Spectroscopy

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

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Electromagnetic Spectrum
 Examples: X rays, microwaves, radio waves,
visible light, IR, and UV
 Frequency and wavelength are inversely
proportional
 c = , where c is the speed of light
 Energy per photon = h, where h is Planck’s
constant

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 The Electromagnetic Spectrum

High Frequency Low

High Energy Low

X-ray UV IR Micro Radio

wave

uv visible Vibrational IR NMR

200 nm 400 nm 800 nm 2.5  15  1m 5m

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 Energy Transitions

Table 1. Types of energy transitions of

the electromagnetic spectrum

Region of spectrum Energy transition

X-rays Bond breaking
UV/Visible Electronic
IR Vibrational
Microwave Rotational
Radiofrequencies Nuclear spin (NMR)
Electron spin (ESR)

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The Spectrum and Molecular Effects

=>
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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 (4000 -
400 cm-1)
 Wavenumbers are proportional to frequency
and energy

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Molecular Vibrations
 Light is absorbed when radiation frequency =
frequency of vibration in molecule
 Covalent bonds vibrate at only certain allowable
frequencies
 Associated with types of bonds and movement of
atoms
 Vibrations include stretching and bending

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 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”
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Interpretation
 Looking for presence/absence of functional
groups
 Correlation tables
 A polar bond is usually IR-active
 A nonpolar bond in a symmetrical molecule
will absorb weakly or not at all

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 Carbon-Carbon Bond Stretching
 Stronger bonds absorb at higher frequencies:
 C-C 1200 cm-1
 C=C 1660 cm-1
 CC 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

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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

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An Alkane IR Spectrum

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An Alkene IR Spectrum

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 An Alkyne IR Spectrum

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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)

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An Alcohol IR Spectrum

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 An Amine IR Spectrum

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

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 A Ketone IR Spectrum

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An Aldehyde IR Spectrum

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O-H Stretch of a Carboxylic Acid

This O-H absorbs broadly, 2500-3500 cm-1,

due to strong hydrogen bonding

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 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 C’s or less)
absorb at an even higher frequency

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 An Amide IR Spectrum

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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

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 A Nitrile IR Spectrum

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Summary of IR Absorptions

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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 sample’s IR
spectrum confirms the identity of the compound

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 Infrared Regions

Region wavelength wavenumber frequency

(m) (cm-1) (Hz)

Near 0.78 ~ 2.5 12800 ~ 4000 3.8 x 1014~ 1.2 x 1014

Middle 2.5 ~ 50 4000 ~ 200 1.2 x 1014~ 6.0 x 1012
Far 50 ~ 1000 200 ~ 10 6.0 x 1012~ 3.0 x 1011
Most used 2.5 ~ 15 4000 ~ 670 1.2 x 1014~ 2.0 x 1013

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 IR Application

Near IR: 770 ~ 2500 nm

1. Using photometers or spectrophotometer
similar to UV spectrometry

2. Application: routine quantitative determination

of species, e.g. moisture, proteins, CHs, fats in
agricultural, food, and chemical industries.

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 IR Application

Mid-IR:
1. Used largely for qualitative organic analysis
and structural determination based on
absorption spectra.
2. FT-IR has been used for quantitative analysis
of complex gaseous, liquid, or solid mixtures.

Far-IR:
Used for qualitative analysis of pure inorganic
or metal organic species.
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 IR Sources
 An inert solid heated btw 1500 ~ 2000k, The
max radiation ~ 5900 cm-1 (1.7 M); at long
wavelength, 1% of max ~ 670 cm-1 (15 M).
 Types of Sources
►The Nernst Glower: rare earth oxides,
negative temp coeff of resistance, heated to
red heat
► The Globar Source: a silicon carbide rod,
positive temp coeff, greater output at > 5 m.

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 Types of Instruments for IR
 Dispersive grating photometers: used for
qualitative work
 Fourier transform photometers: used for both
qualitative and quantitative works; speedy,
reliable, and convenient
 Nondispersive photometers: for quantitative
use

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IR Absorption Region
λ= 2.5 ~ 15 m (10 -4 cm = 1 m = 104 Ao).
(4000 cm-1 ~ 666 cm-1 )
wavenumber:  (cm-1, reciprocal centimeters)

  (cm-1) = 1 /  (cm)
ν(Hz) =  c = c (cm/sec) /  (cm)

wavenumber (cm-1) = 104 / wavelength (m)

wavelength (m) = 104 /(cm-1)

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Theoretical Introduction

ΔE = h .ν = h c /λ = h c 

C : velocity of light, 3 x 1010 cm/sec

h : Planck’s constant
ν : frequency (1/sec)
λ : wavelength (mm)
 : wavenumber (cm-1)

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IR Absorption Process
 A Quantized Process:
 Only selected frequencies (energies) of
infrared
 radiation will be absorbed by a molecule

 Bonds have dipole moment, Yes !

