INTRODUCTION TO

GAS ANALYZERS
Why is analysis required?

The purpose of analytical measurement is to provide

information on the chemical contents of a process
stream.
These data are then used to control and improve the
chemical process
Detection of accidental release of gases/vapors
Occupational health and safely measurements
Indoor air quality and ventilation measurements
 CLASSIFICATION OF ANALYZERS

ANALYZERS

LIQUID GAS
ANALYZERS ANALYZERS

CONDUCTIVITY ANALYZER OXYGEN ANALYZERS

DENSITY AND SPECIFIC GRAVITY HYDROCARBON ANALYZERS

MEASUREMENT

pH ANALYZER CARBON MONOXIDE ANALYZERS

DISSOLVED OXYGEN CARBON DIOXIDE ANLYZERS

AMMONIA ANALYZERS
SALIENT FEATURES OF AN ANALYZER

The process analyzer should operate continuously for

extended periods of time with the minimum of skilled
attention and maintenance
It must be engineered to withstand the hostile
environment that will be encountered on any chemical
plant
Its sampling system must be designed and constructed
with a view to get the sample to the analyzer in correct
quality and quantity.
Its span must be stable and free from zero drift.
MAIN FUNCTIONS OF THE SAMPLING SYSTEM

Sampling system is an integral and key part of an analyzer system and should
be designed to

Obtain a sample
Transfer the sample to the analyzer
Condition the sample
To remove moisture from the sample**
Provide facilities for disposal of sample
Ensure the delivery of a clean, cool and a properly pressurized sample in
adequate quantity with a minimum of dead volume and transport lag.
Resist corrosion and thus ensure delivery of an uncontaminated sample
Meet the requirement of intrinsic safety rules according to different
classification of explosive gases
Operate with minimum maintenance and little attention
SAMPLE HANDLING SYSTEM
 CLASSIFICATION OF ANALYSIS

Method of analysis may be classified according to

properties that are utilized in analysis

INFRARED ANALYSIS FOR MULTICOMPONENT MIXTURES

PARAMAGNETISM
THERMAL CONDUCTIVITY
ZIRCONIUM OXIDE ANALYZER
FLAME IONIZATION DETECTION
pH ANALYSIS
CONDUCTIVITY
PARAMAGNETIC
ANALYSIS
 MAIN FEATURES OF THE PARAMAGNETIC
ANALYZER

The oxygen analyzer provides continuous readout of the

oxygen contents of the flowing gas sample

The determination is based on the measurement of the

magnetic susceptibility of the sample gas

The instrument provides a direct readout of oxygen

concentration on a front panel meter
 TEST BODY DETAILS
Displacement
Torque

Platinum Nickel
Alloy suspension ribbon
Restoring Torque

Nitrogen filled hollow glass test body

Electro magnetic axis

Mirror
Balancing Weight

Titanium Wire conductor

Balancing Weight
Restoring current
THERMAL CONDUCTIVITY
GAS ANALYZER
MAIN FEATURES OF THERMAL CONDUCTIVITY
GAS ANALYZER

Thermal conductivity analyzer is designed to continuously

measure the concentration of a single component of interest in
a flowing gas mixture
The measurement is based on the differing thermal conductivity
of individual components of the sample stream
This method is well suited for analysis of two component
sample streams
Analysis of multi-component stream is practical if the various
components of the background gas occurs in relatively in
constant ratio or have similar thermal conductivity.
 1. In thermal conductivity analyzer it
is very important to know how the
conductivity of a mixture varies
with the proportion of constituent
gases.
2. The relationship between the
conductivity of a mixture of gases
and the proportion of constituents
is complicated.
3. Concentrations of Hydrogen,
Helium and Argon can be
determined practically by this
method.

Gas Kt
Hydrogen 7.00
Kt=Thermal
conductivity at Nitrogen 1.00
absolute
Oxygen 1.01
temperature
CO 0.96
Co2 0.59
So2 0.34
THE ZIRCONIUM OXIDE SENSOR
THE ZIRCONIUM OXIDE SENSOR

At Cathode: O2 + 4e 2O2-

At Anode :2O2- O2+4e

+ -
Porous Platinum
(Inside and Outside)
 MATHEMATICAL CALCULATIONS

E.M.F (mV) = RT log Percentage of oxygen in air

Percentage of oxygen in sample
R=Gas Constant
T=Absolute Temperature

At 700OC the voltage is given by

E.M.F (mV) = 48.25 log 20.95
Percentage of oxygen in sample
FLAME IONIZATION
DETECTION
 FLAME IONIZATION
DETECTION
Signal
Negative ion conditioning
C C
C C
Collection ring C

