Infrared Spectroscopy Infrared Spectroscopy Infrared Spectroscopy Infrared Spectros

Infrared
Spectroscopy
Infrared Spectroscopy
Gives information about the
f b h
functional groups in a molecule
Prof. Dr. Taslim Ersam

SPEKTROFOTOMETRIK
INFRA MERAH
E elektronik molekul
4000 666 cm-1
2,5 - 15,4 µm
Gb. Spektrum elektronik

E vibrasi dan rotasi molekul
2
Infrared Spectroscopy
region of infrared that is most useful lies between
f f d h f ll b
2.5‐‐16 μm (4000
2.5 m (4000‐‐625 cm‐1)
depends on transitions between vibrational
depends on transitions between vibrational
energy states
gy
stretching
b di
bending

M1
M2

Infrared Radiation
That part of the electromagnetic spectrum between the
visible and microwave regions
0 8 μm
0.8 (12 500 cm-11) to 50 μm
m (12,500 m (200 cm-11).
)
Area of Interest in Infrared Spectroscopy
The Vibrational portion of infrared spectrum
2.5 μ
μm ((4,000 cm-1) to 25 μ
μm ((400 cm-1)
Radiation in the vibrational infrared region is expressed in
units called wavenumbers ⎯(ν )

Wavenumbers are expressed in units of reciprocal
centimeters (cm-1) i.e. the reciprocal of the wavelength (λ)
expressed in centimeters.
centimeters
⎯ν
(cm-1) = 1 / λ (cm)
Wave Numbers
W N b can be
b converted
t d to
t a frequency
f (ν)
( ) by
b
multiplying them by the speed of light (c) in cm/sec
⎯ν
ν (Hz) = c = c / λ (cm /sec /cm = 1/sec)
Recall: E = h c / λ
Th
Thus, wavenumbers
b are directly
di tl proportional
ti l to
t energy.

Polar Covalent Bonds & Dipole Moments
Organic molecules with polar covalent bonds have an
unequal sharing of the bond electrons setting up an
electrostatic charge difference between the atoms.
atoms
The relative strength of the electrostatic charge
g y
difference is referred to as electronegativity.
Electronegativity impacts the ability of the molecule to
attract or repel other polar entities
The separation of the positive and negative charges in a
polar covalent bond is referred to as a dipole.
A dipole has a dipole moment defined as the product of
the magnitude of the partial charges times the distance
of separation.
The bonds possess rotational and vibrational
frequencies
Th Radiation
The R di ti (Energy)
(E ) Absorption
Ab ti Process
P
The absorption of radiation by a molecule raises the
g
molecule to a higher gy state.
energy
This is a quantized process in which only selected
frequencies are absorbed dependent on the relative
masses of the atoms
atoms, the force constants of the bond
(electronegativity), and the geometry of the atoms.
Only
y those covalent bonds with dipole
p moments are
capable of absorbing infrared radiation.
Every type of bond has a natural frequency of
vibration.
vibration
The same bond in different compounds has a slightly
q y of vibration.
different frequency

When the frequencies of infrared radiation match the
natural vibrational frequencies of a bond with a dipole
moment, the radiation is absorbed increasing the
amplitude of the vibrational motions of the covalent
bonds.
Infrared radiation is absorbed and converted by
y organic
g
molecules with polar covalent bonds and dipole moments
into energy of molecular rotation and molecular vibration.
R t ti
Rotation - Less
L th 100 cm-1
than (S
(Spectrum
t is
i lines)
li )
Vibration - 10,000 cm-1 to 100 cm-1 (Spectrum is bands)
The
Th vibrational
ib ti l bands
b d appears because
b each
h vibrational
ib ti l
energy change is accompanied by a number of rotational
changes
Infrared Spectroscopy is concerned only with the
vibrational spectrum (4,000 cm-1 to 400 cm-1)
Molecular Vibrations
1. Absorption of infrared radiation corresponds to energy
changes on the order of 8-40 KJ/mole (2-10 Kcal/mole
2. The frequencies in this energy range correspond to the
stretching and bending frequencies of the covalent
bonds with dipole
p moments.
3. Stretching (requires more energy than bending)
a. Symmetrical
b. Asymmetrical
4. Bending
a. Scissoring (in-plane bending)
b. Rocking (in-plane bending)
c Wagging
c. (out of plane bending)
(out-of-plane
d. Twisting (out of plane bending)
Stretching Vibrations of a CH2 Group
Symmetric
y Antisymmetric
y

