Gas Analysis For Instrumentation

Gas Analysis
14 - 1
GAS ANALYSIS
How beautiful is night!

A dewy freshness fills the silent air
No mist obscures, nor cloud, nor
speck, nor stain,
Breaks the serene of heaven
- Thalaba the Destroyer Robert Southey
Course 9050 - October 1996
Principles of Instrumentation and Control
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Gas Analysis
Synopsis
The aims of gas analysis and its units of measurement precede a discussion on the
general principles of spectroscopy ie. energy bands, transmittance, absorbance,
absorptivity.
We consider NDIR absorption type analysers, their applicability, operating principles
and error sources; particularly in relation to NDIR and UV (SO2 Etalon). We further
consider thermal conductivity cells, typical gas conductivities and associated Bridge
Circuits.
The survey also includes flame ionisation dectectors - applications and error sources and the principles of chemiluminescence relevant to NOx analysis.
Methods of measuring oxygen are reviewed including:
- an overview of the Zirconia sensor with brief reference to the Nernst equation.
- electrolytic analysis involving polarographic and P2O5 trace moisture technologies.
- paramagnetism; its definition and measurement principles.
We finish with the elements of sampling systems and fundamentals of flow plan design.
Gas Analysis
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Introduction
The analysis of a gas is aimed at determining the concentration, symbol [ ], of that gas in a sample
mixture.
The mixture may be a liquid or gas. A gas is said to be dissolved if it exists in the gas phase within
a liquid mixture.
Units
The most used units concentration are:
- % by weight
weight gas
x 100%
weight sample
1
- mole %
no. of moles gas x 100%

no. of moles sample
1
- parts per million (ppm)
Ratio by weight (or volume) of gas: sample

= 1: 106
e.g.
no. of mg. substance: no. of kg sample

no. of ml substance: kilolitres sample
no. of cm 3 substance: m3 sample
- parts per billion (ppb)
Ratio by weight or volume of gas: sample

= 1: 109
e.g.
no. of g substance: no. of kg sample

no. of mm 3 substance: m3 sample
The detection and determination of precise concentration of gases is vitally important in many
industries. The following provides an overview of techniques used for analysis.
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Gas Analysis
Table. 14.1
Gas Analysis
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Table 14.2
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Gas Analysis
Spectroscopy
Matter is composed of atoms which can be simplified to the simple planetary model below:
Fig. 14.1
Atoms may absorb energy such that the electron jumps temporarily from E1 E2. This climbing
the rungs of a ladder results in an excited state. Energies are absorbed in the Ultraviolet/Visible
spectrum. The electrons will eventually return to their normal rung and radiate electromagnetic
radiation in the Ultra-Violet / Visible spectrum.
The atom may exist in combination (bonded) with other atoms to form a molecule. These molecules
can both vibrate and rotate at fixed energies. When the vibrations/rotations change to other fixed
values, energy may again be absorbed or radiated in the infrared spectrum.
The overall consideration is that an atom alone, or in combination, absorbs/radiates a band of UV/
visible/infrared radiations which are discrete and unique to the substance.
This uniqueness allows us to finger print a substance by looking at its absorbed emitted frequencies.
Each component of the fingerprint, corresponding to a distinctive energy value, is carried by a
photon. It is a bundle of energy of size E.
hc
E =
lambda ()
h = Plancks Constant
c = speed of light
() lambda = wavelength of emitted/absorbed radiation
Diagrammatically, the situation can be imagined as a subtraction and/or a regurgitation process.
Gas Analysis
14 - 7
Fig. 14.2
Principles of Quantitive Measurement in Absorption Spectroscopy

Consider a molecule which will absorb a photon of energy E1, and a spectrophotometer which will
provide 100 photons of energy E 1. If the molecule absorbs 1 photon, the 99 photons will reach the
detection system of the instrument. In other words, 99% of the photons will be transmitted through
the sample containing the absorbing molecule.
Fig. 14.3
The term Transmittance is used to describe the ratio of the intensity of photon energy transmitted
by the sample to the intensity incident upon it.
Transmittance
Intensity Transmitted Radiation (I)
Intensity Incident Radiation (Io)
In the example above, intensity refers to the no. of photons having a given energy.
Quantitative analysis is based on the fact that the transmitted intensity, I, decreases as the number of
absorbing molecules increases.
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Gas Analysis
As an example, consider a sample which absorbs half of the incident intensity. We would thus state
that the sample is 50% transmitting. In addition, let us assume the sample had a concentration of 50
grams per litre. On this basis, refer to Diagram and note the effect of passing 100 units of intensity
through a series of samples.
T =
50 =
100
.5
25 =
50
.5 12.5 = .5 6.25 = .5 3.125

25
12.5
6.25
.5
Fig. 14.4
c = concentration
b = path length, distance traveled through the solution
Fig. 14.5
As you will note, we could now make a transmittance measurement and immediately determine the
path length of sample which the radiation transversed. As an example, if b were 10 cm and we
had obtained a transmittance reading of 0.0625, we could determine that the path length traversed
was 4b which is 40 cm.
If path length remains constant but concentration of the sample is doubled progressively. The plot
looks the same as the above.
To simplify the relationship between the intensity of radiation absorbed and the path length
concentration variable, the term absorbance was defined. It is equal to the negative logarithm of
Transmittance.
Gas Analysis
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Absorbance = A = -log T (Beer-Lambert Law)

A = abc where
A = absorbance
a = absorptivity
b = path length
c = concentration
Alternatively
I = I o K e -abc
The term absorptivity can be considered a
proportionality constant relating A to bc. It can also be
considered the probability of absorption occurring at a
given wavelength.
The important point in this discussion is that Beers Law
allows a chemist to determine the concentration of a known
compound in a sample. This is accomplished by
measuring the absorbance of standard samples having
known concentrations and plotting some sort of a working
curve (not necessarily linear).
Fig. 14.6
By then, measuring the absorbance of the unknown sample under identical instrumental conditions,
its concentration immediately be determined from the working curve. As an example, if the unknown
had an absorbance of 0.4, then its concentration would be 2.75 concentration units.
Absorption doesnt have a linear relationship to concentration. A more typical graph is
(Fig. 14.7).
shown
Fig. 14.7
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Gas Analysis
If the absorption of electronic energy is to be utilised as a discriminating property for the identification
of the presence of one or more molecules, then the wavelength selected for seeing the presence of a
specific molecule must be one where no other molecules absorb energy. Sometimes the presence of
other absorbing molecules (interferences) can be ruled out because of the chemical composition of
the sample. For most samples, however, it is not sufficient to rely upon this information, and
instead, one must select wavelengths of unique absorption. By utilising the ultraviolet, visible, and
infrared spectral regions, and by using high resolution optical techniques (wherein two nearby
absorption features can be separated - resolved), it is almost always possible to locate a wavelength
where the molecule of interest can be quantitatively measured in the presence of unknown other
species, without interference.
Absorption spectroscopy is a standard analytical technique utilised for a chemical species
identification because of its ability to provide a specific identification for many different species, as
well as being relatively simple and well developed.
Non-Dispersive Infrared (NDIR) Absorption Spectroscopy

