Mass Spectrometry,

Infrared Spectroscopy,
and Ultraviolet/Visible
Spectroscopy

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Spectrally Identifiable Functional Groups

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 When the electron beam hits a molecule, it knocks out an electron, producing
a molecular ion, which is a radical cation—a species with an unpaired
electron and a positive charge.

The energy of the electron beam can be varied, but a beam of about 70
electron volts (eV) is commonly used.

The mass spectrometer records a mass spectrum—a graph of the relative

abundance of each fragment plotted against its m>z value. Because the
charge (z) on essentially all the fragments that reach the collector plate is +1,
m>z is the molecular mass (m) of the fragment. Remember that only positively
charged species reach the collector.
The Mass Spectrometer
A mass spectrum
records only positively
charged fragments,
either cations or radical
cations

m/z = mass-to-charge
ratio of the fragment

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Information obtained from a mass spectrum:
• The molecular ion (M): measured to the nearest whole
number or up to four decimal places (high-resolution
mass spectrometry).
• Isotope peaks (M + 1, M + 2 etc.).
M
Typically M and the isotope peaks
are the highest masses in the
M+1 spectrum
…
Exception: a compound whose
molecular ion completely fragments

• The high-resolution mass of the molecular ion provides

the molecular formula directly.
• The whole-number mass of the molecular ion and the
relative intensities of M + 1, M + 2, etc., can also
provide the molecular formula.
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• Fragment masses and intensities together provide
structural information.

M-29 • The base peak has the greatest

Base peak intensity in the spectrum.
• Intense peaks correspond to
relatively stable cationic and/or
M-15 relatively stable radical species
lost.
• The fragments lost also provide
structural information.
For example:
• Fragment m/z 57 resulted from the
M loss of methyl (m/z = 15) from the
molecular ion.
… • Given its intensity, m/z 57 must be
the sec-butyl carbocation (not the
primary butyl carbocation).
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The Mass Spectrum of Pentane

Note weak m/z = 57 peak,

primary butyl carbocation

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The base peak of m/z 43 in the mass spectrum of
pentane indicates the preference for C-2 to C-3
fragmentation:

All fragments originate

from the molecular ion

The mass of the radical species lost in a fragmentation is

the difference between the m/z values of the fragment ion
and the molecular ion
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The Mass Spectrum of Isopentane
Note strong m/z = 57 peak,
secondary butyl carbocation

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2-Methylbutane is more likely than pentane to lose a
methyl radical because a secondary carbocation can be
formed:

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Two-Fragment Loss from the
Molecular Ion
What are the structures of m/z 42 and 41?

These ions arise from loss of the ethyl radical and

either hydrogen atom or H2 from the pentane molecular
ion:

Note: All fragments originate from the molecular ion.

Exception: Tandem Mass spectrometry where
fragments of fragments are observed.
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 Isotopes in Mass Spectrometry

• M + 1 peak: a contribution from 2H or 13C.

• M + 2 peak: a contribution from 18O or from two heavy
isotopes (2H or 13C) in the same molecule.

• A large M + 2 peak suggests a compound containing

either chlorine or bromine: a Cl if M + 2 is one-third the
intensity of M; a Br if M + 2 is the same intensity as M.

• To calculate the molecular masses of molecular ions

and fragments, the atom mass of a single isotope of an
atom must be used.
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Fragmentation Patterns of Alkyl Halides

79Br 81Br

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The Mass Spectrum of
2-Chloropropane

35Cl 35Cl

37Cl 37Cl

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a-Cleavage results from the homolytic cleavage of a
C—C bond at the a carbon:

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a-Cleavage occurs because the C—Cl and C—C bonds
have similar strengths, and the species that is formed is
a relatively stable cation:

a-Cleavage is less likely to occur in alkyl bromide

because C—C bond is stronger than C—Br bond

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Fragmentation Patterns of Ethers

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A C—C bond is cleaved homolytically at an a-position
because it leads to a relatively stable cation:

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A C—O bond is cleaved heterolytically, with the electrons
going to the more electronegative atom:

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Fragmentation Patterns of Alcohols

Because they fragment, molecular ions

obtained from alcohols usually are not
observed 20
Like alkyl halides and ethers, alcohols undergo
a-cleavage:

In alcohols, loss of water results in a fragmentation peak

at m/z = M-18:

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 Common Fragmentation Behavior in
Alkyl Halides,
Ethers, and Alcohols

1. A bond between carbon and a more electronegative

atom breaks heterolytically

2. A bond between carbon and an atom of similar

electronegativity breaks homolytically

3. The bonds most likely to break are the weakest bonds

and those that lead to formation of the most stable
cation
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Fragmentation Patterns of Ketones

An intense molecular ion peak:

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McLafferty rearrangement may occur:

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Spectroscopy and the Electromagnetic Spectrum
Spectroscopy is the study of the interaction of matter and
electromagnetic radiation

