,CO,NH₃ ,H₂O…(Hetero atomic molecules)

For H₂ ,Ci₂ ,O₂ ,N₂ ……Homo atomic molecules μ=0.So rotational spectrum is not
possible.
2.△J=±1 △J=Energy diff-b/w rotational levels.
Characterstic absorption bands of various functional group
In organic compounds there are various types of functional groups.Each functional
group has its characterstic absorption frequency in IR-range.based on these absorption
frequency
bands it is possible to detect nature of the functional group in the compound.

Some functional groups and their absorption frequencies are given below.

Functional
C-H(Akane)
group
-N+(2°)
C-C
C=C
C=C
C=C(aeromatic)
O-H(Hydrogen Bond)
O-H(Fee)
C=0
C=N
-NO₂
-NH₂(1°)
Absorption frequency region(cml)
2960-2850
1300-800
1650-1600
2260-2100
1660 -1500
3400-3200
3600-3400
1750-1650
3210-2280
1540
 ELECTRONIC SPECTROSCOPY
(OR)
UV-VISSIBLE SPECTROSCOPY
Uv-Spectroscopy is the study of electronic transitions or rearrangement in the
molecule produced from irradiation with UV-Vissible light.

O UV-Vissible radiation brings about changes in electronic levels of molecules,also reffered

as electronic spectroscopy,mainly valence electrons are involved in Transitions.
Bonding,Anti bonding molecular orbitals:
O Linear combination of Atomic orbitals(LCAO)produces molecular orbitals.(M.O.S)

O Number of molecular orbitals produced are equal to no.of atomic orbitals mixed.

O Half of the molecular orbitals posses low energy than Atomic orbitals and produced by
addi- tion method are called Bonding molecular orbitals.

O Half of the molecular orbitals posses High energy than the Atomic orbitals and produced
by subtraction method are called Antibonding molecular orbitals.

→Antibonding mo's
n Atomic ehitale LCA0 1

(A.O'S)
(h=even -2.4.6……)
±→号 bonding mos
→()Ant bonding mo's
n-Atomic orbitals LCAOn-molecular → 1-Nonbonding m.o's
otbitals (A.O'S)
(n=odd 3.5.7……)
>(")Bonding m.o's
 flectronic Transition:-
Promoton of electron from lowereneryy M.O to Highereneray M.O by nteractlng wilthradn
tion is called electronic transition.

(Ground state) (excited state)

The Range of UV-Vissible radiation is 200 -800 nm

λ=200-400nm -UV -radiatlon

400-800nm -Vissible light
Energy levels of molecules:-
Generally molecules pocess 4 types of energy levels.In molecules certain quantity

d energy is stored internally,this energy is called Internal energy.It is associated with the

following

4 types of energies.

1)Translational Energy 2)Vibration Energy

3)Rotational Energy 4)Electronic Energy

In the above four types of energies except translational energy remaining are quantised.The

order of various energies is Electronic energy>Vib.energy >Rotation energy.

In b/w every two electronic energy levels,a number of vib.energy levels are present
simillarly in b/w every two vib.energy levels,a number of rotational energy levels are present.
When electronic transiton occurs that can leads to change in vib.and rotational energy

levels of the molecules.

TN E

Rotational
vib.energy
energy levels levels electronic
energy level
V₀
TRN
E
 rypes of electrons:
In organic compounds mainly there are three types of electron(bonds)

(1)o-bonded electrons -Ex:All org-molecules

(2)π-bonded electrons -Ex:Unsaturated compound
(3)non-bonded electrons -Ex:Compound with Lone pair of electrons

σ,π—Less energy σ
* 光 一 More energ)
Kvpes of electronic Transitions:

