GAS CHROMATOGRAPHY

DETECTORS

Prof Ramalingam
SOP
MKU
 DETECTION SYSTEMS
1. Thermal Conductivity Detector
2. Flame Ionization Detector
3. Electron Capture Detector
4. Nitrogen Phosphors Detector
5. Radio Chemical Detector
6. Microwave Induced Plasma Atomic Emission Detector
7. Fourier Transform Infra Red (FTIR) Detector
8. Gas chromatography - Mass spectrometry
 DESIRABLE PROPERTIES OF THE DETECTOR

High sensitivity
Uniform response for a wide variety of compounds
Linear response
Fast speed of response
Good stability over extended periods
Low background noise
Reliabilty
Ease of operation

Detection devices for a gas-liquid chromatograph must respond

rapidly and reproducibly to the low concentrations of solutes
emitted from the column.

No single detector meets all of these requirements

 1. THERMAL CONDUCTIVITY DETECTOR
Katharometer
The sensing element of this device is an electrically heated
source whose temperature at constant electrical power depends
upon the thermal conductivity of the surrounding gas. The
heated element may consist of a fine platinum or tungsten wire
or, alternatively, a semiconducting thermistor. The resistance of
the wire or thermistor gives a measure of the thermal
conductivity of the gas.
In chromatographic applications, a double detector is always
employed, one element being placed in the gas stream ahead of
the sample injection chamber and the other immediately beyond
the column. In this way, the thermal conductivity of the carrier
gas is cancelled, and the effects of variation in flow rate,
pressure, and electrical power are minimized.
The resistances of the twin detectors are usually compared by
incorporating them into two arms of a simple Wheatstone bridge
circuit such as that shown in Fig
KATHAROMETER
The thermal conductivities of hydrogen and helium are roughly
six to ten times greater than those of most organic compounds.
Thus, the presence of even small amounts of organic materials
causes a relatively large. decrease in the thermal conductivity
of the column effluent; the detector undergoes a marked rise in
temperature as a result.
The conductivities of nitrogen and carbon dioxide more closely
resemble those of organic constituents; thus, detection by
thermal conductivity is less sensitive when these substances
are used as carrier gases.
Thermal conductivity detector is Universal detector
Simple, Rugged, Inexpensive, Nonselective
Accurate, Nondestructive of the sample.
It can be used to determine water vapour.
Ex: used to determine water in some BP assays for ex, water in
the peptides Menotrophin, Gonadorelin, Salcatonin.
 2. FLAME IONIZATION DETECTORS
Compounds are burnt in the flame producing ions and thus an
increase in current flow between the jet and collector
Most organic compounds, when pyrrolyzed at the temperature of
a H2/air flame, produce ionic intermediates that provide a
mechanism by which electricity can be carried through the
flame.
By employing an apparatus such as that shown in Fig these ions
can be collected and the resulting ion current measured. An
electrometer must be employed for their measurement.
The number of ions produced is roughly proportional to the
number of reduced carbon atoms in the flame.
FID
 FID…
Functional groups such as carbonyl alcohol, and amine produce
fewer ions or none at all.
The hydrogen flame detector currently is one of the most popular
and most sensitive detectors. It is more complicated and more
expensive than the thermal conductivity detector, but has the
advantage of higher sensitivity.
In addition, it has a wide range of linear response. It is, of
course, destructive of the sample.
It detects carbon/ hydrogen containing compounds.
Insensitive to carbon atoms attached to Oxygen, Nitrogen or
chlorine.
In combination with capillary GC it may detect as low as 100pg
to 10ng
 3. ELECTRON CAPTURE DETECTOR
Electron-capture detectors operate in much the same way as a
proportional counter for measurement of X-radiation.
Here, the effluent from the column is passed over a β emitter
such as
Nickel 63 or
Tritium (adsorbed on Platinum or Titanium foil).
An electron from the emitter causes ionization of the carrier gas
(often nitrogen) and the production of a burst of electrons.
In the absence of organic species a constant standing current
between a pair of electrodes results from this ionization process.
The current decreases, however, in the presence of organic
molecules that tend to capture electrons.
The response is nonlinear unless the potential across the
detector is pulsed.
3. ELECTRON CAPTURE DETECTOR
The electron-capture detector is selective in its response and is
highly sensitive toward electronegative functional groups such
as Halogens
Peroxides
Quinones
Nitro groups
It is insensitive to compounds such as
Amines, Alcohols Hydrocarbons.
An important application of the election- capture detector has
been for the detection and determination of chlorinated
insecticide.
Mainly used for analysis of drugs in bode fluids.
Has wide application in environmental monitoring ex
Chlorofluorocarbons in atmosphere
Highly halogenated compound can be detected at the 50fg to 1pg
Electron capture detectors are highly sensitive and possess the
advantage of not altering the sample significantly (in contrast to
the flame detector).
 4. NITROGEN PHOSPHORS DETECTOR
Nitrogen and Phosphrous containing compounds react with the
alkali metal salt in the detector to produce species such as CN,
various phosphorus anions or electrons all of which produce an
increase in current which generates the signal.