 Symmetric bonds, No ! (e.g. H2, Cl2)

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IR Application
 Infrared spectrum can be a fingerprint used
for identification.
 Infrared spectrum gives the structural
information about a molecule.

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 Absorption
UV example

Transmittance: T = I/Io
Absorbance: A = Log Io/I
if no absorption, T = 1; A = 0

Most spectrometers display absorbance on vertical axis,

and the commonly observed range from 0 (100% T)
to 2 (1% T)

max: The wavelength of maximum absorbance

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An Infrared Spectrum

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 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”
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 Vibration Modes

                          

Symmetric Stretch Asymmetric Stretch Symmetric Bend

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Vibration Modes of CH2 Group

 Gas Phase IR Spectrum of Formaldehyde, H2C=O

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Vibration Modes
H H H H
H H

Sym. Stretching Scissoring wagging

(~ 2853) (~ 1450) (~ 1250)

H H H
H H H

Asym. Stretching Rocking Twisting

(~ 2926) (~ 720) (~ 1250)
in plane Out of plane
Stretching vibrations Bending Vibrations
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 Basic Principle
As for any harmonic oscillator, the energy of bond vibration:
Eosc  h νosc
Applying Hooke’s Law
K = - k .Δr
K Restoring force
-   Arising force opposed to extension
k Elasticity constant (unit: N / m = kg . m / sec2 / m)
( ~ bond strength between two atoms)
Δr extension k
m1 m2

m1 m2

x1 ro x2
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Basic Principle
The natural frequency of the oscillation

νosc = ½  . √k / 
Wave equation of quantum mechanics

E = (n + ½) ½  h. √k / 
h : Planck’s const.
n : vibration quantum number

Take (1) into (2):

Evib = h νosc  (n + ½ )
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Basic Principle

From SchrÖdiger Equation:

Evib = h νosc  (n + 1/2)
vibration quantum number, n = 0, 1, 2, 3 ----

Ground state (n = 0): E0 = ½ hνosc

First excited state (n = 1): E1 = 3/2 hνosc

ΔEvib = E1 – E0
= 3/2 hνosc - ½ hνosc = hνosc
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Basic Principle
The frequency of radiation, ν
 vibrational frequency, νosc

E radiation = h ν = ΔEvib = hνosc

= ½  h . √k / 
or

ν = νosc = ½  . √k / 

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 Basic Principle
νosc = 1/2  . √k /
 = m1. m2 / (m1 + m2) = reduced mass of atoms
in AMU (unit: kg)

ΔE vib = h . νosc = h / 2  . √k /

ν(cm-1) = E vib / h c = 1 / 2  c .√k /

= 5.3 x 10 –12 sec/cm . √k /

[ unit of √k /sec -1 ]

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 Example
Calculate the wavenumber and wavelength of the fundamental
frequency peak due to the stretching vibration of C=O group.

Solution:
m1 = 12 x 10 -3 kg / mol / 6.0 x 10 23 atoms / mol
= 2.0 x 10 –26 kg
m2 = 16 x 10 -3 kg / mol / 6.0 x 10 23 atoms / mol
= 2.7 x 10 –26 kg
 = m1. m2 / (m1 + m2) = 1.1 x 10 –26 kg
(cm-1) = 5.3 x 10 –12 s/cm . √1 x 10 3 N /m /2.7 x 10 –26 kg
= 1.6 x 103 cm-1

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Example

(cm-1) = E vib / h c = 1 / 2  c .√k / 

7.76 x 1011/2  c √k / ’
(taking 6.02 x 1023 out of root square)
= 4.12√k / ’
‘ = M1M2/(M1+M2); both are atomic weights.
K : force constant in dynes/cm.
1 N = 1 kg  m/sec2
1 Dyne = 1 g  cm/sec2
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 Force Constants

k (Chemical bond force constant) :

single bond 5 x 102 N/m = 5 x 105 dynes/cm

double bond 1.0 x 103 N/m = 106 dynes/cm

triple bond 1.5 x 103 N/m = 1.5 x 106 dynes/cm

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 Force Constants

C=C bond:
 = 4.12√k / 
K = 106 dynes/cm
m = 12x12/(12+12) = 6

= 4.12√106/6
= 1682 cm-1 (calculated)

