Near Infrared Spectroscopy

Introduction into the method

NIR Spectroscopy: Some characteristics

NIR: = 780 2500 nm (12500 4000 cm-1)

Combination and overtones of CH-, OH-, and NH- vibrations

Normal mode vibration (MIR) Combination and overtones High degree of excitation

Low degree of excitation

(NIR)

NIR Spectroscopy: Some characteristics

In contrast to sharp absorption peaks in the MIR region, NIR spectra show less intensity and broad bands A assignment of peaks to individual vibrations is not possible Reflection intensity in the NIR region is higher than in mid infrared.

Example spectra
User Spectra
100048 Ethanol 96% 139492 Ethanol absolut 021687 Triethanolamin Isoprop. 119866 Propylenglykol 140273 Triethylcitrat (Citroflex 2)

0.75 0.50

C-H 2.O

N-H, O-H 1.O

0.25
C-H 1.O

0.00
Kombin.

-0.25

5000

6000

7000 1/cm

8000

9000

Advantages
Liquids, powders and even high-viscosity substances can be measured without sample preparation Silica can be used as transmittance material for cuvettes, fibers and probes. Measurement period! One NIR spectra is a characteristic fingerprint of an individual extract and covers all organic compounds!

Evaluation of NIR spectra

International Chemometrics Society: Chemometrics is the science of relating measurements made on a chemic system or process to the state of the system via application of mathemati or statistical methods.

Qualitative classification Sufficiently big sample set with a certain variety concerning to the expected determination range Development of a qualitative model, e.g. principal component analysis

Quantitative Analysis Reference data of all samples have to be determined Spectral data and refernce data are combined in a calibration, e.g. PLS

Identification procedure
Original Spectra
All Spectra 1,50 Transflectance 1,25 1,00 0,75 0,50 5000 6000 7000 1/cm 8000 9000
Weizenkeiml Mandell Jojobal NIRCal : Fette le 1.nir Fettl0,93SNVdg12/5 19.08.2003 10:22:49 gr

Pretreated Spectra
All Spectra 1,0 Transflectance 0,5 0,0 -0,5 -1,0 -1,5
Weizenkeiml Mandell Jojobal NIRCal : Fette le 1.nir Fettl0,3SNVdg12/5 19.08.2003 10:25:17 gr

5000

6000

7000 1/cm

8000

9000

Pretreated Spectra
All Spectra
Weizenkeiml Mandell Jojobal NIRCal : Fette le 1.nir Fettl0,93SNVdg12/5 19.08.2003 10:26:24 gr

Loadings / Loadings
All Spectra 0,4 Loading Value 2 0,2
Weizenkeiml Mandell Jojobal NIRCal : Fette le 1.nir Fettl0,93SNVdg12/5 19.08.2003 10:27:42 gr

0,2 Transflectance

0,1

-0,0 -0,2 -0,4 -0,3 -0,2 -0,1 -0,0 0,1 Loading Value 1 0,2 0,3

0,0

-0,1 5000 6000 7000 1/cm 8000 9000

Principles for NIR measurements

NIR detector

Diffuse reflection

NIR detector

Transmission

NIR detector

Transflection

Spectrometer types
Dispersive spectrometer (e.g. Foss NIRSystems 5000):
sa mple via l sa mple me a sure ment window re fe renc e

mirror 4 PbS dete ctors (set a t 45)

hologra phic grid

ha logen la mp

Spectrometer types
Fourier transform spectrometer (e.g. Bchi NIRflex)
Interferometer Interferogramm

Fourier transformation

Diode array spectrometer

Interim statement
In NIRS single compounds influence not only individual regions, but often the whole spectrum Visual analysis of the spectra is impossible NIR spectra have no significant peaks, but they are unique reproductions of a substance or a mixture Data have to be combined with multivariate mathematical methods We need a different thinking, when working with NIRS !