INFRARED SPECTROSCOPY

(IR)
 IR SPECTROSCOPY
- Used for qualitative identification of organic and
inorganic compounds

- Used for checking the presence of functional groups in molecul

- Can also be used for quantitative measurements of compounds

- Each compound has its unique IR absorption pattern

- Wavenumber with units of cm-1 is commonly used

- Wavenumber = number of waves of radiation per centimeter

 IR SPECTROSCOPY

- The IR region has lower energy than visible radiation and

higher energy than microwave

The IR region is divided into

Near-IR (NIR): 0.8 µm– 2.5 µm

Mid-IR: 2.5 µm – 20 µm

Far-IR: 20 µm – 400 µm
 IR ABSORPTION BY MOLECULES
- Molecules with covalent bonds may absorb IR radiation

- Absorption is quantized

- Molecules move to a higher energy state

- IR radiation is sufficient enough to cause rotation and vibration

- Radiation between 1 and 100 µm will cause excitation to

higher vibrational states

- Radiation higher than 100 µm will cause excitation to

higher rotational states
 IR ABSORPTION BY MOLECULES

- Absorption spectrum is composed of broad vibrational

absorption bands

- Molecules absorb radiation when a bond in the molecule vibrates

at the same frequency as the incident radiant energy

- Molecules vibrate at higher amplitude after absorption

- A molecule must have a change in dipole moment during

vibration in order to absorb IR radiation
IR ABSORPTION BY MOLECULES

Absorption frequency depends on

- Masses of atoms in the bonds

- Geometry of the molecule

- Strength of bond

- Other contributing factors

 DIPOLE MOMENT (µ)
µ=Qxr

Q = charge and r = distance between charges

- Asymmetrical distribution of electrons in a bond renders the

bond polar

- A result of electronegativity difference

- µ changes upon vibration due to changes in r

- Change in µ with time is necessary for a molecule to absorb

IR radiation
 DIPOLE MOMENT (µ)
- The repetitive changes in µ makes it possible for polar molecules
to absorb IR radiation

- Symmetrical molecules do not absorb IR radiation since they

do not have dipole moment (O2, F2, H2, Cl2)

- Diatomic molecules with dipole moment are IR-active

(HCl, HF, CO, HI)

- Molecules with more than two atoms may or may not be

IR active depending on whether they have permanent
net dipole moment
 PRINCIPAL MODES OF VIBRATION

Stretching

- Change in bond length resulting from change in

interatomic distance (r)

Two stretching modes

- Symmetrical and asymmetrical stretching

- Symmetrical stretching is IR-inactive (no change in µ)

 PRINCIPAL MODES OF VIBRATION

Bending

- Change in bond angle or change in the position of a group of

atoms with respect to the rest of the molecule

Bending Modes
- Scissoring and Rocking
- In-plane bending modes (atoms remain in the same plane)

- Wagging and Twisting

Out-of-plane (oop) bending modes (atoms move out of plane)
PRINCIPAL MODES OF VIBRATION

3N-6 possible normal modes of vibration

N = number of atoms in a molecule

Degrees of freedom = 3N

H2O for example

- 3 atoms
- Degrees of freedom = 3 x 3 = 9
- Normal modes of vibration = 9-6 = 3
PRINCIPAL MODES OF VIBRATION
Linear Molecules

- Cannot rotate about the bond axis

- Only 2 degrees of freedom describe rotation

3N-5 possible normal modes of vibration

CO2 for example

- 3 atoms
- Normal modes of vibration = 9-5 = 4
 TRANSITIONS
Fundamental

- Excitation from the ground state Vo to the first excited state V1

- The most likely transition and have strong absorption bands

V3
V2
V1

Vo
 FUNDAMENTAL TRANSITIONS
Overtone

- Excitation from ground state to higher energy states V2, V3, ….

