Spectroscop

Spectroscopy Fourier Transform Infrared (FT-IR)

Spectroscopy

PROGRAM STUDI ANALISIS KIMIA

POLITEKNIK AKA BOGOR
2020
Spectroscop
Spectroscopy
Introduction to FTInfrared Spectroscopy

 What is infrared spectroscopy?

 Theory of FT-IR
 FT-IR Advantages?
Spectroscop
Spectroscopy
What is Infrared?
 Infrared radiation lies between the visible and microwave portions of
the electromagnetic spectrum.
 Infrared waves have wavelengths longer than visible and shorter than
microwaves, and have frequencies which are lower than visible and
higher than microwaves.
 The Infrared region is divided into: near, mid and far-infrared.
 Near-infrared refers to the part of the infrared spectrum that is
closest to visible light and far-infrared refers to the part that is
closer to the microwave region.
 Mid-infrared is the region between these two.
 The primary source of infrared radiation is thermal radiation. (heat)
 It is the radiation produced by the motion of atoms and molecules in
an object. The higher the temperature, the more the atoms and
molecules move and the more infrared radiation they produce.
 Any object radiates in the infrared. Even an ice cube, emits infrared.
Spectroscop
Spectroscopy
What is Infrared? (Cont.)

Humans, at normal body temperature, radiate most

strongly in the infrared, at a wavelength of about 10
microns (A micron is the term commonly used in
astronomy for a micrometer or one millionth of a meter).
In the image to the left, the red areas are the warmest,
followed by yellow, green and blue (coolest).

The image to the right shows a cat in

the infrared. The yellow-white areas are the
warmest and the purple areas are the
coldest. This image gives us a different view
of a familiar animal as well as information
that we could not get from a visible light
picture. Notice the cold nose and the heat
from the cat's eyes, mouth and ears.
Spectroscop
Spectroscopy
Infrared Spectroscopy

The bonds between atoms in the molecule stretch and

bend, absorbing infrared energy and creating the
infrared spectrum.

Symmetric Stretch Antisymmetric Stretch Bend

A molecule such as H2O will absorb infrared light when the

vibration (stretch or bend) results in a molecular dipole moment
change
Spectroscop
Spectroscopy
Energy levels in Infrared Absorption

Excited
states
hn

Infrared Absorption and Emission

h(n2 - n1) (overtone)

n
3n h(n1 - n0 ) h(n1 - n0)
Ground
n2 (vibrational)
n
1 states
0
Infrared absorption occurs among the ground vibrational states, the
energy differences, and corresponding spectrum, determined by the
specific molecular vibration(s). The infrared absorption is a net
energy gain for the molecule and recorded as an energy loss for the
analysis beam.
Spectroscop
Spectroscopy
Infrared Spectroscopy

A molecule can be characterized (identified) by its molecular

vibrations, based on the absorption and intensity of specific
infrared wavelengths.
Spectroscop
Spectroscopy
Infrared Spectroscopy
For isopropyl alcohol, CH(CH3)2OH, the infrared absorption
bands identify the various functional groups of the molecule.
Spectroscop
Spectroscopy
Capabilities of Infrared Analysis

 Identification and quantitation of organic solid, liquid or

gas samples.
 Analysis of powders, solids, gels, emulsions, pastes,
pure liquids and solutions, polymers, pure and mixed
gases.
 Infrared used for research, methods development,
quality control and quality assurance applications.
 Samples range in size from single fibers only 20
microns in length to atmospheric pollution studies
involving large areas.
Spectroscop
Spectroscopy
Applications of Infrared Analysis

 Pharmaceutical research
 Forensic investigations
 Polymer analysis
 Lubricant formulation and fuel additives
 Foods research
 Quality assurance and control
 Environmental and water quality analysis methods
 Biochemical and biomedical research
 Coatings and surfactants
 Etc.
Spectroscop
Spectroscopy Comparison Beetween Dispersion Spectrometer
and FTIR
To separate IR light, a grating is used.
Detector Dispersion
Grating
Slit Spectrometer
In order to measure an IR spectrum
the dispersion Spectrometer takes
Sample several minutes.
Also the detector receives only
a few % of the energy of
original light source.
To select the specified IR light,
Light source A slit is used.

Fixed CCM An interferogram is first ma

de by the interferometer usi FTIR
ng IR light. In order to measure an IR spectrum
Detector FTIR takes only a few seconds.
Moreover, the detector receives
up to 50% of the energy of original
B.S. light source.
(much larger than the dispersion
spectrometer.)
Sample

Moving CCM
The interferogram is calculated and transformed
IR Light source into a spectrum using a Fourier Transform (FT).
Spectroscop
Spectroscopy
The Principles of FTIR Method
Interferogram
is made by an interferometer.