Based on nature of the electrons there are total six types of electronic transitions are
possible in
org.compounds,the are

y 分-o”Transition σ-π”Transition

1)σ-g*Transition 5)π-π*Transition 6)n-π*Transition

Allthough six transitions are posslble but in reallty only two types of transition (π-
π',n-n') are detectable,remaining are ruled out because they occur in out of range of
radiation.
(<200mm(or)>400mm)
——
1)σ-g*Transition: h 长 苷
Promotion of electron from o-bonding M.O to o*antibonding M.O in the absorption of
UV- light..
Ex:-Alkanes(CH₃-CH₃ ),Cyclo alkanes,All org-compounds

2)π-π*Transiton:
Promotion of e9 from π-bonding M.O to π'-Antibonding M.O by absorbing
light Ex:Unsaturated compounds (Alkenes,Alkynes,Carbonyl etc…
Compounds)

3)n-π*Transiton:
Promotion of e9 from Non-bonding M.O toπ*-Antibonding M.o.
Ex:Unsaturated compounds with Lone pair of electrons (Carbonyl
compounds) 4)n-g”Transition:

Promotion of ee from Nonbonding M.O to c*-Antibonding M.o.

Ex:Saturated comp.With lone pair of ees (Alcohols,Amines…)
 Electron Transitions on carbonyl compounds

Energy
E

Selection Rules;
1.During the electronic transitions Retention of spin of electron is Allowed,Inversion of spint

electron in Forbidden.

2.In electronic Transitions involved orbitals with different symmetry are allowed and orbitas
wth samesymmetry areforbiuden.

3.In electronictransttion change in multipleity is forbidden,Retention in mutiplicity is Alowe

(multiplici exclusion principle

 rminology:-
chromophore ·

The group which is responsible for absorption of UV-Vissible range of radiation is called

tnomophore.These groups imparts colour to the molecules.

Ex:All unsaturated groups are chromophores

Nitro (-NO₂ )group imparts yelow colour to the compound

Azo(-N=N)-group imparts Colour to the compounds
2.Auxo chrome:
Groups which cannot absorbs UV-vissible range of radiation it self,but enhances absorption
wavelengths of chromophores are called auxochromes.

Ex:-Group with lone pair of electrons.

-OH,-OCH₃,-NH₂,-NHR,-NR₂,-X:etc.
Auxo chromes are called colour intensifiers.
3.Batho chromic shift /Red shift:
Shiftting of UV-Vissible band towards longer wave lengths(or)Right side in a spectrum is

called Batho chromic shift (or)Red shift.

OH

benze phenol
λmax =255 nm λmax=283 nm

4.Hipsochromic shift /Blue shift:

Shifting of UV-Vissible band towards shorter wavelength(or)Left side in a spectrum is
ualed Hypsochromic shift (or)Blue shift.
 2 Ex:

λmax =270 nm λmax =260 nm

Hypsochromic shift

Bathochromic shift

r e
aemebertL'sam aw
rt's;-law and it's limitatio
When a mono chromatic light is passed through a solution the decrease in the intensity c
radiation is directly propontional to thickness of the

I₀ =intensity of incident light

I=intensity of absorbed light

t =thickness of solution

Beer's
law
:-
:I=lg.e-k
When a monochromatic light is passed through a solution.The decreasein the t
of light is directly proportional to concentration of the solution.

:I=lo.e-k C=concentration of solution

Beer-Lambert's law;-
From lambert's law →I=I₀·e-kt
 ro
F
m Beer's law

B eer lambert's
The intensity of incident light passed through a solution depends on concentration
olution and thickness of the medium
imitation
The law is applicable only
when plot a graph between absorbance(A)and concentration(C)gives straight line
through the origin.
ising monochromatic light
Salution contain a group which absorb a definite wave length of ligh
Important questions

Define chromophore and auxochrome.(SQ)

Write about various types of electronic transitions occurs in molecules.(LQ)

What are batho chromic shift &Hypsochrmoic shifts?(SQ)

Give the selection rules of UV-Vissible spectroscopy.(SQ)

What is Beer-Lambert's law give its limitations.(SQ)

ROTON MAGNETIC RESONANCE SPECTROSCOPY

ature of Nucleus:-

Magnetic moment (μ)

.Magnet

Angular moment (L/I)

Spinning nucleus
Rotation of particle around it's own axis called spinning.
nucleus produces magnetic field,Therefore nucleus act as tiny bar
Spinnin
spectroscopy.
g for
Spinning nucleus associates with magnetic moment vector(μ)and Angular
vector (L)Both are parallel to each other at nucleus.

