1.

DETECTORS USED INGASCHROMATOGRAPHY&HIGH

PERFORMANCE LIQUIDCHROMATOGRAPHYprof.
RavisankarVignan Pharmacy collegeValdlamudiGuntur
Dist.Andhra
PradeshIndia.banuman35@gmail.com00919059994000
2. Contents: Definition Ideal properties of a detector
Detectors used in GC- concentration dependent
detectors- mass flow dependent detectors Detectors
used in HPLC- selective detectors- universal detectors
3. Detectors: The detector senses the presence of the
individualcomponents as they leave(elute) the column.
The detector output after amplification is traced on a
recorder. The duration of the intervals is usually a
single second or evenless than that. Hence the
detector is considered to be the brain of
theinstrument. The detector converts a change in
effluent into an electricsignal that is recorded by data
system
4. Ideal properties of a detector:The detectors used in
both GC and HPLC should havefollowing ideal
properties:1) High sensitivity.2) Good stability and
reproducibility.3) A linear response to solutes.4)
Negligible base line noise.5) Should be inexpensive.6)
Capable of providing information on the identity of
solute.7) A temperature range from room temperature
to at least4000c.8) A short response time independent
of flow rate.9) High reliability and ease of
operation.10)The detector should be nondestructive.11)Response independent of mobile phase
composition.
5. Detectors used in GC:Detection devices for a GC
must respond rapidly andreproducibility to the low

concentrations of the solutes emittedfrom the

column.Concentration dependent detectors:- Thermal
conductivity detector(TCD)- Electron capture
detector(ECD)- Argon ionization detector- Helium
ionization detectorMass flow dependent detectors:Flame ionization detector(FID)- Nitrogen phosphorous
detector(NPD)- Flame photometric detector(FPD)
6. In addition to these other detectors used are:Thermionic detectors- Photoionization detectorsAtomic emission detectors- Sulfur chemiluminescence
detector The most widely used detectors are TCD, FID,
ECD.Thermal conductivity detector(TCD): TCD was one
of the old detectors for GC, is still widely in use. It is
also known as katharometer and hot wire detector.
Principle in TCD is change in thermal conductivity of
gasstream. Thermal conductivity of most of the
samples is lesser thanmost commonly used carrier
gases like H, and He.
7. The thermal conductivity of He is 6-10 time greater
than thatof the most organic compounds. It is simple,
inexpensive, non-selective, accurate, andnondestructive type.Thermal conductivity detector
8. Since the detector response depends upon the
difference inthermal conduction between sample and
carrier gas, a largedifference is essential. An increase
in temperature of the detector causes a change inthe
resistance of thermistor and this resistance gives
ameasure a measure of thermal conductivity of gas.
TCD consists of a temperature controlled metal block in
whichtwo cylindrical chambers are present, which
consists of twofilaments made up of platinum or
tungsten. Both the filaments are connected to the
arms of Wheatstonebridge arrangement. Resistance of

filaments are constant as only the carrier gas ispassed

through them, once the effluent passes through
themthe change in conductivity is seen and is recorded.
9. Flame ionization detector(FID): FID is the most
widely used and generally applicable detectorfor GC.
With an FID the effluent from the column is directed
into smallair-hydrogen flame. Most of the organic
compounds produce ions and electronswhen pyrolyzed
at the temperature of air-hydrogen flame. Detection
invovles monitoring the current produced bycollecting
this charge carriers. A few hundred volts applied
between the burner tip and acollector electrode located
above the flame causes the ionsand electrons to move
towards the collector. The resulting current is then
measured with high-impedancepicoammeter.
10. The ionization of carbon compounds in the FID is
not fullyunderstood, although the number of ions
produced is roughlyproportional to the number of
reduced carbon atoms in flame. Because the FID
responds to the number of carbon atomsentering the
detector per unit time. The detector is insensitive
towards non-combustible gasessuch as H2O, CO2, SO2,
CO. Functional groups like carbonyl, alcohol, halogen,
and amineyield fewer ions or none at all in a flame.
These properties make the FID a most useful general
detectorfor the analysis of most organic samples,
including thosecontaminated with water and oxides of
nitrogen and sulfur.
11. The FID exhibits a highsensitivity (10-13g/s),large
linear responserange(107), and low noise. It is
generally rugged andeasy to useDisadvantages: It
destroys sample. It requires additionalGases and
controllers.

