Organic Chemistry

4th Edition
Paula Yurkanis Bruice

Chapter 13

Mass Spectrometry
and
Infrared Spectroscopy

Irene Lee
Case Western Reserve University
Cleveland, OH
©2004, Prentice Hall
Information Obtained from Mass
Spectrometry

The molecular mass

The molecular formula

Certain structural features

of the compound
 A Mass Spectrometer
The mass spectrometer records a mass spectrum
A mass spectrum records only positively charged
fragments

m/z = mass to charge ratio of the fragment

• Nominal molecular mass: the molecular mass to the
nearest whole number

• Each m/z value is the nominal molecular mass of the

fragment

• The peak with the highest m/z value represents the

molecular ion (M)

• Peaks with smaller m/z values__called fragment ion

peaks__represent positively charged fragments of the
molecule
• The base peak is the peak with the greatest intensity,
due to its having the greatest abundance

• Weak bonds break in preference to strong bonds

• Bonds that break to form more stable fragments break

in preference to those that form less stable fragments
The base peak of 43 in the mass spectrum of pentane
indicates the preference for C-2 to C-3 fragmentation

To identify fragment ions in a spectrum, determine the

difference between the m/z value of a given fragment ion
and that of the molecular ion
Carbocations can undergo further fragmentation
2-methylbutane has the same m/z as pentane
but the peak at m/z = 57 (M – 15) is more intense
 Isotopes in Mass Spectrometry

• peaks that are attributable to isotopes can help identify

the compound responsible for a mass spectrum

• M + 2 peak: a contribution from 18O or from two heavy

isotopes in the same molecule
• a large M + 2 peak suggests a compound containing
either chlorine or bromine: a Cl if M + 2 is 1/3 the height
of M; a Br if M + 2 is the same height as M

• In calculating the molecular masses of molecular ions

and fragments, the atom mass of a single isotope of an
atom must be used
The Mass Spectrum of Bromopropane
The weakest bond is the C–Br bond

The base peak is at m/z = 43 [M – 79, or (M + 2) – 81]

The propyl cation has the same fragmentation pattern

it exhibited when it was formed in the cleavage of
pentane
The Mass Spectrum of
2-Chloropropane
The compound contains a chlorine, because M + 2 peak
is 1/3 the height of the molecular ion peak

The base peak at m/z = 43 results from heterolytic

cleavage of the C–Cl bond

The peaks at m/z = 63 and m/z = 65 have a 3:1 ratio,

indicating the presence of a chlorine atom
a cleavage results from the homolytic cleavage of a
C–C bond at the a carbon
The Fragmentation Pattern of Ethers
The Fragmentation of Alcohols
 Common Fragmentation Behavior in
Alkyl Halides,
Ethers, and Alcohols

1. A bond between carbon and a more electronegative

atom

2. A bond between carbon and an atom of similar

electronegativity break homolytically

3. The bonds most likely to break are those which lead

to formation of the most stable cation
Fragmentation Pattern of Ketones

An intense molecular ion peak

McLafferty rearrangement may occur
 Infrared Spectroscopy
An infrared spectrum is obtained by passing infrared
radiation through the sample

hc
E = hu =
l

wavenumber (~ u) is another way to describe the frequency

of electromagnetic radiation

High frequencies, large wavenumbers, and short

wavelengths are associated with high energy
The covalent bonds in molecules are constantly vibrating

Each stretching and bending vibration of a bond occurs

with a characteristic frequency
An Infrared Spectrum

The spikes are absorption bands

The functional group The fingerprint
region region
It takes more energy to stretch a bond than to bend it
The greater the change in dipole moment, the more
intense the absorption

When the bond stretches, the increasing distance

between the atoms increases the dipole moment

The intensity of an absorption band depends on the

number of bonds responsible for the absorption
Bond order affects bond strength, so bond order affects
the position of absorption bands

The approximate wavenumber of an absorption can be

calculated from Hooke’s law

f(m1 + m2) 1/2

u~ = 1
2pc m1m2

u~ the wavenumber of the stretching vibration

f the force constant
m1 and m2 masses of the atoms
The exact position of the absorption band depends on
electron delocalization, the electronic effect of
neighboring substituents,and hydrogen bonding

O O-
O
CH3CCH2CH2CH3

C O C O
at 1720 cm–1 at 1680 cm–1
Putting an atom other than carbon next to the carbonyl
group causes the position of the carbonyl absorption
band to shift

The predominant effect of the nitrogen of an amide is

electron donation by resonance

The predominant effect of the oxygen of an ester is

inductive electron withdrawal
The position of a C–O absorption varies because

CH3CH2 OH ~1050 cm–1

CH3CH2 O CH2CH3 ~1050 cm–1

O O-
C C
H3C OH H3C OH ~1250 cm–1

O O-
C C ~1250 cm–1 and 1050 cm–1
H3C O CH3 H3C O CH3
The position and the breadth of the O–H absorption
band depend on the concentration of the solution

It is easier to stretch an O–H bond if it is hydrogen

bonded
The strength of a
C–H bond depends
on the hybridization
of the carbon
Examine the absorption bands in the vicinity of 3000 cm–1
If a compound has hydrogen bonded to sp2 carbon

The detection of sharp absorption bands at ~1600 cm–1

and 1500–1430 cm–1: benzene

The detection of absorption bands at ~1600 cm–1: alkene

The N–H bending vibrations also occur at ~1600 cm–1,
but they are broader and more intense

They will be accompanied by N–H stretching at

3500–3300 cm–1
Stretch of C–H Bond in an Aldehyde
If a compound has sp3 carbon, absorption at ~1400 cm–1
identifies the methyl group
 Analyzing Infrared Spectra

The absence of absorption bands can be useful in

identifying a compound in IR spectroscopy

Bonds in molecules lacking dipole moments will not be

detected
wavenumber (cm–1) assignment
3075 sp2 CH
2950 sp3 CH
1650 and 890 a terminal alkene with two substituents
absence of 720 has less than four adjacent CH2 groups
wavenumber (cm–1) assignment
3050 sp2 CH
2810 and 2730 an aldehyde
1600 and 1460 benzene ring
1700 a partial single-bond
character carbonyl
wavenumber (cm–1) assignment
3300 OH group
2950 sp3 CH
2100 alkyne
wavenumber (cm–1) assignment
3300 N–H
2950 sp3 CH
1660 amide carbonyl
1560 N–H
wavenumber (cm–1) assignment
>3000 sp2 CH
<3000 sp3 CH
1605 and 1500 a benzene ring
1720 a ketone carbonyl
1380 a methyl group