Theory and Instrumentation of GC

GC Detectors

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Aims and Objectives

Aims

To highlight the various detector types available for GC

To describe the performance characteristics associated with a range of common
detectors for GC
To explain the working principles behind the following detectors:
o Flame Ionisation
o Electron Capture
o Nitrogen Phosphorous
o Thermal Conductivity
o Flame Photometric
To describe the optimisation process for each of the detector types and typical
uses
To illustrate the various performance characteristics of each of the detector types
To highlight the use of various other detector types and give brief descriptions of
them

Objectives

At the end of this Section you should be able to:

Explain the parameters and performance measures by which GC detectors are

characterised
Describe the components and working principle of a number of common GC
detectors
Give suggestions of how each detector type might be optimised and demonstrate
an understanding of each detector type in a practical context
Choose the correct detector type for a variety of analyte and application types

Content
Overview of GC Detectors
Concentration versus Mass Flow
Selective versus Universal
Destructive versus Nondestructive
Characteristics of GC Detectors
Noise
Signal to Noise Ratio
The Flame Ionisation Detector
Overview
Operating and Optimising
Uses and Performance
The Nitrogen Phosphorous Detector (NPD)
Overview
Operating and Optimising
Use and Performance
The Electron Capture Detector (ECD)
Overview
Operating and Optimising
Uses and Performance
The Thermal Conductivity Detector (TCD)
Overview
Operating and Optimising
Uses and Performance
Other GC Detectors
Flame Photometric Detector (FPD)
Photoionisation Detector (PID)
Electrolytic Conductivity Detector (ELCD)
Mass Spectrometer (MS)

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Overview of GC Detectors
There have been over 60 detectors designed for GC applications since the inception of
the technique. Probably 10-12 detectors are used commonly in routine GC applications
and of these only 3-4 are used in non-specific applications.
All GC detectors monitor a physical property of the analyte the property chosen must
significantly change, and therefore cause a large detector response, when the eluent gas
flowing into the detector is contaminated by the analyte. Several properties have been
used in GC detectors and these are outlined in the next table. Detectors that exhibit an
enhanced response to certain analyte types are known as selective detectors.
Table 1. Selected GC detectors
Detector type
Detector (Property)
Ionisation
Flame Ionisation Detector (FID)
Thermal Conductivity Detector (TCD)
Electron Capture Detector
Nitrogen Phosphorous Detector (NPD)
Photoionisation Detector (PID)
Emission
Flame Photometric Detector (FPD)
Plasma Atomic Emission (AED)
Electrochemical
Hall Electrolytic Conductivity (HECD)
Others
Chemiluminescent
Mass Spectrometer (MSD)
Fourier Transform Infra-red (FTIR)

Selective
No
No
Halogens
N, P, Halogens
Aromatics
S, P
Metal, Halogen, C, O
S, N, Halogen
S
Yes
Yes

There are three important classifications of GC detector and these are:

Concentration versus Mass Flow
Concentration sensitive detectors respond to the concentration of the analyte in the
detector flow cell / chamber.
If the flow to the detector were interrupted the signal (peak) height would not decrease,
however the peak area would change.
Mass Flow sensitive detectors respond to the amount of analyte in the detector at any
time, irrespective of the volume of carrier gas. If the carrier flow is reduced the detector
response (peak height) will decrease but the peak area will remain constant. The diagram
below shows the effect of altering carrier flow on the two detector types:

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Therefore, when using GC temperature programming and operating in constant pressure

mode Concentration Sensitive Detectors (TCD, ECD) will have a variable peak area
response as the flow rate changes, but Mass Flow sensitive detectors (FID, NPD) will
show a constant peak area response as the flow rate changes. In reality, the use of
constant flow with temperature programs is recommended to ensure constant peak
widths.
Selective versus Universal
This classification describes the number of analytes that a detector will respond to. A
Universal detector will theoretically respond to all solutes, whilst Selective detectors
respond to specific types or classes of compound. Universal detectors are good for
screening unknown mixtures and for situations where it is important to ensure all solutes
are detected and quantified. Selective detectors usually show enhanced sensitivity to
particular compounds and are able to simplify complex chromatograms by only detecting
certain classes of compound.

MS in Total Ion mode universal detector

MS in Selected Ion mode responds to only compounds producing certain fragment ions.
The chromatogram is simplified compared to the top example due to the specificity of the
detection mode.
Destructive versus Nondestructive
Nondestructive detectors are required where the separated intact analyte components
need to be recovered for further analysis or characterisation. This can be accomplished
using destructive detectors (where the analyte is destroyed) by splitting the carrier effluent
stream just prior to the detector entrance.

