LAB.

S4

Identification of Drugs Using Attenuated Total

Reflectance
Fourier Transform Infrared Spectroscopy
(ATR-FT-IR Spectroscopy)
Objectives
By the end of the lab students should be able to

Differentiate between transmittance mode and reflectance mode

Sample preparation for transmittance mode and reflectance

mode

Advantage and disadvantages of transmittance mode and

reflectance mode.

Use OMNIC software to obtain a spectrum for unknown

compounds.

Compare the spectrum to the digital library.

Interpretation of the obtained spectr.

 Infrared Sampling Methods

detector source

Internal Reflection
Transmission
Attenuated Total Reflection (ATR)

3
 sample
sample

radiation
radiation

Transmission Mode Reflection Mode

4
 Transmission Mode
To obtain an IR spectrum in the
transmission mode, the sample
must be placed in a container or
cell that is transparent in the IR
region of the spectrum.

Sodium chloride or salt plates are

a common means of placing the
sample in the light beam of the
IR transparent Salt Plates
instrument.

5
 Transmission Mode

Dessicator

Water-free
Environment
for
Water-sensitive
Salt Plates.

6
Transmission Mode
Preparing a Neat IR liquid Sample

7
Transmission Mode

8
Transmission Mode

9
Transmission Mode

10
Transmission Mode

11
 Transmission Mode

Light Path
(shown by red line)

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 Transmission Mode
Preparing a KBr Disk for solid samples

1 2 3

5
4

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Reflectance mode Attenuated Total Reflectance (ATR)

sample

Infrared energy propagates through an internal reflection crystal (IRE), usually ZnSe, Ge and KRS-5
(mixture of thallium iodide and bromide) and recently we use diamond as the internal reflection
element.
Although the infrared radiation is completely internally reflected, an evanescent wave extends
beyond the surface of the crystal.
Any sample that is in intimate contact with the crystal will interact with the infrared energy,
reducing the internal reflectance (attenuated).

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 FT-IR Sampling

Traditional transmission experiment

Employs alkali halide (salts) matrix
True transmission spectrum is collected

Attenuated Total Reflection

Simple and faster to use.
Minimal sample preparation (simply place the sample in
contact with the ATR element)
Often 1 step process
Easy to clean-up
Reflectance-type spectrum is collected.
solids/liquids/films.
Spectral features are usually weaker than those of transmission
spectrum.

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 Traditional ATR Disadvantages
(using ZnSe as IRE)

Chemically vulnerable
Clean only with a non-corrosive solvent
Physically susceptible
Soft nature of internal reflectance element (IRE)
restricts the application of force
Surface can be scratched
Not suitable for:
Corrosive liquids
Harder powders

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 Diamond ATR Advantages
Diamond ATR overcomes the limitations of traditional ATR
Small ATR element size allows intimate contact with samples
and greatly reduces sample size requirements.
Reproducible results are achievable because, by filling the ATR
element every time, path length and sample area are constant.
Mechanical strength of the diamond ATR element allows for
compression of the sample for intimate contact.
Resistant to all corrosive and abrasive solvents and samples.
Cleans up easily because of the low friction coefficient of
diamond.
Control sensitivity.

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 Diamond ATR Disadvantages

Diamond interferes (absorbs IR) between 2200 cm-1 to 1900

cm-1
Not major; however, some cyano group information could
be lost
Spectrum usually weaker than traditional transmittance
experiments
due to the small penetration depth of the evanescent
wave into the absorbing medium, typically around
10 m in the infrared

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 Infrared Spectra
(KCl matrix versus ATR)
Transmittance / Reflectance

KBr matrix

ATR

4000 3000 2000 1600 1200 800 400

Wavenumber (cm-1) 19