 WHAT IS ELUCIDATION ?

 WHAT IS INORGANIC STRUCTURE ?

 WHAT IS SPECTROSCOPY?

EMR
“Spectra”

 Atoms and molecules interact with electromagnetic radiation (EMR) in a

wide variety of ways.
 Atoms and molecules may absorb and/or emit EMR.
 Absorption of EMR stimulates different types of motion in atoms and/or
molecules.
 The patterns of absorption (wavelengths absorbed and to what extent)
and/or emission (wavelengths emitted and their respective intensities)
are called ‘spectra’.
 The field of spectroscopy is concerned with the interpretation of spectra
in terms of atomic and molecular structure (and environment).
 ~1019 ~1017 ~1015 ~1013 ~1010 ~105 Frequency (ν) in Hz

~.0001 nm ~.01 nm ~10 nm ~1000 nm ~0,01 cm ~100 m Wavelength (λ)

> 300 300-30 300-30 ~10-4 ~10-6 Energy (kcal/mole)

g-rays X-rays UV IR Microwave Radio

Nuclear Core Electronic Molecular Molecular Nuclear

excitation Electron excitation vibration Rotation Magnetic
excitation ( π to π* ) Resonance
(x-raycryst) NMR (MRI)

SPECTROSCOPY
Frequency and Energy Relation
to
the Interaction of Element in Molecule
Visible
EFFECT OF ELECTROMAGNETIC RADIATION ON MOLECULES

Ionization

Electronik transitions

Molecular vibration
Rotasional motions

Nuclear Spin transitions

  What we observe ?
 What type of information we can
get ?
 What type of transition occur ?

LIGHT
SOURCE
 What is light ?
 What is spectra ?
ENERGI/FREKWENSI SPECTRA JENIS INTERAKSI INFORMASI KIMIA YANG DIPEROLEH
DALAM MOLEKUL
~.0001 nm ~.01 nm~10 nm~1000 nm ~0,01 cm ~100 m

Nuclear
~105

~10-6

IR Microwave Radio
Magnetic
Resonanc
e NMR
(MRI)
~10-4
~1010

Molecular Gugus Fungsional

Rotation
Penyusun Molekul
> 300 300-30 300-30

Molecular
~1015 ~1013

vibration
Electronic Kuantitatif Analisis logam

Visible
excitation
Electronic ( π to π* ) Ion komplek berwarna
UV

excitation
( π to π* )

Komposisi Kristal dan

g-rays X-rays
~1017

Core Electron
excitation mineral dalam material
(x-raycryst)

SPECTROSCOPY
~1019

Nuclear Frequency and Energy Relation

excitation
to
the Interaction of Element in Molecule
  What we observe ?
 What type of information we can
get ?
 What type of transition occur ?

INFRA
RED
SPECTRA
Kesimpulan :
 Sinar adalah gelombang elektromagnetik polikromatis, sedangkan
Spectra adalah gelombang elektromagnetis monokromatis
 Karakterisasi material atau molekul dapat diperoleh dengan
menggunakan sumber spektra tertentu atau monokromatis
 Sumber spektra monokromatis disesuaikan dengan jenis interaksi yang
diinginkan dalam molekul
 Sumber spektra menentukan informasi yang diperoleh dari materi
 Pada prinsipnya spektroskopi tidak dapat menentukan senyawa yang
belum diketahui (tanpa adanya senyawa standar), tetapi informasi
tentang karakter dalam senyawa dapat menjadi informasi yang berharga
dalam menentukan suatu senyawa dalam materi
 INFRARED SPECTROSCOPY
 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
 For a simple diatomic molecule, this model is easy to visualize:
 Infrared spectra are traditionally displayed as %T (percent
transmittance) versus wave number (4000-400 cm-1).
 Useful in identifying presence or absence of functional groups.
 As a covalent bond oscillates – due to the oscillation of the dipole of the
molecule – a varying electromagnetic field is produced

 When a wave of infrared light encounters this oscillating EM field

generated by the oscillating dipole of the same frequency, the two
waves couple, and IR light is absorbed
 The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

EM oscillating wave “coupled” wave

from bond vibration
 INFRARED SPECTROSCOPY

 In the IR region of the electromagnetic spectrum, the absorption of radiation by

a sample is due to changes in the vibrational energy states of a molecule.
 Infrared radiation is largely thermal energy.
It induces stronger molecular vibrations in covalent bonds, which can be
viewed as springs holding together two masses, or atoms.

Specific bonds respond to (absorb) specific frequencies

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 VIBRATIONAL MODES

• Covalent bonds can vibrate in several modes, including stretching, rocking, and scissoring.
• The most useful bands in an infrared spectrum correspond to stretching frequencies, and
those will be the ones we’ll focus on.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 Typical Vibration of Methane Molecule

H H H H H H

C C C

H H H H H H
Asymmetrical stretching Symmetrical stretching Bending or scissoring

H H H H H H

C C C

H H H H H H
Rocking or in Twisting or out-of- Wagging or out-of-plane
plane bending plane bending bending
 INFRARED SPECTROSCOPY

Informasi apakah yang diperoleh dari

spektrokopi Infra Red ?

 Vibrasi antar unsur dalam molekul

 Gugus fungsional penyusun senyawa bukan senyawa
 Molekul

H2C=CH-CH2-CH2-CH2-CH3

Vibrasi C – H dalam CH
Vibrasi C – H dalam CH2
Vibrasi C – H dalam CH3
Vibrasi C – C
Vibrasi C = C
Spektra molekul organik CH2=CH(CH2)3CH3
 Clay Structure

Bagaimana spektra Infra Red ?