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Characteristics of GC Detectors
There are several important detector characteristics that apply to all Gas Chromatography
detectors and help to describe the detector performance. The important characteristics of
GC detectors include:

Sensitivity (the signal output per unit concentration or mass of analyte)

Minimum Detectability (usually measured by signal to noise ratio)
Linearity (the range of concentrations over which reliable quantitative
measurements can be made)

These characteristics will be explored further using some of the terms outlined in the brief
definitions above.
Noise
Noise is the background signal produced by the detector in the absence of analyte. It
arises from electronic noise, stray environmental signals and contamination or leaks.
Good design and shielding can help to reduce the inherent noise. Noise is a rapid
random variation in output, whereas drift is a slow systematic change in detector output.
Signal to Noise Ratio
The ratio of the detector signal to the inherent background noise is a useful measure of
detector performance to convey information about the lower limit of detection.
Conventionally the lowest signal to noise ratio that can be attributed to an analyte would
have a signal to noise (S/N) ratio of 2. From the figure opposite showing a S/N value of 2,
the signal is only just perceptible from the background noise. Different regulatory
authorities in various industries may specify limit of detection as a signal to noise value
the actual value will vary from authority to authority but will usually be either 2 or 3.

Schematic representation of the determination of detector (FID) noise using the ASTM
method

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Schematic representation of a peak representing a signal to noise ratio value of 2

The Flame Ionisation Detector

Overview
The Flame Ionisation Detector is the most widely used GC detector and was invented
specifically for GC applications. Its high sensitivity and linear range for carbon-containing
compounds make it very popular in organic analysis. A typical FID design is shown
opposite. The column effluent is mixed with hydrogen and a make-up gas (for capillary
systems) before exiting via a small orifice (jet-tip) which is surrounded by a high flow of
air. The Hydrogen is combustible in air and can be lit via a remote glow plug. The
stiochiometric ratios of the air / hydrogen / carrier and make-up gas are important and will
be studied further.

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As the column effluent is burned in this flame, ions are created which form a small current
when a potential difference is applied. When no analyte (carbon containing compounds)
are being burned, a small background current (10-20 picoamperes) arises from impurities
in the carrier and detector gases. Conventionally the jet forms the anode and a cylindrical
electrode held just above the flame is the cathode. A voltage of between 200 and 300V
across these components is usually optimal but depends on detector design. The exact
mechanism of ion production is not well characterised, however the formation of carbon
ions via pyrolysis and the formation of small organic fragment ions produced via high
energy combustion products are popular theories. The flame ionisation detector produces
a proportional response to the number of carbon atoms in a molecule. One suggested
reason for this constant response factor is the conversion of all solute carbon molecules to
methane in the combustion process. When heteroatoms are present within the analyte
molecule the sensitivity of the detector is much reduced. A calibration curve should be
constructed for each analyte prior to quantitative analysis to take into account response
variations due to detector settings.

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Operating and Optimising

Since water is a product of combustion, the FID detector should be maintained at
temperatures above 125 oC to prevent condensation of water and high boiling sample
species. Typically most FID detectors will operate at 250 oC or above depending upon
the application. Temperature does affect the sensitivity of the detector although in
practice, the detector temperature is rarely a parameter that is important in optimising an
analysis. If required start with a detector temperature of 250 oC and raise and lower the
temperature in 20 oC steps to investigate the temperature / sensitivity relationship for
particular analytes or compound groups.
For efficient operation the ratio (stoichiometry) of the gases used must be correct. This is
usually in the order of 1 effluent (carrier): 1 fuel (hydrogen): 10 oxidiser (air) for capillary
applications this is usually in the order of 300-400 mL/min. For capillary column
applications where the carrier flow is less than 30ml/min. a makeup gas is used to
increase the column effluent volume this serves to dilute the effluent stream (to keep
within the detector linear range) and propels the analyte up into the body of the flame.
The makeup gas is usually chosen to be different from the carrier nitrogen is the most
popular as its viscosity ensures good mixing with the effluent stream.
The ratio of fuel to makeup + carrier is vital in determining the sensitivity of the instrument
this ratio can be optimised for each analysis if required. The air flow (ratio) is not so
important (as can be seen opposite) so long as a minimum flow is established.
The makeup (nitrogen in this case) and hydrogen ratio have an affect on the sensitivity of
the detector this is demonstrated on the plot. Each makeup flow (actually carrier +
makeup) is plotted against a range of fuel (hydrogen) flow rates. As can be seen below
there is a maximum value for each combination representing a possible increase of
around 10% response by optimising the gas flow rates.

Once past a critical minimum value the actual flow of the oxidiser seems to make little
difference to the detector sensitivity. Typically this value will be between 300 and
400mL/min. The critical ratio for sustaining a flame is 8-12% hydrogen in air.

