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Chapter 12: Infrared Spectroscopy (IR) and Mass Spectrometry (MS)

Infrared Spectroscopy
Infrared Spectroscopy is a type of imaging technique that uses infrared light that
causes the bonds of a molecule to vibrate, or stretch. The energy that is absorbed
to stretch the bonds of a molecule is measured through a spectrum, which can be
used to analyze properties of the molecule of interest. An infrared spectrum is
the actual graph that shows the energy absorbed by the molecule in relation to the
wavelength of light used. Below is an example of what an IR spectrum looks like

Usually, you will see the IR spectrum graph the transmittance (absorbance) versus
the wavenumber (inverse of wavelength, in units of cm -1). Notice the region
between 400 cm-1 and 1400 cm-1. This region is called the fingerprint region,
because the bands (the peaks representing the different stretches of the molecule),
is unique to each different molecule. As far as O.Chem II is concerned, you will
NEVER use the fingerprint region because it is too complex to memorize
each specific peak within that region! The region that will be commonly used is
the region from 1500 cm-1 to 4000 cm-1. This region contains peaks that
indicate specific functional groups that you will be responsible for! Ive
listed some important facts about IR that you should keep in mind below.

IR is mainly used to identify the functional groups of a molecule only! It


cant give you the molecular formula, molecular mass, or the exact structure
of the molecule
As the wavenumber (or frequency) increases, the energy required to
stretch the bond increases since the bond becomes more stif
(remember from physics that wavelength is inversely proportional to the
energy of the wave, so since wavenumber is the inverse of wavelength, it is

directly proportional to the energy). The term wavenumber and frequency


are used interchangeably for IR spectrums
Each functional group has a certain peak at a specific location
(wavenumber), of a specific strength (weak, strong), and a specific
shape (broad, or sharp). It is the characteristics of the peak, as well as
the wavenumber position that allows you to determine the specific
functional group present.
There has to be some dipole moment in a bond that is stretched for a peak
to show up on the IR spectrum. If there is no dipole moment within the
bond, it will not show up on the IR spectrum. For example, the carboncarbon bond on benzene will not show up because there is zero
dipole moment within the bond if it is stretched. Keep this in mind
when you are looking at IR spectrum graphs and you dont see a
functional group on the IR even though it is present on the molecule!

I will separate the guide into the type of bonds (functional groups) that can be seen
from the IR spectrum, and Ill emphasize which ones to know
Carbon-Carbon Bond stretching
There are 3 types of carbon-carbon bond stretching you can see from an IR: a
single, double, or triple C-C bond. The wavenumber for the specific stretches are
listed below. Keep in mind that the higher bond strength, the higher
wavenumber (energy) it is required to absorb.
C-C single bond: 1200 cm-1 (you will never use this peak)
C-C double bond: 1600-1660 cm-1 (depending on degree of conjugation).
Benzene (3 double bonds in conjugation) is around 1600 cm -1
C-C triple bond: slightly below 2200 cm-1
The most useful C-C bonds that you will need able to recognize are the C-C
double and triple bonds.
A carbon-carbon double bond is shown as a weak to moderately
strong, sharp peak around 1640-1680 (not absolute, but very close
enough). An example is shown below (2-hexene)

Depending on the degree of conjugation (how many double bonds


are in resonance with each other), the wavenumber of the peak of
focus will be lower (about 20 cm-1 lower per 1 extra double
bond in conjugation). The more double bonds in conjugation,
the lower the wavenumber. This is very important for all
functional groups, including carbonyls! Conjugated double bonds
are usually around 1620-1640 cm-1, and aromatic (such as benzene)
double bonds are around 1600 cm -1. Below is an example of 1,3pentadiene. Notice the carbon-carbon peak is lower around
1620, compared to 2-hexene.

A carbon-carbon triple bond is shown as a weak to moderately


strong, sharp peak slightly less than 2200 cm-1. An example is shown
below (2-hexyne). It is important to note that it is LESS than 2200 cm-1
since there is a different functional similar in characteristic that is GREATER
than 2200 cm-1

Carbon-Hydrogen bond stretches


There are 3 types of Carbon-Hydrogen bond stretches on an IR spectrum:
The sp3 hybridized C-H bond (alkane hydrogen), the sp 2 hybridized C-H bond (alkene
hydrogen), and the sp hybridized C-H bond (alkyne hydrogen). The bond stretch
wavenumber is listed below
sp3 hybridized C-H bond (alkane hydrogen): 2800-3000 cm-1 (NEVER above
3000 cm-1)
sp2 hybridized C-H bond (alkene hydrogen): 3000-3100 cm-1 (BARELY above
3000 cm-1)
sp hybridized C-H bond (alkyne hydrogen): 3300 cm-1 (HAS to contain an
alkyne hydrogen bond)
These peaks are not as important as some of the other peaks. However, it is good
to note that if you see a sharp, strong peak HIGHER than 3000 cm -1, you
have either an alkene or alkyne present as a functional group. Below Ill
explain the stretches and peaks in more detail.

