Infrared Spectroscopy

Introduction
Spectroscopy is an analytical technique
which helps determine structure.
It destroys little or no sample.
The amount of light absorbed by the
sample is measured as wavelength is
varied.

Types of Spectroscopy
Infrared (IR) spectroscopy measures the bond
vibration frequencies in a molecule and is used
to determine the functional group.
Mass spectrometry (MS) fragments the molecule
and measures the masses.
Nuclear magnetic resonance (NMR)
spectroscopy detects signals from hydrogen
atoms and can be used to distinguish isomers.
Ultraviolet (UV) spectroscopy uses electron
transitions to determine bonding patterns. =>

Spectroscopy is the study of the interaction of matter with the electromagnetic

spectrum
1. Electromagnetic radiation displays the properties of both
particles and waves
2. A particle of electromagnetic energy is called a photon
3. The energy (E) of a photon is proportional to the frequency .
Where h is Plancks constant and is the frequency in Hertz
(cycles per second)
E = h
5. Because the speed of light is constant, the frequency (number
of cycles of the wave per second) must be inversely
proportional to the wavelength.
c
___
=

c = 3 x 10 cm/s
10

E = h =

hc
___

The Spectrum and

Molecular Effects

=>
=>

Infrared Spectroscopy
I. Introduction
B. Spectroscopic Process
1. Every spectroscopic method works using the same principle
2. Each method uses a method of irradiation, absorption, excitation, reemission, relaxation, and detection.

Energy

tio
a
it
c
Ex

excited state

h
n
tio
xa
la
Re

Absorption: Molecule takes

on the quantum energy of a
photon that matches the
energy of a transition and
becomes excited
n

rest state

h h h

Irradiation: Molecule is
bombarded with
photons of various
frequencies over the
range desired

Detection: Photons that

are re-emitted and
detected correspond to
quantum mechanical
energy levels of the
molecule

rest state

The IR Region
Just below red in the visible region.
Wavelengths usually 2.5-25 m.
More common units are wavenumbers, or
cm-1, the reciprocal of the wavelength in
centimeters.
Wavenumbers are proportional to
frequency and energy.
=>

The IR Spectroscopic Process

1.
2.
3.
4.

The quantum mechanical energy levels observed in IR spectroscopy

are those of molecular vibration
We perceive this vibration as heat
When we say a covalent bond between two atoms is of a certain
length, we are citing an average because the bond behaves as if it
were a vibrating spring connecting the two atoms
There are two types of bond vibration:

Stretch Vibration or oscillation along the line of the bond

H

C
H

asymmetri
c

symmetric

Bend Vibration or oscillation not along the line of the bond

H
C

C
H

H
scissor

rock
in plane

C
H

twist

wag
out of plane

Vibrational Modes
Nonlinear molecule with n atoms usually has
3n - 6 fundamental vibrational modes.

=>

The IR Spectroscopic Process

5.
6.

7.
8.
9.

Each stretching and bending vibration occurs with a characteristic

frequency
When a molecule is bombarded with electromagnetic radiation
(photons) that matches the frequency of one of these vibrations, it is
absorbed and the bonds begin to stretch and bend more strongly
(emission and absorption)
When this photon is absorbed the amplitude of the vibration is
increased but NOT the frequency
The molecule will slowly decay to its resting state by emission of a
photon of this particular frequency, which is detected by the
spectrometer (detection)
The spectrometer produces a graphical output or spectrum:

The IR Spectrum
1. The x-axis of the IR spectrum is in units of wavenumbers, ~, which
is the number of waves per centimeter in units of cm-1 (Remember
E = hor E = hc/)
1
~
___
(cm 1) =
(cm)

1. This unit is used rather than wavelength (microns) because

wavenumbers are directly proportional to the energy of transition
being observed.
High frequencies and high wavenumbers equate higher energy
is quicker to understand thanShort wavelengths equate higher
energy
2. This unit is used rather than frequency as the numbers are more
real than the exponential units of frequency
1. IR spectra are observed for what is called the mid-infrared: 4004000 cm-1