Angular mormentumL/F₁ =√TC+1).

I=sum of spin Quantum members

)Spin quantum number zero -nucleus is non-magnetic.

 S.No No.of.'P'S No.of.'n'S At.No Man No. Spin Q.No(1) Example
Even Even Even Even Zero

2 Even Odd Even Odd Non Integer c¹³4=5).g⁷ (=3)

3 Odd even Odd Odd Non -Integer
Non-Integer ?³'(=5).H(=5)
4 Odd Zero Odd Odd

5
Integer(1,2,3… N(t=1).D(I=1)
Odd Odd Odd Even
Principle:-
Din the absence of external magnetic field spin orientation of nuclei are random:once t.
·magnetic field is applied at the nuclei disorder /random arrangement of nuclei disappears ang
nuclei orients in two possible directions.
In one orientation nuclear spins are parallel to direction of external magnetic field(Aligne
orientation Ea),In another orientation nuclear spins are Ir to direction of external magneticfie:
(opposed orientation Eg).Little excess of nuclei with aligned arrangment,then opposed arrang
ment.
Under resonance condiuon,if nuclei irradiated with Radio frequency(RF)radiation nucle
absorbs energy and participate in upward transitions with change in spin orientations are
calleda
Flipping of nuclei.

Resonance:- Matching of energy of R.F.radiation and energy gap of two nuclear energy
levels called Resonance.
The Absorbed energy by nuclei converted into H¹-NMR signal.

R.F radiation

Flipping
S bsorbec
N ener
Ex Converted
E into
C

Random orientation
(Absence of mag.field) HNMR
spectrum
Ho| Bo

external mag.field
Ho/Bo=Strength of ext.mag.field
units:Tesla(mks)
Gauss (C.G.S)
NMR spectrum
Equivalent and Non-equivalent protons:-
Equivalent protons:-
protons which possesses same chemlcalenvlronmentsandslmlllar chemical
shift(ö)values are called equivalent protons.
Ex:-(1)CH₄→4-protons of methane are equivalent i.c.1 sct

∴H₁,H₂,H₃,H₄Protons are equivalent =1 set

(2

All the 6-H of benzene are equivalent

Non-equivalent protons:-
Protons which possesses different chemical environments and shows different chemical
shift (δ)values are called Non-equlvalent protons.
 Ex--CH₃—CH₂—CH₃--Propane

(1),(3)are Identical →equivalent

(2)→different
∴ .Two types of protons =2 sets

(2)ci₃-Ch₂-ol-Ethanoi
Ethanol pocess three Non-equivalent sets of protons.

Examples:

Ex:- G
H ortho ∴3 types
ort
H H K
O (Ortho-H,Meta;Hara-H are
O non-equivalent)
H H Meta HMeta
H
Hpara
6H's equivale (1- Mo substituted
.benzene
 (1)
(1 type)
(2)
(ees
(3)
(aype)
(4)
(1type)
(5)
(2 types)

(6)
85-S2-0-s-ghg(2types)

Chemical Shift(δ)
The change in the position of nmr signal when compared with reference compound due to

shielding(or)deshielding effect of protons is called chemical shift (δ)

The reference compound used in NMR spectroscopy is TMS (Tetramethyl silane)