Infra-red Absorption corresponds to molecules vibration and rotational energy. These fixed, discrete
energies are unique to a particular substance.
Gases can be categorised in three groups with respect to infrared absorption:
1.
Diatomic gases (N 2, O2, H 2, C12) - do not absorb infrared; thus cannot be measured by
NDIR.
2.
Monoatomic gases (He, Ne, Ar, Kr, etc.) - do not absorb infrared energy; thus cannot be
measured by NDIR.
3.
Heteroatomic gases - these are molecules consisting of two or more different atoms. Most
heteroatomic molecules absorb infrared energy and can be measured by NDIR.
Commonly measured heteroatomic gases: CO, CO2, SO2, CH4, NH3, N-Hexane (Benzene), NO.
Fig. 14.8
Gas Analysis
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Basic Absorption Analyser
Fig. 14.9
Molecules absorb energy at wavelengths determined by their molecular structure.
Optical Filter transmits a narrow wavelength of energy received at component of interest wavelength.
Detector measures amount of energy received at component of interest wavelength.
Length of Sample Cell

The analyser in affect counts the number of absorbing molecules in the measuring path. Any factor
affecting this number, independent of concentration will also affect the sensitivity proportionally.
Thus, the sensitivity can be controlled through the selection of the length of the measuring cell and
the pressure of the sample cell.
Scaling
Using the following simple procedure, the percent absorption for a certain gas mixture can be
determined:
1.
With the sample beam blocked by an opaque shutter, the amplifier gain pot is adjusted to read
full scale on the meter.
2.
Next, the opaque shutter is removed and, with nitrogen in the sample cell, the amplifier meter
reads zero.
3.
With the same amplifier gain setting as in Step 1., the gas mixture of interest is purged through
the sample cell and the meter deflection is observed.
4.
The observed percent of full scale meter deflection is the percent modulation or attenuation.
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Gas Analysis
Principle of Operation of the Luft Detector System

Inside the NDIRAnalyzer 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 continuously flowing reference gas.
The infrared radiation is interrupted by a chopper at a frequency of 5Hz. Depending on the application,
the radiation may then be optically filtered to reduce background interference from other infraredabsorbing 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.
Fig. 14.10
Gas Analysis
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Luft Detector System with gas filter
Fig. 14.11
The gas filter is filled with interfering gas, often at high pressure. Energy at interfering gas wavelength
is absorbed before reaching the detector. It reduces interference, caused by changing concentration
in sample cell. This works because response is non-linear with concentration of interfering gas and
response changes become progressively less with increasing concentration of interfering gas.
Fig. 14.12
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Gas Analysis
Principle of Operation of a SO2 Etalon Analyser

Sulphur dioxide (SO2) gas absorption consists of a periodic series of absorption lines within the
295nm to 305nm region of the ultraviolet spectrum. These lines (1) indicate where ultraviolet light
is being absorbed. The flat areas between the lines (2) indicate where ultraviolet light is not being
absorbed. No two gases have the same pattern of periodic absorption lines.
In the Etalon Analyzer, ultra violet light from a light source is collimated with a lens and then
passes through a sample cell which contains SO2. The electro-optic Etalon assembly which consists
of polarizers, an Etalon crystal, a phase modulator, a U.V. filter, and a detector, processes and
detects the ultra violet light after it passes through the sample cell.
The Etalon crystal is constructed to match the periodic absorption line spacing of SO2. When the
ultra violet light passes through the sample cell and the Etalon crystal, the detector senses the signal
intensity of SO2 absorption. However, reference is needed to accurately determine the intensity of
the SO2 signal. This reference is provided by using the phase modulator to create a phase shift. This
phase shift moves the Etalon transmission off the SO2 absorption lines to the flat areas between the
SO2 absorption lines. As a result, when voltage is applied to the phase modulator, the detector
senses the signal intensity without SO2 absorption. The difference between these two readings is
used to determine the actual SO2 concentration.
Fig. 14.13
Fig. 14.14
Gas Analysis
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Fig. 14.15
Fig. 14.16
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Gas Analysis
Thermal Conductivity
Consider two differing gases in equal cylindrical enclosures. If a heating element is inserted, the
rate of thermal conduction between element and container wall will be inversely proportional to the
density of the gas. This effect is somewhat independent of gas pressure.
Fig. 14.17
As the absolute temperature increases, the lighter molecules (say) move even more quickly. This
thermal conductivity also depends upon the temperature too.
Kt = K o
b + 273
b+T
(T)3/2
(273)
Kt = Thermal Conductivity at absolute temperature T.

Ko = Thermal Conductivity at Reference Temperature
b = Constant for the substance.
If air has a Kt of 1.00, then the relative conductivities of some
gases are shown (Table 14.1).
Application to Gas Analysis

In gas analysis, the conductivities of pure gases are of limited value.
It is more important to know how the conductivity of a mixture
varies with the proportion of constituent gases. Unfortunately, the
relationship between the conductivity of a mixture of gases and
the proportion of the constituents is complicated. When collisions
occur between molecules of different gases the mathematics of
the collisions are no longer simple, an the relationship between
the conductivity of the gas mixture and the proportions of the
constituents depends upon the molecular and physical constants
of the gases and the law of force between molecules during
Gas
Kt
Hydrogen
7.00
Nitrogen
1.00
Oxygen
1.01
Chlorine
0.32
CO
0.96
CO2
0.59
SO2
0.34
Table 14.3
Gas Analysis
14 - 17
collision. For the purpose of calibrating thermal conductivity instruments it is therefore necessary
to establish the required composition - conductivity curves experimentally.
Concentrations of Hydrogen, Helium and Argon can be determined practically by this method.
Thermal Conductivity Cell and Associated Bridge Adjustments

