MODULE 3

INDUSTRIAL ANALYZERS
 SYLLABUS
4.1.0 To comprehend the working of Industrial Analyzers
4.1.1 To state the principle of Thermal conductivity analyzer
4.1.2 To explain the -construction and operation of Thermal conductivity gas
analyzer
4.1.3 To state the principle of Paramagnetic analyzer
4.1.4 To explain the construction and operation of magnetic force type and wind
type
Paramagnetic oxygen analyzers
4.1.5 To describe the construction and operation of Zirconia oxygen analyzer
4.1.6 To state the principle of Infrared analyzers
4.1.7 To Classify Infrared analyzers
4.1.8 To explain the construction and operation of positive filter type IR analyzer
4.1.9 To illustrate the construction and operation of negative filter type IR
analyzer
4.1.10 To State the principle of Electrical conductivity analyzer
4.1.11 To describe the construction and operation of Electrical conductivity
analyzer
4.1.12 To explain Measurement circuit used in Electrical conductivity analyzer
 THERMAL CONDUCTIVITY ANALYZER
• PRINCIPLE:-
– This thermal conductivity analyzer measures gas
concentration by utilizing the difference
of thermal conductivities between two gas
components. The resulting thermal change is
taken out as a change in electric resistance,
according to which the concentration of measured
gas is calculated
Thermal conductivity gas analyzer
 Thermal conductivity gas analyzer
• PRINCIPLE:-

– This thermal conductivity gas analyzer measures gas

concentration by utilizing the difference of thermal
conductivities between two gas components.

• CONSTRUCTION:-

– In the detector, there are a reference chamber and a measuring

chamber, in each of which a thin platinum wire is stretched. The
reference chamber is filled with reference gas.
 Thermal conductivity gas analyzer
• WORKING:-
– The sample gas is flowed through the measuring chamber.

– Each platinum wire composes a bridge circuit in combination with an

external fixed resistor, and is heated by flowing a constant current.

– When there is a change in the concentration of the component under

measurement, the thermal conductivity of sample gas will change to
affect the temperature of the platinum wire in the measuring chamber.

– The resulting thermal change is taken out as a change in electric

resistance, according to which the concentration of measured gas is
calculated.
 Thermal conductivity gas analyzer
• Applications

– H2 monitoring in semiconductor manufacturing

equipment, hydrogen generation equipment, calcining
furnaces

– Ar, He, CH4 measurement in gas generation plants

– He measurement in superconducting devices

– Ar measurement in air-separation plants

 Paramagnetic O2 Analyzer
• Oxygen has the property of being paramagnetic in nature (i.e. it does

not have as strong magnetism as permanent magnets, but at the same

time it is attracted into a magnetic field).

• Nitric oxide and nitrogen dioxide are other two gases which are

paramagnetic in nature.

• Most gases are, however, slightly diamagnetic (i.e. they are repelled

out of a magnetic field).

 Paramagnetic O2 Analyzer
• PRINCIPLE:-
– The operating principle of the paramagnetic sensor is
the paramagnetic susceptibility of the oxygen
molecule, a physical property which distinguishes
oxygen from most other gases.
Magnetic force type Paramagnetic O2
Analyzer
 Magnetic force type Paramagnetic O2
Analyzer
• The operating principle of the paramagnetic sensor is the paramagnetic
susceptibility of the oxygen molecule, a physical property which
distinguishes oxygen from most other gases.

• The sensor incorporates two nitrogen-filled glass spheres mounted on a

rotating suspension.

• This assembly is suspended in a strong magnetic field.

• The oxygen in the surrounding gas is attracted to the magnetic field,

resulting in a force on the glass spheres.

• The strength of the torque acting on the suspension is proportional to the

oxygen content of the surrounding gases.
 Magnetic force type Paramagnetic O2
•
Analyzer
The measuring system is “null-balanced”.

• First the “zero” position of the suspension assembly, as measured in

nitrogen, is sensed by a photo-sensor that receives light reflected from
a mirror attached to the suspension assembly.

• The output from the photo-sensor is fed back to a coil around the
suspension assembly. This feedback achieves two objectives.

• First, when oxygen is introduced to the cell, the torque acting upon the
suspension assembly is balanced by a re-storing torque due to the
feedback current in the coil.
 Magnetic force type Paramagnetic O2
Analyzer
• The feedback current is directly proportional to the volume magnetic
susceptibility of the sample gas and hence, after calibration, to the
partial pressure of oxygen in the sample. Therefore, the current gives
an accurate measurement of the concentration of oxygen in the gas
mixture.

