2019 Chap5 Infra-Red Spec

Infrared
Spectrometry
Analytical Chemistry ACH260S
M.M. Wicht 2019
Holler, Skoog and Crouch, Chapter 16-17, pages 430 - 480
Infrared Spectroscopy 1
Introduction to Infrared Spectroscopy
• Encompasses radiation with wavenumbers (തυ) 12800 to 10 cm-1
(wavelengths 0.78 to 1000 μm)
• Subdivided into three regions: near-IR; mid-IR and far-IR
Current IR measurements
• Appearance of relatively inexpensive Fourier Transform
spectrometers has increased the applications of mid-IR
radiation
• Interferometric instruments show improvements of order
of magnitude in signal-to-noise ratio and detection limits
over dispersive instruments
• Although qualitative, more quantitative analysis of
absorption and emission
• Near-IR quantitative applications in industrial and
agricultural materials
• Far-IR limited because of experimental difficulties
Electronic and Vibrational Energy Levels:
The Stadium Analogy
• Electronic energy levels in atoms are simple transitions between
orbitals: the peaks are sharp.
• The situation complicates once covalent bonds enter the picture.
• Chemical bonds behave like flexible springs connecting 2 balls:
they vibrate, showing motions stretching, bending, twisting, etc.
• At the molecular level, these energies are quantized; like steps on
a staircase or ladder, each motion has a particular energy level.
• The steps between these “vibrational” energy levels are much
smaller than the “steps” between electronic energy levels (i.e.
orbitals); less energy is required for transitions between
vibrational energy levels than for electronic transitions.
Visualise this as a stadium
“Decks” vs “Rows”
• Think of the “decks” as the energy levels of orbitals, and
the “rows” as the vibrational energy levels.
• The existence of these vibrational energy levels explains

why delta E can take on a range of values; and hence why
UV spectra for molecules can be broad.
• Why? Because each of the following would be a valid

electronic transition between orbitals:
Ground level, row 1 → Lower deck, row 1 (ΔE1)
UV-vis spectrum of vibrations
• The ΔE values correspond to
a series of absorbance peaks
spaced by the difference in energy
between the vibrational energy
levels (“spacing between rows” in
analogy).
• The spacing between these peaks

(so-called “fine structure”) can be
seen in fine structure in UV spectra,
such as in the UV spectrum of
benzene. The individual peaks UV-Vis spectrum of benzene shows
represent transitions into individual individual peaks corresponding to
vibrational energy levels. differences in vibrational energy levels
Visualizing Vibrational Energy Levels: The
“Ball And Spring” Model
• Imagine two atoms (balls) attached by a spring (the bond).
• The spring allows for vibration : visualize as standing waves.
• In a resting state a simple standing wave with no nodes (i.e. no

locations where the amplitude is zero) along its length.
• If the energy is increased by an integer amount corresponding

to ΔE, a transition occurs to a higher vibrational energy level
with a single node. This is the first “excited” vibrational state.
• As more energy is applied, additional energy levels will appear

with an increasing number of nodes, roughly in integer
increments of ΔE
What does IR spectrum look like?
• Transmittance is inverse of absorbance. A clear, colourless pane of
glass has 100% transmittance of visible light. A piece of coloured
glass has 100% transmittance at certain frequencies, with
transmittance (strong absorbance) at other frequencies.
• When we graph transmittance versus λ we obtain an appearance

“flipped” in relation to a UV spectrum: baseline at the top;
“absorbance peaks” point towards bottom, depending on strength.
• Wavenumber is the inverse of wavelength (1/ λ) : the number of

cycles in a given unit of length, therefore a measure of frequency.
The left-hand region of spectrum (at 4000 cm-1) is high-frequency;
right-hand region (at about 400 cm-1) is low frequency.
Water IR spectrum
Y-axis : Percentage transmittance Polystyrene IR Spectrum
X-axis: Wavenumber cm-1

Theory
Two rules for active IR absorbance:
• Absorption of IR radiation molecular species
with small energy differences between vibrational or
rotational states
• To absorb IR molecule must undergo net
change in dipole moment as it vibrates or rotates
Example polar H+ Cl-
• No net change in dipole moment occurs on homonuclear

species such as O2, N2 or Cl2
Types of molecular vibrations
• Basic categories of stretching and bending
Stretching – change in interatomic

distance along bond
axis
Bending – characterised by change in angle between

two bonds and are of 4 types: scissoring,
rocking, wagging and twisting
Vibrations
Development of conditions for
quantitative absorptions
• Selection of wavelength
For highest sensitivity measurements made at λ of
absorption maximum, λmax
• Variables that influence Absorbance

Nature of solvent; pH; temperature; high electrolyte
concentrations; presence of interfering substances
• Cleaning and handling of cells