Sample

Interferogram
is transformed
into a spectrum using a FT.

Sample
BKG

SB SB

Sample/BKG
3000 2000 1000 3000 2000 1000

[cm-1] [cm-1]
%T

IR spectrum
3000 2000 1000 [cm-1]
 IR light FTIR
source
Spectroscop
Spectroscopy seminar

IR Light Source

Intensity Distribution and Temperature Dependency versus Wavelength of

Black Body Radiation Energy
105

6000K
104
4000K
103
Spectral irradiance W

102 2000K

10

1000K
1

10-1
500K

10-2
300K
10-3
200K
10-4
0.1 0.2 0.5 1 2 5 10 20 50 100
Wavelength m
Spectroscop
Spectroscopy FTIR seminar

FT Optical System Diagram

Light He-Ne gas laser

source

(ceramic)

Beam splitter
Movable mirror

Sample chamber

(DLATGS)
Fixed mirror
Detector
Interferometer
Spectroscop
Spectroscopy FTIR seminar

Interference of two beams of light

Movable mirror
Fixed mirror
Ａ
Movable mirror

Same-phase interference
wave shape
-2 - 0  2
Fixed mirror Continuous phase shift

Signal strength
Ｂ
Ｉ
Movable mirror Opposite-phase (X)
interference
wave shape

Fixed mirror
Ｃ
Movable mirror
-2 - 0  2
Same-phase interference
0  wave shape Ｄ Interference pattern of light
manifested by the optical-path
difference
Spectroscop
Spectroscopy FTIR seminar

Interference is a superpositioning of waves

Relationship between light source spectrum and the signal output from interferometer

Light source spectrum I Signal output from interference wave

(a) Monochromatic
light
Az

Wavenumber 
Time t
 I
(b) Dichroic light

Az

Wavenumber  Time t
(c) Continuous I(t)
spectrum light



 Time t
Wavenumber
All intensities are standardized.
Spectroscop
Spectroscopy FTIR seminar

Sampling of an actual interferogram

Interferometer interferogram

Output of a Laser interferometer

Primary interferometer interferogram

that was sampled

Optical path difference x

Spectroscop
Spectroscopy
Fourier Transform
strength
Single

Fourier transform SB

Optical path difference[x] 4000 Wavenumber[cm-1] 400

(Interferogram) (Single beam spectrum)

Time axis by FFT Wavenumber

Spectroscop
Spectroscopy FTIR seminar

Detector Properties

MCT
Operates at the temperatur
1010 of liquid nitrogen
D* (, f) (cmHz1/2W-1)

109 TGS
Operates at room temperature

108
4000 600
Wavenumber[cm-1]
Spectroscop
Spectroscopy
FT-IR Advantages and Disadvantages
1.Better sensitivity and brightness
- Allows simultaneous measurement over the entire wavenumber range
- Requires no slit device, making good use of the available beam
2.High wavenumber accuracy
- Technique allows high speed sampling with the aid of laser light interference
fringes
- Requires no wavenumber correction
- Provides wavenumber to an accuracy of 0.01 cm-1
3. Resolution
- Provides spectra of high resolution
4. Stray light
- Fourier Transform allows only interference signals to contribute to spectrum.
Background light effects greatly lowers.
- Allows selective handling of signals limiting intreference
5. Wavenumber range flexibility
- Simple to alter the instrument wavenumber range

CO2 and H2O sensitive

 FT-IR Advantages
Spectroscop
Spectroscopy

 Fellgett's (multiplex) Advantage

 FT-IR collects all resolution elements with a complete scan of the
interferometer. Successive scans of the FT-IR instrument are
coadded and averaged to enhance the signal-to-noise of the
spectrum.

 Theoretically, an infinitely long scan would average out all the

noise in the baseline.

 The dispersive instrument collects data one wavelength at a time

and collects only a single spectrum. There is no good method for
increasing the signal-to-noise of the dispersive spectrum.
 FT-IR Advantages
Spectroscop
Spectroscopy

 Connes Advantage
 an FT-IR uses a HeNe laser as an internal
wavelength standard. The infrared wavelengths are
calculated using the laser wavelength, itself a very
precise and repeatable 'standard'.
 Wavelength assignment for the FT-IR spectrum is
very repeatable and reproducible and data can be
compared to digital libraries for identification
purposes.
 FT-IR Advantages
Spectroscop
Spectroscopy

 Jacquinot Advantage
 FT-IR uses a combination of circular apertures and interferometer
travel to define resolution. To improve signal-to-noise, one simply
collects more scans.

