taibah university

college of sciences
chemistry department

chem 314

Chapter 2:Infrared spectroscopy

 Spectroscopy is an instrumentally aided studies
of the interactions between matter (sample
being analyzed) and energy (any portion of the
electromagnetic spectrum, EMS)
EMS refers to the seemingly diverse collection
of radiant energy, from cosmic rays to X-rays to
visible light to microwaves, each of which can be
considered as a wave or particle traveling at the
speed of light.

Chemists can use portions of the EMS to

selectively manipulate the energies contained
within a molecule, to uncover detailed evidence of
its chemical structure and bonding.
Chapter 2:Infrared spectroscopy
EMS and Molecular Effects

=>

Chapter 2:Infrared spectroscopy

 Energy (E) E = h = hc/
where h is Planck s constant, c is the speed of light, is
frequency or the number of vibrations per second and l is the
wavelength

Wavenumber ( ) = 1/
given in cm-1

Thus, the energy will be: E = hc

Period (P) P = 1/
the time between a vibration

Energy, frequency, and wavenumber are

directly proportional to each other.

Chapter 2:Infrared spectroscopy

 The four most common spectroscopic methods used in
organic analysis are: :‫اﻟﻄﺮق اﻟﻄﻴﻔﻴﺔ اﻷرﺑﻌﺔ اﻷﻛﺜﺮ ﺷﻴﻮﻋًﺎ اﳌﺴﺘﺨﺪﻣﺔ ﰲ اﻟﺘﺤﻠﻴﻞ اﻟﻌﻀﻮي ﻫﻲ‬
Method Abbrev Energy Units
. used
Ultraviolet-Visible UV-Vis ultraviolet- nm
Spectroscopy visible
Infrared IR infrared m or
Spectroscopy cm-1
Nuclear Magnetic NMR radio Hz
Resonance frequencies
Mass Spectroscopy MS electron amu
volts
What actually happens to the sample during an analysis?
{How do the sample and energy interact ?}
Chapter 2:Infrared spectroscopy
 Infrared spectroscopy (IR) measures the bond
'
vibration frequencies in a molecule and is used
‫ﻳﻘﻴﺲ اﻟﺴﻨﺪ‬
to determine the functional group ‫ﺗﺮددات اﻻﻫﺘﺰاز ﰲ ﺟﺰيء وﻳﺴﺘﺨﺪم‬
‫ﻟﺘﺤﺪﻳﺪ اﺠﻤﻟﻤﻮﻋﺔ اﻟﻮﻇﻴﻔﻴﺔ‬
Mass spectrometry (MS) fragments the
molecule and measures the masses ‫اﻟﺸﻈﺎﻳﺎ اﳉﺰيء وﻳﻘﻴﺲ اﻟﻜﺘﻞ‬
Nuclear magnetic resonance (NMR)
spectroscopy detects signals from hydrogen
atoms and can be used to distinguish isomers
‫ﻳﻜﺘﺸﻒ اﻟﺘﺤﻠﻴﻞ اﻟﻄﻴﻔﻲ إﺷﺎرات ﻣﻦ ذرات اﻟﻬﻴﺪروﺟﲔ وﳝﻜﻦ اﺳﺘﺨﺪاﻣﻪ ﻟﺘﻤﻴﻴﺰ اﻷﻳﺰوﻣﺮات‬
Ultraviolet (UV) spectroscopy uses electron
transitions to determine bonding patterns
‫ﻳﺴﺘﺨﺪم اﻟﺘﺤﻠﻴﻞ اﻟﻄﻴﻔﻲ اﻟﻜﺘﺮون اﻻﻧﺘﻘﺎﻻت ﻟﺘﺤﺪﻳﺪ أﳕﺎط اﻟﺘﺮاﺑﻂ‬

Chapter 2:Infrared spectroscopy

 Matter/Energy Interactions
What happens when a sample absorbs UV/Vis energy?