Detects phosphorus compounds at the pg level,

Nitrogen compounds at the low ng level.

Highly sensitive for nitrogen and phosphorus containing

compounds.

Used mainly in the analysis of drugs and their metabolites in

tissues and bodily fluids.
 5. RADIO CHEMICAL DETECTOR
14C and 3H present in the molecules are respectively converted
into 14CO2 and 3H2.

Its sensitivity depends on the degree of radioactivity of the

analyte.

Useful for metabolic labelling studies, making metabolites of

drugs easy to detect.

The detector tends to work better with packed columns since it

has a large internal space
6. MICROWAVE INDUCED PLASMA ATOMIC EMISSION DETECTOR
A hot plasma of argon is produced by heating to > 6000oC which
causes all the elements in the compound to produce emission
spectra.
The individual emission lines are passed through diffraction
grating and detected by diode array detector.
Detects individual elements
Ex. Chlorine in organo chlorine pesticides
Metals in organo mettallics compounds
Sensitive to the PG level for some elements.
Most widely used in
Environmental monitoring
Impurity profiling of drugs
Metabolism studies.
(Plasma gas : Ionized gas Ex: Argon)
 GAS LIQUID CHROMATOGRAPHY
WITH
SELECTIVE DETECTORS

Second general method involves the use of a selective detector

to monitor the column effluent continuously.

A. Automatic Titration Detectors

B. Coupling of Gas Chromatography to Mass Spectroscopy

C. Coupling of Gas Chromatography to Infrared Spectroscopy

 A. AUTOMATIC TITRATION DETECTORS
James and Martin employed an automatic titration cell as a
detector for volatile fatty acids, aromatic and aliphatic amines.
Method
In this method, the effluent from the column was led directly
into a cell containing an acid-base indicator solution. The
absorbance of the solution was monitored photometrically, the
output from the cell being employed to control continuously the
addition of titrant; the volume of the latter was recorded on a
chart to produce an integral curve of volume versus time.

Both qualitative and quantitative information could be

retrieved from the recorded curve.

A coulometric cell has been employed as the detector in the

analysis of the various chlorinated compounds contained in
pesticide residues.
 B. FOURIER TRANSFORM INFRA RED (FTIR) DETECTOR
Essentially just an FT IR instrument coupled to a GC, thus
allowing IR spectra of compounds eluting from the GC column
to be obtained.
Generally, the effluent from the column is led into a long narrow
tube equipped with infrared-transparent windows. Scanning is
triggered by the output from a nondestructive chromatographic
peak detector and begins after a brief delay to allow the
component to travel from the detector region to the infrared cell.
The spectral data are digitalized and stored in a computer from
which printed spectra are ultimately derived.
More useful for structure elucidation rather than quantitative
studies.
The detector is sensitive to the 10 ng level.
Used as a tool for qualitative identification.
There are some examples quantitative applications
Ex: Determination of propandiol in Acyclovir cream.
C. COUPLING OF GAS CHROMATOGRAPHY TO MASS SPECTROSCOPY
Chromatographic columns have been directly interfaced to
rapid-scan mass spectrometers, thus permitting the
instantaneous display of the spectrum of each species as it
leaves the column.
Generally, these instruments are also interfaced with a
computer so that each spectrum is digitalized and stored for
later reproduction on paper.
Instruments of this type make possible the identification of the
hundreds of components that may be present in natural and
biological systems.
For example, the interfacing of chromatography with
spectroscopy has permitted
Characterization of the odor and flavor components of foods

Identification of pollutants

Medical diagnosis based on breath components

Studies of drug metabolites.

GAS CHROMATOGRAPHY - MASS SPECTROMETRY
Mass spectrometry is based upon the ionization of solute
molecules in the ion source and the separation of ions generated
on the basis of their mass/charge ratio by an analyser unit
Magnetic sector analyser
A Quadrupole mass filter
Ion trap analyser
Ions are detected by ion detector such as Dynode electron
multiplier.