Mass Sensitivity
Chromatography detectors are in general are either mass sensitive or concentration sensitive. A mass sensitive detector responds to the mass of solute passing through it per unity time and a concentration sensitive detector responds to the mass of the solute per unit volume of mobile phase passing through it. The flame ionization detector (FID) is mass sensitive whereas the UV detector is concentration sensitive. The advantage of the mass sensitive detector is that the column eluent can be diluted without affecting the detector response. This characteristic is particularly useful when using a capillary column as, for example, the mobile phase can pass directly into the hydrogen flow to the FID and although the column eluent is extensively diluted, because the FID is mass sensitive, the response of the detector is unaffected.
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Sensor-Volume
is mass sensitive,
the response depends on the mass per unit time
passing through it and not the mass per unit volume that
passes through it. This is clear when the operation of the flame ionization
detector (FID) is considered. In practice, for example, the eluent from a
capillary column is mixed with a hydrogen, or hydrogen/nitrogen stream, which
is then burnt at a small jet and the ions produced measured by an appropriate
pair of electrodes. The response of the detector will depend on the mass of
solute eluted per unit time from the capillary column and, thus, will be
independent of the hydrogen or hydrogen/nitrogen flow (as this will not effect
the rate of solute elution, in terms of mass per unit time). In contrast, if
the FID was a concentration device (like the katherometer), as the hydrogen or
hydrogen/nitrogen flow dilutes the sample, the response will be directly
related to the flow rate of the diluting gas. It follows, that for a mass
sensitive device, the sensing volume
EC-Dispersion Sensor-Volume
Author: RPW Scott
Book:Gas Chromatography - Tandem Techniques
Section:GC-Tandem Mass-Spectroscopy
(or both) the ions can be separated from one another on the basis of their individual masses. By means of a suitable scanning procedure, each individual ion mass is then sensed and its mass identified. The advantages of this type of analytical approach and its value combined with a GC instrument are very obvious.
There are three basic types of mass spectrometer, the sector mass spectrometer, the quadrapole mass spectrometer (which includes the mass analyzer) and the time-of-flight mass spectrometer. All three types of mass spectrometer have been used (and, indeed, are still used) in combined configurations with gas chromatographs. It follows, that the basic principles of all three types of mass spectroscopic systems will need to be described. It should be noted, however, that the quadrapole mass spectrometer in one of its various forms is by far the most popular mass spectrometer to be used in a combined system, but the function of the sector instrument is the simplest to
GC-Tandem Mass-Spectroscopy
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Ionization-Detectors Electron-Capture
is connected to the sensor at
the base and makeup gas can be introduced into the base of the detector if
open tubular columns are employed as these columns are usually operated with
hydrogen or helium as the carrier gas. The electron capture detector is
extremely sensitive, probably one of the most sensitive GC detectors available (minimum detectable concentration ca. 10-13
g/ml) and is widely used in analysis of pesticides. Unfortunately, its
sensitivity is often given in terms of the minimum mass of solute eluted, which
can be misleading. The detector is concentration sensitive and thus the
concentration of the solute for a given mass will vary with the position it is
eluted in the chromatogram (for a given
mass of solute, an early peak would be narrow and have a small volume and a
high concentration at the peak maximum: however, if eluted as a late peak it
would be broad, have a relatively large volume and a lower concentration at the
peak maximum). Consequently, a mass of solute
GC-Detectors Ionization-Detectors Electron-Capture
Author: RPW Scott
Book:Gas Chromatography
Section:YES Detectors Flame-Ionization
nbsp;
Figure 22. The Flame
Ionization Detector
The ionization
process is not very efficient, only 0.0018% of the solute molecules produce ions,
(about two ions or electrons per 105 molecules).
Nevertheless, because the noise level is very small, the minimum detectable
mass of n-heptane is only 2 x 10-12
g/sec. At a column flow rate of 20 ml/min. this is equivalent to a minimum
detectable concentration of about 3 x 10-12
g/ml. The detector responds to mass per unit time entering the detector,
not mass per unit volume consequently the response is almost independent
of flow rate. This is particularly advantageous and allows it to be used very
effectively with capillary columns. Although the column eluent is mixed with
the hydrogen prior to entering the detector, as it is mass sensitive and not
concentration sensitive, the diluting effect has no impact on the sensitivity.
The FID detects virtually all carbon containing solutes, with the
YES Detectors Flame-Ionization
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Classification
of Detectors
Detectors can
be classified into two types, bulk property detectors and solute
property detectors. The bulk property detector measures some bulk physical
property of the eluent (such as dielectric constant or refractive index) and
the solvent property detector, measures some physical or chemical property that
is unique to the solute (such as heat of combustion or fluorescence). Detectors
can also be classified as concentration sensitive devices such as the
katharometer or mass sensitive devices such as the flame ionization
detector (FID). Another method of classification is to define detectors as specific
or non-specific. An example of a specific detector would be the nitrogen
phosphorous detector (NPD), which as its name implies detects only those
substances that contain nitrogen or phosphorous. A non-specific detector would
be the katharometer detector which senses all vapors that have specific heats
or thermal conductivities different from those of the carrier
GC-Detectors Classification
Author: RPW Scott
Book:Capillary Chromatography
Section:Capillary Detectors Flame-Ionization-Detector
Detectors for Use with Capillary Columns
Detectors for use with capillary columns must have high sensitivities due to the limited sample size that can be used whith such columns. In addition, due to the very small peak volumes produced by the column, the sensing volume must also be extremely small. As the flame ionization detector (FID) is mass sensitive as opposed to concentration sensitive (see book 4 of this series for the meaning of mass and concentration sensitivity) the dilution by hydrogen does not effect the detector response. Thus, the FID has both the high sensitivity and the small sensor volume that is necessary and is, consequently, ideal for use with capillary columns. The nitrogen phosphorous detector (NPD) is also appropriate for capillary columns (the function of which is very similar to that of the FID) for the
Capillary Detectors Flame-Ionization-Detector