*
excitation of ground state electrons
(typically p and n electrons)
UV/Vis *
sample transition
Eelectronic increases momentarily ( 200 nm)

What happens when a sample absorbs IR energy?

stretching and bending of bonds
IR
(typically covalent bonds) -O-H -O H
Evibration increases momentarily ( 3500 cm-1)

Chapter 2:Infrared spectroscopy

 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 (104/ m = 4000-400 cm-1)
Wavenumbers are proportional to frequency
and energy
The IR region is divided into three regions: the near,
mid, and far IR. The mid IR region is of greatest
practical use to the organic chemist.

Chapter 2:Infrared spectroscopy

Molecular Vibrations
and
IR Spectroscopy

Chapter 2:Infrared spectroscopy

Molecules are made up of atoms linked by chemical bonds.
The movement of atoms and chemical bonds like spring and
balls (vibration)

Chapter 2:Infrared spectroscopy

 Vibrations
What is a vibration in a molecule?
Any change in shape of the molecule- stretching
of bonds, bending of bonds, or internal rotation
around single bonds
.‫ﻫﻨﺎك ﻧﻮﻋﺎن ﻣﻦ اوﺿﺎع اﻻﻫﺘﺰاز اﻟﺮﺋﻴﺴﻴﺔ‬
There are two main vibrational modes :
[Link]: change in bond length
(higher frequency)

Stretching vibration

Chapter 2:Infrared spectroscopy

Stretching Types

Symmetric Asymmetric

2. Bending: change in bond angle (lower frequency)

Bending Types

In-plane (Scissoring) Out-plane (Twisting)

Chapter 2:Infrared spectroscopy
Modes of vibrations
Stretching: change in bond distance. Occurs at higher
energy: 4000-1250 cm 1.

Bending: change in bond angle. Occurs at lower energy: 1400-

666 cm 1.

H2 O -CH2-

Chapter 2:Infrared spectroscopy

More complex types of stretching and bending are possible

Can a vibration change the dipole moment of a

molecule?

Asymmetrical stretching/bending and internal

rotation change the dipole moment of a
molecule. Asymmetrical stretching/bending are
IR active.
Symmetrical stretching/bending does not. Not
IR active
Infrared active vibrations (those that absorb IR
radiation) must result in a change of dipole moment

Chapter 2:Infrared spectroscopy

Fundamental Vibrations (Absorption Frequencies)
A molecule has as many as degrees of freedom as the
total degree of freedom of its individual atoms.
Each atom has 3 degree of freedom (x,y,z)
A molecule of n atoms therefore has 3n degrees of
freedom.
Non linear molecules (e.g. H2O)
Vibrational degrees of freedom or Fundamental Vibrations
= 3n 6

H H H H H H
O O O

Symmetrical Asymmetrical Scissoring

Stretching Stretching ( as OH) ( s HOH)
( s OH) 3652 cm- 3756 cm-1 1596 cm-1
1

Chapter 2:Infrared spectroscopy

 For linear molecule (e.g. CO2) : Vibrational degrees of
freedom or Fundamental Vibrations = 3n 5

O C O O C O
Symmetrical Asymmetrical
Stretching ( s CO2) Stretching ( as CO2)
1340 cm-1 2350 cm-1

O C O O C O

Scissoring (bending out

Scissoring (bending in
of the plane of the paper)
the plane of the paper)
( CO2) 666 cm-1
s
( s CO2) 666 cm-1

Chapter 2:Infrared spectroscopy

Carbon Dioxide and Water

H-O-H
H-O-H

O=C=O

Chapter 2:Infrared spectroscopy

 The theoretical no. of fundamental vibrations will seldom be
observed because overtones (multiples of a given frequencies)
and combination tones (sum of two other vibrations) increase
the no. of bands.

Other phenomena reduce the no. of bands including:

Fundamental frequencies that fall outside the 4000-400
cm-1 region.
Fundamental bands that are too weak to be observed.
Fundamental bands that are so close that they coalesce.
The occurrence of a degenerate band from several
absorptions of the same frequency in highly symmetrical
molecules.
The failure of certain fundamental vibrations to appear in
the IR because of the lack of change in molecular dipole.

Chapter 2:Infrared spectroscopy

Which of the following atoms or molecules will
absorb IR radiation:

I Cl H2 N2 Cl2

Why?