Within the thermal conductivity cell are four resistive filaments, suspended in individual cavities in
a metal block and connected electrically as legs of a Wheatstone bridge. Although physically the
cell block is one piece, functionally it may be considered to have two sides, as shown.
Fig. 14.18
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Gas Analysis
Fig. 14.19
1.
Sample Side. Here two filaments that constitute opposite legs of the bridge are positioned in
an interconnected passage that receives a continuous flow of the sample gas.
2.
Reference Side. Here the remaining two filaments, which also constitute opposite legs of the
bridge, are positioned in an interconnected passage filled with the reference gas. Depending
on the applications, the reference gas may flow continuously through the passage, or may be
sealed within it.
Principles of Measurement
a.
The temperature of the elements is proportional to the resistance. Thus the Wheatstone Bridge
indirectly measures the temperature of the elements.
b.
The current heating the two cells is also used to trim the bridge balance.
c.
If the two cells are filled with the same gas, the temperatures (resistances) of the wires remain
the same; the bridge is automatically balanced and fine trimming can be made.
d.
The introduction of a higher thermally conductive gas into the sample will decrease the wires
temperature in that cell. Resistance drops and the bridge is still automatically balanced but a
different current flows in the arms of the bridge. This change in current corresponds to the
change in conductivity.
Gas Analysis
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Chemiluminescence
Since air contains a high level of nitrogen, and the nitrogen goes through the flame where temperatures
can reach 1800C or even more, some of the nitrogen in the air reacts with the oxygen in the air to
form nitric oxide, NO. In addition, any nitrogen in the fuel (primarily coal or oil) will be converted
to NO in the combustion zone. Under high excess air levels, the NO will be partially oxidised to
form NO2. Also, the NO emitted from the stack is oxidised in the atmosphere over time to NO2.
The sum of NO and NO2 is called NOx.
The primary control over NO formation is the control of flame temperature, in fact NO formation
increases with temperature to the fourth power. Flame temperature can be lowered by reducing
excess air. As an example, for gaseous fuels, a decrease in excess O2 from 3.0 - 0.5% can result in
a 15 - 20% decrease in NO formation. The most widely accepted control strategy for NOx is to
create an oxidisation reduction reaction with ammonia, to form nitrogen and water.
Principle of Operation
The chemiluminescent method is based upon the principle that nitric oxide (NO) reacts with ozone
(O3) to give nitrogen dioxide (NO2), oxygen (O2), and about 10 percent electronically excited NO2.
The transition of electronically excited NO2 to its normal state NO2 gives a light emission (HLAMBDA)
between 590-2750 nm, i.e.:
NO + O 3 NO2 + O2 + HLAMBDA
The intensity of this emission is proportional to the mass flow rate of NO into the reaction chamber.
The light emission is measured by means of a photomultiplier tube and associated electronics.
O3 for the reaction is generated by passing cylinder air or oxygen over an ultraviolet light source.
As O3 and NO mix, the chemiluminescent reaction produces a light emission which is proportional
to NO concentration and is measured by the photomultiplier tube.
NOx analysis (NO + NO2) is obtained by dissociating the NO2 to NO and then proceeding with the
reaction, i.e.:
catalyst
NO2 NO + O
NO + O 3 NO2 + O2 + HLAMBDA
Fig. 14.20
This technique has a width dynamic range (10,000 : 1) and is simple, reproducible and sensitive.
Its applications include heavy duty engine, turbine and stationary (stacks) source situations.
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Gas Analysis
Flame Ionisation Detection (FID)

Principle of Operation
The flame ionisation detection (FID) method is employed to determine the concentration of
hydrocarbons present in a gaseous sample. Hydrogen burned in air produces a flame containing a
negligible number of ions; introduction of a hydrocarbon sample into the flame results in a complex
ionisation, creating a large number or ions. A polarising voltage applied between the burner jet and
collector produces an electrostatic field that results in ion migration. Positive ions are attracted to
the collector and negative ions to the burner jet, establishing an ionisation current between the two
points. This current is directly proportional to the hydrocarbon concentration in the flame.
The sample is admitted to the burner at a precise flow, determined by the sample pressure regulator,
which provides a controlled back pressure at the sample capillary. Bypass flow rates may be adjusted
to control system response. Fuel and air flow rates to the burner are determined by regulating the
gas pressures against controlled porosity restrictors.
Fig. 4.21
Applications
*
Ideal for bag, continuous dilution or raw exhaust vehicle emissions applications
Detects trace levels of hydrocarbon contaminants in purity gases used in the semiconductor
industry
Monitors hydrocarbon contaminants in ambient air and other gases
Monitors engine combustion efficiency
Cryogenics/liquefaction
Gas Analysis
14 - 21
Oxygen Synergism
In applications of hydrogen flame ionisation analysers, the synergistic effect of oxygen-bearing
samples on analyser response is an anomaly which must be dealt with.
In a literal sense, synergism is the cooperative action of the discrete agencies, such that the total
effect is greater than the sum of the two effects taken independently. The parts add up to more than
the whole.
In most cases, the response of the FID to samples containing varying amounts of oxygen is similar
to this effect, but in reverse. Total response is usually less than expected, except for certain isolated
compounds. Perhaps the name oxygen reverse-synergism would more accurately describe the
effect, but the term oxygen-synergism is in common usage.
The oxygen we are talking about here is internal oxygen, already mixed in the sample prior to
entry into the analyser. It has nothing to do with the oxygen content of the combustion air, or
external oxygen.
Mixed 40/60 fuel, with either N2 or He as the 60% diluent, considerably reduces the magnitude of
oxygen synergism in FID response.
Electrolytic Analysis
a.
Polarographic Analysis
Electrolysis current is proportional to the concentration of electrolysis material. Only a small
fraction of the sample material is electrolysed and the current generated is limited by the rate
of chemical diffusion through an electrolytic gel.
Typically one of the two electrodes is a noble metal: the other, a base metal which is slowly
consumed.
This technique can successfully detect O2 is gaseous samples or dissolved in aqueous, a nonaqueous solution.
Applications
i.
Typical gaseous oxygen measurements include:

Food - to monitor residual oxygen in food packaging processes, storage atmospheres,
and to monitor inert blanketing gas over vats and other process vessels.
Automotive Exhaust - to evaluate engine performance.
Safety - to monitor for the absence or presence of oxygen in hazardous environments.
General Process Use - to monitor the oxygen level during catalyst regeneration and to
monitor oxygen content of feed, product, and intermediate process streams.
ii.
Typical dissolved oxygen measurements include:

