Thermal Conductivity Detector (TCD)

Introduction
A TCD detector consists of an electrically-heated wire or
thermistor. The temperature of the sensing element depends
on the thermal conductivity of the gas flowing around it.
Changes in thermal conductivity, such as when organic
molecules displace some of the carrier gas, cause a
temperature rise in the element which is sensed as a change
in resistance. The TCD is not as sensitive as other detectors
but it is non-specific and non-destructive.
Instrumentation
Two pairs of TCDs are used in gas chromatographs. One pair is
placed in the column effluent to detect the separated
components as they leave the column, and another pair is
placed before the injector or in a separate reference column.
The resistances of the two sets of pairs are then arranged in a
bridge circuit.
The bridge circuit allows amplification of resistance changes

Schematic of a bridge circuit for TCD detection

Two filament in one cell ( reference side ) --- carrier gas only
The other cell ( sample side ) --- carrier plus sample flowing

1. Universal
2. Used primarily for gas analysis
3. Sensitive few ppm

Detectors: Thermal
Conductivity
TCD can be used for organic and inorganic
analytes.
The key aspect is the ability of the carrier gas
and the analytes to change the conductivity of
a wire filament, which will vary with different
analytes.
The carrier gas should have different thermal
conductivity of analytes.
TCD is a non-destructive type of detection that
uses a Wheatstone bridge style. Downsides are
the response to impurities, leakage in air, and
poor response to LOD.

Detectors: Flame Ionization

FID uses fuel mixed with
carrier and organic analyte.
Analyte forms ions in the
flame.
Cations from the flame are
gathered by the negative
electrodeproduces a
current.
Advantage:inorganics do not
respond (He carrier gas), so
the low background signal
allows for LOD 100- to 1000fold lower then TCD.

Flame Ionization Detector

Introduction
The flame ionization detector (FID) is the most sensitive gas
chromatographic detector for hydrocarbons such as butane or hexane.
With a linear range for 6 or 7 orders of magnitude (106 to 107) and limits
of detection in the low picogram or femtogram range, the FID is the gas
chromatographic detector for volatile hydrocarbons and many carbon
containing compounds.

FID
Responds to all organic compounds except for formic acid.
Response greatest with hydrocarbons and decreases with substitution.
Except for vapor of elements in Groups I and II, does not respond to
inorganic compounds.
Sensitivity high due to low noise level.
Insensitivity to water, the permanent gases, and inorganic compounds
simplifies the resolution of components in analysis of aqueous extracts
and in air pollution studies.

Flame Ionization Detector

Consists of a stainless steel burner assembly installed in the
detector compartment and a electrometer system in a
separate unit adjacent to the gas chromatograph
Often it is installed in the tandem with the thermal
conductivity cell
Effluent form the column enters burner base through millipore
filters which remove contaminates
Hydrogen mixed with gas stream at bottom of jet and air or
oxygen is supplied axially around the jet.
Hydrogen flame burns at the tip, which also functions as the
cathode and is insulated form the body by a ceramic seal
Collector electrode is above the burner tip and is made of
platinum

An FID consists of a hydrogen/air flame and a collector plate.

The effluent from the GC column passes through the flame,
which breaks down organic molecules and produces ions. The
ions are collected on a biased electrode and produce an
electrical signal. The FID is extremely sensitive with a large
dynamic range, its only disadvantage is that it destroys the
sample.
FIDs are normally heated independently of the
chromatographic oven. Heating is necessary in order to
prevent condensation of water generated by the flame and
also to prevent any hold-up of solutes as they pass from the
column to the flame. With the flame extinguished, the column
end should be passed up through the jet and then lightly held
in position by slightly tightening the coupling. Gradually draw
the column end back into detector jet until it is approximately

Mechanism
The effluent from the column is mixed with hydrogen and air and then
ignited electrically at a small metal jet. Most organic compounds
produce ions and electrons that can conduct electricity through the
flame. There is an electrode above the flame to collect the ions
formed at a hydrogen/air flame. The number of ions hitting the
collector is measured and a signal is generated.
In series with flame gases is a selection of resistors 107 to 1010 ohms.
Vibrating reed electrometer used to provide sensitivities up to 5
1013 Amps.
Carbon counting device that produces a current proportional to
number of ions or electrons formed in the flamed gases.
The organic molecules undergo a series of reactions including thermal
fragmentation, chemi-ionization, ion molecule and free radical
reactions to produce charged-species. The amount of ions produced is
roughly proportional to the number of reduced carbon atoms present
in the flame and hence the number of molecules. Because the flame
ionization detector responds to the number of carbon atoms entering
the detector per unit of time, it is a mass-sensitive, rather than a

Normal Combustion: i.e. burn methane in air and get carbon

dioxide and water vapor...
CH4 + O2 CO2 + H2O
or:
CH4 + 3O2 CO2 + 2H2O

Flame Ionization: during combustion, a uniform proportion (about

0.0002%) of the molecules in this reaction do this instead:
(simplified for clarity)
CH4 + O2 C++ H2O + e- CO2 + H2O
or:
CH4 + 3O2 C++ O2 + 2H2O + e- CO2 + 2H2O

These oppositely-charged, intermediate products can then be detected

by the FID:

Limitations
Molecules that contained only carbon and hydrogen
respond best in this detector but the presence of
"heteroatoms" in a molecule, such as oxygen, decreases
the detector's response. For instance, the FID's methane
response (CH4) is fabulous but formaldehyde's (CH2O) is
quite poor. Therefore, highly oxygenated molecules or
sulfides might best be detected using another detector
instead of the FID. Sulfides determination by the flame
photometric detector and aldehydes and ketones analyzed
with the photoionization detector are alternatives to the
use of the FID for those molecules.

SMOKE METER
ThetermSmokeMetergenerallyreferstoasmokemeasuringinstrumentbasedonoptical
propertymeasurements.Awide variety ofapproaches to suchinstrumentsexists.
Many measure opacity directly through the
smoke column. Othersmeasure opacity through a sampledfractionofthecolumn.
Anothermeasurement
classoftheseinstrumentssamplestheexhaustandflowsitthrough a filter membrane,
or paper. Reflective and/or transmissive optical measurements
quantifyhowblackenedthefilterpaperhasbecomefromthesootcontentofthesmok
e. The blackening effect is usually considered to be caused by the elemental
carbon componentof thesoot.Theclassesofinstruments
thatmeasurethereflectiveproperties
aregenerallycalledSmokeMeterswiththeirresultsreportedinspecialunitscalledSmoke
Numbers. A variety of such
Smoke Number scales have evolved (e.g. Hartridge Smoke Units, Bosch Units, etc.).
More sophisticated
instruments may measure combinations of reflective and transmissive optical
properties.These instruments are usually specially designed and calibrated to
measure primarily the elemental carbon and are
generally referredtoasBlackCarbonmeasurementdevices.