- Result in overtone bands that are weaker than fundamental

- Frequencies are integral multiples of fundamental absorption

- Fewer peaks are seen than predicted on spectra due to IR-inactive

vibrations, degenerate vibrations, weak vibrations

- Additional peaks may be seen due to overtones

 COUPLING
- The interaction between vibrational modes

- Two vibrational frequencies may couple to produce a new

vibrational frequency

Combinational Band
ν1 + ν2 = ν3

Difference Band
ν1 - ν2 = ν3
 VIBRATIONAL MOTION
- Consider a bond as a spring

~ 1 f
ν 
2 πc μ

c = speed of light (cm/s)

f = force constant (dyn/cm; proportional to bond strength)
f for a double bond = 2f for a single bond
f for a triple bond = 3f for a single bond
M 1M
μ  reduced mass in grams  2

M 1
M 2

- M1 and M2 are masses of vibrating atoms connecting the

bond
INSTRUMENTATION
Components

- Radiation source

- Sample holder

- Monochromator

- Detector

- Computer
 RADIATION SOURCES
Intensity of radiation should
- Be continuous over the λ range and cover a wide λ range
- Constant over long periods of time
- Have normal operating temperatures between 1100 and 1500 K
- Have maximum intensity between 4000 and 400 cm-1
(mid-IR region)

- Modern sources include furnace ignitors, diesel engine heaters

- Sources are usually enclosed in an insulator to reduce noise

 RADIATION SOURCES

Mid-IR Sources

Nernst Glowers
- Heated ceramic rods
- Cylindrical bar
- Made of zirconium oxide, cerium oxide, thorium oxide
- Heated electrically to 1500 K – 2000 K
- Resistance decreases as temperature increases
- Can overheat and burn out
 RADIATION SOURCES

Mid-IR Sources

Globar
- Silicon carbide bar

- Heated electrically to emit continuous IR radiation

- More sensitive than the Nernst glower

 RADIATION SOURCES

Mid-IR Sources

Heated Wire Coils

- Heated electrically to ~ 1100 oC
- Similar in shape to incandescent light bulb filament
- Nichrome wire is commonly used
- Rhodium is also used
- May easily fracture and burn out
 RADIATION SOURCES
Near-IR Sources

Quartz halogen lamp

- Contains tungsten wire filament

- Also contains iodine vapor sealed in a quartz bulb

- Evaporated tungsten is redeposited on the filament

increasing stability

- Output range is between 25000 and 2000 cm-1

 RADIATION SOURCES

Far-IR Sources

High pressure Hg discharge lamp

- Made of quartz bulb containing elemental Hg

- Also contains inert gas and two electrodes

 RADIATION SOURCES
IR Laser Sources

- Excellent light source for measuring gases

Two types
Gas-phase (tunable CO2) laser and solid-state laser

Laser
- Light source that emits monochromatic radiation
 MONOCHROMATORS

- Salt prisms and metal gratings are used as dispersion devices

- Mirrors made of metal with polished front surface

- Spectrum is recorded by moving prism or grating such

that different radiation frequencies pass through
the exit slit to the detector

- Spectrum obtained is %T verses wavenumber (or frequency)

 FT SPECTROMETERS
- Based on Michelson interferometer

- Employs constructive and destructive interferences

- Destructive interference is a maximum when two beams are

180o out of phase

- An FT is used to convert the time-domain spectrum obtained into

a frequency-domain spectrum

- The system is called FTIR

 FT SPECTROMETERS
- Has higher signal-to-noise ratio

- More accurate and precise than dispersive monochromators

(Conne’s advantage)

- Much greater radiation intensity falls on the detector due

to the absence of slits
(throughput or Jacquinot’s advantage)
 FT SPECTROMETERS

Focusing Mirrors of Interferometer

- Made of metal and polished on the front surface

- Gold coated to prevent corrosion

- Focus source radiation onto the beam splitter

- Focus light emitting from sample onto detector

 FT SPECTROMETERS
Beam Splitter of Interferometer

- Made of Ge or Si coated onto a highly polished

IR-transparent substrate

- Ge coated on KBr is used for mid-IR

- Si coated on quartz is used for NIR

- Mylar film is used for far-IR

- Transmits and reflects 50% each of beam (ideally)

 DETECTORS

Two classes

Thermal detectors

and

photon-sensitive detectors
 DETECTORS

Thermal Detectors

- Bolometers

- Thermocouples

- Thermistors

- Pyroelectric devices
 DETECTORS
Thermal Detectors

Bolometers
- Very sensitive electrical resistance thermometer

- Older ones were made of Pt wire

(resistance change = 0.4% per oC)

- Modern ones are made of silicon placed in a wheatstone bridge

- Is a few micrometers in diameter

- Fast response time

 DETECTORS
Thermal Detectors

Thermocouples
- Made up of two wires welded together at both ends
- Two wires are from different metals
- One welded joint (hot junction) is exposed to IR radiation
- The other joint (cold junction) is kept at constant temperature
- Hot junction becomes hotter than cold junction
- Potential difference is a function of IR radiation
- Slow response time
- Cannot be used for FTIR
 DETECTORS
Thermal Detectors