Food and Beverage - to protect against changes in colour, flavour, or odour of edibles.
Water Treatment - portable use for random checking of aerobic waste reduction
efficiency; to maintain prescribed dissolved oxygen levels in effluents.
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b.
Gas Analysis
Trace Moisture
The water vapour in the flowing gas stream is absorbed into either a film of concentrated
phosphoric acid, or a layer of phosphorous pentoxide (P2O5) which coats two electrodes.
The moisture renders the film or oxide conductive allowing current to flow which is proportional
to the concentration of water.
Electronics
*
Transistor manufacturing - monitoring nitrogen, helium, or argon for H2O content
Relay manufacturing - monitoring dry fill gas from cylinders
Petroleum
*
Natural Gas transportation - monitoring natural gas for water content
Petrochemical
*
Air-purged process instrumentation - monitoring instrument air for H2O content
Chemical
*
Oxygen manufacturing and bottling for aircraft and space pilots - monitoring oxygen
for water content
Dry ice (CO 2) manufacturing - monitoring water content in CO2
Metals
*
Heat treating, carburising and polishing - monitoring the H2O content of the feed gas or
furnace atmosphere
Welding titanium, stainless and other alloys - monitoring water contact of argon and
helium
Missiles
*
Loading missile pressure tanks - monitoring feed gas for H2O content
Refrigeration
*
Manufacturing refrigeration equipment - monitoring water in refrigerants
Lamp Manufacturing
*
Lamp bulb assembly - monitoring inert gas (e.g. nitrogen, argon) used to fill bulb
Gas Analysis
14 - 23
Oxygen Measurement
Paragmagnetism
The strength of a magnet is measured in terms of its magnetic moment which is the product of the
pole strength of the magnet and the distance between the poles.
When a material; such as a piece of soft iron, is placed in a magnetic field it becomes magnetised by
induction, and the magnetic moment of the material divided by its volume is known as its intensity
of magnetisation. The ratio of the intensity of magnetisation of the material to the intensity of the
magnetising field is called the volume susceptibility (k) of the material.
All materials show some magnetic effect when placed in a magnetic field, but apart from substances
such as iron, nickel, cobalt and certain alloys such as steel, known as ferromagnetics, the effect
shown is very small. Intense magnetic fields are required to make it measurable.
Substances which are magnetised in the direction of the applied field (thus having positive values
of k) are called paramagnetics. There are relatively few paramagnetic materials, the most important
being oxygen, oxides of nitrogen, the metals from titanium to nickel, platinum and palladium.
A ferro- or paramagnetic substance when placed in a vacuum or a less paramagnetic medium always
tends to move from the weaker to the stronger parts of the magnetic field. Thus when a rod of such
substance is suspended between the poles of an electromagnet it will set with its length along the
direction of the magnetic field.
Experiments show that for paramagnetic substances the susceptibility is independent of the strength
of the magnetising field but decreases with increase of temperature according to the Curie-Weiss
Law
Atomic susceptibility =
Atomic weight
x Volume susceptibility
Density
C
T-
where T is the absolute temperature and C and are constants.

The susceptibilities of ferromagnetic materials vary with the strength of the magnetising field and
above a certain temperature, called the Curie Temperature (1,000 for iron), ferromagnetics become
ordinary paramagnetics obeying the Curie-Weiss law.
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Gas Analysis
Fig. 14.22
Gas Analysis
14 - 25
Measurement Principles
As shown, oxygen is strongly paramagnetic. The paramagnetism of oxygen may be regarded as the
capability of an oxygen molecule to become a temporary magnet when placed in a magnetic field,
analogous to the magnetisation of a piece of soft iron.
The volume magnetic susceptibility of the flowing gas sample is sensed in the detector/magnet
assembly. As shown in the functional diagram, a dumbbell-shaped nitrogen-filled hollow glass test
body is suspended on a platinum/nickel alloy ribbon in a non-uniform magnetic field.
Fig. 14.23
If the gas being measured is more paramagnetic than the test body, the measured gas lines up
preferentially along the test body, the measured gas lines up preferentially along the lines of force
and displaces / expels the test body from the field. This results in a displacement torque that is
proportional to the volume magnetic susceptibility of the gas surrounding the test body.
Since the magnetic susceptibilities of most gases are very small, whilst oxygens is large, the
susceptibility of the gas surrounding the dumb-bell will depend almost entirely upon the percentage
of O2 present.
Measurement is accomplished by a null-balance system, where the displacement torque is opposed
by an equal, but opposite, restorative torque. The restorative torque is due to electromagnetic forces
14 - 26
Gas Analysis
on the spheres, resulting from a feedback current routed through a titanium wire conductor wound
lengthwise around the dumbbell. In effect, each sphere is wound with a one-turn circular loop. The
current required to restore the test body to null position is directly proportional to the original
displacement torque, and is thus a linear function of the volume magnetic susceptibility of the
sample gas.
The restoring current is automatically maintained at the correct level by an electro-optical feedback
system. A beam of light from the source lamp is reflected off the square mirror attached to the test
body, and onto the dual photo-cell. The output current from this combination is equal to the difference
between the signals developed by the two halves of the photocell. The difference, which constitutes
the error signal, is applied to the input of an amplifier circuit that provides the restoring current.
Additionally, the output from the amplifier is conditioned as required to drive the display, and
recorder if used.
Measurement accuracies can be as high as .01% of measurement.
Zirconium Oxide Measurement of Oxygen