 More energy is available for the normal infrared scan and various
accessories can be used to solve various sample handling problems.

 The dispersive instrument uses a rectangular slit to control

resolution and cannot increase the signal-to-noise for high resolution
scans. Accessory use is limited for a dispersive instrument.
 FT-IR Application Advantages
Spectroscop
Spectroscopy

 Opaque or cloudy samples

 Energy limiting accessories such as diffuse reflectance or FT-IR
microscopes
 High resolution experiments (as high as 0.001 cm -1 resolution)
 Trace analysis of raw materials or finished products
 Depth profiling and microscopic mapping of samples
 Kinetics reactions on the microsecond time-scale
 Analysis of chromatographic and thermogravimetric sample
fractions
Spectroscop
Spectroscopy
FT-IR Terms and Definitions
Resolution (common definition) –
The separation of the various
spectral wavelengths, usually
defined in wavenumbers (cm-1).
A setting of 4 to 8 cm-1 is
sufficient for most solid and
liquid samples. Gas analysis
experiments may need a
resolution of 2 cm-1 or higher.
Higher resolution experiments
will have lower signal-to-noise.
Spectroscop
Spectroscopy
FT-IR Terms and Definitions
Resolution – FT/IR Case
A spectrum is said to be collected
at a resolution of 1 cm-1 if 4 data
points are collected within each
spectral interval of 1 cm-1 .
In order to acquire a spectrum at
higher, an increased number of
data points is needed, requiring a
longer stroke of the moving
mirror.
For higher resolution instruments
an aperture is needed in order to
improve parallelism within
interferometer.
Spectroscop
Spectroscopy
FT-IR Terms and Definitions

Apodization - a
mathematical operation to
reduce unwanted oscillation Apodization
and noise contributions
from the interferogram and
to avoid aberrations coming
from the “finite” nature of
real (non theoretical
interferograms). Common
apodization functions
include Beer-Norton, Cosine
and Happ-Genzel.
Spectroscop
Spectroscopy
FT-IR Terms and Definitions

Scan mode - Either

single beam or ratio.
Single beam can be a
scan of the background
(no sample) or the
sample. Ratio mode
always implies the
sample spectrum
divided by, or ratioed
against, the single
beam background.
Spectroscop
Spectroscopy
FT-IR Terms and Definitions
 Scan(s) - a complete cycle of movement of the
interferometer mirror. The number of scans collected
affects the signal-to-noise ratio (SNR) of the final
spectrum. The SNR doubles as the square of the
number of scans collected; i.e. 1, 4, 16, 64, 256, ….
 Scan speed or optical path velocity - the rate at which
the interferometer mirror moves. For a DTGS detector,
the SNR decreases as the scan speed increases.
 Scan range - spectral range selected for the analysis.
The most useful spectral range for mid-infrared is 4000
to 400 cm-1.
Spectroscop
Spectroscopy
FTIR4000 Series
No additional optics for IR microscope interface
Standard apertures for optimum S/N and resolution capability
Easy replacement of light source and detector
FT/IR-4100
FT/IR-4200 Microscope

Polymer shell
Improved instrument design
Compact size
Sample compartment with
same size as a higher class
Aperture
model

FT/IR-400 Plus
Spectroscop
Spectroscopy
FTIR4000 Series Purge System
Instrument purge is standard for all models of the FT/IR-4000 Series.
N2 gas inlet

Control valve

FT/IR-4000 Series purge design

Spectroscop
Spectroscopy
S/N ratio (Oversampling system)
Accurate mirror drive
FT/IR-4000 & 6000 series And reduce flutter at
Voice Coil Conventional method Voice Coil low wavenumber range.
DAC DSP

Analog circuit ADC

Pre-amp.
system ) Pre-amp.

Photo coupler Photo coupler

Clock

24-bit AD

HeNe laser
HeNe laser
Over sampling method
Find the zero crossings, then interpolate
Reduction of high frequency noise by over sampling with a 16 times greater
a matching set of IR data points.
number of sampling points enables improvement of the S/N ratio.
Spectroscop
Spectroscopy
FTIR6000 Series
- Upgradeability
- Wide wavenumber range
- Full vacuum capability
- Step scan upgrade
FT/IR-6100 / 6200 / 6300
Microscope

FT-Raman

Polymer shell
Improved instrument design
Compact size

FT/IR-600Plus

FT/IR-6000 Series Optical design

Spectroscop
Spectroscopy FTIR6000 Series Purge/Vacuum
System
N2gas inlet
Instrument purge is standard for all models of the FT/IR-6000
Series.