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Electromagnetic radiation has wave-like properties

High frequencies and short wavelengths are

associated with high energy
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Vibrational Transitions Observed
in IR Spectroscopy

Functional groups
stretch at different
frequencies, and IR
spectroscopy is
used to identify
functional groups

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Infrared transitions require a bond dipole to occur:

d d d d
hn
C H C H
Higher Energy
Vibrational State

The more polar the bond, the more intense the absorptions:

The intensity of an absorption band also depends on

the number of bonds responsible for the absorption
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 Influence of symmetry on IR activity of the alkene
stretch:

1-butene — infrared active

2,3-dimethyl-2-butene — infrared inactive
2,3-dimethyl-2-heptene — infrared active, but very weak absorption band

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The Vibrating Bond as a Quantized
Harmonic Oscillator
Quantum levels for a
stretching vibration: Ball-and-spring model:

Fundamental transition: no ® n1
Overtone: no ® n2

Overtones are twice the

frequency of the fundamental
transition and are always weak

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The approximate wavenumber of an absorption can be
calculated from Hooke’s law:

1 K
v=
2pc Reduced Mass =
M 1M 2
M1 + M 2

n = wavenumber
c = speed of light
K = force constant
M1 and M2 = masses of atoms
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Hooke’s law predicts that lighter atoms will vibrate at a
higher frequency than heavy atoms:

C—H ~3000 cm–1

C—D ~2200 cm–1
C—O ~1100 cm–1
C—Cl ~700 cm–1

Increasing the s character of a bond (higher K value)

increases the stretching frequency:

sp
sp2
sp3

sp2
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Note the influence of mass and s character on stretching frequency:

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 Beer’s Law
The peak intensity in infrared spectra is depend on the concentration of
molecules in the sample

Describes the relationship between the absorbance of

a solution, and its concentration:
— “The amount of light absorbed is proportional to the
concentration of the solution.”

A=εLc solution
absorbance concentration
(mol/L)

molar absorptivity length of path

constant traveled by light
(depends on combination
of solute/solvent/λ)
Absorbance

!!
A = 𝑙𝑜𝑔
Absorbance !

"
A=#
Transmittance
 An Infrared Spectrum
The functional group The fingerprint
region (4000–1400 cm–1) region (1400–600 cm–1)

High energy Low energy

The functional group, or diagnostic region, is used to determine
the functional group present
The fingerprint region is used for structure elucidation by spectral
comparison
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Functional group regions: Both Fingerprint regions: Compounds
compounds are alcohols are different alcohols

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The exact position of the absorption band depends on
electron delocalization, the electronic effect of
neighboring substituents, and hydrogen bonding:

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 Carbonyl
overtone

Esters have a carbonyl and a C—O stretch Ketones have only a carbonyl stretch

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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
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The position of a C—O absorption varies because of
resonance release in acids and esters:

~1050 cm–1

~1050 cm–1

~1250 cm–1

~1250 cm–1 and 1050 cm–1

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Acids are readily distinguished from alcohols

Higher-frequency
Broad C─O stretch
OH stretch
C═O stretch

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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

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The strength of a
C—H bond depends
on the hybridization
of the carbon

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Examine the absorption bands in the vicinity of 3000 cm–1

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 Benzene in-plane and
out-of-plane C—H bends
Benzene ring:
• Sharp absorption bands at ~1600 cm–1 and 1500–1430 cm–1.
• Overtones at 1700–1900 cm–1 for the in-plane and out-of-
plane benzene C—H bends.
• The benzene overtones in the diagnostic region are readily
recognized.
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Stretch of C—H Bond in an Aldehyde

The stretch of the C—H bond of an aldehyde shows one

absorption band at ~2820 cm–1 and another one at ~2720
cm–1

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Identifying a functional group by the bending vibrations:

• Primary amine: two N—H stretches at 3350 cm–1.

• Amine: N—H bend.
• “Isopropyl split” at 1380 cm–1 indicates the presence of
an isopropyl group.

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 Analyzing Infrared Spectra
The position, intensity, and shape of an absorption band
are helpful in identifying functional groups

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

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wavenumber (cm–1) assignment
3075 sp2 CH
2950 sp3 CH
1650 and 890 a terminal alkene with two substituents
absence of bands has less than four adjacent CH2 groups
1500–1430 and 720
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wavenumber (cm–1) assignment
3050 sp2 CH
2810 and 2730 an aldehyde
1600 and 1460 benzene ring
1700 a partial single-bond
character carbonyl
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wavenumber (cm–1) assignment
3300 OH group
2950 sp3 CH
2100 alkyne

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wavenumber (cm–1) assignment
3300 N—H
2950 sp3 CH
1660 amide carbonyl
1560 N—H Bend

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wavenumber (cm–1) assignment
>3000 sp2 CH
<3000 sp3 CH
1605 and 1500 a benzene ring
1720 a ketone carbonyl
1380 a methyl group
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