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Uses and Performance

The FID detector shows excellent sensitivity to carbon containing compounds the
response being proportional to the number of carbon atoms in the molecule. Compounds
containing halogens show a reduced response in FID detection and analytes not
containing organic carbon do not burn and are therefore not detected. These include
some significant compounds in organic analysis and are listed below perhaps the most
significant being water.
Table 2. Compounds giving little or no response in FID Detection
NH3
He
CS2
Ar
COS
CO
Kr
H2S
CO2
Ne
SO2
H2O
Xe
NO
SiCl4
O2
N2O
SiHCl3
N2
NO2
SiF4
Flame Ionisation Detector Characteristics

Minimum Detectability (LOD) ~ 10-11g (~50ppb)

Response organic carbon containing compounds, exceptions shown above
Linearity 107 (very wide dynamic range)
Stability excellent stability, virtually no response change on flow or temperature
fluctuation
Temperature Limit ~ 400oC (instrument / column dependant)
Gases Combustion: Hydrogen and air, Makeup: helium or nitrogen

The presence of water in samples often produces very large tailing solvent peaks and
induces tailing in analyte peaks. Having a detector that effectively ignores the water is
sometimes useful at simplifying the chromatogram. Other solvents (such as carbon
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disulphide) are also ignored by the detector and have utility when dealing with very early
eluting analytes that may otherwise elute beneath the solvent peak.
The general uses of FID are too widespread to categorise fully here open any column
manufacturers catalogue to find a host of relevant applications. A few typical examples
have been shown cited opposite for general reference.
The FID performance figures of merit are shownhighlighting just why this detector is the
most popular GC detector in use today. Its excellent sensitivity, linearity and wide
applicability make it the foremost detector in general organic analysis.

Sulphur containing compounds analysis. HP-PlotQ 6890. 53m0.30mm40m

Where:
1. Hydrogen sulphide
2. Carbonyl sulphide
3. Ethanelthiol
Analysis conditions.
Inlet
Oven
Split flow
Detector
Concentrations

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4. iso- propyl mercaptan

5. n- propyl mercaptan
6. n- butyl mercaptan

250oC, split mode, 0.25cc injection

Temperature programmed
100mL/min
FID 250oC
Mercaptans less than 10%

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Blood analysis compounds on a DB-ALC1 30m0.32mm1.8m

Where:
1. Methanol
2. Acetaldehyde
3. Ethanol
Headspace conditions.
Oven:
70oC
Loop:
80oC
Transfer line:
90oC
Vial equil time:
10oC
Press time:
0.20min

4. Isopropanol
5. Acetone
6. 1-Propanol

Loop fill time:

Loop equil time:
Inject time:
Sample loop size:
Samp comp:

0.20min
0.05min
0.1-0.20min
1.0mL
0.1% ethanol

Analysis conditions.
Carrier
Oven
Injector
Detector

Helium at 69 cm/sec, measured at 40oC

40oC Isothermal
Headspace to split inlet, split 1:10, 250oC injection
FID 300oC, nitrogen makeup gas at 23mL/min

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The Nitrogen Phosphorous Detector (NPD)

Overview
Although the nitrogen phosphorous detector (NPD) is based on a similar design to the
FID, and whilst belonging to the family of ionising detectors it works on a different
principle to the FID. First introduced in 1964 by Karmen and Giuffrida this detector is also
known as the Thermionic detector and is popular because of its enhanced sensitivity and
selectivity towards compounds containing nitrogen and/or phosphorous, as its name
suggests.
Whilst the main structure of the detector looks essentially similar to the FID, the main
difference is the addition of a resistively heated bead just above or in the vicinity of the jet.
The bead contains or is coated with an alkali metal salt usually caesium or rubidium
silicate. When heated this bead emits thermionic electrons which migrate to the collector
electrode and form the background current.
The hydrogen flow into the detector is appreciably less than used in the FID and is too low
to sustain a flame at the jet tip. Rather a plasma of fuel (hydrogen), oxidiser (air), carrier
effluent and makeup passes over the bead at which point partial combustion occurs due
to the heating filament. When a suitable analyte is eluted into the plasma, the partially
combusted nitrogen or phosphorous materials are adsorbed onto the surface of the bead.
This reduces the work function of the bead surface effectively making it easier to emit
electrons at the applied voltage / temperature. Thus the emitted electron density
increases, which causes an increase in the current in the detector which is amplified and
becomes the chromatographic peak.