Chapter 2:Infrared spectroscopy

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

Chapter 2:Infrared spectroscopy

Factors determining where
a chemical bond absorb
(Bond Properties)

Chapter 2:Infrared spectroscopy

Hooke s Law
M1 M2

-1)

c = Velocity of light (cm/s)

f = force constant of bond (dyne/cm)
M1 and m2 are mass (gr) of atom M1 and M2

Chapter 2:Infrared spectroscopy

 increasing

C-H > C-C > C-O > C-Cl > C-Br

3000 1200 1100 750 650

The CH strech occurs at about 3000cm-1. As the atom

bonded to carbon increases in mass, the frequency of
vibration decreases (wavenumbers get smaller)

Chapter 2:Infrared spectroscopy

2-How does the force constant of bond influence the
vibration?
In general, triple bonds are stronger than double or single bonds
between the same two atoms and have higher frequency of
vibration (higher wave number)

1 K
=
2 c
multiple bonds have higher K s

C C > C C> C C
2150cm-1 1650cm-1 1200 cm-1

Chapter 2:Infrared spectroscopy

Summary
constants
larger K,
higher frequency
1 K
=
2 c increasing K

=
C=C > C=C > C-C
2150 1650 1200
larger atom masses,
lower frequency

increasing
C-H > C-C > C-O > C-Cl > C-Br
3000 1200 1100 750 650

Chapter 2:Infrared spectroscopy

Stretching Frequencies

Frequency decreases with increasing atomic mass.

Frequency increases with increasing bond energy.

Chapter 2:Infrared spectroscopy

Bending motions occur at lower energy (lower
frequency) than the typical streching because of the
lower value for the bending force constant.

C-H streching C-H bending

~ 3000 cm-1 ~ 1340 cm-1

Chapter 2:Infrared spectroscopy

 100%
Transmission
50%
0%

4500 4000 3500 3000 2500 2000 1500

Wavenumber (cm-1)

Chapter 2:Infrared spectroscopy

Hybridization affects the force constant also. Bonds
are stronger in the order sp> sp2 >sp3, and the
observed frequencies of C-H vibration illustrate this
nicely
C-H > =C-H > -C-H
sp sp2 sp3
3300 3100 2900 cm-1

Chapter 2:Infrared spectroscopy

Resonance also affects the strength and length of a
bond and hence its force constant. Thus, whereas a
normal ketone has its C=O streching vibration at
1715 cm-1, a ketone that is conjucated with a C=C
double bond absorb at a lower frequency, near 1675
to 1680 cm-1. That is because resonanace
lengthens the C=O bond distance and gives it more
single-bond character .

Chapter 2:Infrared spectroscopy

Conjugation of a C=C double bond with either carbonyl
group or another double bond provides the mulptiple
bond with more single-bond character (through
resonnance, as shown in the following example), a lower
force constant, and thus a lower frequency of vibration.

Chapter 2:Infrared spectroscopy

 Region I Region II
3600-2700 cm-1 1800-1600 cm-1
100
O-H N-H C-H C=O
Transmittance (%)

80 bond stretching Fingerprint

alcohols
acid chlorides Region
60 phenols
anhydrides (below 1500 cm-1)
esters
carboxylic acids
ketones
40 amines aldehydes
amides carboxylic acids
amides
20 alkynes C-H
alkenes =C-H
alkanes -C-H
0
4000 3500 3000 2500 2000 1500 1000
2.5 3.0 4.0 5.0 6.0 10.0
Wavenumber or Frequency (cm ) -1
/ Wavelength (microns, m)
Chapter 2:Infrared spectroscopy
 Instrumentation
1. Radiation source 2. Monochromator
3. Solvents, sample cells, samples 4. Readout / Recorder

schematic diagram of a double beam double-grating

infrared spectrophotometer
Chapter 2:Infrared spectroscopy
SOLVENTS, CELLS, SAMPLES
Solvents
[Link] be transparent in the region studied: no single
solvent is transparent throughout the entire IR region
2. Water and alcohols are seldom employed to avoid O-H
band of water .
[Link] be chemically inert (does not react with substance
or cell holder). CCl4, CS2, or CHCl3; may be used but we should
consider its IR spectrum