The IR Spectrum
So how does the IR detect different bonds?
When applied to a bond within a molecule, Hookes law describing the
motion of a vibration, becomes:

~
=

Where:

1
2 c

f (m1 + m2)

1/2

m1m2

~
= wavenumber of the stretching vibration

f
= the force constant (bond strength)
m1, m2 = masses of atoms joined by the bond
c
= speed of light
Therefore - stronger bonds and lighter atoms give rise to higher wavenumbers
the stronger the bond the more energy required to stretch it
Frequency is inversely related to mass, so heavier atoms occur at lower
frequencies
Since different functional groups contain different combinations of atoms and
bonds this provides a method for qualitative analysis of the groups in a
molecule

Stretching Frequencies

Frequency decreases with increasing

atomic weight.
Frequency increases with increasing
bond energy.

6.

The IR Spectrum
The y-axis of the IR spectrum is in units of transmittance, T, which is
the ratio of the amount of IR radiation transmitted by the sample (I)
to the intensity of the incident beam (I0); % Transmittance is T x 100
T = I / I0
%T = (I / I0) X 100

7.

IR is different than other spectroscopic methods which plot the yaxis as units of absorbance (A). A = log(1/T)

8.

As opposed to chromatography or other spectroscopic methods, the

area of a IR band (or peak) is not directly proportional to
concentration

The IR Spectrum
10. The intensity of an IR band is affected by two primary factors:

Whether the vibration is one of stretching or bending

Electronegativity difference of the atoms involved in the bond:

For both effects, the greater the change in dipole moment in a
given vibration or bend, the larger the peak.
The greater the difference in electronegativity between the
atoms involved in bonding, the larger the dipole moment
Typically, stretching will change dipole moment more than
bending
11. It is important to make note of peak intensities to show the effect of
these factors:

Strong (s) peak is tall, transmittance is low

Medium (m) peak is mid-height

Weak (w) peak is short, transmittance is high

* Broad (br) if the Gaussian distribution is abnormally broad

(*this is more for describing a bond that spans many energies)

Exact transmittance values are rarely recorded

Fingerprint of Molecule
Whole-molecule vibrations and bending
vibrations are also quantitized.
No two molecules will give exactly the
same IR spectrum (except enantiomers).
Simple stretching: 1600-3500 cm -1.
Complex vibrations: 600-1400 cm-1,
called the fingerprint region.
=>

IR-Active and Inactive

A polar bond is usually IR-active.
A nonpolar bond in a symmetrical
molecule will absorb weakly or not at all.

=>

An Infrared Spectrometer

=>

FT-IR Spectrometer

Uses an interferometer.
Has better sensitivity.
Less energy is needed from source.
Completes a scan in 1-2 seconds.
Takes several scans and averages them.
Has a laser beam that keeps the
instrument accurately calibrated.
=>

Infrared Group Analysis

1.

The primary use of the IR spectrometer is to detect functional

groups
2.
Because the IR looks at the interaction of the EM spectrum with
actual bonds, it provides a unique qualitative probe into the
functionality of a molecule, as functional groups are merely
different configurations of different types of bonds
3.
Since most types of bonds in covalent molecules have roughly
the same energy, i.e., C=C and C=O bonds, C-H and N-H bonds they
show up in similar regions of the IR spectrum
4.
Remember all organic functional groups are made of multiple bonds
and therefore show up as multiple IR bands (peaks)
There are 4 principal regions:
Bonds to H

Triple bonds

O-H single bond

N-H single bond
C-H single bond

Double bonds

CC
CN

Single Bonds

C=O
C=N
C=C

C-C
C-N
C-O
Fingerprint
Region

4000 cm-1

2700 cm-1

2000 cm-1

1600 cm-1

600 cm-1

Carbon-Carbon
Bond Stretching
Stronger bonds absorb at higher
frequencies:
C-C
C=C
CC