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Operating and Optimising

Typically NPD detectors are run at slightly higher temperatures than FID detectors 260 to
350 oC being typical. The temperature of the detector does not have a radical effect on
response but higher temperatures do extend bead lifetime.
The voltage applied to the bead (and hence the resulting temperature) does have a
marked effect on the detector response. If unsure start at 2V and make 10mV
adjustments until the optimum response is obtained.
It is essential to ensure that the hydrogen flow rate is low enough NOT to sustain a flame
at the jet tip otherwise measurement of nitrogen containing compounds will not be
possible. The detector is sensitive to variations in the hydrogen flow rate and a constant
flow of hydrogen is recommended to ensure steady baselines.
The main disadvantage of this detector is that its performance deteriorates with time
usually seen via the need to increase the bead voltage in order to generate a signal. The
water formed from combustion of hydrogen hydrolyses the alkali silicate to the metal
hydroxide and silica. As the alkali metal hydroxide is volatile under typical operating
conditions, the rubidium or caesium is constantly lost from the bead ultimately leaving an
inert bead of silica.
To conserve bead life it is possible to turn off the detector (conventionally by interrupting
the hydrogen flow) whilst solvent peaks elute or between injections when the GC oven is
cooling.
As the detector is flow sensitive it is recommended that constant flow mode is used
during temperature programming.

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Extending the life of the bead

Use the lowest practical adjust offset or bead voltage.

Run clean samples.
Turn the bead off when not in use.
Keep the detector temperature high (320 to 335C).
Turn the hydrogen flow off during solvent peaks and between runs.
If your NPD is Off for a long time in a high-humidity environment, water may
accumulate in your detector. To evaporate this water:
o Set the detector temperature at 100C and maintain it for 30 minutes
o Set the detector temperature to 150C and maintain it for another 30 minutes

Use and Performance

The NPD detector is a factor of around 500 times more sensitive to nitrogen and
phosphorous containing compounds than to carbon containing compounds in general
this makes the detector effectively selective towards nitogenated and phosphorylated
compounds. The NPD has a very high sensitivity, i.e., about an order of magnitude less
than that of the electron capture detector (ca.10-12 g/mL for phosphorus and 10-11 g/mL for
nitrogen).
The high selectivity of the detector leads to its high sensitivity and the ability of the
detector to simplify chromatograms by effectively ignoring other compound classes.
The specific response of the NPD to nitrogen and phosphorus, coupled with its relatively
high sensitivity, makes it especially useful for the analysis of many pharmaceuticals and in
environmental samples containing herbicides. Employing appropriate column system
traces of herbicides at the 500 pg level can easily be determined.
Nitrogen Phosphorous Detector Characteristics

Minimum Detectability (LOD) ~ 10-11g (~10pg)

Response selective to nitrogen and phosphorous containing compounds
Linearity 106 (very wide dynamic range)
Stability excellent stability, hydrogen flow and bead temperature should be
carefully controlled
Temperature Limit ~ 400oC (instrument / column dependant)
Gases Combustion: Hydrogen and air, Makeup: helium or nitrogen

Nitrogen/Phosphorous containing Pesticides (carrier gas 30cm/sec He), EPA method 507
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Where:
1. Prometon
2. Atrazine

3. Prometryne
4. Ametryne

Oven and detector parameters.

Oven
Initial temp:
80oC
st
o
1 ramp: 30 C/min to 178oC
2nd ramp: 2oC/min to 205oC
3rd ramp: 30oC/min to 310oC
Final temp: 310oC for 4min

Detector
Temperature:
Makeup gas:
Hydrogen:

290oC
He, 30mL/min
4mL/min

Injection and pressure programming.

Pressure programming

Injection parameters
Temp:
Vol injected:
Pneumatics:
Purge delay:

250oC
1L
Splitless mode
1min

Initial head pressure:

13.6 psi
0.5psi/min to 21psi
1st ramp:
1psi/min to 31psi
2nd ramp:
Void time:
1.63 min

Determination of carbaryl

Conditions.
Injection parameters

Pressure programming

Oven:
70oC (1min) to 230oC
(5min) at 20oC/min
Column:
HP-5,
300.32mm0.25mmL
N2, 15mL/min
Makeup gas:

Column flow:
2mL/min
Detector temp:
330oC
Detector: 3mL/min of H2, air at 60mL/min
Inlet: SL mode, 60mL/min purge 0.75min
Inlet temp:
250oC

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Determination of triazines in pond water extract

Where:
1.
2.
3.
4.
Conditions.
Oven
Initial temp:
1st ramp:
2nd ramp:
Final temp:

Propazine
Atrazine
Simazine
Terbuthylazine

170 C for 1min

to 195oC at 2oC/min
to 230oC at 2oC/min
230oC for 3min

5.
6.
7.
8.