Purge control valve – front side

FT/IR-6000 Series purge design

Spectroscop
Spectroscopy Step-by-step Analysis Procedure.

There are five steps to interpret FTIR:

Step 1: Identification of number of absorption bands in the entire IR spectrum.

If the sample has a simple spectrum (has less than 5 absorption bands, the
compounds analyzed are simple organic compounds, small mass molecular weight,
or inorganic compounds (such as simple salts). But, if the FTIR spectrum has more
than 5 absorption bands, the sample can be a complex molecule.
Spectroscop
Spectroscopy Step 2: Identifying single bond area (2500-4000 cm-1). There are several peaks in
this area:

(1) A broad absorption band in the range of between 3650 and 3250 cm -1, indicating
hydrogen bond.
This band confirms the existence of hydrate (H2O), hydroxyl (OH), ammonium, or amino. For
hydroxyl compound, it should be followed by the presence of spectra at frequencies of 1600–
1300, 1200–1000 and 800–600 cm-1. However, if there is a sharp intensity absorption in the
absorption areas of 3670 and 3550 cm-1, it allows the compound to contain an oxygen related
group, such as alcohol or phenol (illustrates the absence of hydrogen bonding).

(2) A narrow band at above 3000 cm-1, indicating unsaturated compounds or

aromatic rings.
For example, the presence of absorption in the wavenumber of between 3010 and 3040 cm-1
confirms the existence of simple unsaturated olefinic compounds.

(3) A narrow band at below 3000 cm-1, showing aliphatic compounds.

For example, absorption band for long chain linear aliphatic compounds is identified at 2935
and 2860 cm-1. The bond will be followed by peaks at between 1470 and 720 cm-1.

(4) Specific peak for Aldehyde at between 2700 and 2800 cm-1.
Spectroscop
Spectroscopy 3. Step 3: Identifying the triple bond region (2000-2500 cm-1)
For example, if there is a peak at 2200 cm-1, it should be absorption band of C=C.
The peak is usually followed by the presence of additional spectra at frequencies
of 1600–1300, 1200–1000 and 800–600 cm-1.

4. Step 4: Identifying the double bond region (1500-2000 cm-1)

Double bound can be as carbonyl (C = C), imino (C = N), and azo (N = N) groups.
(1) 1850 - 1650 cm-1 for carbonyl compounds

(2) Above 1775 cm-1, informing active carbonyl groups such as anhydrides, halide
acids, or halogenated carbonyl, or ring-carbonyl carbons, such as lactone, or
organics carbonate.

(3) Range of between 1750 and 1700 cm-1, describing simple carbonyl
compounds such as ketones, aldehydes, esters, or carboxyl.

(4) Below 1700 cm-1, replying amides or carboxylates functional group.

(5) If there is a conjugation with another carbonyl group, the peak intensities for
double bond or aromatic compound will be reduced.
Therefore, the presence of conjugated functional groups such as aldehydes, ketones,
esters, and carboxylic acids can reduce the frequency of carbonyl absorption.
 (6) 1670 - 1620 cm-1 for unsaturation bond (double and triple bond).
Spectroscop
Spectroscopy
Specifically, the peak at 1650 cm-1 is for double bond carbon or olefinic compounds (C = C).
Typical conjugations with other double bond structures such as C = C, C = O or aromatic
rings will reduce the intensity frequency with intense or strong absorption bands.

When diagnosing unsaturated bonds, it is also necessary to check absorption below 3000
cm-1. If the absorption band is identified at 3085 and 3025 cm-1, it is intended for C-H.
Normally C-H has absorption above 3000 cm-1.

(7) Strong intensity at between 1650 and 1600 cm-1, informing double bonds or
aromatic compounds.

(8) Between 1615 and 1495 cm-1, responding aromatic rings. They appeared as
two sets of absorption bands around 1600 and 1500 cm-1.

These aromatic rings usually followed by the existence of weak to moderate absorption in
the area of between 3150 and 3000 cm-1 (for C-H stretching).

For the simple aromatic compounds, several bands can be also observed between 2000
and 1700 cm-1 in the form of multiple bands with a weak intensity.

It is also support the aromatic ring absorption band (at 1600/1500 cm-1 absorption
frequency), namely C-H bending vibration with the intensity of medium absorption to
strong which sometimes has single or multiple absorption bands found in the area
between 850 and 670 cm-1.
Spectroscop
Spectroscopy 5. Step 5: Identifying the fingerprint region (600-1500 cm-1)
This area is typically specific and unique. See detailed information in Table 1. But, several
identification can be found:

(1) Between 1000 and 880 cm-1 for multiple band absorption, there are
absorption bands at 1650, 3010, and 3040 cm-1.