= 1650 cm-1 (experimental)

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 Force Constants
C-H Bond:
= 4.12√k / m
K = 5 x 105 dynes/cm
m = 12x(1)/(12+1) = 0.923
= 4.12√5 x 105/0.923
= 3032 cm-1 (calculated)
= 3000 cm-1 (experimental)

C-D Bond:
 = 2206 cm-1 (experimental)
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 Frequencies of vibration

CC C=C C-C

2150 cm-1 1650 cm-1 1200cm-1

increasing K

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 Frequencies of vibration

As the atom bonded to carbon increases in mass, the

Quantity  increases, the frequency of vibration goes down.

C-H C-C C-O

3000 cm-1 1200 cm-1 1100 cm-1

C-Cl C-Br C-I

800 cm-1 550 cm-1 ~ 500 cm-1

Increasing 
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 Frequencies of vibration

Bending motion easier than stretching motions

(The force constant K is smaller)

C-H stretching C-H bending

~ 3000 cm-1 ~ 1340 cm-1

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 Frequencies of vibration

Hybridization affects the K values

sp sp2 sp3
C-H =C-H -C-H
3300 3100 2900 cm-1

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 Example

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Frequencies of Vibration

CC C=C CC

2150 cm-1 1650 cm-1 1200 cm-1

Increasing K

CX stretching
CH CC CO CCl CBr CI
3000 1200 1100 800 550 ~500 cm-1
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Frequencies of Vibration
Resonance:

O O
+
C=O C

1715 cm-1 1675 ~ 1680 cm-1

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 Substituent Effects
Hyperchromic

Hypsochromic Bathochromic
 (blue shift) (red shift)

Hypochromic

UV Profiles 400 800 nm

blue red
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Substitution Effects on IR Peaks

 Electronic effects
 Intramolecular factors
 Inductive effects

R-COR C=0 1715cm-1 ; R-COH C=0 1730cm -1 ；

R-COCl C=0 1800cm-1 ; R-COF C=0 1920cm-1 ;
F-COF C=0 1920cm-1 ; R-CONH2 C=0 1928cm-1 ;

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  Conjugated Effects

O O O
O
C CH3 C CH3 C
H3C C CH3

1715 1685 1685 1660

cm -1 cm -1 cm -1 cm -1

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 Space Effects
 Steric Hindrance
 Ring Strain
3060-3030 cm-1 2900-2800 cm-1
C H2 1781cm -1
1576cm -1 C H2
1678cm -1
1611cm -1 1657cm -1
C H2
C H2 -1
1644cm-1 1651cm
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2 ． Intermolecular Factors

C=O ÉìËõ N-H ÉìËõ N-H ±äÐÎ

O H NH ÓÎÀë 1690 3500 1620-1590
R R
O 1650 3400 1650-1620
HN H Çâ¼ü

H O
O
C OCH3 HO
H3C
O-H Éì Ëõ 2835 3705-3125
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Example

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Symbols of Vibrations

s = symmetric
as = asymmetirc
ν = stretching vibrations (bonding vibrations)
δ = deformation vibrations (bending vibrations)
γ = out-of-plane deformation vibrations
τ = torsional vibrations

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Characterization of IR Spectra

Fingerprint Region: 1450 to 600 cm-1 region

Group Frequency Region: 4000 to 1450 cm-1 region

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 Degree of Freedom (DF)

According to Cartesian to describe positions:

Each atom has 3 degrees of freedom, (x, y, z).

A molecule of n atoms has 3n DF.

For nonlinear molecules: 3n-6 are fundamental vibration of DF.