Prometryne
Ametryne
Simetryne
Terbutryne

Detector:
NPD 250oC
Makeup gas:
He at 28mL/min
Injector:
Split 1:10, 250oC
Column: DB-35 30m0.25mm0.25m

The Electron Capture Detector (ECD)

Overview
The invention of the Electron Capture Detector is attributed in Lovelock in 1961. The
detector measures the electrical conductivity of the effluent gas stream resulting from
exposure to ionising radiation from a radionulclide. It is a selective detector that responds
to compounds capable of capturing electrons more especially, halogenated compounds.
The radionuclide is 63Nickel which emits beta particles (low energy electrons).
63

Ni

These negatively charged particles collide with carrier gas molecules and produce further,
higher energy, electrons (remember that beta particles are themselves low energy
electrons).
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 + N 2 2e + N 2+
The electrons formed by this process establish a high standing current between the anode
(usually the inlet tube or detector body) and the cathode (usually a cylindrical electrode in
the centre or top of the detector). The potential difference applied is usually 20-100V dc).
When an electronegative analyte elutes, the analyte molecules capture some of the
background electrons and this results in a reduction of the standing (background)
current.

A + e A
The negative analyte ions formed are slow moving and are not collected by the anode.
The extent of electron absorption, and hence the reduction in standing current, is
proportional to the concentration of the analyte.

Operating and Optimising

The carrier gases used for ECD operation should be pure and dry. Oxygen and water are
both electronegative and as such contribute to a noisy baseline if they are present in the
carrier or makeup gases even in trace amounts. When the detector is used with capillary
columns, a makeup gas is generally required in this case it is convenient to use less
expensive (but high quality) nitrogen as the makeup gas and the more expensive helium
as the carrier. It is recommended that ultrapure gases are used at all times when
operating an ECD detector.
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63

Ni sources are preferred to 3H (tritium) sources as they can be operated at higher

temperatures (up to 400 oC vs 220 oC), and are inherently less radioactive, however they
produce a less linear response.
Improved performance and linearity can be obtained by operating the detector in a
pulsed mode. A square wave pulse (amplitude 50V, width 1 m s at intervals of 20-50 s)
is applied at a frequency that maintains a constant current in the detector cell in order to
maintain the current in the presence of an analyte the pulse frequency has to be
increased. The signal is generated in proportion to the frequency of the applied pulse.
The cleanliness of the detector needs to be maintained at all times, which often means
care with sample preparation. Chromatographic peaks obtained from a dirty ECD
detector have a distinctive shape and the sensitivity of the detector can often increase as
detector performance deteriorates.

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As the ECD is a non-destructive detector, contamination builds up on the inner surfaces of

the detector. As a result the magnitude of the standing current decreases although the
decrease in the current per analyte molecule remains the same. Unusually this may lead
to an increase in the instrument sensitivity as the detector becomes dirtier. This
behaviour is less likely when the detector is operated in the pulsed mode.
Typically, when the detector performance in deteriorating a marked deviation away from
the expected linear range is seen especially at higher analyte concentrations as shown.
Further, a typical chromatographic symptom od detector performance loss is the formation
of a negative dip either before or after each peak.
Uses and Performance
One drawback of the ECD is the necessity to use a radioactive source, which may require
a license or at least regular radiological testing.
The sensitivity of the electron capture detector is variable, depending upon the electron
affinity of the analyte. For compounds of high electron affinity, such as halogenated
compounds, minimum detectability of picograms on column are not untypical with the
added benefit that chromatograms are much simplified due to the very high selectivity.
The linearity of the detector is limited, although as discussed the use of the detector in
pulsed mode does extend the minimum detectability, and hence the dynamic range.
Ranges of X50 are typical for 63Ni sources. It is vital that any analysis is carried out
against a multi-point calibration curve that covers the anticipated range of sample
concentrations.
The detector is perhaps, one of the more tricky to operate in practice. It will also require
periodic cleaning. Given that it contains a radioactive source this may need to be carried
out by the equipment manufacturer.
Electron Capture Detector Characteristics

Minimum Detectability (LOD): ~ 10-9 - 10-12g

Response: highly selective towards analytes with electronegative atoms
(especially halogens)
Linearity: 103 - 104 (limited dynamic range- better in pulsed mode)
Stability: fair but susceptible to impurities in gases used and leaks in the detector
body
Temperature Limi:t ~ 400oC (63Ni) / 220oC (3H)
Gases Carrier: Helium, Makeup: nitrogen or 5% methane in argon (all gases must
be ultra high purity)

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Organochloride pesticides
Where:
1. Trifluralin
2. Chloroneb
3. Propachlor
4. HCB
5. -BHC
6. r-BHC
7. -BHC
8. Chlorothalonil
9. Heptachlor
Conditions.
Oven
Initial temp:
1st ramp:
Dwell:
2nd ramp:
Final temp:

10. -BHC
11. Alachlor
12. Aldrin
13. DCPA
14. Heptachlor
epoxide
15. r-Chlordane
16. o,p-DDE
17. -Chlordane

140 C for 2min

to 240oC at 10oC/min
240oC for 5 min
to 265oC at 5oC/min
265oC for 10min

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18.
19.
20.
21.
22.
23.
24.
25.
26.