Bending Vibrations of a CH2 Group
Bending Vibrations of a CH
In plane In plane

Bending Vibrations of a CH2 Group
Bending Vibrations of a CH
Out of plane Out of plane

sama-sama bergantian
menjauh/mendekat
keluar bidang
14
Example of infrared spectrum
Transmittance (%)
100
Hexane
C—H stretching bending
bending
bending
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Example of infrared spectrum
Transmittance (%)
100
Hexane
no peaks higher than 3000 cm-1
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

1--hexene
Infrared spectrum of 1
Transmittance (%)
100
C=C—
C=C —H C=C
CH2=C
=C——
peak higher than 3000 cm-1
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Table Infrared
Table Infrared Absorption Frequencies
Absorption Frequencies
Structural unit Frequenc cm‐1

Frequency, cm
Stretching vibrations (single bonds)
sp C—H 3310‐‐3320
3310
sp2 C—H 3000‐‐3100
3000
sp3 C—H 2850‐
2850‐2950
sp2 C—O 1200
sp3 C—O 1025
1025‐‐1200

Table Infrared
Infrared Absorption Frequencies
Structural unit Frequency, cm‐1
Stretching vibrations (multiple bonds)
C C 1620--1680
1620
—C C— 2100--2200
2100
—C N 2240--2280
2240

Table Infrared
Table Infrared Absorption Frequencies
Stretching vibrations (carbonyl groups)
S hi ib i ( b l )
Aldehydes and ketones
and ketones 1710‐
1710‐1750
Carboxylic acids 1700
1700‐‐1725
Acid anhydrides 1800‐‐1850 and 1740
1800 1850 and 1740‐‐1790
Esters 1730‐
1730‐1750
Amides 1680
1680‐‐1700
C O

Table Infrared
Bending vibrations of alkenes
B di ib i f lk
RCH CH2 910--990
910
R2C CH2 890
cis--RCH
cis CHR' 665--730
665
trans--RCH
trans CHR' 960--980
960
R2C CHR'
CHR 790--840
790

Infrared spectrum of 1
1--hexene
Transmittance (%)
100
C=C stretch
CH2=C
=C——
bend
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Infrared spectrum of tert
tert--butylbenzene
Transmittance (%)
100
Ar—
Ar —H stretch;
> 3000
monosubstituted
benzene
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Table Infrared
St
Stretching vibrations (single bonds)
t hi ib ti ( i l b d )
O—H (alcohols) 3200‐
3200‐3600
O—H (carboxylic acids) 3000‐‐3100
3000
N—H 3350‐‐3500
3350

Infrared spectrum of 2-
2-hexanol
Transmittance (%)
100
O—H stretch C—H stretch
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Infrared spectrum of 2-
2-hexanone
Transmittance (%)
100
C—H stretch
C=O stretch
0
4400 3600 2800 2000 1600 1200 800
Wave number, cm-1

Hukum Hook’s untuk
Perhitungan frequensi gugus
fungsional tersebut di atas
_ k ½
ν = 1/2πc [ m1 m2/(m1 + m2) ]
k ± 5x105 dyne cm-1
27
1 k m1m2
vm = (1-1) μ= (1-2)
2π m m1 + m2
1 k 1 k (m1 + m2 )
vm = = ((1-3))
2π μ 2π m1m2
1 k −12 k
v= = 5.3 x10 (1-4)
2πc μ μ
Values you need to know in the
range of 4000 - 2400 cm-1
O
O‐H
H 3300 cm‐1 (alcohol)
O‐H 3300 cm‐1 (acid, broad and ugly)
N‐H 3400 cm‐1
34
C‐H sp3 < 3000 cm‐1
p2 > 3000 cm
C‐H sp 3 ‐1
C‐H sp 3300 cm‐1
C‐H aldehyde, pair @ 2850 and 2750 cm
y p ‐1

