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Spectroscopy:
Electromagnetic Radiation and
Molecular structure
electronic UV-Vis
vibrational infrared
rotational microwave
nuclear spin radiofrequency
1H and 13C
+ +
+
+
An external magnetic
field causes nuclear +
magnetic moments to
align parallel and
antiparallel to applied
field. +
+
H0
+
+
There is a slight
excess of nuclear +
magnetic moments
aligned parallel to
the applied field.
+
+
H0
+
+
Energy Differences Between Nuclear Spin States
!E !E '
Units
The frequency (") of absorbed
electromagnetic radiation Hz (s-1)
is proportional to
H0
Shielding
applied field.
C H
A stronger external field is
needed in order for energy
difference between spin
states to match energy of
rf radiation. H0
Chemical Shift
Chemical shift is a
measure of the degree to
which a nucleus in a
molecule is shielded.
C H
Protons in different
environments are shielded
to greater or lesser
degrees; they have
different chemical shifts. H0
Downfield Upfield
Decreased shielding Increased shielding
(CH3)4Si (TMS)
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
H0
Chemical shift (#, ppm)
measured relative to TMS
Cl
# 7.28 ppm
H C Cl
Cl
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
H0
Chemical shift (#, ppm)
Effects of Molecular Structure
on
1H Chemical Shifts
CHCl3 CH3Cl
CH2Cl2
Protons attached to sp2 hybridized carbon
are less shielded than those attached
to sp3 hybridized carbon
H
H H H H
H H C C CH3CH3
H H H
# 7.3 ppm # 0.9 ppm
# 5.3 ppm
Information contained in an NMR
spectrum includes:
1. number of signals
environments
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
H0
Chemical shift (#, ppm)
1H and 13C NMR compared:
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
1H H0
Chemical shift (#, ppm)
ClCH2CH2CH2CH2CH3
a separate, distinct
peak appears for
each of the 5 carbons
Solvent
CDCl3
Increasing electronegativity
H0
As the atom attached to a carbon becomes more
electronegative, the carbon atom signal is observed
at lower field
OH
61 23
H0
O
202 138 23