History
Early oxygen systems consisted of paramagnetic analysers using sampling systems. Although
there have been thousands of flue gas sampling systems installed worldwide, all have required high
maintenance, although there are now some new dilution air systems available for measurement of
gases other than oxygen. In 1970 Westinghouse made a breakthrough using zirconia technology to
build an in-situ oxygen probe, designed to be inserted directly into flue gas streams. This immediately
overcame the problems of sampling systems and gradually all large users replaced their paramagnetic
analysers and sampling systems with the new technology. Today there are more than 100
manufacturers of oxygen probes and analysers worldwide.
The Zirconia Oxygen Sensor
Fig. 14.24
Gas Analysis
14 - 27
An oxygen probe contains a solid electrolyte zirconia sensor and a thermocouple. The sensor is an
oxygen ion-conducting solid electrolyte.
The heater is controlled to approximately 720C, however probes operating in a combustion
environment above 700C do not require a heater.
The equipment measures oxygen percentage by reading the voltage developed across a heated
electrochemical cell which consists of a small YTTRIA-Stabilised Zirconia disc. Both sides of the
disc are coated with porous metal electrodes.
When operated at the proper temperature (maintained by electronic temperature control), the millivolt
output Voltage of the cell is given by the following Nernst Equation:
EMF = KTlog10 (P1/P2) + C
Where:
P2
is the partial pressure of the oxygen in the measured gas on one side of the cell.
P1
is the partial pressure of the oxygen in the reference gas on the other side.
is the absolute temperature (>650C)
is the Cell Constant
is an Arithmetic Constant
When the cell is at operating temperature and there are unequal oxygen concentrations across the
cell, oxygen ions will travel from the
high partial pressure of Oxygen side
to the low partial pressure side of the
cell. The resulting logarithmic output
voltage is approximately 50mV per
decade. Because the magnitude of the
output is proportional to the logarithm
of the inverse of the sample oxygen
partial pressure, the output signal
increases as the oxygen concentration
of the sample decreases. This
characteristic enables the Oxygen
Analyser to provide exceptional
sensitivity at low oxygen
concentrations.
Aspects of Zirconia Sensors
The most difficult aspect with zirconia
oxygen sensors is that they are often
exposed to flue gas streams which are
hostile. They often contain corrosives
such as sulphur, and particulates such
as fly ash. One good aspect of zirconia
oxygen sensors is that they are an
absolute device. Unless they have
poisoned electrodes which is unusual,
Fig. 14.25
14 - 28
Gas Analysis
absolute device. Unless they have poisoned electrodes which is unusual, they will produce a very
precise e.m.f. even after many years of operation. Their calibration will be either very accurate, or
if the sensor has lost it electrode material, the output will contain a large error. This enables a
simple automatic calibration of the analyser electronics.
Applications of O2 Measurement
a.
Combustion Control
Fig. 14.26
On very large installations, such as power stations, the correct oxygen level in the flue gas is
normally determined from mass balance measurements. When operating at optimum efficiency
it is unusual for a power station to be generating any CO.
When the oxygen measurement system is used for closed loop control, limits must be set so
that it cannot produce dangerous, fuel-rich conditions during system malfunction. On small
installations this is achieved with mechanical limits on the burner linkages. On larger
installations it is normally electronically limited. The oxygen signal is used as a trim signal
with high and low alarms. Apart from savings in fuel costs, oxygen monitors and trim systems
provide an early warning device for impending combustion problems.
b.
Metal heat treatment or carburising control where oxygen levels are measured at 10-23 to
calculate the free carbon potential of the atmosphere.
c.
An instrument which measures high temperature relative humidity is also produced. Relative
humidity is calculated by measuring the amount of oxygen displaced by water vapour in a
dryer atmosphere.
d.
Another product is a parts per million analyser for food package leak testing and gas purity
testing for gas manufacturers.
e.
Oxygen is measured in oxygen enrichment systems for foundry and other industries.
Gas Analysis
14 - 29
Sampling Systems
Most gas analysers will not operate from a gas sample taken directly from the plant source. Typically
analysers require the sample gas to have a flow of 0.5 to 2.0 l/min at 7 to 15 psig and at ambient
tmperature . It is also important that particle size is kept below typically 2 microns. Thus a sampling
system needs to be incorporated into the plant for efficient operation of the analyser.
What a Sampling System Is: Before defining sampling systems, it might be helpful to first define
a process analysis system.
A process analysis system is an assemblage of equipment which measures chemical composition
and which provides a visual or written indication of the variable(s) measured. A process analysis
sampling system includes all equipment containing the process sample, including necessary
accessories; exclusive of the analyser itself. Materially, a sampling system consists of filters,
regulators, valves, flowmeters, condensers, catchpots, pressure gauges, and other pneumatic-hydraulic
components.
What It Does: Overall, the functions of any sampling system are fourfold:
1.
To take a sample representative of the flowing process stream.
2.
To transport the sample to the analyser.
3.
To condition it to be compatible with the analyser.
4.
To transport it from the analyser to the desired point of rejection.
These functions should be accomplished with the timeliness, accuracy, and automaticity required
by the objectives of the analysis system. A well-designed sampling system optimises the above
performance factors with the costs of equipment, installation, operation and maintenance that are a
part of anything mechanical.
Importance of Proper Sampling System Design: Because any analyser is designed to work with
clean, dry, non-corrosive, non-interfering samples at design conditions of temperature and pressure,
it follows that use with samples in other conditions will adversely affect analyser operation. Failure
of the sampling system to supply a compatible sample may only affect analysis accuracy, or it may
prevent any operation of the system beyond a few minutes time. A further danger exists that the
sampling system may introduce more problems of maintenance and/or accuracy than it solves. It
is, therefore, important to consider all factors which influence the overall analysis system and the
performance required by the application.
Fundamentals - Flow Plan Design

While design of the sampling system flow plan is necessarily limited by the components which are
available, most factors involved are connected with the natures of the analyser process stream, and
the plant environment. Specifically, these can be outlined as follows:
I.
Nature of Process Streams

A.
Composition
1) Condensables
2) Corrosivity
3) Foreign material, such as dirt, fogs or aerosols, bubbles, etc.
14 - 30
II
III.
Gas Analysis
B.
Pressure
C.
Temperature
D.
Location
E.
Size, type and orientation of pipe or duct
F.
Type of connection
G.
Number of streams
Nature of Analyser
A.
Flow required
B.
Temperature of operation
C.
Component(s) to be measured
D.
Location relative to sample point
E.
Speed of Response
F.
Interfering Components
G.
Method of calibration
Nature of Environment
A.
Surrounding atmosphere
1) Temperature extremes
2) Precipitation
3) Corrosiveness
4) Hazardous area requirements
B.
Available utilities1) Electricity

2) Steam
3) Water
4) Air
5) Sample Return Point
6) Waste Rejection
An important factor not mentioned above is cost. Cost is meant here to include total cost, both
short and long term.
Gas Analysis
14 - 31
Sampling System Components

