Flame Photometric Detector

Analytical Laboratories Applications

GC with Flame Photometric Detector (GC-FPD)
Gas Chromatography Flame Photometric Detector or GC-FPD is a technique used
to analyse sulphur or phosphorous containing compounds and metals such as tin,
boron, arsenic and chromium. An FPD uses a Hydrogen/Air flame into which the
sample is passed. Phosphorous and sulphur containing hydrocarbons generate
chemiluminescene at specific wavelengths which when passed into a photomultiplier gives an electrical signal which can then be measured.
As common with other GC techniques, a carrier gas is required with low Water and
Oxygen impurities since Water and Oxygen can interact with the stationary phase
and cause significant problems such as high baseline noise and column bleed in the
output gas chromatogram which both reduces the analyser sensitivity and
decreases column lifetime. The FPD is extremely sensitive to Hydrocarbon
impurities in the Hydrogen and Air supply for the flame. Hydrocarbon impurities can
cause increased baseline noise and reduce the detector sensitivity.
A make-up gas can be used in GC-FPD at the exit of the column to increase the flow
rate into the detector. The routine calibration of the analyser using a
calibration mixture is common.
Our range of Experis ultra high purity gases and patented BIP technology offer
you the optimum gas for your GC-FPD requirements. Dont forget your choice of
cylinder equipment also affects your analytical results. Our range includes high
quality cylinder regulators, manifolds, valves and purge systems which will help to
optimise the smooth operation and accuracy of your analysis.
http://www.airproducts.com/industries/analytical-laboratories/analytical-labapplications/product-list/gc-with-flame-photometric-detector-gc-fpd-analyticallaboratories.aspx?itemId=5E12372B85BB4009A5425A215D56C92A

GC Solutions #11: The Flame Ionization

Detector
by Matthew Klee
In this article we initiate a discussion on the workhorse detector of gas chromatography:
the flame ionization detector.

The flame ionization detector (FID) is the premier detector in gas chromatography. It has unique
properties and performance that puts it above and beyond all other general-use detectors in gas
chromatography (or any other form of chromatography, for that matter).
Topping the list of unique attributes are (1) unit carbon response and (2) wide linear operating
range (up to 7 orders of magnitude). When combined with its other attributes of low cost, ease of use,
speed of response, and ruggedness, it is no wonder why the FID is the premier detector of choice for
GC.
The FID is a mass sensitive detector. That means that its response is proportional to the mass of
carbon that passes through it. In that regard, FID response is stated in terms of picograms carbon per
sec. Detection limits for FIDs are in the low pg C /sec.

Equation 1

Unit carbon response means that the FID responds linearly to the mass of carbon flowing through it,
independent of compound structure. The FID gives unit response for most hydrocarbons within a
couple per cent error. Exceptions to this will be discussed next month. This attribute of unit carbon
response allows one to quantify mixtures without having calibration standards for every component.
Amounts of components in a sample relate to their relative peak areas. So, a simple area per cent
report will fairly closely reflect the mass per cent of each component in a mixture. This is extremely
useful when analysing complex samples such as those in the petroleum industry wherein samples can
contain well over 1000 components. In the same vein, the relative ratio of the area of one peak to
another (e.g., the peak of an unknown component relative to a calibrated reference peak) closely
reflects its relative amount in the sample. This is useful when estimating concentration levels of
components in a sample when identities are unknown or when standards are not available for
calibration.

Figure 1: H2 (and sometimes N2 makeup gas) enter the bottom of the FID jet and mix with column effluent prior to
exiting. Air is added above the jet and flame is established.

The FID was first described by two independent groups at approximately the same time [1,2]. FIDs
were commercially available soon thereafter (the early 1960s.) Most of the developments since the
original functional designs have been primarily in areas of usability, adaptation for capillary instead of
packed columns, and in improvements of associated electronics, and signal processing.
The Flame
In a hydrogen flame, hydrogen gas (H2) reacts exothermically with the oxygen (O 2) to form water. A
hydrogen/air flame temperature burns at 2210 C.*
2H2 + O2 4H + 2O 2H2O + heat
In the above reaction, one part oxygen reacts with two parts hydrogen. This ratio (1:2) is called the
stoichiometric ratio. Because air is approximately 20% oxygen (O 2), a stoichiometric mixture would
require an air/hydrogen gas flow ratio of 2:5; 2.5 times more air than hydrogen. Although
stoichiometric ratios of oxygen to hydrogen can provide a reasonable dynamic range for the FID,
experience has shown (in part because of the complex combustion processes described below) that an
excess flow of air is required to ensure complete combustion, unit carbon response and the widest
linear dynamic range. In addition, higher than stoichiometric air flow helps to avoid carbon deposits
from forming in the jet when high concentrations of analyte or solvent pass through.
A ratio of at least 6:1 of air to hydrogen has empirically been found necessary to achieve the widest
dynamic range possible with FID. Many manufacturers recommend ratios of 10:1 or more
air/hydrogen flows. The higher the sample load to the FID, the more flame gases are required to
prevent blowout and carbon formation. That is why gas flows used with packed columns (higher
sample loads) generally need to be higher than when capillary columns are used. Exact flow rates are

somewhat instrument specific and also relate a bit to carrier gas flow rates, so following manufacturer
recommendations is wise.

Figure 2: Sample components are combusted in the fl ame, creating positive ions and electrons. The positive ions are
attracted to the negatively-biased collector while the (negatively charged) electrons are repelled toward the jet.

Sample Combustion and Signal Generation

A very nice explanation of FID flame chemistry has been provided by Holm [3]. Therein he supports a
mechanism whereby most organic compounds are reduced to saturated counterparts in the initial
portion of the flame, where temperatures are lower. As they continue up the flame, these saturated
counterparts then continue to react with hydrogen atoms to form methane, as illustrated in Equation
1.
Still further in the flame, methane is combusted to form formylium ion CHO+, the primary FID
signal-producing ion.

CH4 H2 + :CH

CHO* CHO+ + e-

Other reactions can of course occur, including ones that form other positive ions such as hydronium
ion.

CHO+ + H2O H3O+ + CO

All positive ions are collected by a negatively biased collector causing a current to flow, which is then
electronically amplified and digitized (Figure 1). The current is proportional to the number of ions
collected. The yield of ions from carbon passing through the detector is on the order of one ion per
106 carbon atoms [4], yet this is still enough for the FID to give picogram-level detection. Electrons in
the flame flow in the opposite direction and are grounded out on the FID jet (Figure 2). By biasing the
collector high enough relative to the jet (e.g., -200 V), recombination of positively charged ions and
electrons is minimized, and signal maximized.

References
1. J. Harley, W. Nel and V. Pretorious, Nature, London, 181(1958)177.
2. I. G. McWilliams and R. A. Dewer, Gas Chromatography 1958, (Ed. D. H.Desty), Butterworths
Scientific Publications (1957) 142
3. T. Holm, J. Chrom. A, 842 (1999) 221227
4. D.K. Bohme, in: P.J. Ausloss (Ed.), Kinetics of IonMolecule Reactions, Plenum Press, New York,
1979
Dr Matthew S. Klee is internationally recognized for contributions to the theory and practice of gas
chromatography. His experience in chemical, pharmaceutical and instrument companies spans over 30
years. During this time, Dr Klees work has focused on elucidation and practical demonstration of the
many processes involved with GC analysis, with the ultimate goal of improving the ease of use of GC
systems, ruggedness of methods and overall quality of results.

http://www.sepscience.com/Techniques/GC/Articles/208-/GC-Solutions-11-The-FlameIonization-Detector