Endosulfan I
p,p-DDE
Dieldrin
o,p-DDD
Chlorobenzilate
Endrin
o,p-DDT
p,p-DDD
Endosulfan II

27.p,p-DDT
28.Endrin
aldehyde
29.Endosulfan
sulphate
30.Dibuthyl
chlorendate
31.Methoxychlor
32.HBB

Detector:
ECD 325oC
Makeup gas:
N2 at 30mL/min
Carrier:
He at 35cm/sec measured, 250oC
Column:
DB-5 30m0.53mm1.5m

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Haloacetic acid methyl esters (optimized for resolution)

Where:
1. Chloroacetic acid
2. Bromoacetic acid
3. Dichloroacetic acid
4. Dalapon
5. Trichloroacetic acid
6. Bromochloroacetic acid
Conditions.
Oven
Initial temp:
1st ramp:
Dwell:
2nd ramp:
Dwell:
3rd ramp:
Final temp:

35 C for 10min
to 75oC at 5oC/min
75oC for 15 min
to 100oC at 5oC/min
100oC for 5 min
to 135oC at 5oC/min
135oC for 5min

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7. 1,2,3,-Trichloropropane (ISTD)
8. Dibromoacetic acid
9. Bromodichloroacetic acid
10. Chlorodibromodichloroacetic acid
11. 2,3,-Dibromopropionic acid (SSTD)
12. Tribromoacetic acid

Detector:
ECD 260oC
Makeup gas:
N2 at 30mL/min
Injector:
Splitless, 200oC, 30sec purge
Column:
DB-1701 30m0.25mm0.25m

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Purgeable halocarbons (EPA method 502.1)

Where:
1.
2.
3.
4.
5.

Fluorotrichloromethane
Methylene chloride
trans-1,2-Dichloroethylene
1,1-Dichloroethylene
2,2- Dichloroethane, cis-1,2
Dichloroethylene
6. Bromochloromethane
7. Chloroform
8. 1,1,1-Trichloroethane
9. Carbon tetrachloride
10. 1,2-Dichloroethylene
11. 1,2-Dichloropropane
Conditions.
Oven
Initial temp:
35oC for 5min
Ramp:
to 135oC at 4oC/min

12. Bromodichloromethane
13. 1,1,2-Trichloroethane, 1,3dichloropropane, tetrachloroethylene
14. Dibromochloromethane
15. 1,2-Dibromoethane (ECB)
16. 1,1,1,2-Tetrachloroethane
17. Bromoform
18.1,2,3-Trichloropropane, 1,1,2,2tetrachloroethane
19. Pentachloroethane
20. bis-(2-chloroisopropyl) ether
21. 1,2-Dibromo-3-chloropropane

Detector:
ECD 300oC
Makeup gas:
N2 at 40mL/min
Injector: Purge and trap (desorption 8mL/min)
Column:
DB-624 30m0.53mm3.0m

The Thermal Conductivity Detector (TCD)

Overview
The Thermal Conductivity Detector (TCD) was used on most early GC instruments and
was developed from a traditional gas analyser. Its simplicity, robustness and ability to
monitor almost any analyte make it still popular today especially for the analysis of
inorganic compounds and permanent gases. The detector is a heated metal (usually
stainless steel) block drilled with two passageways or cavities. Each cavity contains a
filament made from a high temperature coefficient of resistance metal such as Rhenium or
Tungsten. These two filaments are heated and connected to the arms of a Wheatstone
Bridge as shown opposite. Pure carrier (or reference gas) is allowed to flow over one
filament (the reference cell) whilst the column effluent flows over the other (the analysis
cell).
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When an analyte elutes into the analytical cell the thermal conductivity of the gas
changes which causes a change in the rate of heat loss from the analytical filament. The
Wheatstone Bridge becomes unbalanced and current needs to be supplied in order to
restore the balance.
Whilst the gas flowing over the two filaments is equal the thermal conductivity will be
equal and the filaments will have the same rate of heat loss the Wheatsone bridge will be
balanced and the signal will be zero. If an analyte elutes with the carrier, the thermal
conductivity of the gas in the analysis cell changes, the rates of heat loss of the two
filaments will not be balanced and a current will have to be applied to balance the
Wheatstone bridge. It is this current which is recorded as the signal. The size of the
applied current will be related to the concentration of analyte in the effluent gas. The size
of the cell is critical in determining the sensitivity of the detector with 140 L being typical
in a detector used for packed column GC. These devices cannot be used with narrow
bore capillary columns and the cell volume must be drastically reduced. Several
manufacturers offer single cell devices of very low volume (~5L) for use with capillary
columns in which the reference and analysis streams are switched onto the single filament
in the order of 5-10Hz. Ultra-small detector devices etched onto silica wafers are also
available but are not used routinely.