Thermistors
- Made of fused mixture of metal oxides

- Increasing temperature decreases electrical resistance

which is a function of IR radiation

- Resistance change is about 5% per oC

- Slow response time

 DETECTORS
Thermal Detectors

Pyroelectric Detectors
- Made of dielectric materials (insulators), ferroelectric materials,
or semiconductors

- A thin crystal of the material is placed between two electrodes

- Change in temperature changes polarization of material

which is a function of IR radiation exposed

- The electrodes measure the change in polarization

 DETECTORS
Photon Detectors

- Made of materials such as lead selenide (PbSe),

indium gallium arsenide (InGaSa), indium antimonide (InSb)

- Materials are semiconductors

- S/N increases as temperature decreases (cooling is necessary)

- Very sensitive and very fast response time

- Good for FTIR and coupled techniques

 RESPONSE TIME

- The length of time that a detector takes to reach a steady

signal when radiation falls on it

- Response time for older dispersive IR spectrometers

were ~ 15 minutes

- Response time is very slow in thermal detectors due to slow

change in temperature near equilibrium
 RESPONSE TIME
Semiconductors

- Are insulators when no radiation falls on them but conductors

when radiation falls on them

- There is no temperature change involved

- Measured signal is due to change in resistance upon

exposure to IR radiation ( is rapid)

- Response time is the time required to change the semiconductor

from insulator to conductor (~ 1 ns)
 SATURATION

- Very high levels of light can saturate detector

- Linearity is very important especially in

the mid-IR region
 TRANSMISSION (ABSORPTION) TECHNIQUE

- Can be used for both qualitative and quantitative analysis

- Provides very high sensitivity at relatively low cost

- Sample cell material must be transparent to IR radiation

(NaCl, KBr)

- Samples should not contain water since materials are

soluble in water
 TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Mulling
- Samples are ground to power with a few drops of viscous
liquid like Nujol (size < 2 µm)

- 2-4 mg sample is made into a mull (thick slurry)

- Mull is pressed between salt plates to form a thin film

 TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Pelleting
- 1 mg ground sample is mixed with 100 mg of dry KBr powder

- Mixture is compressed under very high pressure

- Small disk with very smooth surfaces forms (looks like glass)
 TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Thin Film
- Molten sample is deposited on the surface of KBr or NaCl plates

- Sample is allowed to dry to form a thin film on substrate

- Good for qualitative identification of polymers but not

good for quantitative analysis
 TRANSMISSION (ABSORPTION) TECHNIQUE

Liquid Samples

- Many liquid samples are analyzed as is

- Dilution with the appropriate solvent may be necessary

(CCl4, CS2, CH3Cl)

- Solvent must be transparent in the region of interest

- Salt plates are hygroscopic and water soluble (avoid water)

- Special cells are used for water containing samples (BaF2, AgCl)
 TRANSMISSION (ABSORPTION) TECHNIQUE

Gas Samples

- Gas cells have longer pathlengths to compensate for very

low concentrations of gas samples

- Generally about 10 cm
(commercial ones are up to 120 cm)

- Temperature and pressure are controlled if quantitative

analysis is required
 TRANSMISSION (ABSORPTION) TECHNIQUE

Background Absorption

- Absorption from material other than sample

Two sources
- Solvent
- Air in the light path

- Background spectrum is subtracted from sample spectrum

- CO2 and H2O absorb IR radiation

(sealed desiccants are used to reduce CO2 and H2O absorption)
 ATTENUATED TOTAL REFLECTION
(ATR) TECHNIQUE
- Uses high refractive index optical element

- Called internal reflection element (IRE) or ATR crystal

(germanium, ZnSe, silicon, diamond)

- Sample has lower refractive index than the ATR crystal

- Sample is placed on the ATR crystal

- When light travelling in the crystal hits the crystal-sample

interface, total internal reflection occurs if the angle
of incidence is greater than the critical angle
 ATTENUATED TOTAL REFLECTION
(ATR) TECHNIQUE

