CH 15

Organic Chemistry
Second Edition
David Klein
Chapter 15
Infrared Spectroscopy and Mass Spectrometry
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry 2e
15.1 Introduction to Spectroscopy
• Spectroscopy involves an interaction between matter
and light (electromagnetic radiation)
• Light can be thought of as waves of energy or packets
(particles) of energy called photons
• Properties of light waves include wavelength and
frequency
• Is wavelength directly or inversely proportional to
energy? WHY?
• Is frequency directly or inversely proportional to
energy? WHY?
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. 15-2 Klein, Organic Chemistry 2e
• There are many wavelengths of light that can not be
observed with your eyes
• When light interacts with molecules, the effect depends
on the wavelength of light used
• This chapter focuses on IR spectroscopy

15.2 IR Spectroscopy
• Molecular bonds can vibrate by stretching or by bending
in a number of ways
• This chapter will focus mostly on stretching frequencies

• WHY do objects emit IR light?
• WHY do some objects emit more IR radiation than
others?
• WHERE does that light come from?
• Some night vision goggles can detect IR light that is
emitted
• IR or thermal imaging is also used to detect breast
cancer
• The energy necessary to cause vibration depends on the
type of bond
• An IR spectrophotometer irradiates a sample with all
frequencies of IR light
• The frequencies that are absorbed by the sample tell us
the types of bonds (functional groups) that are present
• How do we measure the frequencies that are absorbed?
• Most commonly, samples are deposited neat on a salt

(NaCl) plate. WHY is salt used?
• Alternatively, the compound may be dissolved in a

solvent or embedded in a KBr pellet
• Analyze the units for the wavenumber,
• ν = frequency and c = the speed of light
• A signal on the IR spectrum has three important
characteristics: wavenumber, intensity, and shape
15.3 IR Signal Wavenumber
• The wavenumber for a stretching vibration depends on
the bond strength and the mass of the atoms bonded
together
• Should bonds between heavier atoms require higher or

lower wavenumber IR light to stretch?
• Rationalize the trends below using the wavenumber
formula
1.
2.
• The wavenumber formula and empirical observations
allow us to designate regions as representing specific
types of bonds
• Explain the regions above
• The region above 1500 cm-1 is called the diagnostic
region. WHY?
FINGERPRINT REGION
DIAGNOSTIC REGION
• The region below 1500 cm-1 is called the fingerprint

region. WHY?
• Analyze the diagnostic and fingerprint regions below
• Analyze the diagnostic and fingerprint regions below
• Compare the IR spectra
• Greater difference in masses of atoms attached, greater
the greater the wavenumber
• C-H stretch ≈ 3000 cm-1

• O-H stretch ≈ 3400 cm-1
• Practice with conceptual checkpoint 15.1
• Compare the IR stretching wavenumbers below
• Are the differences due to mass or bond strength?

• Which bond is strongest, and WHY?
• Note how the region ≈3000 cm-1 in the IR spectrum can
give information about the functional groups present
• Is it possible that an alkene or alkyne could give an IR
spectra without any signals above 3000 cm-1?
• Predict the wavenumbers that would result (if any)
above 3000 cm-1 for the molecules below
• Resonance can affect the wavenumber of a stretching
signal
• Consider a carbonyl that has two resonance contributors
• If there were more contributors with C-O single bond

character than C=O double bond character, how would
that affect the wavenumber?
• Use the given
examples to
explain HOW
and WHY the
conjugation
and the –OR
group affect
resonance
and thus the
IR signal?

15.4 IR Signal Strength
• The strength of IR signals can vary
• The more polar the bond, the greater the opportunity
for interaction between the waves of the electrical field
and the IR radiation
• Greater bond polarity = stronger IR signals

• Note the general strength of
the C=O stretching signal vs.
the C=C stretching signal
• Imagine a symmetrical
molecule with a completely
nonpolar C=C bond: 2,3-
dimethyl-2-butene
• 2,3-dimethyl-2-butene does
not give an IR signal in the
1500-2000 cm-1 region
15.5 IR Signal Shape
• Some IR signals are broad, while others are very narrow
• O-H stretching signals are often quite broad