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Thermal conductivity detector. In order to reduce volume single cell TCDs are used with
capillary columns this design has a cell volume of around 5L. The switching occurs
around to times/second

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Operating and Optimising

It is important that the filaments are held at a temperature ABOVE that of the body of the
detector so that the effects of filament temperature change are optimised.
The larger the heating current applied to the filament, the greater the temperature
differential and the greater the detector sensitivity. However, high filament temperatures
also mean shorter filament life and the potential that the filament will burn out if no gas is
flowing in the cell.
The detector is susceptible to changes in the detector body, the filament temperature (and
hence the current supplied), and the nature and flow of the carrier gas. Therefore, all of
these parameters should be kept as stable as possible. This usually means covering the
detector with a thermal cladding and ensuring that constant flow mode is used during
temperature programming analysis. These factors inhibit the inherent stability of the
detector.
The sensitivity of the detector very much depends upon the difference in thermal
conductivity between the eluting analyte and the carrier / reference gas. Interestingly this
precludes the use of Area Normalisation as a method of quantitation! Hydrogen and
helium have a much larger thermal conductivity value than most common analytes and as
such they are preferred as the carrier. The use of nitrogen or argon as the carrier
severely impairs the sensitivity of the detector.
Table 3. Thermal Conductivities and TCD Response Values for Selected Compounds.
Item
Compound
Thermal
Relative Molar
Conductivity
Response
Carrier gases
Argon
12.5
Carbon Dioxide
12.7
Helium
100
Hydrogen
128
Nitrogen
18
Samples
Ethane
17.5
51
n-Butane
13.5
85
n-Nonane
10.8
177
i-Butane
14.0
82
Cyclohexane
10.1
114
Benzene
9.9
100
Acetone
9.6
86
Ethanol
12.7
72
Chloroform
6.0
108
Methyl iodide
4.6
96
Ethyl Acetate
9.9
111
Thermal Conductivity values relative to Helium
Relative Molar Response in Helium: Standard
Benzene = 100

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Uses and Performance

The thermal conductivity detector is capable of detecting almost any species, as long as
their thermal conductivity is differentiated from that of the carrier gas used, therefore its
universality is excellent. By default, the selectivity of the detector is poor, however it is
possible to use an interfering species as the carrier to increase selectivity. An example is
the analysis of oxygen in argon, which are virtually impossible to separate
chromatographically. However by using argon as the carrier, the argon peak is eliminated
and the oxygen peak can be clearly seen in the chromatogram.
Sensitivity of the detector again depends upon the equipment set-up and the differential in
thermal conductivity between the analyte and the carrier gas. It is one of the few detectors
that can be used to detect the inorganic gases (such as H2O, CO, CO2, H2 etc.) and
therefore it is the detector of choice for permanent gases.
As the detector is non-destructive, it is often used in series with other detectors to detect
gaseous or highly volatile sample components. The use of the TCD alongside an FID for
the analysis of Transformer Oil Headspace gas is highlighted opposite.
The linearity of the detector is widest when the differential between the carrier and analyte
thermal conductivity is widest. The dynamic range can be extended by using micro or
nano cell devices or by employing low volume single cell instruments with stream
switching as described previously. Detector stability is reasonable but precautions should
be taken to avoid temperature drift or fluctuation and a consistent flow of carrier should be
established prior to analysis.
Thermal Conductivity Detector Characteristics

Minimum Detectability (LOD): ~ 10-9g (~10ppm)

Response: all compounds
Linearity: 104 (limited range)
Stability: moderate
Temperature Limit: ~ 400oC
Gases Carrier: (usually) Helium / Makeup: Same as carrier

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Fuel cell gas extract analysis

Where:
Conditions.
Carrier gas:
Helium
Inlet:
Purged packed 55oC
Sample loop:
0.1mL
TCD:
180oC

Oven
Initial temp:
50oC for 10min
Ramp:
to 120oC at 10oC/min

Permanent gas analysis (GS-Molosieve, 30m0.53mm I.D.)

Where:
1. Neon
2. Oxigen
3. Nitrogen
Conditions.
Carrier gas: Helium at 35
cm/sec (4.6mL/min)
Oven: 50oC isothermal

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4. Methane
5. Carbon monoxide

Injector:
Detector:
Makeup:

Split 1:10, 250L, 100oC

TCD 125oC
He at 10mL/min

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Inorganic gases (GS-GasPro, 30m0.32mm I.D.)

Where:
1.
2.
3.
4.

Nitrogen
CO2
SF6
COS

5. H2S
6. Ethylene oxide
7. SO2

Conditions.
Carrier gas:
Helium at 53 cm/sec
Oven:
25oC for 3 min
o
o
25-200 C (10 C/min) -200oC hold

Crawford Scientific

Injector: Split 1:50, 50L, 200oC

Detector:
TCD 250oC

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C1-C10 Hydrocarbons (GS-Q, 30m0.53mm I.D.)