V l
Values d to
you need t know
k iin th
the
range of 2250 - 2100 cm-1
y C=N 2250 cm-1
y C=C 2100 cm-1

range off 1800 - 1650 cm-11
• This is the carbonyl region!! All
bands are very strong!!
s value iss 1715 cm-1 ((ketone))
• Base

range of 1650 - 1450 cm-1
y The C=C is found at about 1650 cm-1. It is often very
y
weak.
y The double bonds in a benzene ring are found in the
range of about 1600 to 1450 cm-11
Values you need to know for the

nitro g
group:
p 1550 and 1350 cm-1
• The nitro group appears as two very strong
peaks at about 1550 and 1350 cm-11.

Values y
you need to know in the
range of 1300 - 600 cm-1
y C-O 1300 - 1000 cm-1, along with a lot
of fingerprint bands!!
y C-Cl 800 - 600 cm-1, at the extreme right edge of
the chart;; hard to spot
p them among g the
fingerprint!
The C-H stretching region

•C C-H
H sp3 stretch < 3000 cm-1
• C-H sp2 stretch > 3000 cm-1
• C-H sp
p stretch ~ 3300 cm-1
• C-H aldehyde, pair ~ 2850 and 2750
cm -1
Sample
Compartment
IR Source Detector

The measurement of the
type and amount of light
transmitted by the sample
gives information about the
structure of the molecules
comprising the sample.

Infrared
Source
D t t
Detector
Sample
Compartment
In the IR region of the
electromagnetic spectrum,
the absorption
p of radiation
by a sample is due to
changes in the vibrational
energy states
t t off a
molecule.

The
h pattern off absorption
b i
as a function of wavelength
i called
is ll d an IR spectrum.
t

To obtain an IR spectrum,
the sample must be placed
in a “container” or cell that
is transparent in the IR
region of the spectrum.
Sodium
S di chloride
hl id or saltlt
plates are a common
means off placing
l i th the
sample in the light beam of
th instrument.
the i t t
IR transparent Salt Plates
These plates are made of
salt and must be stored in a
water free environment
such as the dessicator
shown here
here.

Dessicator
Water-free
Water-
Environment
for
Water--sensitive
Water
S lt Plates.
Salt Pl t

The plates must also be
handled with gloves to
avoid contact of the plate
with moisture from one’s
hands.

To run an IR spectrum of a liquid
sample,
p a drop p or two of the liquid
q
sample is applied to a salt plate.

A second
d salt
lt plate
l t is
i
placed on top of the first
one suchh th
thatt th
the li
liquid
id
forms a thin film
“
“sandwiched”
d i h d” between
b t the
th
two plates.

The
Th two
t plates
l t are then
th
secured in a sample holder
that
th t is
i compatible
tibl with
ith the
th
particular instrument being
used.
d

Slide 11

The cell holder is then
placed in the beam of the
instrument.

The light beam traverses
p compartment,
the sample p ,
as illustrated by the red
line.

Light Path
(shown by red line)

The sample is then scanned
by the instrument utilizing
predesignated parameters.
parameters
A relevant
l t background
b k d scan
should already have been
t k
taken.

Click Here to Start Scan

A satisfactory spectrum
has well defined peaks-
peaks-but
not so intense as to cause
flattening
g on the bottom of
the peaks.
Major peaks can be labeled

using the peak function of
th software
the ft

Well-defined
Well-
peaks are
labeled with the
Wavenumbers
of the Absorption
Maxima.

The spectrum can then be printed
using
g the p
print function of the
software.

