By shining light through samples,

we can learn about the molecular

structure of the sample and
(sometimes) deduce its structure.

IR

UV

RA
DI
O

By the end of this course you will

be able to interpret these light
absorbing properties of molecules
and deduce molecular structures!

H
H C H C1H4
Saturated alkanes (CH only
H compounds) have the general
H H
formula:
H C C H C2H6 CNHN+2
H H

H H H Note: it doesn’t matter how the

H C C C H C3H8 atoms are configured:
H H H
H
H C H
H H H H C4H10 H H C4H10
H C C C C H H C C C H
H H H H H H H

1
CNHN+2 CNHN CNHN-2
H H H H
H C C H C C HC CH
H H H H

C2H6 C2H4 C2H2

H H H H H H H
C C
H C C C H H C C H
C C
H H H H H H H

C3H8 C3H6 C3H6

HHCH H
H H H H H H H H C C H
H H H H H H H H C
H C C C C C C C H C H
H C C C C C C C H
H H H H H H C C HH
H H H H H H H H
H

C7H16 C7H14 C7H12

Two less hydrogens per double bond or ring!

The molecular formula can tell you about the structure:

FORMULA TELLS US THE NUMBER OF DOUBLE BONDS OR
RINGS:
IHD = index of hydrogen deficiency.
a.k.a. Degree of unsaturation.

For CNHM

IHD = 2N+2-M
2

2
Example: C6H10 •Two double bonds
•Two rings
IHD = (6 x 2)+2-10 = 4 = 2
2 2 •One triple bonds
•One double bond plus one ring

C H O N

For each Carbon Oxygen Each added

(valence =4) you add to F (valance = 2) nitrogen
a structure requires the can be added (valence =3)
addition of two more into a structure requires one
Hydrogens Cl without additional
H H X= changing the hydrogen
Br number of
H C C H
hydrogens
H H
C I

Each halogen
(valance = 1),
H H H takes the place of
H C C C H a hydrogen
H H H

3
 For CNHXXON
IHD = 2N+2-X-(#halogens)+(#Ns)
2
Example:
IHD =
C3H5BrO

Example:
IHD =
C4H7NO

We can tell something about the molecules you have by the

frequencies of light it absorbs

CH3
OH
C C H

4
Different frequencies of light (electromagnetic radiation) interact with
different aspects molecular motion (potential and kinetic energy).
UV: IR: Radio waves:
X-ray: valance
core electron molecular Nuclear spin states
excitation electronic vibrations (in a magnetic field)
excitation

Molecules have quantized energy levels:

ex. electronic energy levels.
energy

General Principle of Spectroscopy: A molecule absorbs light

when the frequency of light correlates with an energy transition.

hv
energy

energy

} ΔΕ = hv

5
Some (not all) nuclei have spin.
Nuclear spin can be examined by Nuclear Magnetic Resonance (NMR)
Only atoms with an odd number of protons or neutrons (or both) have
nuclear spins that can be observed by NMR.

Energy
= In the absence of a magnetic
field, both spin states have
equal energy

No Field Magnetic Field Stronger

Magnetic Field
Energy

} ΔΕ = hv
Energy

hv

In a strong magnetic field, the energy

level difference corresponds to the
energy of radio waves

6
 How an NMR spectrometer
works:
RF RF
transmitter Receiver

N S

Note modern
+ - NMRs use
superconducting
magnets to attain
very strong
magnetic fields

13C-NMR

We can examine the nuclear magnetic properties of carbon atoms

in a molecule to learn about a molecules structure.
NOTE: most carbons are 12C. 12C has an even number of protons
and neutrons and cannot be observed by NMR techniques.
However approximately 1% of carbons are 13C, and these we can
see in the NMR. (this will be come later when we consider
nuclear spin coupling)

7
 Here is what’s cool about 13C-NMR:
A 13C-NMR spectrum.
Different carbons appear at different
frequencies! - Now you know how
many different types of Carbons you
have!
An internal
RF absorbance

standard
called TMS
is used to
set the
scale to
zero

RF Frequency
The intensity of the peak doesn’t does not necessarily
correlate to the number of carbons.

Example: Two alcohols (-OH compound) with formula C3H8O

1. IHD = 0
2. Possible structures:

8
How Many 13C NMR resonances?
OH
Cl
F

F F F

=
equivalent resonance structures 1

OH Br Br Br
Br

Br
Br

Cl Br

Br

9
An isolated 13C atoms have the same chemical shift. (resonate at
the same frequency) Nucleus
C
Electron “cloud”

The electron cloud of the atom partially shields the nucleus from the
surrounding magnetic field

When the carbon nucleus is adjacent to an electronegative atom, the

carbon nuclei has fewer Electrons around it.

C F

Nuclei with less electron density around them will resonate at a different
frequency: It requires shorter wavelength radio waves (or a weaker magnetic
field) to cause a carbon nuclei to resonate if it has less electron density around it.

Conversely atoms that donate electron density cause nuclei to resonate at

lower frequencies (higher field strengths).