Cells
- NaCl or KCl cells may be used (moisture from air and sample
should be avoided: even with care, their surfaces eventually
become fogged due to absorption of moisture)
- Very thin (path length = 0.1 to 1.0 mm)
- Sample concentration = about 0.1 10% Chapter 2:Infrared spectroscopy
Preparation of Samples for IR spectroscopy

1. Solid KBr disk (1 mg solid sample + 100 mg KBr pressed into a disk)
Mull: 1 mg solid sample suspended in Nujol (heavy liquid hydrocarbon)

2. Liquid Neat (thin film of liquid between two NaCl plates solution in
CCl4 and put in special NaCl cells.

3. Gas IR spectrum is obtained directly by permitting the sample to

expand into an evacuated special cells.

Chapter 2:Infrared spectroscopy

Use of IR spectra

Identification of functional groups on a

molecule this is a very important tool in
organic chemistry

Spectral matching can be done by computer

software and library spectra

Since absorbance follows Beer s Law, can do

quantitative analysis

Chapter 2:Infrared spectroscopy

FEATURES OF AN IR SPECTRUM
An IR spectrum is a plot of per cent
transmittance (or absorbance) against
wavenumber (frequency or wavelength). A
typical infrared spectrum is shown below.
A 100 per cent transmittance in the spectrum implies
no absorption of IR radiation. When a compound
absorbs IR radiation, the intensity of transmitted
radiation decreases. This results in a decrease of per
cent transmittance and hence a dip in the spectrum.
The dip is often called an absorption peak or
absorption band.
Different types of groups of atoms (C-H, O-H, N-H,
etc ) absorb infrared radiation at different
characteristic wavenumbers.

Chapter 2:Infrared spectroscopy

 IR Spectrum

Baseline

Absorbance/
Peak

No two molecules will give exactly the same IR

spectrum (except enantiomers)
Simple stretching: 1600-3500 cm-1
Complex vibrations: 400-1400 cm-1, called the
fingerprint region

Chapter 2:Infrared spectroscopy

IR absorptions are described by their frequency
and appearance.
Frequency (n) is given in wavenumbers (cm-1)
Appearance is qualitative: intensity and shape
conventional abbreviations:
vs very strong
s strong
m medium
w weak
br broad
sh sharp OR shoulder

Chapter 2:Infrared spectroscopy

 When analyzing the spectrum of an unknown,
concentrate your first effort on determining the
presence (or absence) of a few major functional groups.
The C=O, O-H, N-H, C-O, C=C, C C, C N and NO2
peaks which give structural information if they are
present.
Do not try to make a detailed analysis of the analysis of
C-H absorption near 3000 cm-1, almost all compounds
have these absorptions.
D not worry about subtleties of the exact environment in
which the functional group is found.
Following is a major checklist of the important gross
features

Chapter 2:Infrared spectroscopy

Acids: Is O-H also present? Broad absorption near
2400-3400 cm-1 (usually overlaps C-H).
Amides: Is N-H also present? Medium absorption near
3400 cm-1; sometimes a double peak with equivalent
halves.
Esters: Is C-O present? Strong-intensity absorption near
1000-1300 cm-1.
Aldehydes: Is aldehydes C-H present? Two weak
absorptions near 2750-2850 cm-1 on right side of the
aliphatic C-H absorptions.
Anhydrides: two C=O absortions near 1760-1810 cm-1.
Ketones: The preceding five choices have been
eliminated.

Chapter 2:Infrared spectroscopy

Alcohols; Phenols: Check for O-H:
* Broad absorption near 3300-3400 cm-1;
* Confirm this by finding C-O near 1000-
1300 cm-1.

Amines: Check for N-H

* Medium absorption(s) near 3400 cm-1.
Ethers: Check for C-O near 1000-1300 cm-1
(and absence of O-H near 3400 cm-1).

