BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 17

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Summary of Lecture 16
N Blocal / 2N B / 2
Blocal = B + Badd = B(1-)
Shielding constant: = local + neighbour+ solvent
local : due to the shielding from the electrons immediately
surrounding the nucleus. (Electron density around the nuclei)
If electron density around the
If electron density around the
nuclei is decreased : Nuclei is
nuclei is increased: Nuclei is
deshielded Lower local peak
shielded higher local peak
observed at higher : DOWNFIELD
observed at Lower : UPFIELD

Chemical shift: = {( )/} X 106 ppm

Chemical shift are reported on scale...
[x-axis in the NMR spectrum]
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local : Shielding/Deshielding
Depending on their chemical environment, protons in a
molecule are shielded/deshielded by different amounts.
Lower

Relatively
Higher

TMS

The number of signals

shows
how
many
different
kinds
of
protons are present.
The location of the
signals
shows
how
shielded or deshielded
each proton is.
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Number of peaks (intensities)

No. of peaks equals the no. of distinct sets of equivalent protons.
Equivalent Hydrogens have same chemical Shifts.
Intensity of a peak is directly proportional to the no. of equiv.
protons responsible for the peak (its given by area under peak).

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Eg.: No. of peaks in 1H NMR spectrum

One peak (12H)

One peak (6H)

Two peaks (6:4)

Four peaks (6:1:2:2)

Two peaks (6:2)

Two major* peaks (5: 1)

One
peak (9H)

Three peaks
(3:2:2)

One peak is an overlap of peaks due

to 2 ortho-H, 2-meta-H, 1-para-H

One peak (12H)

Two peaks (9: 1)

Two peaks (6:4)

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Two peaks
(6:1)
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neighbour

: Effect of neighboring environment.

Benzene ring has an anisotropic magnetic susceptibility.

A ring current is produced to the applied magnetic field.
Aliphatic-C-H, approx. 1-2
Shielding zone
Shielded

Induces the field

that reinforces
with the external
magnetic field.

Deshielding zone

AromaticC-H, approx. 7-8

Highly Deshielded
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neighbour

Effect of neighboring environment.

Similarly, Alkenes & Aldehydic proton shows anisotropic

behavior.

CH=CH-H, approx. 5-6

O=CR-H, approx. 9-10

Deshielded

Highly Deshielded
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Solvent

Effect of Solvent

A solvent may influence the local magnetic field experienced

by a nucleus in a variety of ways. Minor effects
Solute Solvent interactions:
i) Hydrogen Bonding
ii) Lewis acid base complex formation
iii) Solvents such as benzene having magnetic susceptibilities
can provide shielding or deshielding effects.
iv) Steric interactions.
Deuterium labeled Solvents: Chloroform-d (CDCl3),
deuterium oxide (D2O),
benzene-d6 (C6D6),
acetone-d6 (CD3COCD3)
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 range for different Protons in different

chemical environment

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O-H and N-H Signals

Chemical shift of O-H & N-H depends on concentration & the
solvent used for recording NMR.
Hydrogen bonding in concentrated solutions deshield the
protons. Hydrogen bonding involves electron clouds transfer
from hydrogen atom to neighboring electronegative atoms.

(O-H) in o-hydroxyacetophenone is more deshielded

than (O-H) in phenol
However, value of OH/NH may vary in aliphatic or aromatic
systems (no fixed region).
O-H and N-H peaks are observed as broad peaks.
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Examples: No. of peaks In NMR spectrum

CH3COCH3

CH3CH2OH

Why splitting
of peaks

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The fine structure: Spin-spin coupling

The splitting of the groups of resonances (peaks) into individual
lines is called fine structure.
Nuclei themselves are little magnets they influence each other,
changing the energy and hence frequency of nearby nuclei as
they resonatethis is known as spin-spin coupling.
This coupling interaction between two nuclei occurs through
chemical bonds, (and can typically be seen up to three bonds
away) results in splitting of spectral lines, called the
multiplicity or splitting or coupling pattern of each signal.

The strength of interaction is expressed by spin-spin coupling

constant J (Hz): J is independent of magnetic field (B).
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The fine structure (Effect of X on A)

Consider the protons A and X (in general spin nuclei) with 3
bond distance away.

Case I: Neglecting spin-spin coupling,

the total energy of two 1H nuclei in a magnetic field
B is the sum of their individual energies

E = - N(1-A)BmA - N(1-X)BmX
A and X are the shielding constants
of A and X.
Assuming different orientations ( or ) of two nuclei
possible: Four energy levels could be predicted.
Nuclear transitions of a nuclei (A) are of same energy and
only one peak should be observed for it (A) at its respective
value (Neglecting spin-spin coupling).
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The fine structure (Effect of X on A)

Case II: Considering spin-spin coupling,

Espin-spin = hJAXmAmX

A and X are close

enough such that
their magnetic
moments will perturb
each other.

Etotal = E + Espin-spin
Etotal = E + hJAXmAmX
Different levels gets stabilized
or destabilized by a factor of
Espin-spin
Nuclear transitions of a nuclei
(A) will be of different energy
and two peaks will be observed
for hydrogen (A) at its respective
value.
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The fine structures: Splitting of peaks

Effect of X on A: This could be thought that magnetic moment
of A nuclei (in or orientation) will get perturb by the
magnetic moments of both or states of nuclei X.
Effect of A on X: (vice versa)

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The fine structure: Splitting of peaks (AX)

One neighboring X nuclei splits
the peak of A into two by a
coupling factor of JAX

Similarly, one neighboring A

nuclei splits the peak of X into
two by a coupling factor of JXA

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The fine structure

AX2

1 :2: 1

The two X nuclei may

have the 22 = 4 spin
arrangements.

The middle two

arrangements are
responsible for the
coincident resonance of
A.

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The fine structure

AX3
There are 23 = 8
arrangements of the
spins of the three X
nuclei, and their
effects on the A
nucleus gives rise to
four groups of
resonances.

1 :3 : 3 : 1
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Examples to solve:

Triplet (t): 2
Adjacent Protons

Doublet (d):
1 Adjacent
Proton

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