A sample of a printout of
an IR spectrum.

Sample of a
printout of an IR
spectrum.

The salt plates are cleaned
by rinsing into a waste
container with a suitable
organic solvent-
solvent-commonly
cyclohexane..
cyclohexane
NEVER WATER!

CYCLOHEXANE
Solvent

yp
Cloudy plates must be
polished to return them to a
transparent
p condition.
To polish cloudy windows,

windows
rotate salt plate on
polishing cloth.
cloth

The
Th clean
l plates
l t and
d cell
ll
holder are stored in the
moisture
i t ffree atmosphere
t h
of a dessicator.

Alat untuk sample larutan murni dan padatan
70
Peralatan dalam pengolahan sampel
71
Cairan Murni
Jika jumlah sampel sedikit sekali atau tidak ada
pelarut yang cocok, maka setetes cairan murni diapit
dan ditekan diantara dua lempeng natrium klorida. klorida
Ketebalan dapat diatur antara 0, I -0,3 mm.
Padatan
Ada dua cara untuk pengolahan sample padatan;
1. Mull atau pasta, 1 mg dari zat padat digerus hingga
halus dalarn mortir dengan meneteskan hidrokarbon
cair (Nujol, Kaydol), atau jika vibrasi C-H akan
diidentifikasi ditambahakan heksaklorobutadiena.
Mull selanjutnya di tekan antara dua plat natrium
kiorida.
2. Lempeng kalium bromida, dibuat dengan menggerus
sample (0,1-
(0 1 0,2%)
0 2%) dengan KBr dalam mortir dan
kemudian ditekan sehingga diperoleh sebuah lempeng
transparan. Prof. Dr. Taslim Ersam
72
Larutan
Sampel dilarutkan dalam pelarut CCI4, CS2, CHCI3
(1-5%),
(1 5%), selanjutnya larutan dimasukkan ke dalam
sel larutan yang mempunyai jendela transparan
dengan alat pengatur ketebalan (0,1-1,0 mm), sel
k d
kedua ( l
(pelanutt murni)
i) diletakkan
dil t kk pada
d berkas
b k s
baku, sehingga serapan dan pelarut ditiadakan dan
diperoleh spectrum serapan dari sampel.
73
The electromagnetic spectrum. The lines across the figure correspond to the frequency
scale; the ticks along the right vertical axis correspond to the wavelength scale; and
the ticks along the left vertical axis correspoud to the energy scale.
74
Infrared spectrum of nanane. The light transmitted through a sample af nonane
is platted as a function of wavelength (upper horizontal axis) or wavenumber
(l
(lower h
horizontal
i t l axis).
i ) Ab
Absorptions
ti are indicated
i di t d bby th
the iinverted
t d peaks.
k
75
IR spectra of (a) 1 -ocrene
77
IR spectra of (b) trans-3-hexene.
78
79
80

Infrared Spectroscopy Infrared Spectroscopy Infrared Spectroscopy Infrared Spectros

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Infrared

Prof. Dr. Taslim Ersam

Gb. Spektrum elektronik

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Out of plane Out of plane

Prof. Dr. Taslim Ersam

C—H stretching bending

Wave number, cm-1

no peaks higher than 3000 cm-1

Wave number, cm-1

Wave number, cm-1

Structural unit Frequenc cm‐1

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

R2C CH2 890

Prof. Dr. Taslim Ersam

Wave number, cm-1

Wave number, cm-1

Prof. Dr. Taslim Ersam

O—H stretch C—H stretch

Wave number, cm-1

Wave number, cm-1

Prof. Dr. Taslim Ersam

Values you need to know in the

Prof. Dr. Taslim Ersam

Values you need to know for the

Prof. Dr. Taslim Ersam

The C-H stretching region

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

 Major peaks can be labeled

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

 To polish cloudy windows,

Prof. Dr. Taslim Ersam

Prof. Dr. Taslim Ersam

Major peaks can be labeled

To polish cloudy windows,