For linear molecules: 3n-5 fundamental vibration of DF.

fundamental vibration involves no change in the center of

gravity of molecules

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Degree of Freedom (DF)
DF of Linear CO2:

O Cb O
O Cb O

(1) Symmetric (2) Asymmetric

stretching (vs CO2)
stretching (vs CO2)
1340 cm-1 2350 cm-1

- + -
O Cb O
O Cb O

(3) Scissoring (bending)

(ds CO2), 666 cm-1 (4) Scissoring (bending)
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(ds CO2), 666 cm-1 70
Degree of Freedom (DF)
Three fundamental vibrations of
nonlinear triatomic water molecule:

H H H H H H
O O O

Symmetrical Asymmetrical Scissoring

stretching (vs OH) stretching (vs OH) stretching (ds HOH)
3652 cm-1 3756 cm-1 1596 cm-1

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Vibration Modes
CH2 group
A.  Stretching vibrations H H
Change of bond length
C C
  H H
 
Symmetric Asymmetric
 
B.  Deformation vibrations (two types: planar or non-planar)
Change of bond angle
+ +
H H H H

C C C _ C
H H H +
H

in plane out-of-plane
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bending
 Fingerprint Regions

Localized vibrations:
spectra below 1500 cm-1 are
difficult to interpretation, which, we call it
“fingerprint region”, are characteristic for the molecule
as a whole. Most of them are derived from overtone or
combination vibrations.

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 Group Frequency Regions

Absorption bands in the 4000 to 1450 cm-1 region

are usually due to stretching vibrations of diatomic units

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 Some General Trends

i) Stretching frequencies are higher than corresponding

bending frequencies. (It is easier to bend a bond than
to stretch or compress it.)
ii)   Bonds to hydrogen have higher stretching frequencies
than those to heavier atoms.
iii)  Triple bonds have higher stretching frequencies than
corresponding double bonds, which in turn have higher
frequencies than single bonds.
        (Except for bonds to hydrogen).

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 Characterization of IR Spectra

Carbonyl/ethylene groups

C=O 1850 ~1630 cm-1, sharp & intensity

C=C 1680 ~ 1620 cm-1, generally weak

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 Characterization of IR Spectra

Important infrared frequencies:

The IR spectra of complicated molecules have many peaks,
only a few of which can be easily interpreted.
Here are the places to look at:

1500 – 1800 cm-1 : A strong signal for (C=O) or an imine.

2000 – 2200 cm-1 : stretch vibrations of triple bonds and cumulenes
(-C≡N, -C≡C , -N=C=O, -C=C=O).
2900 – 3000 cm-1 : stretch vibrations of aliphatic C – H bond.
3000 – 3100 cm-1 : vinyl C – H bond stretches.
3100 – 3600 cm-1 : O – H bond stretches (broad if inter-molecularly at
H-bonded). Be careful, since water appears in this region.

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 Characterization of IR Spectra

N-H & O-H regions usually overlap

O-H 3650 ~ 3200 cm-1, broad peak

N-H 3500 ~ 3300 cm-1,

1 or 2 sharp absorption bands of low intensity,
O-H in this region usually gives broad peak.

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 Characterization of IR Spectra

Hydrogen Bonding
X— H --- Y
: s-orbital of proton overlapping with p- or -orbital of the acceptors.

Common proton donor groups: -COOH, -OH, Amines, or amides.

Common proton acceptors: O, N, halogens

X— H : move to lower frequency with increased intensity.

The acceptors, Y ( e.g. C=O), also move to lower frequency
but to a less degree.
Intermolecular H-bonding: usually in dimers (e.g. RCOOH), or
in neat or concentrated solutions of R-OH.

Temperature, concentration affect the inter or intra- H-bonding.

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 Characterization of IR Spectra

Intra- H-bond is stronger when a six-membered ring is formed.

RO

O H

H-bond is strongest when the bonded structures is stabilized by resonance.

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 Characterization of IR Spectra

Stretching frequencies in hydrogen bonding

Intermolecular bonding intramolecular bonding
Frequency reduction(cm-1) Frequency reduction(cm-1)
X— H --- Y ν OH ν CO comp’ds ν OH ν CO comp’ds

Weak 300 15 R-OH, PhOH < 100 10 1,2-diols

intermol OH to CO most -OH ketones

Medium 100 ~ 300 50

Strong >500 50 RCOOH dimers > 300 100

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 Analysis of Spectra

1. If C=O
1820 ~ 1660 cm-1 : the strongest peak
Acid: is OH present? Broad near 3400~2400
Amide: is NH present? Medium peak ~3500
Ester: is C-O present? Strong at 1300~1000
Anhydride: two C=O ~ at 1810 & 1760
Aldehyde: is C-H present? Two peaks ~ 2850 & 2750
Ketone: the above 5 choices were eliminated