- The beam of light penetrates the sample a very short distance

- This is known as the evanescent wave

- Light beam is attenuated (reduced in intensity) if the evanescent

wave is absorbed

- IR absorption spectrum is obtained from the interactions

between the evanescent wave and the sample
 SPECULAR REFLECTANCE TECHNIQUE

- Occurs when angle of reflected light equals angle of incident light

(45o angle of incidence is typically used)

- Occurs when light bounces off a smooth surface

- Nondestructive method for studying thin films

- Beam passes through thin film of sample where absorption occurs

- Beam is reflected from a polished surface below the sample

- Reflected beam passes through sample again

 DIFFUSE REFLECTANCE TECHNIQUE

- DR OR DRIFTS

- Used to obtain IR or NIR spectrum from a rough surface

- Beam penetrates sample to about 100 µm

- Reflected light is scattered at many angles

- Scattered radiation is collected with a large mirror

- Good for powdered samples (sample is mixed with KBr powder)

 IR EMISSION
- Certain samples are characterized using emission spectrum

- Sample molecules are heated to occupy excited vibrational states

- Radiation is emitted upon returning to the ground state

- Emitted IR radiation is directed into the spectrometer

- Radiation source is not needed (sample is the source)

- Method is nondestructive

- Emitted radiation is used to identify sample

 FTIR MICROSCOPY

- For forensic analysis

- Analysis of paint chips from cars (hit-and-run accidents)

- Examination of fibers, drugs, explosives

- Characterization of pharmaceuticals, adhesives and gemstones

 NEAR-IR (NIR) SPECTROSCOPY
- Region covers 750 nm – 2500 nm (13000 cm-1 – 4000 cm-1)

- Long wavelength end of IR region

- Bands occurring in this region are due to OH, NH, and CH bonds

- Bands are primarily overtone and combination bands

- Light source is tungsten-halogen lamp

- Detector is lead sulfide photodetector

- Quartz or fused silica sample cells with long pathlengths are used
NEAR-IR (NIR) SPECTROSCOPY

Primary absorption bands seen in NIR

C−H Bands
2100 – 2450 nm and 1600 – 1800 nm

N−H Bands
1450 – 1550 nm and 2800 – 3000 nm

O−H Bands
1390 – 1450 nm and 2700 – 2900 nm
 NEAR-IR (NIR) SPECTROSCOPY

- Used for quantitative analysis of solid and liquid samples

containing OH, NH, CH bonds

- For quantitative characterization of polymers, food,

proteins, agricultural products

- Pharmaceutical tablets can be analyzed nondestructively

- Forensic analysis of unknown wrapped powders believed to be

drugs are analyzed without destroying the wrappers
 APPLICATIONS OF IR SPECTROSCOPY
Quantitative

- Measure absorption intensities of standard solutions and

unknown at exactly the same wavenumber

- All measurements must be made from the same baseline

- Plot a calibration curve

- Use the relationship obtained to determine the concentration

of unknown

- Not as accurate as using UV-VIS spectroscopy

 APPLICATIONS OF IR SPECTROSCOPY

Quantitative

- Determination of impurities in raw materials (quality control)

- Analysis of contaminations from oil or grease

- Determination of reaction rates of slow reactions

 APPLICATIONS OF IR SPECTROSCOPY

Qualitative

- Identification of unknown samples by matching the absorption

spectra with that of known compounds

- Identification of functional groups present in a sample

(classification of unknowns)
 PREDICTING STRUCTURE OF UNKNOWN
- Identify the major functional groups from the strong
absorption peaks

- Identify the compound as aromatic or aliphatic

- Subtract the FW of all functional groups identified from the given

molecular weight of the compound

- Look for C≡C and C=C stretching bands

- Look for other unique CH bands (e.g. aldehyde)

- Use the difference obtained to deduce the structure

 INTERPRETATION OF IR SPECTRA

Functional Group Region

- Strong absorptions due to stretching from hydroxyl, amine,
carbonyl, CHx

4000 – 1300 cm-1

Fingerprint Region
- Result of interactions between vibrations

1300 – 910 cm-1

 INTERPRETATION OF IR SPECTRA

Hydrocarbons

- Absorption bands are due to the stretching or bending of

C−H and C−C bonds

- C−C stretching vibrations are distributed across the

fingerprint region (not useful for identification)

- C−C bending vibrations occur below 500 cm-1

(not useful for identification)

- Observed bands are due to C−H stretching or bending

 INTERPRETATION OF IR SPECTRA
Cyclic Alkanes
- No peak around 1375 cm-1 due to absence of methyl groups

