Sensitivity
Unfortunately, in chromatography, sensitivity has a dichotomy of meaning that has resulted from early definitions of detector performance being changed over the years. Originally, sensitivity was considered to define how small a mass or concentration of a solute could be unambiguously identified by a detector. This concept of sensitivity still persists, although it has been replaced in some cases by minimum detectable mass (MDM) or, alternatively, minimum detectable concentration (MDC). Sensitivity, MDM or MDC are classically defined as the mass or concentration of solute passing through the detector that will give a signal equivalent to twice that of the noise. Originally the signal given by a detector for unit mass or unit concentration change was termed the detector response. However, in modern terminology, the term ‘response’ is often replaced by ‘sensitivity’ which introduces even more confusion. It follows, therefore, when using the terms ‘sensitivity’ or ‘response’, their precise meaning must be clearly defined.
Author: RPW Scott
Book:Gas Chromatography - Tandem Techniques
Section:GC-Tandem GC-Spectroscopic-Systems UV-Visible-Absorption-Measurement Multi-Wavelength-Dispersive-Spectrometer
a small sensor volume, it follows that the radius of the sensor cell must also be reduced as (l) is increased. This results in less light falling on the photoĐcell which, in turn, will reduce the signalĐtoĐnoise ratio and, thus, the sensor sensitivity, or minimum detectable concentration. Consequently, increasing the sensor sensitivity by increasing the path length has limitations and a wellĐdesigned cell involves a careful compromise between cell radius and length to provide the maximum sensitivity. Most modern UV spectrometer sensor's have path lengths that range between 1 and 10 mm and internal radii that range from about 0.5 to 2 mm. From equation (2),
It is seen that the sensitivity of the sensor as measured by the transmitted light will be directly proportional to the value of the extinction coefficient (k) and the path length of the sensor cell (l). It follows, that to increase the sensitivity of the system for a given substance having a given extinction coefficient (k
GC-Tandem GC-Spectroscopic-Systems UV-Visible-Absorption-Measurement Multi-Wavelength-Dispersive-Spectrometer
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Summary
property being measured that will provide a
signal equivalent to twice the noise. The sensitivity defined in concentration
units is, in general, more useful to the analyst.
7.Detector
Dispersion – () –
This is generally not significant in GC detectors
8. Detector Time Constant – (Dt) –
The overall time constant of the sensor and electronics is given in
milliseconds. It is of interest in high speed chromatography.
9. Pressure Sensitivity - (DP)
– The pressure sensitivity of a detector is the output that results from unit
change in pressure. It is usually specified in V/p.s.i. or V/kg/m2
. It is important in detector design.
10. Flow Sensitivity – (DQ)
– The flow sensitivity is the output that results from unit change in flow
rate. It is specified in V/ml/min. It is important in detector design.
11. Temperature Sensitivity – (DT) – Thetemperaturesensitivityisdefined as the output that results from 1oC
change in temperature. It is given in V/oC
GC-Detectors Summary
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Specifications
or the logarithmic dilution method. In the
logarithmic method of calibration, mobile phase, now a liquid, is passed
continuously through an enclosed stirred vessel containing a known mass of
solute, the eluent passing directly into the detector. The logarithm of the
detector output is plotted against the logarithm of the calculated solute concentration
and the magnitude of the response index determined from the slope of the curve
in the manner described in book 4. The response, noise and sensitivity are
measured in exactly the same way as for GC detectors. Pressure sensitivity and
pressure tolerance have a more important significance in LC as in
multidimensional LC, the detector may be situated between two or more columns
and thus must tolerate pressures up to the input pressure (e.g., several
thousand p.s.i). Pressure sensitivity and flow sensitivity are also more
important in LC due to the relatively high pressures involved and the
sensitivity of many sensors to
HPLC-Detectors Specifications
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Flow-Sensitivity
i.e.
Thus, a knowledge of (NP)
can be used in detector design when a particular sensitivity is the objective.
Flow Sensitivity
Flow sensitivity is another detector property
that can have a significant effect on long term noise and, consequently, also
on the detector MDC. Again it is the bulk property detectors that are the most
likely exhibit high flow sensitivities (e.g.,
the katharometer). To reduce its flow sensitivity, the katharometer is usually
fitted with a reference cell through which a flow of mobile phase also passes.
The two sensors for the column flow and the reference flow are placed in the
arms of a Wheatstone bridge so that any changes in flow rate are to a large
extent compensated. The flow sensitivity (DQ) is defined in a
similar manner to pressure sensitivity (i.e.
mV/ml/min). The flow sensitivity can be used to calculate the flow change (NQ)
that would provide a signal equivalent
GC-Detectors Flow-Sensitivity
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Trace-Analysis
.65)
Consequently,
substituting for (Vr) in equation (16) from equation (17) and for (Vo)
from equation (18),
(19)
Thus (mD), the mass sensitivity of the
chromatographic system depends on the detector
sensitivity, column dimensions, column efficiency and the capacity factor of the eluted solute.
However,
irrespective of the column properties, the mass sensitivity is still directly
related to the detector sensitivity. It will also be shown (see Book 22 on
column optimization) that the column radius will also depend on the magnitude
of the extra–column dispersion. It follows that
the design of the chromatographic apparatus, the detector and detector
electronics (to minimize extra column dispersion) together with the detector
sensitivity will determine the mass sensitivity of the overall chromatographic
system
EC-Dispersion Trace-Analysis
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors UV Fixed-Wavelength
nbsp;
Thus
Thus. two
detectors, having the same sensitivity defined as the minimum detectable change
in absorbence, will not necessarily have the same sensitivity with respect to
solute concentration. Only if the path lengths of the two sensors are identical
will they also exhibit the same concentration sensitivity. This can cause some
confusion as it would be expected that two instruments having the same
spectroscopic sensitivity would also have the same chromatographic sensitivity.
To compare the sensitivity of two detectors given in units of absorbence the
path lengths of the cells in each instrument must be taken into account.
UV
HPLC-Detectors UV Fixed-Wavelength