The sp2 hybridized C-H bond (alkene hydrogen), is a moderately strong,


sharp peak around 3000-3100 cm-1. Sometimes, the peak is buried within
the massive amount of sp3 hybridized C-H peaks less than 3000 cm -1, making
it harder to see. Usually, you should be able to see a sharp peak within the
region mentioned above. An example is shown below. Notice that since there
are two peaks of sp2 hybridized C-H bonds for each separate alkene present
in the molecule

The sp hybridized C-H bond (alkyne hydrogen) is a very strong, sharp


peak around 3300 cm-1. Since this peak is far enough from 3000 cm-1, the
peak is usually isolated by itself, making it easy to recognize. An
example is shown below

Alcohols (Oxygen-Hydrogen bond stretching)


O-H bonds are very easy to recognize because they are very unique, but also very
important to know. There are two types of O-H bonds stretches you should
know

Alcohol O-H bond: centered around 3300 cm-1


Acid (carboxylic acid) O-H bond: centered around 3000 cm-1

The alcohol O-H bond is a broad and strong stretch usually centered
around 3300 cm-1, covering the region between 3000 cm-1 to about 3500
cm-1. An example is shown below

An acid O-H bond (carboxylic acids), is shown in an IR as a VERY broad and


strong stretch usually centered around 3000 cm-1, covering a much wider
range between 2500 cm-1 to 3500 cm-1. An example is shown below

Amine groups (Nitrogen-Hydrogen bond stretching)


Amine N-H bonds are weaker than O-H stretches due to less dipole moment. The
Amine N-H bonds are usually broad, weak spikes around 3300 cm -1 (they
look like canine teeth on dogs). The number of peaks present depends on the
number of N-H bonds present in the amine. If it is a primary amine (2 N-H
bonds), then there will be 2 spikes, and if it is a secondary amine (1 N-H
bond), then there will be 1 spike. Tertiary amines have no N-H bonds, so show
no spikes within 3300 cm-1.

Carbonyl groups (Carbon-Oxygen bond stretching)


The carbonyl group C-O bond peak is very important to know! The general
carbonyl group peak is a very strong, sharp peak around 1700 cm -1.
Because the peak is so strong, you will usually see an overtone (a weaker
extension of the peak) around 3400 cm-1, or twice the wavenumber of the
original carbonyl peak. Also, each diferent carbonyl group has diferent
peaks with diferent characteristics which Ill explain how to recognize the
difference. The groups that you need to know are

Ketone
Aldehyde
Ester
Carboxylic Acid
Amide
Acid chloride (dont need to know until Exam 3)
Anhydride (dont need to know until Exam 3)
-A ketone has a strong, sharp peak around 1710 cm-1. This is the only
indicative peak of a ketone.

-An Aldehyde also has a strong, sharp peak around 1725 cm-1 (slightly higher
than ketone, but still very close making it hard to differentiate the two). However,
the most indicative peaks of an aldehyde are 2 sharp C-H spikes around

2700-2800 cm-1, slightly to the right of the sp3 hybridized C-H peaks

An ester has a strong, sharp peak around 1740-1750 cm-1. The peak is higher
in wavenumber compared to aldehyde/ketones, and is usually far enough to be able
to differentiate them apart. Just like ketone, this is the only peak indicative of
an ester

Carboxylic acids have a strong, sharp peak around 1710 cm -1, similar to
ketones/aldehydes. However, carboxylic acids have a broad O-H stretch from
2500-3500 cm-1, as mentioned previously

Amides have a strong, sharp peak that absorb around 1640-1680 (1660 on
average) cm-1. Also, there will be two amine N-H spikes/stretches around
3300-3500. These N-H peaks are usually stronger in absorbance than regular
amines N-H spikes

Acid chloride has a strong, sharp peak carbonyl peak around 1800 cm -1,
much higher than an ester or ketone/aldehyde carbonyl spike. This is due to
the increased stiffness of the bond. Again, you dont need to know this peak until

Exam 3.

Anhydrides give 2 strong, sharp carbonyl stretching peaks, one around


1800 cm-1, one around 1750 cm-1. As far as you are required to know, anhydrides
are the only functional group that gives 2 carbonyl peaks. Again, you dont need to
know this until Exam 3. An example is shown below

Carbonyl groups are probably the most important peaks/stretches to be


able to recognize. Know them and how to diferentiate each group! You
will be required to determine which functional group is present given an
IR spectrum!
Carbon-Nitrogen bond stretching

Carbon-Nitrogen bond stretches are similar to C-C bond stretches in location. The
main diference is that C-N peaks are stronger in absorbance since there is
a greater dipole moment. The three types of C-N bond stretches and their
wavenumber position are shown below

C-N single bond: 1200 cm-1


C-N double bond: 1660 cm-1
C-N triple bond: GREATER than 2200 cm-1. This is the most important CN peak to know!

The C-N triple bond is shown in the IR spectrum as a moderately strong to


strong, sharp peak that is slightly GREATER than 2200 cm-1. This is different
from C-C triple bonds, which is LESS than 2200 cm -1

Miscellaneous alterations
There are two types of alterations that can occur with functional groups
that can alter the location of the peak. The two alterations are:
Resonance: Resonance allows delocalization of the electrons in a functional
group. This allows the bonds of the functional group to be LESS stif,
making the location of the peak LESS in wave number. Each additional
resonance structure will lower the peak location about 20 cm-1. Keep this in
mind when you are looking in IR spectrums, because a peak could represent
multiple functional groups if there is a possibility of resonance. For example:

o
- Carbonyl peak at 1690 cm-1
Ring structure: A functional group placed in a ring will place strain on the
functional group, increasing the energy of the compound. This causes the
bond to become MORE stif, making stretching frequency of the peak
HIGHER. The amount increased in wavenumber depends on the amount of
strain placed on the compound. The more strain placed by the ring, the
higher the stretching frequency will be.

-Carbonyl peak at 1785 cm-1

It is important to be able to read IR spectrums. It will not be emphasized


as much as NMRs, but will still be asked on the first exam! Be able to
recognize most, if not all, of the functional groups mentioned above in an
IR! It also may be potentially asked in your future exams, so dont forget how to
read them!