Spektra Infra Merah padatan Clay
 Why Infrared absorptions
are
broadening bands ?

 The Doppler effect, in which radiation is shifted in

frequency when the radiation source is moving towards or
away from the observer.
 The broadening of bands due to the collisions between
molecules.
 The energy states of the system do not have precisely
defined energies and this leads to lifetime broadening.
Why Infrared absorptions are broadening bands
 Vibrasi
Molekul air

Amonia Metana

Staggered etane Eclipsed etane Cyclo Butane

 4
3
2 8 6

1 7
5
1. C-H 5. C-H (CH2)
2. C-C 6. C-H (CH3)
3. O-H 7. C-N
4. C-O 8. C-C (sp3)
Phenol Ferocene
[Co(en)3]3+ Pb2+ EDTA complex
complex ion

Pentaammine
isothiocyanatocobalt(III) ion
Zeolite-Y
Zeolite-A
 Normal Modes of Vibration
 These are the stiffness of the bond and the masses of the
atoms at each end of the bond.
 The stiffness of the bond can be characterized by a
proportionality constant termed the force constant, k
(derived from Hooke’s law). The reduced mass, μ, provides
a useful way of simplifying our calculations by combining
the individual atomic masses, and may be expressed as
follows:

μ is reduced mass
wavenumber values for bond vibrational frequencies are

where c is the speed of light.

HOOKE’s LAW

m is reduced mass
 Vibrational Modes of NH4Cl

5 and 6 are lattice vibrational modes

K
Cl K I

KClO3 KIO3

Infrared spectra of KClO3 (solid line)KClO3

and KIO3 (dash line)
 SPEKTRA INFRA MERAH
SENYAWA ANORGANIK

Ferry Khlorida FeCl3

Cobalt Nitrate : [Co(NO3)2.6H2O]

Senyawa FeCl3
 Molekul FeCl3.6H2O ikatan ionik (antara Fe dan Cl)
terlihat pada daerah near infra merah (IR).
 Yang terlihat dalam spektra IR hanya spektra H2O
 Daerah 462 cm−1 bending simetris (ν 2) dari SO42−
 Puncak lebar daerah 1095 cm−1 merupakan bending
asimetris (ν 3) dari SO42−
 Puncak lebar pada daerah kisaran 3410 cm−1
merupakan puncak vibrasi dari gugus OH.
Natrium Sulfat (Na2SO4)

SO42-(Symetric
SO42-(Symetric bending)
stretching)
 SO42-(Symetric
bending)

SO42-(Symetric
stretching)

H2O
H2O
 O

N O
O O H H
Modus vibrasi dari ion Nitrat
• Bil. Gelombang Perkiraan Gugus fungsi
• 3510,45 O–H
• 1627,92 N=O
• 1388.75 dan 1357.89 N–O
• 316,33 Zn - O
1016,58 cm-1 995,35 cm-1 dan 669,39 cm-1– 665,50 cm-1 serapan
streching asimetric dan simetric O-Al-O yang membetuk
kerangka tetrahedal. Pada Al(NO3)3 tidak terbentuk ikatan
tetrahedral Al-NO

H2O O-N-O
streching
bending
H2O N=O
 v4
v2 -

v3
- OH
SPEKTRA INFRA MERAH [Co(NO3)2.6H2O]
 Struktur senyawa kompleks dari
natrium nitropusid (Na2[Fe(CN)5NO])

 Gugus fungsi yang memberikan

kontribusi dalam serapan spektra IR
antara lain : CN, NO, OH (hidrat)
 Spektra IR (Na2[Fe(CN)5NO])

ν3

NO

ν3 ν2

ν1 CN H2O
ν3
H2O
 IR Spektra Natrium Silikat ( Na2SiO3. )
 1080.14 – 964.41 cm-1,
serapan streching
gugus siloksan (Si-O)

3448.72 – 3749.62 cm-1, serapan

stretching OH dari gugus 478.35 cm-1,bending Si-O
hidroksi dari gugus siloksan
STRUKTUR TIO2
 Spektra Infra merah TIO2

 Serapan lebar pada 678.94 dan 524.64

karakterisitik vibrasi dari Ti-O-Ti.
 Serapan pada daerah 1635.64 karakteristik
adanya serapan H-O dari H2O
 Spektra Diammonium Hidrogen Phosphate
(NH4)2HPO4
daerah 3000-3400 cm-1 identik daerah N-H
strecthing mode dan pada daerah 1450-1700
cm-1 identik daerah N-H bending mode

503,21 cm-1, 603,72 cm-1 dan 1026,13 cm-1

adalah vibrasi bending dan stretching dari
ikatan P-O pada senyawa ion PO4-
SPEKTRA INFRA MERAH [Co(NO3)2.6H2O]
GARAM NaHCO3

1o1o cm-1 8oo cm-1

16o5 cm-1
13o5 cm-1
Interpretasi spektra IR NaHCO3 :
 Pada daerah kurang dari 800 cm-1 terdapat peak yang
menggambarkan adanya simetri in-plane bending CO3 dan
asimetri in-plane bending CO3
 Untuk daerah 1605-1668 cm-1 menunjukkan adanya peak dari
asimetri streaching CO2
 Untuk daerah 1310-1360 cm-1 terdapat peak yang
menunjukkan simetri stretching CO2
 Daerah 1010 cm-1 menunjukkan peak streatching C-OH

Sehingga dapat disimpulkan struktur dari NaHCO3 sebagai

berikut: