BASIC PRINCIPLES OF

ANALYZER

Presented By :
K.V.Divakar
Prakash Patil J

11 April 2008 BPA Training

 Flame ionization detector

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A flame ionization detector (FID) is a type of gas detector used in gas
chromatography
.

• Principle
• Application
• Operation
• Schematic
• Additional Considerations

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Principle

The Flame Ionization Detector (FID) is one of the many methods by which to analyze materials coming
off of gas chromatography column. Below is a chart of the typical types of Gas Chromatography
Detectors and their uses, taken from Principles of Instrumental Analysis (Skoog, 2007: 793).
Applicable Samples Typical Detection Limit
Type
Flame Ionization Hydrocarbons 1 pg/s

Thermal Conductivity Universal Detector 500 pg/mL

Electron Capture Halogenated Compounds 5 fg/s

Mass Spectrometer Tunable for any species 0.25 to 100 pg

(MS)
Thermionic Nitrogen & Phosphorus compounds 0.1 pg/s (P); 1 pg/s (N)

Electrolytic Compounds containing halogens, sulfur, or 0.5 pg Cl/s, 2 pg S/s, 4

Conductivity nitrogen pg N/s
Photoionization Compounds ionized by UV radiation 2 pg C/s

Fourier Transform IR Organic Compounds 0.2 to 40 ng

(FTIR)

The detection of organic compounds is most effectively done with flame ionization.

However, typically the biochemical compounds have a greater amount of carbon present than
other elements.

This means that a particular compound may be more easily detected using flame ionization over
the other methods because of higher carbon concentration and also flame ionizations sensitivity.
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Application

Ionization essentially can only detect components which can be burned.

Other components may be ionized by simply passing through the FIDs flame, but they tend not to create
enough signal to rise above the noise of the detector.This selectivity can be a problem or an advantage. For
example, an Ionization is excellent for detecting methane in nitrogen, since it would respond to the methane
but not to the nitrogen.

Ionization are best for detecting hydrocarbons, and other easily flammable components. They are very
sensitive to these components, and response tends to be linear across a wide range of concentrations.

 Ionization destroy most, if not all of the components they are detecting. For example, with a TCD the
components can continue on to another detector after passing through the TCD, as it is considered a non-
destructive detector. (This can be useful for analyzing complex mixtures where different detectors are
needed because of differing detector selectivities.)

However, with an Ionization, most components are destroyed and no further detection is possible.

For this reason, in multiple-detector situations, the Ionization is almost always the last detector.

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Operation

 As the name suggests, analysis involves the detection of ions.

 The source of these ions is a small hydrogen-air flame.

 Hydrogen-oxygen flames are used due to an ability to increase detection sensitivity, however for most
analysis, the use of compressed breathable air is sufficient. The resulting flame burns such a temperature as
to pyrolyze most organic compounds, producing positively charged ions and electrons.

 In order to detect these ions, two electrodynamics fields are used to provide a porridge soup base. The
positive elementary doubles as the nipple head where the flame is produced. The other, negative electrode is
positioned above the flame.

 When first designed, the negative electrode was either tear-drop shaped or angular piece of platinum.
Today, the design has been modified into a tubular electrode, commonly referred to as a collector plate. The
ions thus are attracted to the collector plate and upon hitting the plate, induce a current.

 This current is measured with a high-impedance Pico ammeter and fed into an integrator. How the final
data is displayed is based on the computer and software. In general, a graph is displayed that has time on
the x-axis and total ion on the y-axis.

 The current signal collected corresponds roughly to the proportion of reduced carbon atoms in the flame.
Specifically how the ions are produced is not necessarily understood, but the response of the detector is
determined by the number of carbon atoms (ions) hitting the detector per unit time.

 This makes the detector sensitive to the mass rather than the concentration, which is useful because the
response of the detector is not greatly affected by changes in the carrier gas flow rate.
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Schematic

The design of the Flame Ionization Detector varies from manufacturer but the principles are the same in
any case. Most commonly, the FID is attached to a Gas Chromatography system, so for the sake of
explanation, that is the starting point that this schematic will take.

FID Schematic

The effluent exits the GC column (A) and enters the FID detector’s oven (B).

The oven is needed to make sure that as soon as the effluent exits the column, it does not come out
of the gaseous phase and deposit on the interface between the column and FID. This deposition would
result in loss of effluent and errors in detection.