Chapter 2:Infrared spectroscopy

Double bonds and/or aromatic rings:
*C=C is a weak absorption near 1650 cm-1
* medium to strong absorptions in the region 1450-1600
cm-1; these often imply aromatic ring.
* Confirm the double bond or aromatic ring by consulting the
C-H region on the left of 3000 cm-1.
Triple bonds:
*C N: is a medium, sharp absorption near 2250 cm-1.
*C C: is a weak, sharp absorption near 2150 cm-1
* Check also for acetylenic C-H near 3300 cm-1
Hydrocarbons:
*None of the preceding is found.
Major absorption are in C-H region near 3000 cm-1.
Very simple spectrum; the only other absorption appear
near 1375-1460 cm1.

Chapter 2:Infrared spectroscopy

In general, the IR spectrum can be split into
four regions for interpretation:
4000 2500 cm-1: Absorption of single
bonds formed by hydrogen and other elements
e.g. O H, N H, C H.
2500 2000 cm-1: Absorption of triple
bonds e.g. C C, C N.
2000 1500 cm-1: Absorption of double
bonds e.g. C=C, C=O.
1500 400 cm-1: This region often consists of
many different, complicated bands. This part
of the spectrum is unique to each compound and
is often called the fingerprint region. It is
rarely used for identification of particular
functional groups.
Chapter 2:Infrared spectroscopy
Chapter 2:Infrared spectroscopy
BASE VALUES These are
the minimum
(+/- 10 cm-1) number of
values to
memorize.
O-H 3600
N-H 3400
C-H 3000

C N 2250
C C 2150
C=O 1715
C=C 1650
C O ~1100 large range
Chapter 2:Infrared spectroscopy
O-H STRETCH

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
O-H WAVELENGTH ( m)
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

The O-H stretching region
O-H 3600 cm-1 (alcohol, free)
O-H 3300 cm-1 (alcohols & acids, H-bonding)

broadens
shifts

FREE H-BONDED

3600 3300

Chapter 2:Infrared spectroscopy

HYDROGEN-BONDED HYDROXYL
R R Many kinds of OH
bonds of different
O H O lengths and strengths
H H This leads to a broad
absorption.
R O O
R O
H R
H Neat solution.
O
R H Longer bonds are
weaker and lead to
lower frequency.

Hydrogen bonding occurs in concentrated solutions

( for instance, undiluted alcohol ).

Chapter 2:Infrared spectroscopy

 FREE HYDROXYL
The free hydroxyl vibrates without interference from any other
molecule.

Distinct bond has a well-

CCl4 defined length and strength.

CCl4
R O CCl4
H
CCl4 Solvent molecules
CCl4 surround but do not
hydrogen bond.

Occurs in dilute solutions of alcohol in an inert solvent like CCl4.

Chapter 2:Infrared spectroscopy

 ALCOHOL

O-H OH CH2
H-bond
C-O

C-H

Chapter 2:Infrared spectroscopy

 CARBOXYLIC
ACID

neat solution

O-H
H-bond

C-O
CH2 O

C-H C=O CH3 CH2 CH2 C OH

Chapter 2:Infrared spectroscopy

 CARBOXYLIC ACID DIMER

O H O
C R
R C
O H O

Strong hydrogen bonding in the dimer weakens the OH

bond and leads to a broad peak at lower frequency.

Chapter 2:Infrared spectroscopy

N-H STRETCH

Chapter 2:Infrared spectroscopy

Typical Infrared Absorption Regions

N-H WAVELENGTH ( m)
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

N-H 3300 - 3400 cm-1

Primary amines give two peaks

H H
symmetric N N asymmetric
H H
Secondary amines give one peak
Tertiary amines give no peak

Chapter 2:Infrared spectroscopy

 PRIMARY AMINE
aliphatic
1-Butanamine

NH2
scissor
CH3
CH2
NH2

CH3 CH2 CH2 CH2 NH2

Chapter 2:Infrared spectroscopy

 PRIMARY AMINE
aromatic
3-Methylbenzenamine

-CH3
NH2
Ar-H

NH2
CH3
benzene
Ar-H

Chapter 2:Infrared spectroscopy

 SECONDARY AMINE

N -Ethylbenzenamine

NH

NH CH2 CH3
CH3

Ar-H
benzene

Chapter 2:Infrared spectroscopy

 TERTIARY AMINE

N,N -Dimethylaniline
Ar-H

-CH3

CH3
no N-H
N
CH3
CH3
benzene Ar-H

Chapter 2:Infrared spectroscopy

C-H STRETCH

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption Regions

WAVELENGTH ( m)
C-H
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

We will look at FREQUENCY (cm-1)