A.
Pumps (for Gases): Two broad types are mechanical and fluid. Mechanical pumps take the
form of the diaphragm, vane and piston type; and fluid pumps are generally of the jet or
aspirator type.
Diaphragm Pumps: Two types are found, the mechanical linkage and the fluid linkage varieties.
The former generally consist of flexible diaphragms connected to the rotating shaft through
some kind of eccentric or connecting rod. Rotation of the shaft causes the diaphragm to
oscillate rapidly back and forth.
Fluid sealed diaphragm pumps employ hydraulic oil, water or other liquid on the opposite
side of the diaphragm. The liquid is pulsed by an ordinary piston type pump.
Vane Pumps: The vanes operate in slots in an eccentrically mounted rotor so that gas is
drawn into the body, compressed and forced to the outlet.
Piston Pumps: Piston pumps are available either oiled or oilless. Oiled pumps utilise steel
piston rings against a cast iron cylinder. Oilless pumps use the familiar graphite or carbon
piston rings.
Fluid Pumps: These are the familiar jet exhausters and can be powered by air, water or steam.
Steam exhausters are the most efficient and can exhaust at suction pressures close to 100 kPa.
B.
Pumps (for Liquids): There are five common types: centrifugal, vane, gear, reciprocating,
and peristaltic.
Centrifugal: These are the common type of process pump in which a rotor generates centrifugal
forces which cause the liquid to flow through the pump. Centrifugal pumps are noted for
their very poor pressure-volume characteristic, that is, their output falls off greatly as the
operating head is increased.
Vane Pumps: This is specialised type, usually employing graphite vanes similar to the gas
type pump mentioned above. Although these are commonly called positive displacement
type they work the best under constant head conditions.
Gear Pumps: These are used generally on lubricating type fluids and are capable of pressurising
to very high pressures, in the range of several thousand psig. They can be obtained
commercially for flow rates ranging from a few ccs per minute up to several gallons per
minute. They are not very suitable for use with non-lubricating type fluids such as water.
Reciprocating Pumps: These are of the piston (reciprocating) type and can be obtained in
many combinations of check valves and packings. They are characterised by pulsating output,
although certain types are available in which two pistons are synchronised so that the net total
output is continuous.
Peristaltic Pumps: This is the type in which a flexible plastic or rubber tube is kneaded by a
series of moving fingers or rollers so that pockets in the tube are moved along its length,
carrying liquid with it. This type has the advantage that no packing is required and thus there
is little possibility of leakage, or of contamination from the outside.
C.
Filters: There are literally hundreds of varieties of filters; however, this discussion will attempt
to deal with only a few of them. Basically filters can be divided into two categories - edge
type and depth type.
14 - 32
Gas Analysis
Edge Type Filters: Edge type filters function by retaining solid particles at the outer surface
or edges of the filtering passages.
Depth Type Filters: Most filters are of the depth type, in that many particles are caught in the
interior of the element. Several varieties are: sintered stainless steel (or most any metal),
impregnated felt, woven fibre, etc.
D.
Phase Separating Devices: These can be classified into three categories, liquid-gas, liquidsolid, and gas-solid. Liquid-gas separators can be further classified as those removing liquids
from gas samples and those removing gases (bubbles) from liquid samples.
Liquid-Removing Separators: Most separators function by a sharp change in direction of the
sample which can be followed by the gas, but not by the liquid. This is succeeded by a
reduction in velocity so as to avoid re-entraining liquid in the gas stream. For most samples,
this type of design is sufficient; where the liquid is finely dispersed as a fog.
Gas-Removing Separators: The sample containing bubbles is generally passed upward through
a coalescing medium, such as glass wool, to bring the bubbles together and make them larger.
The sample then flows into a large volume which reduces its velocity. A sharp change in flow
direction is then provided which the bubbles do not follow. Usually some kind of bypass
flow is required to remove the bubbles.
Liquid-Solid and Gas-Solid Separators: Aside from mechanical filters which were discussed
above, the most common type of separator is the cyclone. This has a conical shape with a
tangential entry at the top and a concentric outlet at the bottom for the bypass sample. A diptube is placed axially in the top of the cyclone so that the clean sample is withdrawn from the
vortex of the swirling liquid or gas. Cyclones work better on liquid-solid systems as they
tend to be self-cleaning; on gases, the particles tend to stick to the sides of the cyclone and an
accumulation problem may occur.
E.
Scrubbers and Dryers: These are devices which remove water or chemical constituents,
such as H2S, SO2, CO2. Both chemical and scrubbers and dryers can be classified as wet or
dry type. Wet scrubbers employ a liquid to dry or remove the contaminant. Dry scrubbers
use solid material such as molecular sieves, drierite, ascarite, solid potassium hydroxide, etc.
Wet scrubbers frequently employ sulphuric acid (or other acids), or caustic solutions.
F.
Heat Exchangers: Although occasionally employed to heat samples, they are more frequently
used to cool them, especially for the purpose of condensing liquids. Exchangers are available
they are relatively expensive and the general practice is to employ tube-in-tube or tube-injacket exchangers. Tube-in-tube heat exchangers can be constructed economically of ordinary
tubing, using heat exchanger type tubing fittings or bored-through tubing tees. Tube-intube heat exchangers can either be straight for short lengths or they may be coiled for longer
lengths. The tube-in-jacket type are easily constructed of scrap pipe by welding or silver
soldering.
G.
Vapourisers: Although there are many techniques employed for vapourising liquid samples,
four have been shown to be most useful. These are the orifice, capillary, packed tube, and
drip types. The purpose of any sample vapouriser is to convert a liquid sample to a vapour
sample while preserving the composition, by a sharp transition from liquid to vapour phase.
Gas Analysis
14 - 33
Case Study
Continuous stack monitoring
The application of automatic instrumental monitoring systems to stationary sources has been feasible
to many years, but, due to their cost and the lack of any incentive, industry has ignored them.
Recent activity on the part of the U.S. Environmental Protection Agency (EPA), and particularly the
promulgation of requirements for the monitoring of certain pollutants has stirred sudden interest in
such systems. This interest has spurred the development of: new instrumental methods, specialised
sample interface components and systems, and systems equivalent to the classical manual analytical
techniques.
Monitoring Stationary Sources
One of the most basic segments of air quality control is the control of pollutant emissions from
stationary sources such as electric generating and industrial manufacturing plants. Since it is presently
impractical to eliminate completely such emissions, controls consistent with available technology
must be developed to provide a practical balance of priorities. With quantitative measurement
techniques, the effectiveness of the controls can be checked by monitoring the performance of a
plant for compliance under typical or peak production conditions, assuming that the plant continues
to operate within the prescribed limits. However, it is advisable that the emission of certain critical
pollutants be monitored on a continuing basis. This requires dependable instrumentation that can
be located permanently at the point of emission.
14 - 34
Gas Analysis
Fig. 14.27
Gas Analysis
14 - 35
Fig. 14.28
There are three basic approaches to source monitoring that could foreseeably meet the current U.S.
requirements:
*
extracting a continuous sample from the stack or duct and feeding it to any appropriate analytical
instrument, after initial conditioning by means of a sample handling/interface system
observing and analysing the stack gases in situ by means of an optical instrument whose light
path traverses the gases inside the stack or duct
observing and analysing the stack gases shortly after they leave the stack by means of remote
optical instrument.
Commercial instrumentation, readily available for the first two approaches but not the third approach,
has already been installed in a number of plants.
Extractive vs In Situ
In the extractive approach, a continuous sample is drawn from the stack, or process stream, and
transported to the analyser, which can be mounted in any convenient location. A probe is mounted
in the stack or duct, and some form of interface system provides the analyser with a sample that is
in an appropriate state of cleanliness, temperature, pressure, and moisture content. This approach
is the oldest and has provided the most experience to date.
With the in situ approach, the instrument is mounted inside or just outside the stack. In the case of
