THE ELECTROMAGNETIC SPECTRUM

high Frequency (n) low

high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum
REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
Infrared Radiation
 Frequencies - 12800 to 10 cm-1
◦ (cm-1 = wavenumbers)
 Divided into three Regions
◦ Near : 12800 to 4000 cm-1
◦ Middle: 4000 to 400 cm-1
◦ Far: 400 to 10 cm-1

50
 Infrared Absorption

 Absorption of IR radiation 
vibrational energy levels
 not sufficient energy for
electronic excitation
 Vibrational energy states are of
greatest importance for IR
spectroscopy
 IR SPECTROSCOPY

IR spectroscopy is based on the interaction between

Electromagnetic Radiation and matters (samples) in IR regions

FTIR spectroscopy
Rapid and sensitive
Non destructive
Ease in sample presentation
used for qualitative
quantitative analyses

FINGER PRINT TECHNIQUE

 FTIR spectra of lard and others (17 edible fats and oils)

Rohman et al. (2011): JAOCS

 Proses absorpsi IR
 Proses absorpsi IR juga proses Quantized
(Hanya frekuensi tertentu yang sesuai
dapat diabsorpsi molekul untuk vibrasi
ikatan)
 Walaupun energi/frekuensi IR sesuai
dengan frekuensi vibrasi ikatan molekul,
tidak pasti transfer energi itu terjadi.
 Hanya ikatan yang berubah dipole
moment sewaktu bervibrasi dapat
mengabsorpsi inframerah  selection rule
 Contoh : CO2
 Bentuk-bentuk vibrasi
 Interaksi antara radiasi infra merah dengan materi dapat
difahami dalam hal perubahan-perubahan dipole molekul
yang berkaitan dengan vibrasi.

 Untuk memulai model dasar, suatu molekul dapat dilihat

sebagai system massa yang dihubungkan dengan ikatan-
ikatan dengan sifat seperti pegas.
 Jenis vibrasi
 The simplest types, or modes, of
vibrational motion in a molecule
that are infrared active—those that
give rise to absorptions—are the
stretching and bending modes.

 Stretching  Change in bond length

 Bending  Change in bond angle

 Jenis-jenis vibrasi

Sym. stretch Scissoring

Rocking

Antisym. Stretch.
Wagging Twisting
APLIKASI INFRA MERAH DALAM
BIDANG FARMASI

Abdul Rohman
Laboratorium Kimia Analisis
Fakultas Farmasi UGM
 Penggunaan Infra merah

Analisis kualitatif (elusidasi

struktur)
Analisis kuantitatif

Quality Control
 Typical Infrared Absorption
Regions
WAVELENGTH (mm)
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)
 BASE VALUES

Guideposts for you to memorize.

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
C-H STRETCH
 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

STRONGER BONDS HAVE LARGER FORCE CONSTANTS
AND ABSORB AT HIGHER FREQUENCIES
increasing frequency (cm-1)

3300 3100 3000 2900

=
=C-H =C-H -C-H

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

increasing CH Bond Strength

increasing force constant K
CH BASE VALUE = 3000 cm-1
METHYLENE GROUP STRETCHING VIBRATIONS
Two C-H bonds share a central carb
(hydrogens attached to the same ca
H H H
C C
Symmetric Stretch
H ~2853 cm-1 H

H H H
C Asymmetric Stretch
C
H ~2926 cm-1
H

Any time you have two or more of the same kind of bond
a central atom you will have symmetric and asymmetric
METHYL GROUP STRETCHING VIBRATIONS
Three C-H bonds share a central ca
(hydrogens attached to the same ca

H
C H Symmetric Stretch
H ~2872 cm-1

H
C H Asymmetric Stretch
~2962 cm-1
H
 ALKANE
Hexane

CH bending vibrations
discussed shortly

CH includes
stretching CH sym and asym
3
vibrations
CH2 sym and asym
CH3 CH2 CH2 CH2 CH2 CH3
C-H BENDING
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

 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

Bending
Vibrations
 ALKANE
Hexane

CH2
rocking
CH3
CH2 bend
bend
CH
stretch

CH3 CH2 CH2 CH2 CH2 CH3

 ALKENE

=CH
C=C CH2
CH3
bend

CH CH oops
CH2 CH CH2 CH2 CH2 CH3

1-Hexene
 AROMATIC

Ar-H CH3

CH3 C=C
benzene

Ar-H oops
Toluene
 ALKYNE

=
C=C

CH2, CH3

= C-H HC C CH2 CH2 CH2 CH3

=C-H

1-Hexyne
O-H STRETCH
 Typical Infrared Absorption
Regions
O-H WAVELENGTH (mm)
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)
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
Effect of Hydrogen-Bonding
on O-H Stretching

Free
OH
Free C-H
OH

H-bonded H-bonded
OH C-H OH C-H

4000 3600 3200 2800 4000 3600 3200 2800 4000 3600 3200 2800

(a) Pure Liquid (b) Dilute Solution(c) Very Dilute Solutio

“neat”
1-Butanol
HYDROGEN-BONDED HYDROXYL

R R Many kinds of
OH
O H O bonds of
H H different
lengths and
R O R O O strengths
H R
This leads
“Neat” to a
solution.
H broad
O absorption.
R H Longer bonds
are weaker and
lead to
lower solutions
Hydrogen bonding occurs in concentrated
frequency.
( for instance, undiluted alcohol ).
 “FREE” HYDROXYL
The “free” hydroxyl vibrates without interference from any
other molecule.

Distinct bond has a

CCl4 well-defined length
CCl4 and strength.
R O CCl4
H
CCl4
CCl4
Solvent molecules
surround but do not
hydrogen bond.

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

 ALCOHOL

neat solution

O-H OH CH2
H-bond
C-O

C-H
Cyclohexanol
 CARBOXYLIC ACID

Butanoic Acidneat solution

O-H
H-bond

C-O
CH2 O

C-H C=O CH3 CH2 CH2 C OH

 CARBOXYLIC ACID DIMER

O H O
R C C R
O H O

Strong hydrogen bonding in the dimer weakens the OH

bond and leads to a broad peak at lower frequency.
N-H STRETCH
 Typical Infrared Absorption
Regions
N-H WAVELENGTH (mm)
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)
The N-H stretching region
N-H 3300 - 3400 cm-1

 Primary amines give two peaks

H H
N N
H H
 symmetric amines give
Secondary asymmetric
one peak
 Tertiary amines give no peak
 PRIMARY AMINE
aliphatic

1-Butanamine

NH2
scissor
CH3
CH2
NH2

CH3 CH2 CH2 CH2 NH2

 PRIMARY AMINE
aromatic

3-Methylbenzenamine

-CH3

Ar-H NH2

NH2

benzene
CH3 Ar-H
oops
 SECONDARY AMINE

N -Ethylbenzenamine

NH

NH CH2 CH3
CH3

Ar-H
benzene
oops
 TERTIARY AMINE

N,N -Dimethylaniline
Ar-H

-CH3

CH3
no N-H
N
CH3
CH3
benzene Ar-H
oops
Contoh spektra molekul obat