this area first

Chapter 2:Infrared spectroscopy

 The C-H stretching region
BASE VALUE = 3000 cm-1

C-H sp stretch ~ 3300 cm-1

UNSATURATED
C-H sp2 stretch > 3000 cm-1
3000 divides

C-H sp3 stretch < 3000 cm-1 SATURATED

C-H aldehyde, two peaks (both weak)

~ 2850 and 2750 cm-1
Chapter 2:Infrared spectroscopy
STRONGER BONDS HAVE LARGER FORCE CONSTANTS
AND ABSORB AT HIGHER FREQUENCIES
increasing frequency (cm-1)

3300 3100 3000 2900 2850 2750

=
=C-H =C-H -C-H -CH=O
(weak)

sp-1s sp2-1s sp3-1s aldehyde

increasing s character in bond

increasing CH Bond Strength
increasing force constant K
CH BASE VALUE = 3000 cm-1

Chapter 2:Infrared spectroscopy

 ALKANE

CH bending vibrations
discussed shortly

CH includes
stretching CH3 sym and asym
vibrations CH2 sym and asym
CH3 CH2 CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

C-H BENDING

Chapter 2:Infrared spectroscopy

THE C-H BENDING REGION
CH2 bending ~ 1465 cm-1

CH3 bending (asym) appears near

the CH2 value ~ 1460 cm-1

CH3 bending (sym) ~ 1375 cm-1

Chapter 2:Infrared spectroscopy

 METHYLENE GROUP BENDING VIBRATIONS
Scissoring Wagging

H ~1465 cm-1
H H H ~1250 cm-1

C C C
H H

H ~720 cm-1 H H H ~1250 cm-1

C C C
H H

Rocking Twisting
in-plane out-of-plane
Bending
Vibrations
Chapter 2:Infrared spectroscopy
METHYLENE AND METHYL BENDING VIBRATIONS

CH2 CH3
C-H Bending, look near
1465 and 1375 cm-1
asym sym

1465 1460 1375

these two peaks C

frequently overlap H H
and are not resolved
H

Chapter 2:Infrared spectroscopy

METHYLENE AND METHYL BENDING VIBRATIONS
ADDITIONAL DETAILS FOR SYM CH3
The sym methyl peak
CH2 CH3 splits when you have
more than one CH3
attached to a carbon.

asym sym
C CH3
one peak
1465 1460 1375

CH3
geminal dimethyl 1380 1370 C
CH3
two peaks
(isopropyl)

t-butyl 1390 1370 CH3

C CH3
CH3 two peaks

Chapter 2:Infrared spectroscopy

 ALKANE

CH2
rocking
CH3
CH2 bend
bend
CH
stretch

CH3 CH2 CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

 ALKENE

=CH
C=C CH2
CH3
bend

CH CH
CH2 CH CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

 AROMATIC

CH3
Ar-H

CH3 C=C
benzene

Ar-H

Chapter 2:Infrared spectroscopy

 ALKYNE

=
C=C

CH2, CH3

=
=C-H C-H HC C CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

Fingerprinting

Similar
C10H22 But Not
Identical

C12H26

Chapter 2:Infrared spectroscopy

C N AND C C STRETCH

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
C=N
=
WAVELENGTH ( m)
2.5 4
C=C
= 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

 C N 2250 cm-1
C C 2150 cm-1

The cyano group often gives a strong, sharp peak

due to its large dipole moment.

