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background spectrum. The following conditions must
remain constant
or be accounted for in quantitative FTIR-PAS analyses:

1. FTIR mirror velocity
2. FTIR and PAS detector amplifier gain settings
3. PAS detector optical alignment
4. FTIR source intensity
5. FTIR interferometer alignment
6. Helium gas concentration in the PAS detector
7. Sample volume
9. Sample matrix
10. Microphone sensitivity
11. Carbon black standard response

The FTIR mirror velocity must be set at the same
value when spectra of the calibration standards (learning set)
and of unknowns are acquired. If the mirror velocity setting
is not maintained, changes in the PAS sampling depth will occur
which are analogous to changing sample thickness or concentration
in transmission spectroscopy.
All amplifier gain settings should be at the same
values when sample spectra are acquired in order to have constant
measurement conditions.
Good quantitative analyses also require that the
detector positioning in the FTIR is reproducible when the accessory
is put in and taken out of the FTIR and that its position remains
fixed when the accessory is installed. Properly designed kinematic
mount and baseplate registration accomplish these requirements.
Scale variations are caused in FTIR-PAS spectra if
changes occur in source intensity, interferometer alignment,
helium concentration; sample volume, morphology, and matrix;
and microphone sensitivity and carbon black response. In some
instances, if proper care is taken, these changes can be held
small enough to yield satisfactory quantitative analyses. But
in most instances, adding a standardization procedure that addresses
all of these potential changes is the best way to insure that
quantitative results will have the degree of reproducibility
necessary for a particular application.
FTIR-PAS spectra are usually best standardized by
one of two methods. The first is applicable to situations where
the spectral changes over the full analyte range are small relative
to the whole spectrum. In this case the spectra can be scaled
so that the area under the whole spectrum from 400-4000 cm is
held constant.
The second method exploits the fact that highly saturated
bands in the FTIR-PAS spectra vary much slower with changes in
analyte concentration than do unsaturated bands. Consequently,
FTIR-PAS spectra can be standardized by scaling spectra so that
a particular intense band's height or area remains constant. |