photometric and spectroscopic instruments, the light source may be mounted on one side of the
stack and the detector on the other, so that the instrument scans the full width of the stack. Alternately
the instrument may incorporate an extended mechanical beam with a mirror on the end or a mirror
may be mounted on the opposite side of the stack so that the light penetrates a fixed distance and is
returned to the instrument on the same side. Since these spectroscopic instruments determine
pollutant concentrations by their discrete spectral absorption, they must be capable of discriminating
against absorption and scattering of the light by particles. These must also have high discrimination
against all other unwanted components that are present in the stack gas, such as water vapour or
carbon dioxide.
14 - 36
Gas Analysis
The in situ approach provides an average reading across the whole stack. This average is an advantage
over the point sampling approach that is most common with the extractive systems. It is possible,
however, to provide the averaging function with the extractive system by using multiple integrating
probes. One problem facing all in situ optical instruments is that of keeping the optical windows
clean. The common solution is to bathe the windows with a stream of clean air. This method
appears to be fairly effective for a reasonable period of time, but periodic mechanical cleaning is
required. Another problem with the in situ instruments is to provide a satisfactory method of
checking zero and span gases to the instrument, this method is more practical with extractive systems.
In the case of extractive systems, there is often some question as to whether the sample interface
system may absorb, or in some way modify the component of interest, particularly if it is chemically
active. Such problems are at least partially overcome by the calibration procedure mentioned earlier
since the zero and span gases can be introduced at the front end of the system, where they receive
the same treatment as the sample. In situ monitors avoid all of the problems of sampling/interface
systems that have been numerous and serious in the past. It is hoped newer developments in sample
handling systems will overcome many of these problems. The extractive instruments are flexible in
more ways than in situ type. Some of the advantages of the extractive type instruments are:
*
mounts in any convenient location, protected from the elements
offers no limitation on stack, duct of process line size, temperature, or location, and can
receive sample from any convenient and appropriate site
provides dry basis analyses directly, with appropriate sample interface systems
eliminates contaminating dust, dirt, and other interfering compounds through sample interface
systems
provides samples for multiple instruments with a single interface system
monitors several stacks or process streams sequentially with one instrument.
In situ monitors require no sample interface system other than an air shield to protect the optics
from solid or liquid contaminants carried by the stack gas. On the other hand, extractive-type
instruments require a sample interface system to remove the sample from the stack or process
stream and deliver it to the instrument in the proper state. Instruments differ in their sample
requirements but, in general, the sample interface system must perform several or all of the following
functions, depending on the nature and condition of the original sample: remove a representative
sample from the stack or process stream; cool the sample, if excessively hot, and reduce its dew
point; remove particulates; remove any condensate; raise the pressure of the sample, if
subatmospheric, and/or regulate it at a constant pressure somewhat above atmospheric for delivery
to the instrument; withstand corrosion by the sample constituents and not react with the component
of interest in such a way as to change its concentration.
Sample Conditioning Hardware
Appropriate hardware must be found or fabricated to perform the various functions indicated above.
Sample acquisition is usually performed by a probe, attached to a pipe coupling which is welded to
a hole in the wall of the stack, flue, or pipe. The probe extends an appropriate distance into the
sample duct. It may be a simple pipe or it may have a coarse (5-30u pore size) filter attached at the
end, fabricated of sintered metal, refractory, metallic screen, or fabric. Ordinary steel pipe is limited
Gas Analysis
14 - 37
to a stack temperature below 1400F (760C) while 316 SS is usable to 16,000F (870C). At
temperatures above this, a water-cooled steel probe may be used, or sillimanite (aluminum silicate)
tubing, if the length is not over three feet. This material withstands temperatures up to 2800F
(1540C), but has limited mechanical strength.
The sample conditioning system may be located directly at the sampling point, or it may be located
some distance away, for convenience in installation and maintenance. In the latter case, a suitable
sample line must be provided. Due to the reactive nature of several components normally found in
combustion gases and sulfuric of nitric acid plant stacks, this sample line should be stainless steel
or high temperature fluorocarbon and should be at least 1 - 1.3cm inside diameter to avoid plugging.
It is always mounted with a downward slope, and condensate pockets are carefully avoided. It may
be heated to avoid condensate. This is particularly advantageous if the sample contains sulfur
trioxide; the acid dew point for a concentration of 15 ppm being about 250F (120C). Steam, or
electrical tracing is used for heating; steam being easier to control and providing a more uniform
temperature, but electrical heating being more popular. Integral heated lines of either stainless steel
or Teflon are available.
Fig. 14.29
Sample cooling is simply for gases which have relatively low thermal capacity. A few inches of
stainless steel sample line or a couple of feet of fluorocarbon line normally provide adequate cooling
to protect an analyser. Streams with dew points above the operating temperature of the instrument
are normally cooled well below that temperature, however, to avoid any possible condensation
within the analyser itself. This may be accomplished with an air-cooled heat exchanger or with
forced cooling, as with a refrigerated condenser or a Ranque Hilsch vortex tube.
Particulate removal can be achieved by many types of filter bodies and filter elements, utilising
different forms of both organic and inorganic material. Selection is based on the particle size and
stream-loading factors, as well as the nature of the gases. Stainless steel is most commonly used for
body material for stack gas filters and the filter element is selected for pore size and filtration area
to remove even the submicron particles while not requiring too frequent maintenance.
Condensate removal after the heat exchanger can be effected by various types of traps. Corrosion
resistance is obtained with stainless steel or other metallic alloys, or plastic. A good design provides
minimum contact between the ongoing sample and the liquid condensate, and minimises the
likelihood of droplet carry-over by means of baffles or partitioning. Traps are available with either
14 - 38
Gas Analysis
manual or automatic drain valves. The latter are more expensive and complex, but require less
attention.
Pressure control/adjustment, in the case of process streams where sufficient pressure usually exists
to move the sample through the interface system and the analyser, is by regulators of appropriate
materials of construction or by relief valve on a side branch. In the case of stacks, flues, and vents,
the pressure may be anywhere from 12 kPa above atmospheric to 12 kPa below. In this case some
sort of mechanical pump must be used ahead of the regulator. Until recent years, appropriate
pumps have not been plentiful and even now much needed development is under way in this area.
Rotating carbon vane pumps have seen considerable use in the past, but bellows and diaphragm
pumps with inert, internal coatings are coming into greater popularity now, particularly as more
resistant and longer wearing components are being developed.
Monitoring Methods
I
STEAM GENERATOR
A. Burning solid, liquid or
gaseous fuel
B. Burning solid or liquid fuel
II
NITRIC ACID PLANT
III
SULPHURIC ACID PLANT
IV
PETROLEUM REFINERY
A. fluid cat cracker
catalyst regenerator
1. All
2. Regenerators without
waste heat boilers
Monitor
Basic Approach
Instruments
Nitrogen Oxides
In situ
Extractive
Smoke opacity
Sulphur dioxide
In situ
In situ
Extractive
Spectroscopic
Spectroscopic
Chemiluminescent
Polarographic
Photometric
Spectroscopic
Spectroscopic
Flame photometric
Polarographic
Nitrogen oxides
In situ
Extractive
Spectroscopic
Spectroscopic
Chemiluminescent
Polarographic
Sulphur dioxide
Extractive
In situ
Spectroscopic
Spectroscopic
Flame photometric
Polarographic
Particulate opacity
In situ
Photometric
Carbon monoxide
Extractive
Spectroscopic
3. Regenerators with
waste heat boilers
B. Process heaters, boilers and
waste gas disposal systems
1. Firing higher level
H2S (with H 2S removal)
Stack gas SO2
Extractive
Polarographic
Stack gas SO2
In situ
Extractive
Spectroscopic
Spectroscopic
Flame photometric
Polarographic
Firing gas containing less than