1200 cm-1
1660 cm-1
2200 cm-1 (weak or absent if internal)

Conjugation lowers the frequency:

isolated C=C
1640-1680 cm-1
conjugated C=C 1620-1640 cm-1
aromatic C=C
approx. 1600 cm-1

=>

Carbon-Hydrogen Stretching
Bonds with more s character absorb at a
higher frequency.
sp3 C-H, just below 3000 cm-1 (to the right)
sp2 C-H, just above 3000 cm-1 (to the left)
sp C-H, at 3300 cm-1
=>

An Alkane IR Spectrum

=>

An Alkene IR Spectrum

=>

An Alkyne IR Spectrum

=>

Aromatics

Due to the delocalization of electrons in the ring, where the bond

order between carbons is 1 , the stretching frequency for these
bonds is slightly lower in energy than normal C=C
These bonds show up as a pair of sharp bands, 1500 (s) & 1600 cm1
(m), where the lower frequency band is stronger
C-H bonds off the ring show up similar to vinyl C-H at 3000-3100 cm-1
(m)

c=c
C-H

Ethyl benzene

Aromatics

If the region between 1667-2000 cm-1 (w) is free of interference (C=O

stretching frequency is in this region) a weak grouping of peaks is
observed for aromatic systems
Analysis of this region, called the overtone of bending region, can
lead to a determination of the substitution pattern on the aromatic ring

Monosubstituted
G
G

1,2 disubstituted (ortho or o-)

1,2 disubstituted (meta or m-)

1,4 disubstituted (para or p-)

G

Unsaturated Systems substitution patterns

The substitution of aromatics and alkenes can also be
discerned through the out-of-plane bending vibration
region. However, other peaks often are apparent in this
region. These peaks should only be used for
reinforcement of what is known or for hypothesizing as to
the functional pattern.
cm-1
R
C CH2
H
H
C C
H
R

cm-1

985-997
905-915

730-770
690-710

960-980

735-770

860-900
750-810
680-725

800-860

R
C C
H
H

665-730
R

R
R

C CH2

885-895
R

R
C C
R
H

790-840

Ethers

addition of the C-O-C asymmetric band

Show a strong band for the antisymmetric C-O-C stretch at 10501150 cm-1 (s)

Otherwise, dominated by the hydrocarbon component of the rest

of the molecule

Diisopropyl ether
O

O-H and N-H Stretching

Both of these occur around 3300 cm -1, but
they look different.
Alcohol O-H, broad with rounded tip.
Secondary amine (R2NH), broad with one
sharp spike.
Primary amine (RNH2), broad with two sharp
spikes.
No signal for a tertiary amine (R3N)
=>

An Alcohol IR Spectrum

Show a strong, broad band for the O-H stretch from 3200-3400
cm-1 (s, br) this is one of the most recognizable IR bands
Like ethers, show a band for C-O stretch between 1050-1260 cm-1
(s)
This band changes position depending on the substitution of the
alcohol: 1 1075-1000; 2 1075-1150; 3 1100-1200; phenol 11801260
The shape is due to the presence of hydrogen bonding

=>

An Amine IR Spectrum

Shows the N-H stretch for NH2 as a doublet between

3200-3500 cm-1 (s-m); symmetric and anti-symmetric
modes
-NH2 group shows a deformation band from 1590-1650 cm1
(w)
Additionally there is a wag band at 780-820 cm-1 that is
not diagnostic

2-aminopentane

H2N

An Amine
IR Spectrum

=>

Carbonyl Stretching
The C=O bond of simple ketones,
aldehydes, and carboxylic acids absorb
around 1710 cm-1.
Usually, its the strongest IR signal.
Carboxylic acids will have O-H also.
Aldehydes have two C-H signals around
2700 and 2800 cm-1.
=>

A Ketone
IR Spectrum

=>

An Aldehyde
IR Spectrum
Show the C=O (carbonyl) stretch from 1720-1740 cm-1(s)
Band is sensitive to conjugation, as are all carbonyls
(upcoming slide)
Also displays a highly unique sp2 C-H stretch as a doublet,
2720 & 2820 cm-1 (w) called a Fermi doublet

=>

O-H Stretch of a
Carboxylic Acid
This O-H absorbs broadly, 2500-3500 cm -1,
due to strong hydrogen bonding.