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 Analysis of Spectra

2. If C=O absent
Alcohol/phenol: check for OH
- broad near 3600~3300
- confirm by C-O near 1300~1000
Amine: check for NH
-medium peak near 3500
Ether: check for C-O near 1300~1000

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 Analysis of Spectra

3. Double bonds/or Aromatic rings

Alkene: -C=C is weak near 1650
Aromatic: -medium to strong at 1650~1450
Aromatic & vinyl CH: weak peak at 3000

4. Triple bond
-CN: medium, sharp near 2250
-CC: weak, sharp near 2150
check also for acetylenic CH near 3300

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 Analysis of Spectra

5. Nitro group
- two strong peaks at 1600-1500 & 1390-1300
6. Hydrocarbon
-none of above found
-major peaks of CH near 3000
-very simple spectrum, others at 1450 & 1375

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Summary of IR Absorptions

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 Characterization of IR Spectra

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 Problem Set

 1. Analysis of C5H10O

IR Spectrum
                         

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 Problem Set

 2. Analysis of C8H8O

IR Spectrum

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 Problem Set

 3. Analysis of C7H8O

IR Spectrum

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 Problem Set

 4. Analysis of C8H7N

IR Spectrum

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 Problem Set

5. Analysis: C7H6O
IR Spectrum

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 Problem Set

6. Analysis: C3H7NO
IR Spectrum

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 Problem Set

7. Analysis: C4H8O2
IR Spectrum

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 Problem Set

8. Analysis: C7H5OCl
IR Spectrum

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 Problem Set

9. Analysis: C6H6S
IR Spectrum

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 Problem Set

10. Analysis: C4H6

IR Spectrum

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 Solutions of Problem Set

No. 1:          
3-pentanone
 
No. 2:             No. 3:            
benzyl alcohol
acetophenone

No. 4:             
benzyl nitrile
 
No. 5:            
No. 6:           
benzaldehyde N-methylacetamide

No. 7:          
ethyl acetate
 
No. 8:           No.9:          
benzoyl chloride thiophenol

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No.10:              98

1,3-butadiene
A Survey of the Important Functional Groups
With Examples

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 Characterization of IR Spectra

9. Hydrocarbons: Alkanes, Alkenes, and Alkynes

A. Alkanes

C-H stretch ~2980 - 2800 cm-1

CH2 ~ 1450
CH3 ~ 1375
C-C stretch : not useful for interpretation

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 Characterization of IR Spectra

B. Alkene

=C-H stretch 3100-3000

=C-H out-of-plane (oop) bending, 1000-650
C=C 1660-1600 (w)
symmetrical type, no absorb
symmetrical (cis), stronger

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 Characterization of IR Spectra

Aromatic rings

=C-H stretch, 3100 ~ 3000

=C-H out-of-plane (oop) bending, 900 ~ 690

great utility to assign the ring substituted pattern

C=C ring stretch, occurs in pair at 1600 & 1475

overtone/combination bands, 2000 ~ 1667
used to assign the ring substituted patterns

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 Characterization of IR Spectra

C. Alkynes

C-H stretch ~ 3300 (3.0)

-CC stretch ~ 2150 (4.65 
disubstituted or symmetrical:
no or weak absorption

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 An Alkyne IR Spectrum

112/06/27 104
 Characterization of IR Spectra

Table 2. Physical constants for sp, sp2, sp3

Hybridized carbon and the resulting C-H values

Bond C-H =C-H -C-H

Type sp- 1s sp2- 1s sp2-1s
Length 1.08Å 1.10Å 1.12Å
Strength 121Kcal 106Kcal 101Kcal
IR freq. 3300 ~3100 ~2900

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 Characterization of IR Spectra

C-H Stretch Region

3300 3100 3000 2850 2750

3.03 3.22 3.33 3.51 3.64

acetylenic vinyl =C-H aliph. C-H aldehyde

C-H arom. =C-H
cyclopropyl -C-H -CH=O
sp sp2 sp3
Strain moves absorption to left
Increasing s character moves to left
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 Characterization of IR Spectra
Table 3. The stretching vibrations for various
sp3 hybridized C-H bonds
Stretching vibration
group
asym. sym.
Methyl CH3- 2962 2872
Methylene –CH2- 2926 2853

Methine –C-H 2890 very weak

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 Characterization of IR Spectra
C-H Bending Vibrations
CH2 CH3
H H
H H
C' H C' H

H H

Scissoring Bending (as.) bending (sy.)