230 mg/Nm3 H2S
Fuel gas H2 S
Extractive
content
Chromatographic
V
IRON AND STEEL PLANTS
A. Basic oxygen furnace
Particulate opacity
In situ
Photometric
Gas Analysis
14 - 39
Summary
Gas analysis determines the concentration of a required constituent of a mix.
Units of concentration:
* % by weight
* mole %
* ppm - ratio of weight (volume) 1:106
* ppb - ratio of weight (volume) 1:109
Quantitative analysis involves determination of:
Transmittance (T) =
Intensity of Transmitted Radiation (I)
Intensity of Incident Radiation (Io)
Absorbance = A = -logT (Beer-Lambert)

where A = absorptivity x path length x concentration
Infrared analysis uses distinctive molecular vibrational and rotational energies to detect heteroatomic
gases eg. CO, CO2, SO2, CH4, NH3, N-Hexane (Benzene), NO. Sample cells absorb the radiation to
produce a unique energy curve. A luft detector is an example of such a cell. It uses separate sample
and reference compartments.
Gases have varying thermal conductivities. Analysers using this principle rely indirectly upon
varying electrical resistances calibrated against known sample strengths.
Paramagnetic substances align themselves with a magnetic field displacing a reference body
producing a torque which can be compensated for and thus measured. Oxygen can be measured
this way. The Curie-Weiss law states that the paramagnetic effect varies inversely with temperature.
Etalon analysers will measure SO2 concentration using a U.V. light source. The Etalon crystal, in
conjunction with phase shifting, allows the difference between absorbed/non-absorbed signals to
be registered at the detector. In this way the actual concentration may be determined.
A Zirconium sensor produces a measured voltage, at high temperatures, proportional to the logarithm
of the sample reference ratio.
NO and NO2 together are called NOx. It may be determined by Chemiluminescence. NO2 is broken
down catalytically to NO. The reaction progresses:
NO + O3 NO2 (excited state) NO2 and O2 + HLAMBDA
This light emission HLAMBDA is proportional to NO mass flow rate.
Hydrocarbon concentration in a gas sample can be determined by first dissociating the gas into ions
using a flame. The current produced due to ion migration in an electrical field is proportional to this
concentration. Oxygen atoms in the sample are a source of error as they reduce current flow unless
compensated for.
14 - 40
Gas Analysis
Electrolytic analysis may involve:

i.
Polarography - A small sample is electrolytical and current diffuses through a gel in the
cell. O2 can be determined this way.
ii.
P2O5 film is rendered conductive proportionally to the trace moisture concentration.
A sampling system procures a representative sample of the process, transports and conditions it
prior to analysis and is responsible for waste ejection. Design should consider the nature of the
process and environment nature of the analyser and availability of utilities and finance.
The components of a sampling system may typically include:
*
pumps
filters
phase separators
scrubbers and dryers
heat exchangers
vapourisers
Discussion
Using the case study of Stack Monitoring, answer the following questions:
1.
What are the 3 approaches to source monitoring that are theoretically possible?
2.
What are the advantages/disadvantages of in situ optical analysis?
3.
What are the advantages/disadvantages of extractive analysers?
4.
Outline some of the considerations involved in developing a sampling system for a Stack.
Gas Analysis
14 - 41
Test
1.
Express .5% by weight as ppm

Ans.____________________
2.
Photon A is of 3 times the energy of Photon B. What is the ratio of wave lengths A:B?
Ans.____________________
3.
A sample of gas absorbs 20% of incident radiation.

a. What is its transmittance? Ans.___________________
b. If 100 photons are incident initially, how many would be transmitted after 2 consecutive
passages through the sample cell?
Ans. ____________________
4.
I = I o Ke-abc
I = Intensity of transmitted radiation
A = -log T
Io = Intensity of incident radiation
A = abc
K = constant
a = absorptivity
b = path length
c = concentration
A = absorbance
T = transmittance
Answers (T) True or (F) False:

i.
As c increases; I increases
Ans.___________
ii.
As T increases; A increases
Ans.___________
iii.
As a increases; Io decreases
Ans.___________
iv.
As A increases; I increases
Ans.___________
14 - 42
5.
Gas Analysis
Answers (T) True or (F) False:

i.
NDIR measures concentrations of monoatomic gases.

Ans.________________
ii.
Length of the sample cell in a NDIR analyser effects the sensitivity of the measurement.
Ans.________________
iii.
A gas with higher thermal conductivity will cause higher electrical conductivity in the
associated resistance bridge circuitry.
Ans.________________
iv.
A less paramagnetic medium tends to displace a more paramagnetic medium from the
lines of force of an applied electric field.
Ans.________________
v.
Oxygen can be measured using paramagnetic and zirconia sensors.

Ans.________________
vi.
A Zirconium device measures [O2] proportional to a milliamp signal generated in the

cell.
Ans.________________
vii.
Output signal of a Zirconium sensor increases as measured oxygen partial pressure

increases.
Ans.________________
viii. The light emission measured by a chemiluminescent analyser is a direct result of the
catalytic decomposition of NO2.
Ans.________________
ix.
FID measures the current flow resulting from ionised hydrocarbons in an electrostatic
field.
Ans.________________
x.
Oxygen synergism inflates the FID current reading thus causing measurement error.
Ans.________________
xi.
As trace moisture content increases; electrical resistance of P2O5 decreases.

Ans.________________
Gas Analysis
6.
14 - 43
Define or explain these words:

a. scrubber__________________________________________
__________________________________________________
b. phase separator_____________________________________
__________________________________________________
Third Printing: October 1996

Second Printing: December 1993
First Printed: October 1991

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Gas Analysis

How beautiful is night!

Course 9050 - October 1996

Principles of Instrumentation and Control

Principles of Instrumentation and Control

Course 9050 - October 1996

no. of moles gas x 100%

- parts per million (ppm)

Ratio by weight (or volume) of gas: sample

no. of mg. substance: no. of kg sample

- parts per billion (ppb)

Ratio by weight or volume of gas: sample

no. of g substance: no. of kg sample

Course 9050 - October 1996

Principles of Instrumentation and Control

Principles of Instrumentation and Control

Course 9050 - October 1996

Course 9050 - October 1996

Principles of Instrumentation and Control

Principles of Instrumentation and Control

Course 9050 - October 1996

Principles of Quantitive Measurement in Absorption Spectroscopy

Intensity Transmitted Radiation (I)

Intensity Incident Radiation (Io)

Course 9050 - October 1996

Principles of Instrumentation and Control

.5 12.5 = .5 6.25 = .5 3.125

Principles of Instrumentation and Control

Course 9050 - October 1996

Absorbance = A = -log T (Beer-Lambert Law)

Course 9050 - October 1996

Principles of Instrumentation and Control

Non-Dispersive Infrared (NDIR) Absorption Spectroscopy

Principles of Instrumentation and Control

Course 9050 - October 1996

Basic Absorption Analyser

Length of Sample Cell

Course 9050 - October 1996

Principles of Instrumentation and Control

Principle of Operation of the Luft Detector System

Principles of Instrumentation and Control

Course 9050 - October 1996

Luft Detector System with gas filter

Course 9050 - October 1996

Principles of Instrumentation and Control

Principle of Operation of a SO2 Etalon Analyser

Principles of Instrumentation and Control

Course 9050 - October 1996

Course 9050 - October 1996

Principles of Instrumentation and Control

Kt = Thermal Conductivity at absolute temperature T.

Application to Gas Analysis

Principles of Instrumentation and Control

Course 9050 - October 1996

Thermal Conductivity Cell and Associated Bridge Adjustments

Course 9050 - October 1996

Principles of Instrumentation and Control

Principles of Instrumentation and Control

Course 9050 - October 1996

Course 9050 - October 1996

Principles of Instrumentation and Control

Flame Ionisation Detection (FID)

Monitors hydrocarbon contaminants in ambient air and other gases