• When possible, O-H bonds form H-bonds that weaken
the O-H bond strength
• WHY does H-bonding
affect the O-H bond
strength?
• The H-bonds are transient, so the sample will contain
molecules with varying O-H bond strengths
• Why does that cause the O-H stretch signal to be broad?
• The O-H stretch signal will be narrow if a dilute solution
of an alcohol is prepared in a solvent incapable of H-
bonding
• In a sample with an intermediate concentration, both
narrow and broad signals are observed. WHY?
• Explain the cm-1 readings for the

two O-H stretching peaks
• Consider how broad the O-H stretch is for a carboxylic
acid and how its wavenumber is around 3000 cm-1
rather than 3400 cm-1 for a typical O-H stretch
• H-bonding is often more pronounced in
carboxylic acids, because they can forms
H-bonding dimers
• For the molecule below, predict all of the stretching
signals in the diagnostic region
• Primary and secondary amines exhibit N-H stretching
signals. WHY not tertiary amines?
• Because N-H bonds are capable of H-bonding, their

stretching signals are often broadened
• Which is generally more polar, an O-H or an N-H bond?
• Do you expect N-H stretches to be strong or weak

signals?
• See example spectra on next slide

• The appearance of two N-H signals
for the primary amine is NOT simply
the result of each N-H bond giving a
different signal
• Instead, the two N-H bonds vibrate
together in two different ways
• A single molecule can only vibrate symmetrically or
asymmetrically at any given moment, so why do we see
both signals at the same time?
• Similarly, CH2 and CH3 groups can also vibrate as a group

giving rise to multiple signals
15.6 Analyzing an IR Spectrum
• Table 15.2 summarizes some of the key signals that help
us to identify functional groups present in molecules
• Often, the molecular structure can be identified from an
IR spectra
1. Focus on the diagnostic region (above 1500 cm-1)
a) 1600-1850 cm-1 – check for double bonds
b) 2100-2300 cm-1 – check for triple bonds
c) 2700-4000 cm-1 – check for X-H bonds
d) Analyze wavenumber, intensity, and shape for each signal
• Often, the molecular
structure can be identified
from an IR spectra
2. Focus on the 2700-4000
cm-1 (X-H) region
• Practice with SkillBuilder

15.1
15.7 Using IR to Distinguish
Between Molecules
• As we have learned in previous chapters, organic
chemists often carry out reactions to convert one
functional group into another
• IR spectroscopy can often be used to determine the
success of such reactions
• For the reaction below, how might IR spectroscopy be
used to analyze the reaction?
• Practice with SkillBuilder 15.2

15.7 Using IR to Distinguish
Between Molecules
• For the reactions below, identify the key functional
groups, and describe how IR data could be used to verify
the formation of product
• Is IR analysis qualitative or quantitative?
15.8 Into to Mass Spectrometry
• Mass spectrometry is primarily used to determine the
molar mass and formula for a compound
1. A compound is vaporized and then ionized
2. The masses of the ions are detected and graphed
• The most common method of ionizing molecules is by
electron impact (EI)
• The sample is bombarded with a beam of high energy
electrons (1600 kcal or 70 eV)
• EI usually causes an electron to be ejected from the
molecule.
• What is a radical cation?
• How does the mass of the radical cation compare to the
original molecule?
• If the radical cation remains intact, it is known as the

molecular ion (M+•) or parent ion
• Often, the molecular ion undergoes some type of
fragmentation.
• The resulting fragments may undergo even further
fragmentation
• The ions are deflected by a magnetic field

• Smaller mass and higher charge fragments are affected
more by the magnetic field.
• Neutral fragments are not detected.
• Explain the units on the x and
y axes for the mass spectrum
for methane
• The base peak is the tallest
peak in the spectrum
• For methane the base peak
represents the M+•
• Sometimes, the M+• peak is
not even observed in the
spectrum, WHY?
• Peaks with a mass of less than M+• represent fragments
• Subsequent H radicals can be fragmented to give the

ions with a mass/charge = 12, 13 and 14
• The presence of a peak representing (M+1) +• will be
explained in section 15.10
15.9 Analyzing the M+• Peak
• In the mass spec for benzene, the M+•
peak is the base peak
• The M+• peak does not easily fragment
• Like most compounds,
Base peak
the M+• peak for
pentane is NOT the
base peak
• The M+• peak
fragments easily
M+.
• The first step in analyzing a mass spec is to identify the
M+• peak
– It will tell you the molar mass of the compound
– An odd massed M+• peak MAY indicate an odd number of N
atoms in the molecule
– An even massed M+• peak MAY indicate an even number of N
atoms or zero N atoms in the molecule
• Give an alternative explanation for a M+• peak with an
odd mass
15.10 Analyzing the (M+1)+• Peak
• Recall that the (M+1)+• peak in
methane was about 1% as
abundant as the M+• peak
• The (M+1)+• peak results from

