Linearity
In chromatography, linearity usually refers to the response of the detector. A detector is linear if the output of a detector is given by the product of a constant and the solute concentration (or, for a mass sensitive detector, the mass of solute passing though it per unit time). If a detector is declared to be linear, the linearity is usually limited to a specific concentration range (or range of mass of solute passing though it per unit time). No practical detector is perfectly linear, but its response can approach linearity and therefore, linearity needs to be measured. Linearity is a difficult property to define and measure. One method is to assume that the output of a detector is proportional to a power function of the concentration (or mass of solute passing though it per unit time) and, thus, for a perfectly linear detector the exponent would be unity. The value of this exponent for a given detector has been termed the response index of the detector and has been used to define the detector linearity. If the detector is to be considered sufficiently linear for accurate quantitative analysis it should have a response index that lies between 0.97 and 1.03 over the concentration range stated.
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Detector
Linearity
The E19 committee suggested an alternative
procedure for defining linearity (3). They defined the linear dynamic range as
follows,
"the linear
dynamic range of a detector is that range of concentration of a test substance
over which the response of the detector is linear to within 5%, determined form
a linearity curve".
The range should be expressed as a ratio of
the highest concentration to the minimum detectable concentration. Although
defining linearity by this method ensures an minimum linear performance and,
consequently, a reasonable quantitative accuracy, the definition is not
sufficiently explicit. Conversely, if the response index is employed, any
slight non linearity can be taken into account by correcting the peak height
(or the peak area) using the numerical value of the response index. Thus. in
effect, the useful linear dynamic range of a detector for quantitative purposes
can be significantly extended by employing
GC-Detectors Detector
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Linearity
In practice, no detector has a truly linear
response (despite manufacturers claims) but most detectors will have a response
approaching that of linear. It is difficult to apply a standard to detector
linearity, but the Response Index (1)
does help comparisons to be made between one detector with that of another.
Providing the response of the detector
approaches linearity then its response can be described by the following simple
equation,
y = Acr
where (r) is the response index and the other symbols have the
For a truly linear detector, r=1, and the
extent to which (r) deviates from unity would be a measure of its non
linearity.
GC-Detectors Linearity
Author: RPW Scott
Book:Liquid Chromatography Detectors
Section:HPLC-Detectors Specifications
have
sensitivities of two to three orders of magnitude less than their GC
counterparts and linear dynamic ranges one to two orders of magnitude lower.
Only highly specific LC detectors have sensitivities that can approach those of
GC detectors.
See also the section on detectors in the HPLC supplement.
Detector Specifications
Detector
specifications are like those for GC detectors and are listed as follows,
1. Dynamic Range
2. Response Index or Linearity
3. Linear Dynamic range
4. Detector Response
5. Detector Noise Level
6. Detector Sensitivity or Minimum Detectable
Concentration
7. Total System Dispersion
8. Sensor Dimensions
9. Detector Time Constant
10. Pressure Sensitivity
11. Flow Sensitivity
12. Operating Temperature Range
In general the
HPLC-Detectors Specifications
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Linearity Response-Index Logarithmic-Dilution
The Logarithmic Dilution Method of Linearity Measurement
This method of linearity measurement was
introduced by Lovelock (2). The procedure requires some special apparatus that
is diagramatically represented in figure 3.
Figure 3 The Logarithmic Dilution Apparatus.
A known mass of solute is introduced into a
well–stirred vessel through which passes a flow of gas. The exit gas is
arranged to pass directly into the detector. As a consequence, the mixture is
continuously diluted and the concentration of the solute in
GC-Detectors Linearity Response-Index Logarithmic-Dilution
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Summary
Summary of Detector Criteria
1. Dynamic Range – (RD)
– The dynamic range of a detector is that concentration range over which
it will give a concentration dependent output. The units are dimensionless.
2. The Response Index – (r) – The response
index of detector is a measure of detector linearity and would be unity for a
truly linear detector. In practice the value of (r) should lie between 0.98 and
1.02. If (r) is known, quantitative results can be corrected for any non
linearity.
3. Linear Dynamic Range – (DL)
– The linear dynamic range of a detector is that concentration range over which
the detector response is linear within defined response index limits. It is also dimensionless and is important
when the components of a mixture cover a wide concentration range.
4.
GC-Detectors Summary
Author: RPW Scott
Book:Liquid Chromatography
Section:HPLC UV-Detectors
variable wavelength) the electrical conductivity
detector, the fluorescence detector and the refractive index
detector. These detectors are employed in over 95% of all LC analytical
applications. These four detectors will be described and for those readers
requiring more information on detectors are referred to
Liquid Chromatography Detectors. The subject of detector specifications will not be
discussed here but will also be dealt with in detail there. Detector
sensitivities and detector linearity will, however, be given for each of the
four detectors.
The UV Detector
The UV
detector is by far the most popular and useful LC detector that is available to
the analyst at this time. This is particularly true if multi-wavelength
technology is included in this class of detectors. Although the UV detector has
some definite limitations (particularly for the detection of non polar solutes
that do not possess a UV chromaphores) it has the best combination of
sensitivity, linearity
HPLC UV-Detectors