1465 1450 1375 Lone Me g’p

Sometimes overlap 1380 1370 Gem-dimethyl

CH2, ~ 720 rocking band
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 Characterization of IR Spectra

C=C Stretching Vibrations

Conjugated effects.
1660-1640 cm-1
Ring size effects.
The frequency of (endo) double bonds in
cyclic compounds is sensitive to ring size.

a
C'' C''
C' C'
C' c
b
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 Characterization of IR Spectra
1650 1646 1611 1566 1641

Angle > 90 Angle < 90

~ 1611

Figure 3. C=C Stretching vibrations in

endocyclic Systems
112/06/27 110
 Characterization of IR Spectra

External (exo) double bonds

1950 1780 1678 1657 1655 1651

H2C=C=CH2
Allene

(a) Strain moves the peak to the left

(b) Ring fusion moves the absorption
to the left

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 Characterization of IR Spectra

C-H Bending Vibrations for Alkenes

In-plane scissoring: ~ 1415

Out-of-plane region: 1000 ~ 650

Valuable to indicate the substitution patterns

H
C1 C2
H

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 Characterization of IR Spectra
10 11 12 13 14 15 

Monosubst. s s

cis-1,2 s

trans-1,2 s

1,1-disubst. s
trisubst. m

tetrasubst.
1000 900 800 700 cm -1
Figure. The C-H out-of-plane bending vibrations for
112/06/27 113
substituted alkenes
 11 12 13 14 15 

Monosubst. s s

Ortho s

Meta m s s

Para s

1,2,4- m s

1,2,3-
s m

1,3,5- s m
900 800 700 cm-1
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 Characterization of IR Spectra

D. Alcohols and Phenols

O-H “free” O-H sharp, 3650~3600 if no H-bonding.

H-bonded O-H, broad at 3500~3200
,usually in neat (pure) liquids.

C-O 1250~1000(s)

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An Alcohol IR Spectrum

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 Characterization of IR Spectra

Table. The C-O and O-H stretching vibrations in

Alcohols and Phenol
Compound C-O stretch O-H stretch

Phenols 1220 3610

3  - OH 1150 3620
2  - OH 1100 3630
1  - OH 1050 3640
OH
OH
CH2OH
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1100  1070 1100  1070 1050  1017
 Characterization of IR Spectra

E. Ethers
C-O stretch, 1300 ~ 1000
phenyl & vinyl ethers, shift to higher frequency
(increase of double bond character)
1250 (asy), 1040 (sy).

Epoxides, 3 bands (1250, 950~815, 850~750)

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 Characterization of IR Spectra

F. Carbonyl compounds
1810 1800 1760 1735 1725 1715 1710 1690
acid ester ketone amide
chloride
Anhydride anhydride aldehyde carboxylic
(band 1) (band 2) acid

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 Characterization of IR Spectra

F-1. Factors affect C=O vibration

1. Conjugated effects.
-unsaturated, 30 cm-1 to lower freq.

O O
+
C2 C1 C C1

O O O
CH3 H OH

1715  1690 1725  1700 1710  1680

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 Characterization of IR Spectra

2. Ring size effects

O O O
O
O NH

1715  1745 1715  1780 1735  1770 1690  1705

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 Characterization of IR Spectra

3. Alpha-substitution effects
O

C1

O O

H Cl
Cl H

Axial Cl Equatorial Cl
~ 1725 ~ 1750
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 Characterization of IR Spectra

4. Hydrogen Bonding Effects

OMe
O
H
O
1680

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 Characterization of IR Spectra

5. Cyclic ketones

1815 1780 1745 1715 1715 1705

O O O O
O O
R R

Ring strain

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 Characterization of IR Spectra

6. Carboxylic Acids
O-H stretch, very broad (strongly H-bond)
3400 ~ 2400
C=O stretch, broad, 1730 ~ 1700

C-O stretch, 1320 ~ 1210 (m)

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 Characterization of IR Spectra

7. Esters (R-C(=O)-O-R’)

C=O stretch, 1735

a. conjugation at the R part: ν shift to the right
b. conjugation with O at R’ ν part: shift to the left
c. ring strain (lactones): ν shift to the left

C-O stretch, two or more bands,

one stronger and broader, 1300 ~ 1000

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 Characterization of IR Spectra

