NIR SPECTROSCOPY:
AN ADVANCED
ALTERNATIVE
Electromagnetic spectrum
INFRARED
X-RAY ULTRA-VIOLET VISIBLE MICROVAWE RADIO
0,2 nm 2 nm 400-800 nm 3 mm-20 cm 10 m-30 Km
NEAR MID FAR
ʎ, cm (wavelength) 7.8x10-5 to 3x10-4 3x10-4 to
3x10-3 3x10-3 to 3x10-2
ʎ, cm-1 (wavenumber) 12820 to 4000 4000 to 400
400 to 33
The classical physics considers the atoms as particles with a
given mass in the IR absorption process, and the vibrations of
diatomic molecule described as follows (e.g., HCl):
equilibrium bond length
Spring force
stretched
Spring force
compressed
Mechanical model of a vibrating diatomic molecule
Courtesy Bruker Optics
Modes of vibrations
Region Origin of the absorption
ntisymmetricsymmetric
NIR Overtones and combination bands of
R R fundamental molecular vibrations
H H
stretching
R H R H
MIR fundamental molecular vibrations
R R
H H in-plane
FIR molecular rotations
R H R H bending
scissoring rocking Molecule Degrees of freedom
R Non linear 3N -6
H R
H Linear 3N- 5
R H R H bending
NIR past and present
The history of near infrared (NIR) begins in
1800 with Frederick William Herschel.
He was trying filters to observe sun spots
and when he used a red one, he noticed
that a lot of heat was produced, which was
of a higher temperature than the visible
spectrum. After further studying, he
concluded that there must be an invisible
form of light beyond the visible spectrum.
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cosmic_classroom/ir_tutorial/
discovery.html
NIR past and present
MIR NIR
DIFFICULT?
MIR spectra obtained by ATR and NIR spectra obtined by Diffuse Reflectance
NIR spectroscopy was neglected by spectroscopist who, for long time,
could not find any additional atractive information in that spectral region
which was occuped by broad, superimposed and weak absortion bands
(see reference 1).
NIR past and present
Why NIR now?
1. Optical fibers
2. Computing power
Improvements
in the fields of
3. Chemometrics
4. Interest in procces
analysis
Sample preparation is not required leading to
significant reductions in analysis time.
Waste and reagents are minimized (non-destructive
testing).
Online for process applications
Excellent analytical method for the study of solids.
(For example, in the analysis of minerals)
Lepidolite rock
Spectra may be obtained in non-invasive
manner.
Totally non-invasive analysis of blood glucose by NIR
Remote sampling is possible (good for hazardous materials).
Source
Detector
By Raúl E. Gómez Perez, MS, 2000
NIR allows us to create calibration models for predicting concentrations
of the food industry in real time (during the manufacturing process)
* - M. Blanco, J. Coello, A. Eustaquio, H Iturriaga, and S. Maspoch,
Development and Validation of a Method for the Analysis of a
Pharmaceutical Preparation by Near-Infrared Diffuse Reflectance
Spectroscopy, Journal of Pharmaceutical Sciences, 1999, 88(5), 551 –
556.
Possibility of using it in a wide range of applications (physical and chemical),
and viewing relationships difficult to observe by other means.
Milled sugar Granular sugar
Identification Testing of Raw Materials and Finished Products.
Determination of Water Content.
Determination of Particle Size
Drug Content in Tablets and Powder Mixtures.
Evaluation of Blend Uniformity (in-line monitoring)
Thickness of Film Coating.
Quantitating and tracking polymorphic changes during
pharmaceutical processing.
Overlapping bands (combination), not easy to
interpret.
Differences in spectra are often very subtle.
Usually not for trace level analysis.
Basic Principles of Vibrational Spectroscopy
Scattering technique Absorption technique
Raman Near-Infrared
Mid-Infrared
V V V
n=3
Stokes Anti-Stokes n=3
n=2
n=2
n=1
n=1 n=0
n=0
r r r
Fundamentals Fundamentals Overtones-Combinations
4000 – 50 cm-1 4000 – 200 cm-1 12500 – 4000 cm-1
Source Source
Monochromatic radiation (Dispersed) Polychromatic radiation
Laser VIS - NIR Globular tungsten
A comparison of the basic instrumentation of RAMAN,
MIR, and NIR spectroscopy
RAMAN MIR/ATR NIR
No sample preparation Sample preparation required No sample preparation
(except ATR)
Small sample volume (μL) Large sample thickness
or sample thickness (μm) (Up to cm)
Fiber optics
Quartz Chalcogenide or AgCl Quartz
Light-fiber optics ( > 100 m) light-fiber optics (<10 m) Light-fiber optics ( > 100 m)
A comparison of the basic instrumentation of RAMAN,
MIR, and NIR spectroscopy
RAMAN MIR/ATR NIR
Type of acquiring spectra
Transmission, transflection,
AT-line/In-line probes ATR-probes diffuse-reflection probes
Instrument Design
NIR-Raman (FD) FT-IR Grating, FT-NIR, AOTF,
VIS-Raman (CCD) Diode-array, discrete filter
NIR reflectance vs. NIR transmission
NIR
Reflectance NIR
Transmission
NIR
Absorption
NIR Refelectance NIR Transmission (NIT)
Detector
Detector
IR Beam
Detector
Position
Tablet
R.J. Romañach and M.A. Santos, “Content Uniformity Testing with
Near Infrared Spectroscopy”, American Pharmaceutical Review,
2003, 6(2), 62 – 67.
Reflectance is termed diffuse where the angle of reflected light is independent of
the incident angle
Spectra Affected by:
Particle size of sample.
Packing density of sample, and
pressure on sample.
Refractive index of sample.
Crystalline form of sample.
Absorption coefficients of sample.
Characteristics of the sample’s
surface.
J.M. Chalmers and G. Dent, “Industrial Analysis with Vibrational
Spectroscopy”, Royal Society of Chemistry, 1997, pages 153 -162.
Particle Size and Scattering
High
High scattering
scattering
Smaller particle sizes Low
Low Scattering
Scattering
More remission, less Absorbing power (absence of scattering)
transmission
Absorption coefficient (includes effects of Larger particle sizes
voids, surface reflection, distance traveled) Less remission, more
transmission