- Two peaks at ~ 900 cm-1 and 860 cm-1 due to ring deformation

Alkenes
- Contain many more peaks than alkanes

- Peaks of interest are due to stretching and bending of C−H

and C=C bonds

- C=C band will not appear if there is symmetrical substitution

about the C=C bond
 INTERPRETATION OF IR SPECTRA
Alkynes
- C≡C peak appears around 2100 – 2200 cm-1
- Terminal alkyne ≡C−H stretch occurs near 3300 cm-1

Aromatic Hydrocarbons
- C→H absorption occurs above 3000 cm-1

- Aromatic C=C ring stretching absorption around

1400 – 1600 cm-1 appears as doublet

- Aromatic C↓H oop band around 690 – 900 cm-1

- Overtones around 1660 – 2000 cm-1

 INTERPRETATION OF IR SPECTRA
Alcohols

- OH band in neat aliphatic alcohols is a broad band centered

at ~ 3300 cm-1 due to hydrogen bonding (3100 – 3600 cm-1)

- OH band in dilute solutions of aliphatic alcohols is a sharp

peak ~ 3600 cm-1

- C−C−O stretch ~ 1048 cm-1 for primary alcohols

- Decreasing frequency by 10 cm-1 in the order 1o>2o>3o

- Methyl bending vibrations at ~ 1200 – 1500 cm-1

 INTERPRETATION OF IR SPECTRA
Phenol

- CO→H stretch is broad band

- C→H stretch ~ 3050 cm-1

- C−C→O band ~ 1225 cm-1

- C −O−H bend ~ 1350 cm-1

- Aromatic ring C stretching between 1450 – 1600 cm-1

- Monosubstituted bands ~ 745 – 895 cm-1 and 1650 – 2000 cm-1

 INTERPRETATION OF IR SPECTRA
Aliphatic Acids

- Broad OH band around 2900 cm-1

- C−H stretching bands from CH3 and CH2 stick out at the
bottom of the broad OH band

- C=O stretch ~ 1710 cm-1

- In-plane C −O−H bend ~ 1410 cm-1 and

oop C −O−H bend ~ 930 cm-1

- C −C−O stretch dimer at ~ 1280 cm-1

 INTERPRETATION OF IR SPECTRA

Carboxylic Acids, Esters, Ketones, Aldehydes

- Characterized by very strong carbonyl (C=O) stretching

band between 1650 cm-1 and 1850 cm-1

- Fermi resonance seen in aldehydes

(doublet due to resonance with an overtone of the aldehydic
C−H bend at 1390 cm-1)
 INTERPRETATION OF IR SPECTRA
Nitrogen-Containing Compounds

- 1o amines (NH2) have scissoring mode and low

frequency wagging mode

- 2o amines (NH) only have wagging mode (cannot scissor)

- 3o amines have no NH band and are characterized by C−N

stretching modes ~ 1000 – 1200 cm-1 and 700 – 900 cm-1

- 1o, 2o, 3o amides are similar to their amine counterparts

but have additional C=O stretching band
 INTERPRETATION OF IR SPECTRA

Nitrogen-Containing Compounds

- C=O stretching called amide I in 1o and 2o amides and

amide II in 3o amides

- N−H stretch doublet ~ 3370 – 3291 cm-1 for 1o amines

- 1o N−H bend at ~ 1610 cm-1 and 800 cm-1

- Single N−H stretch ~ 3293 cm-1 for 2o but absent in 3o amine

- C−N stretch weak band ~ 1100 cm-1

 INTERPRETATION OF IR SPECTRA

Amino Acids [RCH(NH2)COOH]

- IR spectrum is related to salts of amines and salts of acids

- Broad CH bands that overlap with each other

- Broad band ~ 2100 cm-1

- NH band ~ 1500 cm-1

- Carboxylate ion stretch ~ 1600 cm-1

 INTERPRETATION OF IR SPECTRA

Halogenated Compounds

- C→X strong absorption bands in the fingerprint and

aromatic regions

- More halogens on the same C results in an increase in intensity

and a shift to higher wavenumbers

- Absorption due to C−Cl and C−Br occurs below 800 cm-1

 LIMITATIONS OF IR SPECTROSCOPY

- Short pathlength

- Pathlength may vary from sample to sample

- Sample cells are soluble in water