• Second, the electromagnetic feedback “stiffens” the suspension,

damping it heavily and increasing its natural frequency, making the
suspension resilient to shock
Magnetic wind type Paramagnetic O2
Analyzer
 Magnetic wind type Paramagnetic O2
Analyzer
• Figure shows a paramagnetic oxygen analyser based on the
phenomenon of magnetic wind, which rises due to the motion of
paramagnetic oxygen molecules into the non-uniform magnetic field.
• The flowing gas is made to pass over a heated filament connected as
one arm of a Wheatstone bridge circuit.
• The gas cools the filament and unbalances the bridge circuit.
• The output voltage from the bridge can be fed to a recorder, to show a
continuous indication of oxygen concentration in the sample.
 Magnetic wind type Paramagnetic O2
Analyzer
• The analyser comprises of a ring chamber, which consists of a
metallic hollow ring arranged in vertical plane, with a gas inlet
below and a gas outlet above.

• The gas is conducted in the upward direction. The two halves of the
ring chamber are connected by a glass tube.

• The transverse tube has taped wire winding on its outside. The
winding forms a part of a Wheatstone bridge circuit, whose one-half
is placed in the field of a permanent magnet.
 Magnetic wind type Paramagnetic O2
Analyzer
• In case the sample gas does not contain any oxygen, there is no flow
in the horizontally placed transverse tube.

• If, however, the sample gas contains oxygen, it is attracted into the
magnetic field.

• This gas flow is heated and due to the increase of the temperature,
the susceptibility of the paramagnetic oxygen molecules decreases.

• In this way, the heated gas is pushed away by the cold gas coming
from the left-hand side.
 Magnetic wind type Paramagnetic O2
Analyzer
• A gas flow thus arises inside the transverse tube.

• This flow is called the Magnetic Wind, whose velocity depends upon
the oxygen concentration in the sample gas.

• The magnetic wind cools down the left side of the heated winding
more than the right side.

• Therefore, a change in the bridge balance takes place, which depends

on the temperature gradient.

• The voltage difference of the bridge is proportional to the oxygen

concentration in the measuring gas.
 The construction and operation of
Zirconia oxygen analyzer
• The zirconia oxygen analyzer is suitable for measurements of ppm to %
levels of oxygen in a gas or mixture of gases.

• The zirconia cell is an electrochemical galvanic cell employing a high

temperature ceramic sensor containing stabilised zirconium oxide.
 Operation of Zirconia oxygen analyzer
• As shown in the figure, when porous platinum electrodes
are attached to both sides of the zirconia element to be
heated up and gases of different partial oxygen
concentrations are brought into contact with the respective
surfaces of the zirconia, the device acts as an oxygen
concentration cell.
• This phenomenon causes an electromotive force to be
generated between both electrodes according to Nernst’s
equation. And it is proportional oxygen concentration.
 The construction and operation of
Zirconia oxygen analyzer
• The zirconia cell is a high temperature ceramic sensor.

• It is an electrochemical galvanic cell comprising of two electrically conducting,

chemically inert, electrodes attached to either side of a solid electrolyte tube.

• The tube is completely gas tight and made of a ceramic (stabilised zirconium
oxide) which, at the temperature of operation, conducts electricity by means of
oxygen ions.

• The potential difference across the cell is given by the Nernst equation.
 The construction and operation of
Zirconia oxygen analyzer

• Where:
• E is the potential difference (volts)
R is the gas constant (8.314 J mol-1 K-1)
T is the absolute temperature (K)
F is the Faraday constant (96484 coulomb mol-1)
P1 & P2 are the partial pressures of the oxygen on either side of the zirconia tube
• The Nernst equation can therefore be reduced to:

• Thus, if the oxygen partial pressure at one of the electrodes is known and the
temperature of the sensor is controlled, then oxygen measurement of the potential
difference between the two electrodes enables the unknown partial pressure to be
calculated.
 Principle of Infrared analyzers
• Infrared gas analysers depend upon the fact that some gases and
vapours absorb specific wavelengths of infrared radiation.

• One of the most commonly measured gases using infrared

radiation absorption method, is the carbon dioxide.

• Infrared analysers are used for the determination of a large number

of components, including CO, CO2, SO2, NH3, nitric oxide as
well as most gaseous hydrocarbons
 Principle of Infrared analyzers
• The absorption spectrum of infrared radiation absorbed by a gas, is unique to the type of
gas, In every absorption-type, optical analyzer, the fundamental equation relating photon
absorption to substance concentration is the Beer-Lambert Law (sometimes called the
Lambert-Beer Law):

Where,

• A = Absorbance

• a = Extinction coefficient for photon-absorbing substance(s)

• b = Path length of light traveling through the sample

• c = Concentration of a photon-absorbing substance in the sample

• I0 = Intensity of source (incident) light

• I = Intensity of received light after passing through the sample

Construction and working of Infrared
analyzers
 Construction and working of Infrared
analyzers
• There is two tubes in the analyzer one is filled with reference gas and other with
the sample gas or process gas which absorbs light.

• The reference gas is usually gases like nitrogen which will not absorb light.

• The incident light (infrared) is split into two parallel beams by the upper mirror.
One beam is used for the measurement and the other is used as the reference.

• The reference light beam passes through the reference cell, which is filled with
air or N2 , and is then reflected off the bottom mirror onto a semiconductor
detector.