Matched and calibrated cells; methanol to clean; soft
tissue to wipe transparent surface.
Mechanical model of stretching vibration
• Two masses connected
by spring : disturbance of
one mass along the axis A
results in vibration called m
Potential Energy E
-A
simple harmonic motion
• If mass displaced y from

eqm position, restoring
force is proportional to
displacement (Hooke’s
law): F = -ky
k is force constant
Displacement y
Vibrational frequency
• Newton’s second law states:
F = ma where m is the mass and a the acceleration
𝒅𝟐 𝒚
𝒂=
𝒅𝒕𝟐
• Substitute and reach the natural frequency of the
mechanical oscillator:
𝟏 𝒌
𝝂𝒎 =
𝟐𝝅 𝒎
• To describe two masses m1 and m2 connected by a

𝒎𝟏 𝒎𝟐
spring, the reduced mass 𝝁 =
𝒎𝟏 +𝒎𝟐
Vibrational frequency
• Thus the vibrational frequency for the system is:
𝟏 𝒌 𝟏 𝒌 𝒎𝟏 +𝒎𝟐
ν𝒎 = =
𝟐𝝅 𝝁 𝟐𝝅 𝒎𝟏 𝒎𝟐
• Or in wavenumbers:
𝟏 𝒌 𝒌
νത = = 5.3 𝑥 10−12
𝟐𝝅𝒄 𝝁 μ
• νത is wavenumber of absorption maximum, k is force constant

in N/m, c velocity of light (cm/s) and μ the reduced mass (kg)
Example
Solutions for analysis
• No single solvent is transparent throughout the entire
mid-IR region
• Water and alcohols show strong absorption bands in IR

region usually between 3500 and 3000 cm-1
• Water and alcohols also attack alkali-metal halides used

for cell windows (NaCl and KBr)
• Care must be taken to dry solvents before use.
Regions of transparency for common infrared solvents
Horizontal lines indicate regions where solvent transmits at least

25% of the incident radiation in a 1 mm cell
Cells
• IR liquid cells much narrower than (0.01 to 1 mm)
• High concentrations (0.1% to 10%) used
• Fixed path-length cells can be filled with hypodermic
syringe
• Window materials chosen based o cost, transparency
range, solubility on solvent, and reactivity with
sample or solvent
• NaCl and KBr most common
• Surfaces become fogged which can be repaired by
polishing with buffing powder
Liquid Cell
• Expanded view of a demountable infrared cell for liquid
samples. Teflon spacers range in thickness from 0.015
to 1mm.
Solids
• Solid sample ground until particle size is less than
wavelength of radiation
• Pelleting
KBr pellet - glasslike transparent properties when sufficient
pressure applied to finely powdered materials
1 mg of finely ground sample mixed with 100 mg dried KBr
powder in pestle and mortar
Mixture pressed in die at 7 x 104 to 1.0 x 105 KPa to yield a
transparent disc
• Other pelleting salts: CsI and CsBr

Solids
• Mulls
Disperse analyte in in mineral oil or fluorinated
hydrocarbon mull.
Grind 2 to 5 mg of finely powdered sample (particle size
< 2 μm) in presence of 1 or 2 drops of oil (Nujol)
Fluorolube, a halogenated polymer, can also be used
Mull examined as film between flat salt plates
• Use reflectance techniques and the photoacoustic

method
A few things to note:
• The region on the left (toward 4000 cm-1) corresponds to high
frequency and short wavelength; the region on the right (toward
400 cm-1) corresponds to low frequency and long wavelength.
• The “baseline” at the top of the page is not very flat. That’s normal.
• The major “peaks” are at 3200-3600 cm-1 (very broad and strong),
1600 cm-1 (relatively sharp) and around 700 cm-1 also quite broad.
• Peak around 2200 is weak and broad and somewhat undefined?
That’s the kind of peak we typically ignore.
• Not: peak corresponds to the vibration of a chemical bond in the
sample which is being promoted by infrared light.
• Each molecule will give a characteristic “IR fingerprint”
corresponding to the bonds present in the molecule.
Qualitative Analysis
• Identification of an organic compound from a spectrum is
a two step process
1. Determine which functional groups are most likely

present by examining the group frequency region
(between 3600 to 1250 cm-1)
2. Detailed comparison of spectrum of unknown with

spectra of pure compounds in fingerprint region
(between 1250 and 600 cm-1)
Glucose IR spectrum
• IR is not generally used to determine the whole structure of an unknown molecule.
• We don’t need to analyse every single peak rather identify certain specific functional
groups, like alcohols and carbonyls.
Typical Infrared absorption values for various types of bonds
• 80% of most useful information can be obtained from two specific