12. Electron-capture detector(ECD): It is most widely

used detector for environmental samplesbecause it
selectively responds to halogen containing
organiccompounds.e.g.: pesticides, polychlorinated
biphenyls In ECD, the sample eluate from a column is
passed over aradioactive emitter, usually nickel-63.
The ECD is selective in its response. An electron from
the emitter causes ionization of carrier gasand the
production burst of electrons. In the absence of
organic species, a constant standing currentbetween a
pair of electrodes results from this ionization. In the
presence of organic molecules
containingelectronegative functional groups that tends
to captureelectrons, hence the current decreases.
13. Compounds such as halogens, peroxides,
quinones and nitrogroups are detected with high
sensitivity. The detector is insensitive to functional
groups such asamines, alcohols and hydrocarbons. An
important application of ECD is for the detection
andquantitative determination of chlorinated
insecticides. The advantage of ECD is that it does not
alter the sample.
14. Electron capture detector
15. Flame photometric detector(FPD): FPD is widely
used in the analysis of air and water
pollutants,pesticides, coal hydrogenation products It is
selective towards compounds containing sulfur
andphosphorous. In this detector the eluent is passed
in to a low temperaturehydrogen-air flame, which
converts part of phosphorous in toHPO species that
emits bands of radiation at about 510 and 526nm. It
also converts sulfur in to S2 which emits a band at
394nm. Suitable filters are used to isolate appropriate

bands and theirintensity is recorded photometrically.

FPD is used to detect elements like halogens, nitrogen
andmetals like tin, chromium, selenium and
germanium.
16. Flame photometric detector
17. Photoionization detector: In this the molecules
eluting from GC column are photoionizedby ultra-violet
radiation from a 10.2 eV hydrogen or a 11.7 eVargon
lamp. This source ionizes species with an ionization
potential belowthe lamp energy. compounds with a
higher ionization potential do not absorb theenergy and
thus they are not detected. The ions and electrons
produced by Photoionization are thencollected at pair of
biased electrode. The detector is most sensitive for
aromatic hydrocarbons andorganosulfur or
organophosphorous.
18. Photo ionization detector
19. Atomic emission detector(AED): In AED, the
effluent from GC column is introduced in to amicrowave
induced plasma(MIP), an inductively
coupledplasma(ICP) or a direct current plasma. Among
these MIP has been most widely used and is
availablecommercially. The MIP is used in conjunction
with diode array or chargecoupled device atomic
emission spectrometer. The plasma is sufficiently
energetic to atomize all ofelements in a sample and to
excite their characteristic atomicemission spectra.
Hence, the AED is an element selective detector.
20. The sample in this case consists of gasoline
containing smallconcentrations of methyl tertiary butyl
ether(MTBE), as well asseveral aliphatic alcohols in low
concentrations. By using oxygen(777nm) rather than

carbon(198nm) in lampwe can obtain a chromatogram

peaks for alcohols and forMTBE which are readily
identifiable.
21. Mass spectrometry detectors: one of the most
powerful detectors for GC is the massspectrometer.
The combination of GC with Mass spectrometry is
known asGC-MS. Currently, nearly fifty instrument
companies offer GC-MSequipment. Currently, capillary
columns are invariably used in GC-MSinstruments and
no other separators are needed. Thermal degradation
of components can be difficulty in GC-MS, lowering the
temperature can minimize degradation. However the
mass spectrometer can be used to
identifydecomposition products, which can lead to
chromatographicmodifications that solve degradation
problem.
22. The most common ion sources used in GC-MS are
electron-impact ionization and chemical ionization.
The most common mass analyzers are quadrapole and
ion-trap analyzers. In GC-MS, the mass spectrometer
scans the massesrepetitively during a chromatographic
experiment. GC-MS instruments have been used for
identification ofcomponents present in natural and
biological systems.e.g.: water pollutants, breath
components and drugmetabolites. MS can also be
used to obtain information about
incompletelyseparated components. It is extremely
powerful tool for identifying components in
themixtures.
23. Several other types of GC detectors are useful for
detection ofspecific components, they are thermionic
detectors and sulfurchemiluminescence detectors.
Thermionic detector is selective towards organic

compoundscontaining phosphorous and nitrogen. The

response to a phosphorous atom is approximately
tentimes greater than a nitrogen atom and 104-106
times largerthan to a carbon atom. Sulfur
chemiluminiscence detector is specific to the
sulfuratom. It is based on the reaction between certain
sulfur compoundsand ozone. This detector has proven
particularly useful for thedetermination of the
pollutants such as mercaptans
24. Detector Type Support gases Selectivity
Detectability Dynamic rangeFlame ionization(FID)Mass
flowHydrogen andairMost organiccompounds.100 pg
107Thermalconductivity (TCD)Concentration Reference
Universal 1 ng 107Electron capture(ECD)Concentration
Make-upHalides, nitrates,nitriles,
peroxides,anhydrides,organometallics50 fg
105Nitrogen-phosphorusMass flowHydrogen
andairNitrogen, phosphorus 10 pg 106Flame
photometric(FPD)Mass flowHydrogen andair
possiblyoxygenSulphur, phosphorus,tin, boron,
arsenic,germanium, selenium,chromium100 pg
103Photo-ionization(PID)Concentration MakeupAliphatics, aromatics,ketones, esters,aldehydes,
amines,heterocyclics,organosulphurs,
someorganometallics2 pg 107Hall
electrolyticconductivityMass
flowHydrogen,oxygenHalide, nitrogen,nitrosamine,
sulphur- 25. Detectors used in HPLC: The function of the
detector used in HPLC is to monitor themobile phase it
emerges from column. The detectors used in HPLC are
of majorly two types:selective detectors(solute
property): Absorbance detectors Fluorescence