• The measurement light beam passes through the measurement cell, and is
reflected onto a semiconductor detector in the same fashion as the reference
light.
 Construction and working of Infrared
analyzers
• The component to be measured in the gas sample flowing through the
measurement cell absorbs some of the measurement light, thus reducing the
strength of the light relative to the strength of the reference light.

• The two light beams are alternately cut off from the detector by a semi-
circular rotary sector.

• This allows the detector to convert the difference in the strengths of the
measurement and reference light beams into an alternating electrical signal
that represents the concentration of the gas being measured.
Classification of Infrared Analyzers
• Dispersive IR analyzer

• Non-dispersive IR analyzer

1. Absorption type NDIR analyzer

2. Positive filter type NDIR analyzer

3. Negative filter type NDIR analyzer

Positive filter type IR analyzer
 Positive filter type IR analyzer
• It includes two infrared sources, a reference cell containing a non-
absorbing gas, a sample cell which the sample flows through, and a
detector.

• Wavelength selection is achieved through selectivity in the detector.

• The detector, a luft type, contains two gas cells filled with an
infrared absorbing gas and separated by a thin metal diaphragm.

• Selectivity is gained because absorption of gas in the detector occurs

only at wavelengths which correspond to the spectrum of that gas
 Positive filter type IR analyzer
• Radiation released from the sources is transmitted through the
reference and sample cells and into corresponding sides of the
detector.

• When the sample cell is empty the radiation reaching each side of the
detector is equal, resulting in identical pressures due to equal
absorption of the radiation.

• However, when a sample flows through the sample cell, infrared

radiation is absorbed reducing the radiation incident on the sample
side of the detector
 Positive filter type IR analyzer
• This results in a pressure difference between the two sides of the
detector.

• The pressure difference causes the diaphragm to flex, changing the

capacitance between the diaphragm and an adjacent stationary
electrode (differential capacitance manometer).

• The resulting voltage output is proportional to the pressure difference

in the detector and the concentration of gas in the sample cell.
Negative filter type IR analyzer
 Negative filter type IR analyzer
• It contains two infrared sources, a sample cell, a sensitising cell, a
compensation cell, two filter cells, and two detectors.
• The sample continuously flows through the sample cell.
• Two beams from the infrared sources pass through the sample cell.
• One of the beams then passes through the compensation cell which contains
a non-absorbing gas, while the other beam passes through the sensitising cell
containing the infrared absorbing gas of interest.
• Both beams then reach two independent detectors which are
bolometers(A bolometer is a device for measuring the power of incident
electromagnetic radiation via the heating of a material with a temperature-
dependent electrical resistance.) electrically connected through a
Wheatstone Bridge
 Negative filter type IR analyzer
• When the sample cell is empty, the radiation reaching each individual
detector is not equal due to absorption of radiation in the sensitising cell.

• The radiation transmitted from the compensation side is therefore

reduced so identical intensities of radiation are reaching each bolometer.

• When the gas of interest flows through the sample cell it diminishes the
radiation on the compensation side from absorption by the gas.

• However, the radiation on the sensitising side is not reduced since the gas
in the sensitising cell has already removed the energy at the wavelengths
specific to the gas of interest.
 Negative filter type IR analyzer
• The radiation on the compensation side now has less energy than the radiation on
the sensitising side, a condition called positive sensitisation.
• Some gases have overlapping regions in the spectrum which can cause
interference.
• An example of two gases with overlapping absorption bands are carbon dioxide
and water. If one was to measure carbon dioxide in a sample, filter cells containing
water vapour must be used to remove interference.
• The filter cells are placed on both reference and sample sides so the two optical
paths are equally decreased by the radiation energy.
• As the radiation passes through the filter cell the water absorbs all of the radiation
at its specific wavelengths. This results in only the difference in energy for the
carbon dioxide being measured.
 Prnciple of electrical conductvity
analyzer
• Analysers based on the electrochemical methods are mostly
used for the determination of oxygen content of a gas.

• They utilise an electrolytic cell and can be broadly classified

as
– galvanic,

– polarographic and

– conductometric methods.
 Conductometric Method
• The conductometric method is convenient and is the most widely
used method for trace gas analysis.

• In practice, the sample gas is passed through a cell containing a

liquid reagent, which can react with the gas of interest.

• The conductivity of the liquid is measured before and after the

reaction with the gas.

• The difference in conductivity is proportional to the gas

concentration.
 Conductometric Method
• In order to obtain reproducible results, flow of gas and reagent must be kept
constant.
• Therefore, the measuring gas must enter the analyser at a constant velocity, which
is generally adjusted by a pneumatic bypass and indicated by a capillary flow
meter.
• A slow stream of reaction solution enters the reaction cell via a second capillary,
and its flow rate is also kept constant.

• In order to minimise errors due to change in ambient temperature, the measuring

cell is kept in precisely controlled temperature environment.

• By proper selection of the reagent, analysers based on this principle can be made
specific for various gas components. The method is especially suitable for
measuring traces of H2S, SO2, NH3 and H2O in the ppb range.