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.

http://coolcosmos.ipac.caltech.edu/
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