detectors Electrochemical detectors Mass

spectrometric detectorsUniversal detectors(bulk
property): Refractive index detectors Evaporative
light scattering detectors
26. UV-Visible Absorption Detectors: In this a Z-shape
flow through cell for absorptionmeasurements on
eluents from a chromatographic column. To minimize
extracolumn band broadening, the volume ofsuch a cell
should be kept as small as possible, typically 1-10l
Many absorption detectors are double-beam devices in
whichone beam passes through eluent cell and other
beam isreference beam. Matched photoelectric
detectors are used to compare theintensities of the two
beams. Single beam instruments are also used, were
the intensitymeasurements of the solvent system are
stored in a computermemory and used for the
calculation of absorbance.
27. UV absorption detectors with filters: These are
used earlier with a mercury lamp as the source. Most
commonly, the intense line at 254nm was isolated
byfilters, by substitution of filters lines at 250, 313,
334, and365nm can also be used. Because of this
reason, these type detectors are restricted asmost of
the organic and inorganic species exhibit
broadabsorption bands.UV absorption detectors with
scanning capabilities: A detector with scanning
spectrophotometer with gratingoptics is most widely
used. Several operational modes can be chosen with
thesedetectors.
28. For example, the entire chromatogram can be
obtained atsingle wavelength or different wavelengths
can be chosen fora single peak. When entire spectra
are desired for identification purposesthe flow of eluent

can be stopped for a sufficient period topermit scanning

the wavelength region of interest.
29. Fluorescence detectors: Fluorescence detectors for
HPLC are similar in design to thefluorometers and
spectrofluorometers. In most, fluorescence is observed
by a photoelectrictransducer located at 900 excitation
of beam. The simplest detectors use mercury
excitation source and oneor more filters to isolate a
band of emitted radiation. More sophisticated
instruments use a xenon source and agrating
monochromator to isolate the fluorescence radiation.
Laser-induced fluorescence is also used because of
itssensitivity and selectivity. An inherent advantage of
these detectors is their highsensitivity, hence used in
LC for separation and determinationof components of
samples that fluoresce.
30. Fluorescent compounds can be obtained by
treating withreagents that form fluorescent
derivatives. For example, dansylchloride forms
fluorescent compoundswith primary amines, secondary
amines, amino acids andphenols, hence widely used for
detection of amino acids inprotein
hydrolyzates.Fluorescent detector
31. Refractive-index detectors: The ability of a
compound or a solvent to deflect light providesa way to
detect it. RI is a measure of molecules ability to
deflect light in aflowing mobile phase in a flow cell
relative to a static mobilephase contained in a
reference cell. The amount of deflection is proportional
to concentration. The RI detector is considered as a
universal detector but it isnot very sensitive. To
achieve high sensitivity, in practice solvents are
selectedthat have a very high or very low refraction

index. The detection limit is in the range of 10-6-10-8

g/ml.
32. Refractive-index detector
33. Electrochemical detectors: This is based on
amperometry, voltammetry, coloumetry,
andconductometry. Electron transfer processes offer
highly selective andsensitive method. Easily adaptable
for use with micro columns. As background noise is
dependent on mobile phase conditions,it is difficult to
utilize these detectors with gradient
elutionseparations. It is of two types:Amperometric
detection: Fixed potential is applied to the electrode
(glassy carbon) anda solute which will oxidize at that
potential yields an outputcurrent
34. Coulometric detection: 100% of the solute species
is converted, which offersadvantages of no mobile
phase flow dependence on signal andabsolute
quantitation through Faradays law.
35. ELSD can outperform traditional detectors when
analysing non-chromophoric samples by HPLC.
Traditional HPLC detectors such as UV and RI have
limitedcapabilities. UV and RI are not compatible with
a wide range of solventsRI detection is not gradient
compatible Different analytes produce different UV
responses depending ontheir extinction co-efficient.
ELSDs can detect anything that is less volatile than the
mobilephase ELSD is universal and compatible with a
wide range of solventsEvaporative Light Scattering
Detector:
36. Three steps are involved in detection:nebulization- mobile phase evaporationdetectionNebulization: Column effluent passes

throughnebulizer needle. It mixes with the nitrogen

gas. Dispersion of droplets are formed.Mobile phase
evaporation: The above formed droplets arepassed
through a heating zone. Mobile phase evaporatesfrom
the particles.
37. Detection: Sample particles pass through an
optical cell. Sample particles interrupt laser beam and
scattered light. Photodiode detects the scattered
light. ELSD is an effective replacement or a perfect
complement toexisting LC detectors.
38. Conclusion:Detector is the key element that is
present in anydevice that is used for the identification
and estimation of anycompound. It detects in a faster
rate i.e. with in seconds henceit is considered as brain if
the instrument. With out a detectorno one can analyze
the compound. Hence, it attains such animportance in
the field of analysis.