areas of the spectrum: 3200-3400 cm-1 and 1650-1800 cm-1.
Overview of peaks
3600 – 2700 cm-1 X-H (single bonds to hydrogen)
2700 – 1900 cm-1 X≡X (triple bonds)
1900 – 1500 cm-1 X=X (double bonds)
1500 – 500 cm -1 X–X (single bonds)
Two high-priority areas to focus on:
1. Is there a broad, rounded peak in the region around 3400-3200 cm-1 ? That’s where
hydroxyl groups (OH) appear.
2. Is there a sharp, strong peak in the region around 1850-1630 cm-1 ? That’s where
carbonyl groups (C=O) show up.
Interpreting IR spectra
• The 2 Most Important Things To Look For :
“Tongue and Sword”
• The concept of bond vibrations, which we can think of

covalent bonds as a bit like balls and springs:
• The springs vibrate, and each one “sings” at a

characteristic frequency, which depends on the strength
of the bond and on the masses of the atoms.
• These vibrations have frequencies that are in the mid-

infrared (IR) region of the electromagnetic spectrum.
Hydroxyl group peaks in 3400 cm-1 to 3200 cm-1 region
• Hydroxyl groups are most common type of broad peak in this region, N-H
peaks can also show in this area.
• Usually sharper appearance; may appear as 1 or 2 peaks depending on
the number of N-H bonds.
C=O peaks, region 1630-1800 cm-1
• Relatively narrow, giving them a somewhat “sword-like”

appearance.
Other regions of IR spectrum
• The line at 3000 cm-1 is a useful “border” between alkene C–H (above
3000 cm-1) and alkane C–H (below 3000 cm-1 ). This helps you
determine if double bonds are present.
• Peak in the region around 2200 cm-1 – 2050 cm-1 is indicator of presence
of triple bond (C≡N or C≡C) . Nothing else shows in this region.
Common Sense Reminder:

• Molecular formula will determine what functional groups you
have. Don’t look for OH groups if you have no oxygens in your molecular
formula; no amine if the formula lacks nitrogen.
• Calculate the degrees of unsaturation from molecular formula. Why?
Don’t look for C=O in a structure like C4H10O which doesn’t have any
degrees of unsaturation.
Alcohols: Hexanol: IR spectrum
3600 cm-1: non-hydrogen bonded O-H
2800-3000 cm-1 : Alkanes
3300 cm-1 : Typical alcohol
Butanol
Aromatic rings
3010 – 3100 cm-1

1500 – 1600 cm-1
690 – 900 cm-1
Carboxylic Acids: butanoic acid
1700 cm-1 C=O

“Hairy beard” for –OH
in carboxylic acids –
goes below 3000 cm-1
Benzoic acid
C=O: 1700 cm-1
C=O: 1780-1700 cm-1

Aldehyde Hexanal IR spectrum
1740 cm-1: C=O peak
C=O: 1740-1690 cm-1

Ketone: 2-Pentanone
C=O: 5.9 μm = 1695 cm-1
C=O: 1750-1680 cm-1

Ester: Ethyl acetate
C=O: 1730 cm-1
C=O: 1750-1735 cm-1

3200 region: Amines, Amides, Terminal Alkyne C-H
• Amines and amides have N-H stretches in this region (3200-3500)

• Primary amine and amide have two “fangs”; secondary amine
and amide have single peak.
• The amine stretches sharper than amide stretches; amides have
strong C=O stretch
Amide: Benzamide
C=O: 1660 cm-1
C=O: 1690-1630 cm-1

C-H Stretch Boundary at 3000 cm-1
Distinctive Triple Bond Region around 2200 cm-1
• Between 2000 cm-1 and 2400 cm-1 is a “ghost town”;

• Peaks could be triple bonded carbon : alkyne or nitrile.
Group frequency and Fingerprint 1
Fingerprint Region
• Well suited for identifying compounds based on
spectral comparisons
• Figures (a) and (b) on slides 48 and 49 show distinct

differences in fingerprint region for a small difference
in structure
• A number of inorganic groups and halides such as

sulphate, phosphate, nitrate and carbonate absorb in
fingerprint region (< 1200 cm-1) and chlorides and
bromides (600 – 800 cm-1)
Chlorobenzene
C-Cl stretch
Quantitative Analysis
• Differ from UV-vis methods because of greater complexity of spectra,
narrowness of absorption bands, instrumental limitations of IR
instruments
• The baseline method is
used to obtain P0 and PT for
a single absorption band
• The solvent transmittance
is assumed to be constant
• Quantities P0 and PT are
obtained as shown in figure
for calculation of A
• P0 is power of solvent and
PT of analyte
Instrumentation
Different types of instruments available are:
• Dispersive spectrophotometers with grating

monochromators
• Fourier Transform spectrometers employing an

interferometer invented by Albert Michelson who was
awarded the 1907 Nobel Prize in Physics
Instruments being used currently are Fourier Transform