CH3
The silicon in tetramethylsilane (TMS)
shields the carbon nuclei and makes them
CH3 Si CH3 appear “up-field”

The chemical shift spectrum is

CH3 measured relative to TMS.

Shift
TMS

10
 THE δ SCALE IS USED TO MEASURE CHEMICAL SHIFT

δ= is used to signify chemical shift.

Because the frequency depends on the
field strength, TMS
one uses a relative units scale of “parts Shift
per million” or ppm

Chemical shifts reported as ppm units give the same values

for the same compound regardless of the instrument used!

δ = (v(compound)- v(TMS))/ v(instrument field strength)

H H
H C OH H C F 71.6 ppm
H H
50.2 ppm
H
H C Cl 25.6 ppm
H
H
H C CH3 H
H H C Br 9.6 ppm
7.3 ppm H

H Cl Cl Cl
H C Cl H C Cl Cl C Cl Cl C Cl
H H H Cl
25.6 54.0 77.2 96.1

11
 Atoms which are not directly attached to an electronegative
atom are still shifted but the effect is significantly attenuated.
The inductive effect (through bond influence) drops off rapidly
with distance.

OH 25 84 25.3 29.3 22.7

64 H2 22 H2 H2 H2 H2
CH C CH3 C C C C
H 3C C C F C C C CH3
H2 H2 H2 H2 H2
14.1
40 27 23 30.6 29.3 31.9

Typical Values of Chemical shift depend on the

1. Hybridization
2. Electronegativity of attached atom(s).

75 50

C O
150 120

aromatic C Br, (Cl)

160 150 105 90 70

210 sp 40 -5
C O
carbonyl
C C sp2 C C
C
sp3

200 150 100 50 0

Some specific values are included in tables 12.1-12.9 in your text book!

12
C4H6

13
C3H6O

OH

13C peaks are in reality split by bonded protons.

Generally Actually looks

shown like this: like this:
H
C A “doublet”

Why??
Adjacent nuclear spin of the proton locally increases
C H magnetic field felt by carbon nuclei.

NOTE: There are only

Carbons next to Carbons next to two possible peaks for
down proton spin up proton spin C’s having one adjacent
proton.
or

14
 H
Appears as a doublet or
C

H
Appears as a triplet
C
H
There are four possibilities which lead to two net spin states:

The distribution of spin states is random so half the time the carbon will feel no net
spin, 25% two up spins and 25% of the time two down spins:

H
H C Appears as quartet.
H

There are eight possibilities:

The general rule is:

The number of peaks observed is equal to the number of attached protons,
(N), plus one.

Splitting = N+1
FOR 13C it is the number of protons directly
attached to the carbon that cause splitting.

15
 Why don’t the spins on adjacent
Carbons split each other?

C C
Only 1% of Carbons have a spin! (Most are 12C and are NMR
inactive). Therefore only 1 in ten thousand pairs of Cs have both
have spin and are coupled. That’s too small to detect!

Note all of these split peaks can quickly get confusing:

Am I looking at two different carbon resonances or a single
doublet?
For this reason we show our spectra without splitting. But we often
see the splitting indicated over the peak:

16
C6H10O
IHD = ???

C3H9N
44.6 (t)
27.4 (t)
11.5 (q)

17
 It is helpful to know what typical values of unfunctinalized C’s

Approximate Chemical Shifts ranges for unsubstituted Alkanes

-CH3 5-22 ppm
-CH2- 15-33 ppm
>CH- 25-35

C=C 110-150

Alkyne 66-90

If your molecule contains Oxygen:

H
C O C O C O O
C
50 - 75 ppm 50 - 75ppm
(but two of them!) 90 - 100 ppm

R = alkyl X = Cl, Br, I

O O O O O O
C C C C C C
R H R R R O R NHR R X O O
195 - 220 195 - 220 165-180
doublet 165-180 165-180 ~155
but singlet!

60.4 34.4
O O
C C
H 3C O H 3C N
H

18
If your molecule contains Nitrogen:
Amines:
H C
C NH2 N N
C C C C

28-47 ppm

Nitro-
O
C N 61 - 85 ppm C C N
O
~120
Imine
R 14-30
N ~155 ppm
C

C3H7N
139 (d)
113 (t)
44.8 (t)

19
 C3H9N
43.0 (d)
26.5 (q)

C3H8O2
72.7 (d)
67.7 (t)
18.7 (q)

OH
HO

20
C6H8O

IHD
Symmetry
What is the O doing?
What other groups can you identify?
Can you account for the IHD?

C8H8O
IHD
Symmetry
What is the O doing?
What other groups can you identify?

21
 What You Should Now
Know!
• Bond Line Formulas
• How to calculate IHDs
• 13C chemical shift scale
• Multiplicities
– s, d, t, q
• Approximate Chemical Shifts
– Alkanes, Alkenes, Alkynes, Aromatics
– Alcohol, Amines, Ethers, Carbonyls