(2) For C-H (out-of-plane bending), it should be combined with absorption bands at 1650,
3010, and 3040 cm-1 which show characteristics of compound unsaturation.

(3) Regarding vinyl-related compound, about 900 and 990 cm-1 for identifying vinyl terminals (-
CH=CH2), between 965 and 960 cm-1 for trans unsatrated vinyl (CH=CH), and about 890 cm-1 for double
olefinic bonds in single vinyl (C=CH2).

(4) Regarding aromatic compound, a single and strong absorption band is around 750 cm-1
for orto and 830 cm-1 for para.
Spectroscop
Spectroscopy
Mid-IR spectrum regions
Spectroscop    IR spectrum for nujol
Spectroscopy
 
 
 
  721

1377
  1462
 
 
 
  2925
2855
  salt plates
 
NaCl 625 cm-1
KBr 400 cm-1
CsI 200 cm-1
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
Optical spectroscopy
- Raman spectroscopy
- UV-VIS spectroscopy
- Colorimetry
- FT IR spectroscopy
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
FT-IR spectroscopy (MID-IR 4000 – 400 cm-1):
- Transmission
- Transmission via microscope
- Reflection (ATR crystals: Diamond,
Germanium, Silicon)
- Multi bounce HATR (Zinc Selenide)
- Real-time kinetic analysis
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
Some examples of Quality Control with FTIR
PE: Branching level, type of comonomer C=C
unsaturation:end, side, trans MAA-content in PE-MAA
PP: C2 and stabilizer content
EPDM: C2/C3 ratio (ASTM D3900) and diene content
(D6047) Stabilizer content
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
C2/C3 ratio in EP(D)M according to ASTM D3900

1,000

0,95 C2
0,90

0,85 720,93

0,80
peak height = 0,8532 A
0,75

0,70

0,65
peak ratio C3 height / C2 height is a measure for C2 content
0,60

0,55
A
0,50

0,45

0,40
peak height = 0,0893 A
1154,73

0,35

0,30
C3
0,25

0,20

0,15

0,100
1250,0 1200 1150 1100 1050 1000 950 900 850 800 750 700 650,0
cm-1
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
Troubleshooting with FTIR

1. Identification
2. Complaints
3. Competitor analysis
4. Research for third parties
Spectroscop
Spectroscopy
Polymer troubleshooting and QC with FTIR

1. FTIR identification
Unknown sample

organic inorganic
FTIR

NMR XRF
Microscopy Microscopy
PyGC
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
Examples of FTIR spectra of inorganics
100,0
talc Mg3Si4O10(OH)2 chalk CaCO3
95

90

85

80
3676,60
75

70

65

60

55
%T
50

45

40

35
993,35
30

25
668,01
20

15

10,0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650,0
cm-1
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
2. FTIR complaints
- Blooming

- Small contaminations (up to 10 µm)

Organic: cellulose, gels, PE wax, SBR, Ca/Zn-stearate, teflon
Inorganic: calcium carbonate, calcium oxide, clay, mica, talc
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
Example of complaint: SBR gel in
30,0 EPDM compound
28

26

24

22

20

18

16
%T

14

12

10
3061,21

8 1493,30
1376,17
965,98
6
910,83

4
699,78

2,0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650,0
cm-1
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
FTIR spectrum of cellulose

90,0

85

80

75

70

65

60

55

50
%T
45

40

35

30

25

20

15

10,0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650,0
cm-1
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
FTIR spectrum of polypropylene
95,0

90

85

80

75

70
807,91

65
%T

60

55
2838,05 1451,77

50

1375,54
2949,50
45

40
2917,45

35,0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650,0
cm-1
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
3. FTIR competitor analysis
Compound composition:
- polymer type
- filler type (chalk, clay, talc)
(via TG: amount of polymer, carbon black, ash rest)
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
4. (FTIR) Research for third parties
Spectroscop
Spectroscopy Polymer troubleshooting and
QC with FTIR
FTIR = A POWERFUL TOOL
- Direct measurement on material
- Quick method
- Much chemical info
- Not destructive
- Small amounts of sample needed
However: it is NOT absolute*
*(reference method is needed for quantification)
Spectroscop
Spectroscopy Example Read Spectrum Practice
Spectroscop
Spectroscopy
Determine the Spectrum
Spectroscop
Spectroscopy
Read Spectrum Practice
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Read Versus Spectrum Practice
Determine the Spectrum
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy
Spectroscop
Spectroscopy