As the effluent travels up the FID, it first mixed with the hydrogen fuel (C) and then the oxidant (D).
The effluent/fuel/oxidant mixture continues to travel up to the nozzle head where a positive bias voltage
exists (E).

This positive bias helps to repel the reduced carbon ions created by the flame (F) pyrolyzing the
effluent.

The ions are repelled up toward the collector plates (G) which are connected to a very sensitive
ammeter, which detects the ions hitting the plates, then feeds that signal to an amplifier, integrator, and
display system.

The products of the flame are finally vented out of the detector through the exhaust port (J).
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 GC column (A)
FID detector’s oven (B)
Hydrogen Fuel (C)
oxidant (D)
Positive bias voltage (E)
Flame (F)
Collector plates (G)
Exhaust port (J)

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Additional Considerations

 However, one thing to note is that the FID is detecting oxidized carbon atoms in ion form. In organic
species that already have oxidized carbons via the presence of oxygen, a weaker signal is given when the
sample enters the detector because the oxidized carbons are not ionized as effectively as compared to
compounds solely of carbon and hydrogen.

 Functional groups such as carbonyl, alcohol, halogens, or amines are sources of these oxidized carbons,
sometimes causing few if any ions. This points out one of the main drawbacks of using an FID to detect
effluent as it comes off a gas chromatograph column.

 Another drawback is the sample is destroyed, making it nearly impossible to make determinations about
the structure or composition. It is for this reason, the FID is typically the final detector or stage in a series of
instruments.

 Some of the benefits of a flame ionization detector are quite useful. FIDs are insensitive to H2O, CO2,
SO2, CO, NOx, and noble gases because they are not able to be oxidized/ionized by the flame. This allows
samples to be studied even if contaminated or if some leakage of ambient room gases occurs at the time of
the injection.

 Additionally, it has the ability to determine when a sample will elute off the column with regards to the
solvents used. Some detectors can be damaged if an effluent too concentrated is analyzed, making it
necessary to turn it off to prevent damage.

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 NON Dispersive Infrared Analyzer

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 Designed for continuous measurement of heteroatomic gases (e.g., CO, CO2, SO2, NO, HC and
NH3), the NGA2000 Next Generation Analysis Non-Dispersive Infrared (NDIR) Analyzer Module delivers
unmatched measurement accuracy, reliability, ease-of-use, simplified maintenance, advanced
communication capability and enough flexibility to reach well into the next century.

 Key to the performance attributes is the highly sensitive Luft detector design. This methodology allows
for a wide range of measurements. From 10 ppm CO2 full-scale to 100% CO full-scale, the NDIR
Analyzer Module family gives you the versatility you need. (Please see configuration parameters for
standard NDIR components and ranges.

 The NGA 2000 Analyzer Module is the industry's first modular infrared analyzer. It is a self-contained
unit complete with detector and microprocessor-based electronics.

 The NGA Analyzer System's expandability allows for simple system integration. The NDIR Analyzer
Module can be part of a sophisticated network or a "stand alone“ analysis instrument when combined with
the NGA Platform and Input/Output (I/O) Modules.

 The NGA 2000 Series is unique because of its advanced communication network which allows
identification of and interaction with other modules in the analytical system.

 Because of this distinctive feature, the NDIR Analyzer Module may be either incorporated into a
panel/rack or placed near the sample source up to a mile away, thereby reducing sample handling
requirements.

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PRINCIPLE OF OPERATION
Inside the NDIR Analyzer Module, two equal-energy infrared beams are directed through
two parallel optical cells: a flow-through sample cell and a reference cell. The reference cell may be
sealed or may contain a continuously flowing reference gas.

NDIR PRINCIPLE OF OPERATION

 Analyzers sampling flammable gas must be protected by a continuous dilution purge system in
accordance with standard ANSI/NFPA 496-1993 chapter 6. Consult factory for recommendations.

 The infrared radiation is interrupted by a chopper at a frequency of 5 Hz. Depending on the

application, the radiation may then be optically filtered to reduce background interference from other
infrared-absorbing components.

 During analysis, a portion of the infrared radiation is absorbed by the component of interest in the
sample. The quantity infrared radiation that is absorbed is proportional to the component
concentration.

 The detector is a "gas microphone" based on the Luft principle. It converts the difference in
energy between sample and reference cells to a capacitance change. This change, which is related
to component concentration is processed and expressed as the primary variable on the network.