The carbon-carbon triple bond gives a sharp peak,

but it is often weak due to a lack of a dipole. This is
especially true if it is at the center of a symmetric
molecule.
R C C R

Chapter 2:Infrared spectroscopy

 NITRILE
BASE = 2250

=
C=N
CH3 CH2 C N

Chapter 2:Infrared spectroscopy

 ALKYNE
BASE = 2150

C C

HC C CH2 CH2 CH2 CH3

C-H

Chapter 2:Infrared spectroscopy

C=O STRETCHING

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
WAVELENGTH ( m)
C=O
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

THE CARBONYL STRETCHING REGION

This region stretches from about 1800 to 1650 cm-1

RIGHT IN THE MIDDLE OF THE SPECTRUM

The base value is 1715 cm-1 (ketone)

The bands are very strong !!! due to the large C=O
dipole moment.

C=O is often one of the strongest peaks

in the spectrum

Chapter 2:Infrared spectroscopy

 KETONE

2-Butanone BASE = 1715

1715

overtone
2x C=O

C-H CH bend
O
C=O
C=O
CH3 C CH2 CH3

Chapter 2:Infrared spectroscopy

C=O IS SENSITIVE TO ITS ENVIRONMENT
EACH DIFFERENT KIND OF C=O COMES AT
A DIFFERENT FREQUENCY
acid carboxylic
chloride ester aldehyde ketone acid amide

O O O O O O
R C R C R C R C R C R C
Cl OR' H R OH NH2
1800 1735 1725 1715 1710 1690
anhydride
O O
BASE THESE VALUES ARE
R C O C R VALUE WORTH LEARNING
all are +/- 10 cm-1
1810 and 1760
( two peaks )
Chapter 2:Infrared spectroscopy
C=O BOND LENGTHS IN CARBONYL COMPOUNDS

shorter longer

1.225 A 1.231 A 1.235 A 1.248 A

acid ester ketone amide

chloride
1780 cm-1 1735 cm-1 1715 cm-1 1680 cm-1

Chapter 2:Infrared spectroscopy

 SUMMARY
Ketones are at lower frequency than Aldehydes because
of the second electron-donating alkyl group.
Acid chlorides are at higher frequency than ketones because of the
electron-withdrawing halide.
Esters are at higher frequencies than ketones due to the
electron-withdrawing oxygen atom. This is more important than
resonance with the electron pair on the oxygen.

Amides are at lower frequencies than ketones due to resonance

involving the unshared pair on nitrogen. The electron-withdrawing
effect of nitrogen is less important than the resonance.
Note that the electronegativity difference, O versus N,
weights the two factors (resonance/ e-withdrawal)
differently in esters than in amides.
Acids are at lower frequency than ketones due to H-bonding.

Chapter 2:Infrared spectroscopy

overtone of strong C=O peak
1719 x 2 = 3438 KETONE
BASE = 1715

overtone
3438

C-H CH bend
O
C=O
CH3 C CH2 CH3

Chapter 2:Infrared spectroscopy

overtone of strong C=O peak
1725 x 2= 3460 ALDEHYDE
BASE = 1725

CHO
3460

CH bend

C=O
O

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C H

Chapter 2:Infrared spectroscopy

overtone of strong C=O peak
1800 x 2 = 3608 ACID CHLORIDE

BASE = 1800

3608

CH bend

C
C=O CH3 (CH2)10 Cl
C-H

Chapter 2:Infrared spectroscopy

overtone of strong C=O peak
ESTER
1735 x 2 = 3482
BASE = 1735

3482

C-O
C-H
O

C=O C
CH3 CH2 CH2 O CH2 CH3

Chapter 2:Infrared spectroscopy

 CARBOXYLIC ACID
BASE = 1710

O-H

C-O C
C-H C=O CH3 CH OH

CH3

Chapter 2:Infrared spectroscopy

 CARBOXYLIC ACID DIMER

RECALL lowers
frequency
of C=O
O H O
C R and also
R C of O-H

O H O
Strong hydrogen-bonding in the dimer weakens the O-H and
C=O bonds and leads to broad peaks at lower frequencies.

Chapter 2:Infrared spectroscopy

two peaks
Propanamide AMIDE
BASE = 1690
sym / asym

C-H O
C=O C
NH2 CH3 CH2 NH2
CH bend

Chapter 2:Infrared spectroscopy

C=C STRETCHING

ALKENES
&
AROMATICS

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
WAVELENGTH ( m) C=C
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

C=C double bond at 1650 cm-1 is often
weak or not even seen.