Where:
1.
2.
3.
4.
5.
6.

Methane
Ethylene
Ethane
Propylene
Propane
Isobutane

Conditions.
Carrier gas:
Oven:

7. 1-Butene
8. n-Butane
9. cis-2-Butene
10. trans-2-Butene
11. Isopentane
12. n-Pentane
Helium at 8 mL/min
70oC for 3 min
70-180oC (20oC/min)
180oC hold for 3 min
180-230oC (5oC/min)
230oC hold for 10 min

Injector:
Detector:

13. n-Hexane
14. n-Heptane
15. n-Octane
16. n-Nonane
17. n-Decane

Split 1:50, 250oC

TCD 300oC

Other GC Detectors
Flame Photometric Detector (FPD)
Compounds are burned in a hydrogen-air flame very similar to an FID detector. Sulphur
and phosphorous containing compounds produce light emitting species (sulphur 394nm
/ phosphorous 526nm). A monochromatic filter allows only one of the wavelengths to
pass and a photomultiplier tube is used to measure the amount of incident light and a
signal is generated. A different filter is required for each detection mode.

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Flame photometric detector

Flame Photometric Detector Characteristics

Minimum Detectability (LOD): ~ 10-100pg (sulphur); 1-10pg (phosphorous)

Response: Sulphur or phosphorous containing compounds (one at a time)
Linearity: The response in the phosphorus mode is linear over four orders of
magnitude. The sulphur response, varies such that the square root of the
response is proportional to the concentration and is linear on a loglog scale over
three orders of magnitude.
Stability: moderate
Temperature Limit: ~ 300oC
Combustion gases: Hydrogen and Air. Makeup: Nitrogen

Photoionisation Detector (PID)

Compounds eluting into a cell are bombarded with high-energy photons emitted from a
lamp. Compounds with ionisation potentials below the photon energy are ionised. The
resulting ions are attracted to an electrode, measured and a signal is generated.

Photoionisation Detector
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Photoionisation Detector Characteristics

Minimum Detectability (LOD) ~ 25-50pg (aromatics); 50-200pg (olefins)

Response: Depends on lamp characteristics, conventionally used for aromatics
and olefins (10 eV lamp)
The response is linear over six or seven orders of magnitude.
Stability: good
Temperature Limit: ~ 200oC
Makeup gas: Same as carrier

Electrolytic Conductivity Detector (ELCD)

Compounds are mixed with a reaction gas and passed through a high temperature
reaction tube. Specific reaction products are created which mix with a solvent and pas
through an electrolytic conductivity cell. The change in the electrolytic conductivity of the
solvent is measured and a signal generated. Reaction tube temperature and solvent
determine the type of reactant detected.

Electrolytic Conductivity Detector

Electrochemical Conductivity Detector Characteristics

Minimum Detectability (LOD): ~ 5 - 10pg (halogens); 10-20pg (sulphur); 10-20pg

(nitrogen)
Response: Halogens, sulphur or nitrogen containing compounds (one at a time)
Linearity: Sulphur 103 - 104; Nitrogen 104 - 105; Halogens 105 - 106.
Stability: good
Temperature Limit: ~ 800 - 1000oC (halogens); 850 - 925oC (nitrogen); 750 - 825oC
(sulphur)
Gases: Hydrogen (halogens and nitrogen); air (sulphur)

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Mass Spectrometer (MS)

The detector is maintained under vacuum. Compounds eluting from the GC column are
bombarded with electrons (EI) or reagent gas ions (CI) in order to ionise them.
Compounds fragment into characteristic charged ions or fragments and the resulting
charged species are focussed and accelerated into a mass analysing device typically a
Quadrupole mass analyser or Ion Trap mass analyser. The mass analyser selectively
allows ions of a selected mass to charge ratio to pass through the analyser to the electron
multiplier where a signal due to that specific mass to charge ration ion is generated. The
mass filter can be adjusted to allow specified ions to pass (selected ion monitoring mode)
or to quickly scan over a range of mass to charge values (scanning mode). The
abundance (total ion count) versus time is plotted to form the chromatogram. A mass
spectrum can be obtained for each scan which plots the number of ions at each different
mass to charge ratio in the range selected.

Mass Spectrometer
Mass Spectrometer Characteristics

Minimum Detectability (LOD): ~ 1-10ng (SCAN); 1-10pg (SIM)

Response: Any compound that produces fragments (or ions) within the selected
mass range of the analysing device. May be an inclusive range of mass to charge
ratios (SCAN mode) or selected ions (Selected Ion Mode (SIM))
Linearity: 105 - 106 (good dynamic range)
Stability: good
Temperature Limit: ~ 250oC
Carrier gas: Helium

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