(FTIR) due to their speed, reliability, signal-to noise
advantage, and convenience
Fourier Transform Instrument
sample
/ detector
Operation of FTIR
• Incident beam split into two by beam splitter
• These move along separate paths to the two different
mirrors, one stationary and one moving
• Two beams recombine at the detector and interact to
form an interference pattern
• Where waves interfere constructively, bright bands
appear; where destructive interference occurs, dark
bands form
• Alternating light and dark bands are called interference
fringes
Interferometer Pattern
Principle of Fourier synthesis
• Any waveform can be represented as a series of
sinusoidal waveforms
• Any combination of sinusoidal waveforms can be

broken down into a series of sinusoids of known
frequency
• Need high-speed inexpensive computers
• Appropriate computational methods to handle huge

number of simple calculations to be applied to the
data
Interferograms
FFT (Fast Fourier
Transform)
converts
Time-domain
spectrum (b) and
(e) into a
Frequency-
domain spectrum
(c) and (f) for one
wavelength (a),
(b) and (c) and for
2 wavelengths (d),
(e) and (f)
60
Movable mirror
Sample
Beam Splitter
Stationary mirror
Infra-red light source
Detector
Interferogram
Michelson
Interferometer
Fourier
IR Spectrum Transformation
61
Advantages of FTIR
• Better speed and sensitivity
• Better light-gathering power
• More accurate wavelength calibration
• Simpler mechanical design
• Elimination of stray light and IR emission
IR Sources
Inert solid heated to temperatures of 1500 to
2200 K
• Nernst Glower
• Globar
• Incandescent wire source
• Mercury Arc
• CO2 laser source
IR Transducers
Three general types:
• Pyroelectric transducers – constructed from single
crystalline wafers of pyroelectric materials with special
thermal and electric properties (FTIR)
• Photoconducting transducers – this film of
semiconductor material deposited on non-conducting
glass surface and sealed in evacuated envelope (FTIR)
• Thermal transducers – responses depend on heating
effect of radiation , examples thermocouple and
bolometer (dispersive)

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Infrared

Holler, Skoog and Crouch, Chapter 16-17, pages 430 - 480

• The existence of these vibrational energy levels explains

• Why? Because each of the following would be a valid

• The spacing between these peaks

• The spring allows for vibration : visualize as standing waves.

• In a resting state a simple standing wave with no nodes (i.e. no

• If the energy is increased by an integer amount corresponding

• As more energy is applied, additional energy levels will appear

• When we graph transmittance versus λ we obtain an appearance

• Wavenumber is the inverse of wavelength (1/ λ) : the number of

X-axis: Wavenumber cm-1

• No net change in dipole moment occurs on homonuclear

Stretching – change in interatomic

Bending – characterised by change in angle between

• Variables that influence Absorbance

• Cleaning and handling of cells

• If mass displaced y from

• To describe two masses m1 and m2 connected by a

• νത is wavenumber of absorption maximum, k is force constant

• Water and alcohols show strong absorption bands in IR

• Water and alcohols also attack alkali-metal halides used

• Care must be taken to dry solvents before use.

Horizontal lines indicate regions where solvent transmits at least

• Other pelleting salts: CsI and CsBr

• Use reflectance techniques and the photoacoustic

1. Determine which functional groups are most likely

2. Detailed comparison of spectrum of unknown with

• IR is not generally used to determine the whole structure of an unknown molecule.

• 80% of most useful information can be obtained from two specific

2700 – 1900 cm-1 X≡X (triple bonds)

1900 – 1500 cm-1 X=X (double bonds)

1500 – 500 cm -1 X–X (single bonds)

Two high-priority areas to focus on:

• The concept of bond vibrations, which we can think of

• The springs vibrate, and each one “sings” at a

• These vibrations have frequencies that are in the mid-

• Relatively narrow, giving them a somewhat “sword-like”

Common Sense Reminder:

2800-3000 cm-1 : Alkanes

3300 cm-1 : Typical alcohol

3010 – 3100 cm-1

1700 cm-1 C=O

C=O: 1700 cm-1

C=O: 1780-1700 cm-1

1740 cm-1: C=O peak

C=O: 1740-1690 cm-1

C=O: 5.9 μm = 1695 cm-1

C=O: 1750-1680 cm-1

C=O: 1730 cm-1

C=O: 1750-1735 cm-1

• Amines and amides have N-H stretches in this region (3200-3500)

C=O: 1660 cm-1

C=O: 1690-1630 cm-1

• Between 2000 cm-1 and 2400 cm-1 is a “ghost town”;

• Figures (a) and (b) on slides 48 and 49 show distinct

• A number of inorganic groups and halides such as

• Dispersive spectrophotometers with grating

• Fourier Transform spectrometers employing an

Instruments being used currently are Fourier Transform

• Any combination of sinusoidal waveforms can be

• Need high-speed inexpensive computers

• Appropriate computational methods to handle huge