=>

Esters
1.
2.

C=O stretch occurs at 1735-1750 cm-1 (s)

Also displays a strong band for C-O at a higher frequency than
ethers or alcohols at 1150-1250 cm-1 (s)

Ethyl pivalate
O

Acid anhydrides

Coupling of the anhydride though the ether oxygen splits the

carbonyl band into two with a separation of 70 cm-1.
Bands are at 1740-1770 cm-1 and 1810-1840 cm-1 (s)
Mixed mode C-O stretch at 1000-1100 cm-1 (s)

Propionic anhydride
O

Acid halides

Dominant band at 1770-1820 cm-1 for C=O (s)

Bonds to halogens, due to their size (see Hookes Law derivation)
occur at low frequencies, where their presence should be used to
reinforce rather than be used for diagnosis, C-Cl is at 600-800 cm-1
(m)

Propionyl chloride
O

Cl

Variations in
C=O Absorption
Conjugation of C=O with C=C lowers the
stretching frequency to ~1680 cm -1.
The C=O group of an amide absorbs at an
even lower frequency, 1640-1680 cm -1.
The C=O of an ester absorbs at a higher
frequency, ~1730-1740 cm -1.
Carbonyl groups in small rings (5 Cs or
less) absorb at an even higher frequency. =>

An Amide
IR Spectrum

=>

Carbon - Nitrogen
Stretching
C - N absorbs around 1200 cm -1.
C = N absorbs around 1660 cm -1 and is
much stronger than the C = C
absorption in the same region.
C N absorbs strongly just above 2200
cm-1. The alkyne C C signal is much
weaker and is just below 2200 cm-1 .
=>

A Nitrile
IR Spectrum

=>

Nitro group (-NO2)

Proper Lewis structure gives a bond order of 1.5 from nitrogen to

each oxygen
Two bands are seen (symmetric and asymmetric) at 1300-1380 cm-1
(m-s) and 1500-1570 cm-1 (m-s)
This group is a strong resonance withdrawing group and is itself
vulnerable to resonance effects

2-nitropropane
O

O
N

A. Effects on IR bands
1.

Conjugation by resonance, conjugation lowers the energy of a double or

triple bond. The effect of this is readily observed in the IR spectrum:
O
O

1684 cm-1
C=O

1715 cm-1
C=O

Conjugation will lower the observed IR band for a carbonyl from 20-40
cm-1 provided conjugation gives a strong resonance contributor
O
C
H3C

H2N

X=

O
C CH3

Strong resonance contributor

NH2

CH3

Cl

NO2

1677

1687

1692

1700

O
N

vs.
O

cm-1

O
C
CH3

Poor resonance contributor

(cannot resonate with C=O)

A. Effects on IR bands
1.

Steric effects usually not important in IR spectroscopy, unless they reduce

the strength of a bond (usually ) by interfering with proper orbital overlap:
O

CH3
-1

2.

-1

C=O: 1686 cm
C=O: 1693 cm
Here the methyl
group in the structure
at the right causes the carbonyl
group to be slightly out of plane, interfering with resonance

Strain effects changes in bond angle forced by the constraints of a ring

will cause a slight change in hybridization, and therefore, bond strength

1815 cm-1

1775 cm-1

1750 cm-1

1715 cm-1

1705 cm-1

As bond angle decreases, carbon becomes more electronegative, as

A. Effects on IR bands
1.

Hydrogen bonding

Hydrogen bonding causes a broadening in the band due to the

creation of a continuum of bond energies associated with it

In the solution phase these effects are readily apparent; in the gas
phase where these effects disappear or in lieu of steric effects, the
band appears as sharp as all other IR bands:
Gas phase spectrum of
1-butanol
Steric hindrance to H-bonding
in a di-tert-butylphenol
OH

H-bonding can interact with other functional groups to lower

frequencies
H
O

C=O; 1701 cm-1

Summary of IR
Absorptions

=>
=>

Strengths and Limitations

IR alone cannot determine a structure.