δ=0

0 Chem.shift of equivalent protons is always same.

0 Chem.shit of non-equivalent protons is always different

Ex:--CH₃,-OH,-NH₂protons

E.N=O>N>C

δ=-0H>-NH₂>-CH₃
 Type of proton Chemical shitt (δ)
Alcohols H-C-OH 3.4。4.0
AldelydesR-CHO 9.0-10.0
Acids H-C-COOH 2.0 -2.5
Armomatic Ar-H 6.0-9.0
Acetylenic -C=CH 2-3
Ethers 3.3 -4.0
H-C-OR
Esters H-C-COOR 2-2.2
Hvdroxy R-OH 1-5.5
Alkane R-CH₃ 0.9
Spin multiplicity:

Total number of lines in a nmr signal is called multiplicity

nmr-Signal Namg Symbol Spin multiplicity

Singlct S 1
One line

Doublet d 2
Two lines

Triplet t 3
Three lines

Quartet q
Pentet 5

P 5

Multiplet m
Splitting of nmr-signal:-
Due to interaction of spin of one partcular set of protons with the spin of
Nelghboun protons leads to splitting of nmr-signals.

O Splitting of nmr signal is due to spin-spin coupling process.

Spin -Spin coupling:-
 The process of spin of one partcular set of protons coupled with the spin of netghounms

protons is called spin-spin coupling.

 C b a
Eg:-CH₃——CH₂—OH -
Ethyl alcohol

n =no.of neighbouring protons

for—ÖH proton =no.ofneighbourng protons (n)=2

muliplicity of -OH proton=n+1
=2+1

= 1

(Triplet)

or-&tz protons no ofneghtouring poos (yltt

∴multiplicity of —CHz protons =n+1
=4+t 3+
=g4

Pente

quartet
for—&t₃protons =no.of neighbouring protons(n)=2 (-CH₂)
:multiplicity of -CH₃ protons =n+1
=2+1

=3

(Triplet)
Coupling constant)(J):
The distance between the two adjacent peaks in a multiplet is called coupling constant.
The value of the coupling constant is independent of the external field.
>itis measured in Hertz(HZ)(or)in cycles per second (CPS).
Турея оГ соирПпдУв1пНУ-НМР;-
1.Geminal coupling Jeem(or)]2

j* x no.o! ntervening bonds between coupled protons,

Couplng lnlteracuonsot protons attachedto same carbon are geminal couplnqs(N)

2. VIcinalсоирИпд 7,іс (or) 33

СоирНпд Ьесиееп аауасепГ сагЬоп аот ргоГоп

З. AIylccouplng: 7alyl (or) 14

СоирПпд Бесиесп оТенпсапд зТунс ргоГоп

Cls-Trans couplng: ’cis/7trans (or) 33

СоирПпд Ьесмееп Сн—ргоtопз IТгans-Ргоtопб

Jay

Н1-NМR spectras ot some org.compounds:-

1)Ethylbromide:-

Сн,-сн,-вг
2-sets of proton a & b

-Cн, ->n=2
from n +l rule

2+1=3{Triple!) (б =1.3)
 b

-CH₂→n=3
from n+1 rule

3+1=4(Quartet)(δ=3.3)

2)Acetaldelyde:-

ch₁; 2-sets of protons

-C&₂ n=1→ 1+1=2(Doublet)(δ=2.2)

-CHO→n=3→3+1=4(Quartet)(δ=9.5)

10.0 9.08.07.0 6.0 5.0 4.03.0 2.0 1.0 0 δPPM

 (3)1 ,2-Tribromo ethane:

2-sets of protons

-C2>n=1=1+1=2(doubet)(6=4.0)
-H²=n-2=2+1-3 y(8-5)

(4)Ethyl acetats:-

→3 sets of protons =3 signals

Acetophenone:-

b a

(o C₆H₅-C-CH
2-sets of protons=2 signals

-Ci₃→n=0→0+1=1(Single)(6=2.09)
-C₆H₅=n=0≥0+1=1(Singlet)(δ=7.3)