 Other modules within an NGA 2000 system may use this variable for a variety of purposes (e.g.
expressing the gas concentration on the Front Panel Display or sending it to external data
acquisition devices).
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 Chemiluminescence's Detector

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The Basics

Chemiluminescence literally means a chemical reaction that produces light.

When an NO (nitric oxide) molecule reacts with ozone, it is oxidized to NO2, in an excited state.

 A small fraction of the molecules in this excited state decay by emitting a photon (i.e. giving off light) in
the near infrared portion of the spectrum.

Thus, if one mixes a gas sample with ozone and measures the amount of light emitted, the concentration
of NOx in the sample may be determined. This technique provides an extraordinarily sensitive, selective,
and linear measurement of NOx, precisely why chemiluminescence has become the standard high-
performance NOx measurement technology.

Any NO2 (nitrogen dioxide, the other component of NOx) in the sample may be converted to NO for
measurement purposes, as discussed below.

11 April 2008 BPA Training

 NOx Measurement Principles

Chemiluminescence

The NO2 concentration is not measured directly in a chemiluminescence principle NOx

analyzer. 

Instead, NO2 levels are calculated by subtracting the NO concentration value from the NOx
concentration. 

Chemiluminescence NOx analyzers measure NO by routing the sample gas directly to

the reaction chamber where is combines with ozone (O3). 

In the reaction between NO and O3, NO2 is formed, some of which is in an excited (unstable)
state. The unstable NO2 molecule emits electromagnetic radiation which is measured as a light by a
photomultiplier tube.

NO + O3 --> NO2 +
O2NO + O3 --> NO2* + O2NO2* represents the excited state molecule.

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Only about 20% of the NO2 that is formed is in the excited state.  This NO2* reverts back to the
ground state while emitting electromagnetic radiation.

NO2* --> NO2 + hv

NO2* + M --> NO2 + M

hv represents the radiated emission, which is in the wavelength range between 600 - 3000 nm, with
intensity maximum at approximately 1200 nm.  This chemiluminescence's signal is detected photo-
electrically.  When O3 is present in excess the signal is proportional to the NO concentration of the
sample gas.

By far, the largest portion of the NO2* returns to the ground state without radiation emission, due to
collisions with other molecules (M).  In order to enhance the light yield the pressure in the reaction
chamber is reduced.  The probability that the NO2* molecule is deactivated by a collision with another
molecule (M) - thus emitting no light - increases proportionally with the reaction chamber pressure.

The collision between the NO2* molecule and another molecule (M) is usually referred to as
"quenching."  Quenching is an unwanted phenomenon and the extent to which it occurs depends on
the character of the colliding molecule (M).  For example, H2O and CO2 quench NO
chemiluminescence's more effectively than N2 and O2.

In order for NO2 to be measured, it first must be converted to NO.  To accomplish this reduction, the
sample gas is passed through a converter heated to a specific temperature (depending on the material
used in the converter).  The temperature of the converter is typically between 350°C and 650°C.  If the
converter contains e.g. carbon as the reducing agent, the following reaction takes place:
NO2 + C --> NO + CO
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 NOx: NO, NO2, and converters

In general, NOx exists as some mix of NO and NO2 together... with the relative fractions of these
species depending upon a number of factors

NO is the thermodynamically favored species at high temperatures, which is why it is the dominant
species of NOx in combustion exhausts. NO2 is the thermodynamically favored species at low
temperatures, making it the dominant species in ambient air.

But, the conversion between the species happens extremely slowly at room temperature...while most
chemical reactions occur in a small fraction of a second, this conversion takes up to a day under normal
atmospheric conditions.

Conversion of NO2 to NO, necessary to get an accurate reading of total NOx since only NO can be
detected, can be accomplished in a number of ways.

 At elevated temperatures, the reaction between NO and NO2 occurs very quickly, and if the
temperature is high enough essentially all NO2 in a sample can be converted to NO.

As the sample cools, the NOx is temporarily "frozen" as NO since the timescale for conversion back to
NO2 is so long. This is the basis for high temperature thermal conversion.

Other converters either try to exploit this basic technique, using catalysts for lower temperature
operation, or use a reducing agent that becomes oxidized by stripping one oxygen atom away from NO2
to convert it to NO.

While these strategies lower the required operating temperature of the converter, they introduce
catalytic or consumptive materials that are often poisoned, depleted, or reacted unpredictably.
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 SMOKEMETE
R

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 Smokemeter

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 Additional Photographs

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