Some signals may be ambiguous.
The functional group is usually indicated.
The absence of a signal is definite proof
that the functional group is absent.
Correspondence with a known samples
IR spectrum confirms the identity of the
compound.

Mass Spectrometry
Molecular weight can be obtained from a
very small sample.
It does not involve the absorption or
emission of light.
A beam of high-energy electrons breaks
the molecule apart.
The masses of the fragments and their
relative abundance reveal information
about the structure of the molecule. =>

Electron Impact Ionization

A high-energy electron can dislodge an
electron from a bond, creating a radical
cation (a positive ion with an unpaired e -).
H H
H C C H
H H
H H

H H
e- +

H C C+

H C C H

H H

H H
H
H C+
H

H
C H
H

=>

Separation of Ions
Only the cations are deflected by the
magnetic field.
Amount of deflection depends on m/z.
The detector signal is proportional to the
number of ions hitting it.
By varying the magnetic field, ions of all
masses are collected and counted. =>

Mass Spectrometer

=>

The Mass Spectrum

Masses are graphed or tabulated according to
their relative abundance.

=>

The GC-MS
A mixture of compounds is separated
by gas chromatography, then identified
by mass spectrometry.

=>

High Resolution MS
Masses measured to 1 part in 20,000.
A molecule with mass of 44 could be
C3H8, C2H4O, CO2, or CN2H4.
If a more exact mass is 44.029, pick the
correct structure from the table:
C3H8

C2H4O

CO2

CN2H4

44.06260

44.02620

43.98983

44.03740
=>

Molecules with
Heteroatoms

Isotopes: present in their usual abundance.

Hydrocarbons contain 1.1% C-13, so there
will be a small M+1 peak.
If Br is present, M+2 is equal to M+.
If Cl is present, M+2 is one-third of M +.
If iodine is present, peak at 127, large gap.
If N is present, M+ will be an odd number.
If S is present, M+2 will be 4% of M+. =>

Isotopic Abundance

81

Br

=>

Mass Spectrum
with Sulfur

=>

Mass Spectrum
with Chlorine

=>

Mass Spectrum
with Bromine

=>

Mass Spectra
of Alkanes
More stable carbocations will be more
abundant.

=>

Mass Spectra
of Alkenes
Resonance-stabilized cations favored.

=>

Mass Spectra of Alcohols

Alcohols usually lose a water molecule.

M+ may not be visible.

12.1 What compound has a

formula of C5H8 and a peak at
3300 cm-1?

Level 2
Medium

Alkane
Alkene
Internal alkyne
Terminal alkyne

12.1 answer

Alkane
Alkene
Internal alkyne
Terminal alkyne

A terminal alkyne has a C-H stretch for

-CC-H at 3300 cm-1.
Level 2
Medium

12.2 What compound has a

formula of C5H12O and a peak at
3200 cm-1?

Level 2
Medium

Ether
Alcohol
Aldehyde
Ketone

12.2 answer

Ether
Alcohol
Aldehyde
Ketone

An alcohol has a very distinct O-H stretch

near 3200 cm-1.
Level 2
Medium

12.3 What compound has a

formula of C6H15N and two peaks
at 3300 cm-1?
1o amide
2o amide
3o amide

Level 2
Medium

1o amine
2o amine
3o amine

12.3 answer
1o amide
2o amide
3o amide

1o amine
2o amine
3o amine

A primary amine has two peaks around

3300 cm-1. An amide has oxygen,
which is not in the formula.
Level 2
Medium

12.4 What compound has a

formula of C5H10O and peaks at
1710, 2700, 2800 cm-1?