C=C benzene ring shows peak(s) near 1600

and 1400 cm-1 , one or two at each value
- CONJUGATION LOWERS THE VALUE.
When C=C is conjugated with C=O it is
stronger and comes at a lower frequency.

Chapter 2:Infrared spectroscopy

 ALKENE

=C-H C=C C-H

bend

C-H
aliphatic oops
CH2 CH CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

 AROMATIC

benzene
C-H CH3 benzene
C=C

oops

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
WAVELENGTH ( m) C-O
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

C-O STRETCHING

Chapter 2:Infrared spectroscopy

The C-O band appears in the range of 1300
to 1000 cm-1

Look for one or more strong bands appearing

in this range!

Ethers, alcohols, esters and carboxylic acids

have C-O bands

Chapter 2:Infrared spectroscopy

 ETHER

Dibutyl Ether BASE = 1100

CH2 CH3
C-H bending
C-O

CH3 CH2 CH2 CH2 O CH2 CH2 CH2 CH3

Chapter 2:Infrared spectroscopy

 AROMATIC ETHER
Anisole BASE = 1100

C-H
aromatic

O CH3

benzene oops
C-O

Chapter 2:Infrared spectroscopy

Cyclohexanol ALCOHOL
BASE = 3600
BASE = 1100

CH2
bend

OH OH

C-O

C-H

Chapter 2:Infrared spectroscopy

 CARBOXYLIC ACID
2-Methylpropanoic Acid

OH

C-O C
CH C=O CH3 CH OH

CH3

Chapter 2:Infrared spectroscopy

Ethyl Butanoate
ESTER

CH
O
C-O
C
C=O CH3 CH2 CH2 O CH2 CH3

Chapter 2:Infrared spectroscopy

N=O STRETCHING

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions

WAVELENGTH ( m)
N-O
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

N=O stretching between 1550 and 1350 cm-1
asymmetric and symmetric stretchings

Often the 1550 cm-1 peak is stronger than the

other one

Chapter 2:Infrared spectroscopy

 NITROALKANE

2-Nitropropane

C-H

N=O

NO2
gem-dimethyl
CH
CH3 CH3 N=O

Chapter 2:Infrared spectroscopy

 Typical Infrared Absorption
Regions
WAVELENGTH ( m) C-Cl
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

Chapter 2:Infrared spectroscopy

C-Cl 785 to 540 cm-1, often hard to find
amongst the fingerprint bands!!

C-Br and C-I appear outside the useful

range of infrared spectroscopy.

C-F bonds can be found easily, but are not

that common.

Chapter 2:Infrared spectroscopy

 Carbon Tetrachloride
Often used as a solvent for IR spectra.
When it is used, spectra show C-Cl absorptions.

Cl

Cl C Cl

Cl
C-Cl

Chapter 2:Infrared spectroscopy

Chlorobenzene benzene ring
combination
bands

Cl
oops
benzene
C=C C-Cl

Chapter 2:Infrared spectroscopy

=C-H OUT OF PLANE BENDING

Chapter 2:Infrared spectroscopy

OUT-OF-PLANE BENDING
(OOPS)

PLANE
above
H

ALKENES
H

H
below

H also with benzenes

Chapter 2:Infrared spectroscopy

 10 11 12 13 14 15
ALKENES
R H
Monosubstituted C C s s
H H
Disubstituted
R R
cis-1,2- C C s
H H
H R
trans-1,2- C C s
R H
R H
1,1- C C s
R H
R R
Trisubstituted C C m
R H
R R
Tetrasubstituted C C =C-H OUT OF PLANE BENDING
R R
Chapter 2:Infrared spectroscopy
1000 900 800 700 cm-1
 BENZENES 10 11 12 13 14 15

Monosubstituted s s
Disubstituted
s
ortho
meta m s s

para s
RING H s
Trisubstituted OOPS
1,2,4 m s

1,2,3 s m

1,3,5 s m
combination bands Chapter 2:Infrared spectroscopy
1000 900 800 700 cm-1
 end of
chapter 2

Chapter 2:Infrared spectroscopy