the presence of 13C in the
sample.
• For every 100 molecules of decane,
what percentage of them are made of
exclusively 12C atoms?
• Comparing the heights of the (M+1)+•
peak and the M+• peak can allow you to
estimate how many carbons are in the
molecule.
• The natural abundance of deuterium is
0.015%. Will that affect the mass spec
analysis?
• Chlorine has two abundant isotopes
• 35Cl=76% and 37Cl=24%
• Molecules with chlorine
often have strong (M+2)+•
peaks
• WHY is it sometimes
difficult to be absolutely
sure which peak is the
(M)+• peak?
• 79Br=51% and 81Br=49%, so molecules with bromine
often have equally strong (M)+• and (M+2)+• peaks
• Practice with
conceptual
checkpoints
15.23 and
15.24
15.12 Analyzing the Fragments
• A thorough analysis of the molecular fragments can
often yield structural information
• Consider pentane
• Remember, MS only
detects charged
fragments
• WHAT type of
fragmenting is
responsible for the
“groupings” of
peaks observed?
• In general, fragmentation will be more prevalent when
more stable fragments are produced
• Correlate the relative
stability of the fragments
here with their abundances
on the previous slide
• Consider the fragmentation below
• All possible fragmentations are generally observed

under the high energy conditions employed in EI-MS
• If you can predict the most abundant fragments and
match them to the spectra, it can help you in your
identification
• Alcohols generally undergo two main types of
fragmentation: alpha cleavage and dehydration
• Amines generally undergo alpha cleavage
• Carbonyls generally undergo McLafferty rearrangement
• Practice with conceptual checkpoints

15.25 – 15.28
15.16 Degrees of Unsaturation
• Mass spec can often be used to determine the formula
for an organic compound
• IR can often determine the functional groups present
• Careful analysis of a molecule’s formula can yield a list
of possible structures
• Alkanes follow the formula below, because they are
saturated
CnH2n+2
• Verify the formula by drawing some isomers of pentane
• Notice that the general formula for the compound,
CnH2n+2, changes when a double or triple bond is present
• Adding a degree of unsaturation decreases the number

of H atoms by two
• How many degrees of unsaturation are there in
cyclopentane?
• Consider the isomers of C4H6
• How many degrees of unsaturation are there?
• 1 degree of unsaturation = 1 unit on the hydrogen
deficiency index (HDI)
• For the HDI scale, a halogen is treated as if it were a
hydrogen atom
• How many degrees of unsaturation are there in C5H9Br?

• An oxygen does not affect the HDI. WHY?
• For the HDI scale, a nitrogen increases the number of
expected hydrogen atoms by ONE
• How many degrees of unsaturation are there in

C5H8BrN?
• Forget this formula below (you can use if you want)
• NOTrogen for Nitrogen
•H alogen
•0xygen (the O is a zero)
• Calculating the HDI can be very useful. For example, if
HDI=0, the molecule can NOT have any rings, double
bonds, or triple bonds
• Propose a structure for a molecule with the formula
C7H12O. The molecule has the following IR peaks
– A strong peak at 1687 cm-1
– NO IR peaks above 3000 cm-1

CH 15

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Organic Chemistry

• This chapter focuses on IR spectroscopy

• This chapter will focus mostly on stretching frequencies

• Most commonly, samples are deposited neat on a salt

• Alternatively, the compound may be dissolved in a

• Should bonds between heavier atoms require higher or

• Explain the regions above

• The region below 1500 cm-1 is called the fingerprint

• C-H stretch ≈ 3000 cm-1

• Practice with conceptual checkpoint 15.1

• Are the differences due to mass or bond strength?

• Practice with conceptual checkpoint 15.2

• If there were more contributors with C-O single bond

• Practice with conceptual checkpoint 15.3

• Greater bond polarity = stronger IR signals

• O-H stretching signals are often quite broad

• Explain the cm-1 readings for the

• Practice with conceptual checkpoint 15.9

• Because N-H bonds are capable of H-bonding, their

• Do you expect N-H stretches to be strong or weak

• See example spectra on next slide

• Similarly, CH2 and CH3 groups can also vibrate as a group

• Practice with SkillBuilder

• Practice with SkillBuilder 15.2

• Is IR analysis qualitative or quantitative?

• What is a radical cation?

• If the radical cation remains intact, it is known as the

• The ions are deflected by a magnetic field

• Subsequent H radicals can be fragmented to give the

• The (M+1)+• peak results from

• All possible fragmentations are generally observed

• Carbonyls generally undergo McLafferty rearrangement

• Practice with conceptual checkpoints

• Adding a degree of unsaturation decreases the number

• How many degrees of unsaturation are there in C5H9Br?

• How many degrees of unsaturation are there in

• Forget this formula below (you can use if you want)

•0xygen (the O is a zero)

• Practice with SkillBuilder 15.4

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