Level 2
Medium

Ketone
Aldehyde
Ester
Carboxylic acid

12.4 answer

Ketone
Aldehyde
Ester
Carboxylic acid

Aldehydes have a C=O stretch at 1710 cm -1

and C-H stretch at 2700 and 2800 cm -1.
Level 2
Medium

12.5 What compound has a

formula of C5H10O2, a peak at
1715 and a broad peak at 3000
cm-1?

Level 2
Medium

Aldehyde
Ketone
Carboxylic acid
Ester

12.5 answer

Aldehyde
Ketone
Carboxylic acid
Ester

Carboxylic acids have a C=O stretch at

1715 cm-1 and an O-H stretch at 3000 cm 1.
Level 2
Medium

12.6 Give the effect of C=C

conjugation on the C=O stretch of
an aldehyde.
Lowers the C=O stretching frequency.
Raises the C=O stretching frequency.
The C=O stretching frequency is
unaffected.

Level 2
Easy

12.6 answer
Lowers the C=O stretching frequency.
Raises the C=O stretching frequency.
The C=O stretching frequency is
unaffected.
The C=O stretching frequency is lowered
from about 1710 cm-1 to near 1685 cm-1.
Level 2
Easy

12.7 Define base peak.

Level 2
Easy

Lowest peak
Highest peak
Weakest peak
Strongest peak

12.7 answer

Lowest peak
Highest peak
Weakest peak
Strongest peak

The strongest or tallest peak is the base

peak.
Level 2
Easy

12.8 List why the bromide isotopes

are recognizable.

Level 2
Easy

The M+2 is half the size of the M.

The M+2 is twice the size of the M.
The M+2 is the same size as the M.
Only one isotope is seen.

12.8 answer

The M+2 is half the size of the M.

The M+2 is twice the size of the M.
The M+2 is the same size as the M.
Only one isotope is seen.

The 81Br isotope is about the same size as

the 79Br isotope.
Level 2
Easy

12.9 Give the fragment at m/z 29

in the mass spectrum of pentane.
CH3CH2
CH3CH2+
CH3CH2
CH3CH2

Level 2
Medium

12.9 answer
CH3CH2
CH3CH2+
CH3CH2
CH3CH2
Only the ethyl cation is seen in the mass
spectrum.
Level 2
Medium

12.10 Give the fragment at m/z

42 in the mass spectrum of 1propanol.
CH3CH=CH2+
CH3CH=CH2
CH3CH=CH2
CH3CH=CH2

Level 3
Challenging

12.10 answer
CH3CH=CH2+
CH3CH=CH2
CH3CH=CH2
CH3CH=CH2
Water is lost from 1-propanol to form
propene as a radical cation.
Level 3
Challenging

SOLVED PROBLEM 12-1

Determinethefunctionalgroup(s)inthecompoundwhoseIRspectrumappearshere.

Solution
First,lookatthespectrumandseewhatpeaks(outsidethefingerprintregion)dontlooklikealkane
peaks:aweakpeakaround3400cm1,astrongpeakabout1720cm1,andanunusualCHstretching
region.TheCHregionhastwoadditionalpeaksaround2720and2820cm1.Thestrongpeakat1725
cm1mustbeaC=Oandthepeaksat2720and2820cm1suggestanaldehyde.Theweakpeakaround
3400cm1mightbemistakenforanalcoholOH.Fromexperience,weknowalcoholsgivemuchstronger
OHabsorptions.Thissmallpeakmightbefromanimpurityofwaterorfromasmallamountofthe
hydrateofthealdehyde(seeChapter18).ManyIRspectrashowsmall,unexplainedabsorptionsintheO
Hregion.

SOLVED PROBLEM 12-2

Youhaveanunknownwithanabsorptionat1680cm1;itmightbeanamide,anisolated
doublebond,aconjugatedketone,aconjugatedaldehyde,oraconjugatedcarboxylicacid.
Describewhatspectralcharacteristicsyouwouldlookfortohelpyoudeterminewhichofthese
possiblefunctionalgroupsmightbecausingthe1680peak.

Solution