Table. The general effects of -unsaturation or aryl

Substitution and conjugation with oxygen on the C=O vibrations

O O O
R O C CH2 R O R H2C C O R
H H
normal
O O
R O O R

1770 1735 1720

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 Characterization of IR Spectra
Table. The Effects of Ring Size, -unsaturation, and
Conjugation with Oxygen in the C=O Vibrations in Lactones

O O O
O O O
1735 1720 1760

O O O
O O O
1770 1750 1800

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O 1820 128
 Characterization of IR Spectra
8. Amides
C=O stretch, 1670 ~ 1640

N-H stretch (1 and 2), 3500, 3100

N-H bending, 1640 ~ 1550

O O O
NH NH
NH
~ 1660 ~ 1705 ~ 1745
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 Characterization of IR Spectra

9. Acid Chlorides

C=O stretch at ~ 1800

conjugation moves to the right

10. Anhydrides

C=O stretch, two bands, 1830~1800 & 1775~1740

ring strain moves to the left
C-O stretch, 1300 ~ 900
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 Characterization of IR Spectra

G. Amines

N-H stretch, 3500~3300

1-, 2 bands; 2-, 1 band
weak, aliphatic amines
stronger, aromatic amines

N-H bend, 1640~ 1560

2-, near 1500
N-H oop bending, near 800
C-N stretch, 1350 ~ 1000
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 Characterization of IR Spectra

H. Nitriles, Isocyanates and Imines

-CN stretch, sharp ~ 2250

-N=C=O a broad, intense band ~ 2270

-N=C=S a broad, intense band ~ 2125

-C=N- in imine or oxime 1690-1640

CC give much weak band at ~ 2250 region.

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 Characterization of IR Spectra

J. Nitro Compounds
N=O stretch, two strong bands,
1600 ~ 1500 & 1390 ~ 1300

Nitroalkanes: ~ 1550, 1380

Nitroarenes: ~ 1530, 1350

Nitroso (R-N=O) one band, 1600 ~ 1500

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 Characterization of IR Spectra

J-1. Carboxylate Salts, RC(=O)-O-

asym ~1600 (s)
sym ~1400 (s)

J-2. Amine Salts

N-H stretch (broad), 3300 ~ 2600

N-H bend, 1610 ~ 1500 (s)

1 (two bands), 1610, 1500
112/06/27 2 (one band), 1610 ~ 1550 134
 Characterization of IR Spectra

K. Sulfur Compounds
Mercaptans S-H stretch, ~ 2550 (w)
Sulfides, R-S-R
Sulfoxides, R-S(=O)-R
S=O stretch, ~1050 (s)
Sulfones, RSO2R
S=O 1300 (s), 1150 (s)
Sulfates RSO3R
S=O 1375(s), 1200(s)
S-O 1000~750
Sulfonamides RSO2NH2, RSO2NHR
S=O 1325 (s), 1140 (s)
N-H 3350, 3250 (1 )
3250 (2 )
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Characterization of IR Spectra
L. Alkyl and Aryl Halides
Fluorides
C-F stretch, 1400~1000 (s)

Chlorides
C-Cl stretch, 800~ 600 (s)

CH2-Cl bend (wagging), 1300 ~ 1200

Bromides/Iodides
C-Br/C-I stretch, ~ 660 out of range

CH2-Br/CH2-I
bend (wagging), 1250 ~ 1150
112/06/27 136
Infrared Sources and Transducers

Infrared sources:
An inert solid with continuous radiation at
heated temperature: 1500 ~ 2000 K.

Range of radiation intensity:

5000 ~ 670 cm-1 (2 ~ 15 M)

112/06/27 137
1. The Nernst Glower
temperature: 1200 ~ 2200 K

2. The Globar Source

a silicon carbide rod
electrically heated (1300 ~ 1500 K)

112/06/27 138
Sample Handling Techniques
 Neat liquids: 一滴樣品夾於二鹽片 (rock-salt plate) 間
( 厚度約為 ≦ 0.01 mm), a neat spectrum obtained.
一般僅適合用於定性的分析 .
 Solids:
 KBr pellet: 2 ~ 5 mg sample, mixing with 100~150 mg
of powdered KBr, pressing with pressure of 5 ~ 10 Ton
to give a transparent disc.
 KBr is hygroscopic, weak OH band at 3450 cm-1

appeared
 Nujol mull: grinding the sample with mineral oil (Nujol)
to create a suspension and placed between salt plates
 Solutions: compound dissolved in common solvents,
ex. CS2, CCl4, CHCl3, dioxane, cyclohexane,
benzene.
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