Infrared Spectroscopy

Infrared Spectroscopy
 Near IR—780-2500 nm (12,800-4000 cm–1)
 Mid IR—2500-50,000 nm (4000-200 cm–1)
 Far IR—50-1000 mm (200-10 cm–1)
 Mid IR most useful (chemical fingerprinting)
 These aboroptions represent vibrational and
rotational transitions
 Change in dipole moment required during
vibration for IR absorption to occur
Typical Mid-IR Spectrum
Types of
Molecular
Vibrations
Vibrational Modes
 Linear molecules: 3N – 5 modes
 Nonlinear molecules: 3N – 6 modes
 Polyatomic molecules may exhibit
coupling which will alter predicted
frequencies:
 stretching-stretching
Note: strong coupling requires
 bending-bending interaction with a common atom
 stretching-bending
Carbon Dioxide
 Stretching :

2330 cm–1

 Bending (scissoring, degenerate):

667 cm–1 667 cm–1

Water
Quantitative Aspects
 Frequency of molecular vibration,  (s–1)
depends on mass of atoms and strength
of bond: 1 k

2 
 The force constant, k, is about 500 N/m
for a typical single bond
 The reduced mass, (kg), is defined
m1m2

m1  m2
Instrumentation
 Source
 Wavelength selector
 Sample holder
 Detector
Sources
 Tungsten lamp
 Nernst glower
 Globar
 Nichrome coil
 Mercury arc lamp
 Carbon dioxide laser
Sources
 Tungsten lamp
 Near IR only
 Nernst glower
 Globar
 Nichrome coil
 Mercury arc lamp
 Carbon dioxide laser
Sources
 Tungsten lamp
 Nernst glower
 A 2-5 cm rod, 1-3 mm in diameter, composed of oxides of Zr, Y,
Th
 Electrically heated to 1200-2000K, emits mid-IR
 Current-limiting required (R/T < 0)
 Globar
 Nichrome coil
 Mercury arc lamp
 Carbon dioxide laser
Sources
 Tungsten lamp
 Nernst glower
 Globar
 Silicon carbide rod, 6 x 50 mm
 Electrically heated to 1600K, emits mid-IR; better than glower at
<5 m
 Self-starting (R/T > 0)
 Nichrome coil
 Mercury arc lamp
 Carbon dioxide laser
Sources
 Tungsten lamp
 Nernst glower
 Globar
 Nichrome coil
 Electrically heated to 1100K, emits mid-IR
 Mercury arc lamp
 Carbon dioxide laser
Sources
 Tungsten lamp
 Nernst glower
 Globar
 Nichrome coil
 Mercury arc lamp
 High pressure (> 1 atm), emits far IR
 Carbon dioxide laser
Sources
 Tungsten lamp
 Nernst glower
 Globar
 Nichrome coil
 Mercury arc lamp
 Carbon dioxide laser
 Many discrete lines from 9-11 m
 Very intense
Wavelength Selection
 Interference filters, wedges
 Prisms
 Quartz (0.8-3 m) near IR
 LiF (1-5 m) near IR
 NaCl (2.5-20 m) mid-IR
 KBr, CsBr (15-40 m) far-IR
 Reflection gratings (Al coated)
Detectors
 Thermopiles
 Thermistors
 Photoconductors
 Pyroelectric detectors
 Golay detector
Thermopiles
 Thermocouples
 Typical junctions
include Pt-Ag, Sb-Bi
 Sensitive to
temperatures
changes of 1 K
Thermistors and
Photoconductors
 Thermistors
 Temperature-sensitive resistors
 Typically have very large R/T values
 Photoconductors
 Temperature-sensitive resistors
 PbS is typical
 Near IR only
Pyroelectric Detectors
 Temperature sensitive capacitors
 Triglycine sulfate (TGS)
 Lithium tantalate (LiTaO3)
 Lithium niobate (LiNbO3)
 Materials have large (dipole)/T
 Response times of 1 ms or less (fast for
IR detectors)
Golay Detector
 Essentially a Xe gas thermometer
 Expensive, not better than other detectors in
near to mid IR
 Very useful in far IR
Sample Handling
 Gases
 10 cm to 120 m pathlengths (may utilize multiple
reflection)
 Liquids—thin (0.1 mm) layers used
 Water or ROH are no-no’s (Why?)
 10% in CCl4 (4000-1333 cm–1)
 10% in CS2 (1333-650 cm –1)
 CHCl3, CH3CN, acetone for more polar substances
 neat liquids
 Evaporated Films
Liquid IR Cell
More Sample Handling
 Mulls (pastes)
 Finely ground solid and mulling agent fashioned
into a thin film
 Mineral oil, Nujol™, Fluorolubes used as mulling
agents
 Pellets
 Finely ground solid (1-100 g) + KBr
 Pressed into a transparent disk at 60,000 to
100,000 psi
Multiple Internal Reflectance
(For spectra of surfaces)
Dispersive IR Spectrophotometer
 Monochromator
after sample
 Low frequency
chopper (10 min–1)
 Works on nulling
principle: reference
beam attenuated to
match sample
beam
Michelson Interferometer
 Difference in path
length,
 = 2(M-F)
 If mirror is moved
at velocity vm,
and time to move
/2 = ,
 Then detector
output frequency
f = 1/ = 2vm /
 Note:
 2v m 
f  
 c 
Why is this important?
 Consider, a typical mid-IR frequency is 1.5 
1013 s–1, impossibly fast for any detector to
directly follow
 But at typical mirror speeds, vm = 0.01 - 10
cm/s, the scaling factor 2vm/c is (6.7-6700) 
10–13
 Thus, the corresponding interferometer output
frequency is 10-10,000 Hz, within the range of
pyroelectric detectors
Detector output for:
1/ = 400 cm-1 vm = 0.01 cm/s
Detector output for:
1/ = 600 cm-1 vm = 0.01 cm/s
Detector output for:
1/ = 400 and 600 cm-1 vm =
0.01 cm/s
 So what can we do with this?
 All frequencies in the original IR beam are
“encoded” at a frequency at the detector
determined by the scaling factor 2vm/c
 Thus there is sufficient information to
reconstruct the entire spectrum if only…
 …we could extract the intensity of each
frequency in the spectrum from the complex
signal received by the detector
Fourier Transforms,
Oversimplified
 How we “decode” the complex
interferogram
1. Multiply interferogram by cos2ft (a
cosine wave of frequency f)
2. Integrate result
3. Repeat for all desired f values
 Mathematically speaking:

P    P t   cos 2ftdt

What you get
 If a signal “encoded” in the interferogram
matches the frequency f, the integral will be
large
 If a signal “encoded” in the interferogram
does not match the frequency f, the integral
will be small
 A plot of the integral values vs. f yields an
absorption spectrum (Voila!)
Advantages of FT
Spectroscopy
 Jaquinot (throughput) advantage
 Few optical elements to attenuate or scatter
radiation  more radiant power reaches the
detector,  S/N
 Felgett (multiplex) advantage
 Entire spectrum collected rapidly at once
 Allows study of transient species
 Allows signal averaging by adding together
spectra
Signal Averaging
 The magnitude of the signal increases as the number
of scans, N
 The magnitude of noise increases as the square root
of the number of scans, N
 Therefore, S/N increases as N
 Signal averaging enables the study of dilute solutions
 Consider:
 dispersive instrument: 600 s/spectrum
 FT instrument: 1 s/spectrum
 In 600 s an FT instrument can improve S/N by 600  25-
fold
FT-IR Spectrophotometer