Positive Carbon Ions

+90V >

Air

Sample Fuel
NON DISPERSIVE INFRARED
ANALYSIS
 SPECTROSCOPY
MATTER IS COMPOSED OF ATOMS WHICH CAN BE
SIMPLIFIED TO THE SIMPLE PLANETARY MODEL BELOW

ATOMS ABSORB ENERGY SUCH

THAT THE ELECTRON JUMPS
ELECTRON
TEMPORARILY FROM E1 TO E2
+
THIS CLIMBING OF THE ‘ RUNGS
NUCLEUS
OF THE LADDER’ RESULTS IN AN
EXCITED STATE

E1
E2

ENERGY LEVELS
(ORBITALS)
 NON-DISPERSIVE INFRARED (NDIR)
ABSORPTION SPECTROSCOPY

Gases can be categorised in three groups with respect to infrared

absorption:
“Diatomic”gases (N2,O2, H2, Cl2) do not absorb infrared, thus cannot
be measured by NDIR.
“Monoatomic” gases (He,Ne,Ar,Kr,etc.) do not absorb infrared
energy , thus cannot be measured by NDIR.
“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, NO
 MAIN FEATURES OF INFRARED ANALYZER
INFRARED VISIBLE ULTRAVIOLET

100nm
10000 5000 2000 1000nm 800 600 400 300 200 0.1um
900 700 500

A NDIR Analyzer continuously determines the concentration of a

particular component of interest in a flowing mixture.
The analysis is based on the differential measurement of the
absorption of the infrared energy
 IR SOURCES

CHOPPER WHEEL

SAMPLE IN

SAMPLE CELL
REFERENCE
CELL
SAMPLE OUT

DETECTOR ,
SAMPLE SIDE

DIAPHRAGM,
DISTENDED

STATIONARY PLATE COMPOUND OF INTEREST

NON –INTERFERING COMPOUNDS
ANOTHER MODEL OF THE
NDIR ANALYZER
 The Luft Detector

The Luft type detector is the oldest type found in common use.
It is found in dual beam analyzers and uses a pair of chambers that are
filled with the absorbing gas interest.
One chamber receives light through the inert gas-filled reference cell, the
other receives light through the sample gas-filled cell.
The chambers are seperated by a capacitive diaphragm which distends in
response to the difference in adsorption-induced gas expansion between
the two detector chambers.
This detector is extremely sensitive and selective, but is expensive to
produce.

“CHOPPER" assembly which prevents the energy from both cells from
falling on the detector simultaneously.
As the wheel spins, energy from the reference and measurement cells fall
on the detector alternately, producing an AC signal with a magnitude
proportional to the difference in energy.
 Water Vapor Interference on NDIR-A common problem

Water Vapor absorbs strongly throughout the Infrared spectral

region and is therefore a common source of interference for most
measurements made by NDIR.
Water Vapor Interference can be reduced in two ways
1. By an optical method ,
2. By treatment of the sample in a sample handling
System.
 Five major manufacturers in the world for catering to
individual requirement of Gas Analyzers are

1. Maihak,Germany
2. Emerson Processes
3. Teledyne,U.K.
4. A.B.B
5. Hartman & Braun
 INTRODUCTION TO
pH AND CONDUCTIVITY
 pH
WHAT IS pH ?
1. pH is the negative logarithm of H+ ion
concentration.
2. The symbol pH represents the acidity or
alkalinity of a solution.
3. It is a measure of a key ingredient of aqueous
solutions of all acids and bases: the hydrogen-
ion concentration.
4. It is a dimensionless quantity and lies on a
scale from 0-14. Pure water is said to be
neutral and lies exactly mid scale.
Mathematically,
pH= -log10[H+]
Or
pH= log1/[H+]

If we know the OH- ion concentration but not the

H+ ion concentration of a aqueous solution , we
can calculate the pH by using the relationship
[OH-][H+]=10-14
If [H+] =[OH-] in a solution, the pH of that solution
is said to be neutral
THE MOLAR CONCEPT
A Mole of a compound is defined as Avagadro’s
number of molecules (6.02* 1023), which has a
mass equal to the molecular weight, expressed
in grams.
For Example ,sodium Hydroxide NaOH, which
has a molecular weight of 23+16+1=40 would
have 40gms in a mole. Since the atomic weight
of the hydrogen ion H+ is one(1), there is one
gram of hydrogen ions in a mole of hydrogen.
A solution with a pH of 10 has 1*10-10 moles of
hydrogen ions or 10 -10 grams in one liter
solution.
Measurement of pH - The Electrode Method

The three main parts in the pH measuring cell are –

The Glass Electrode
The Reference Electrode
The Temperature Compensator.
KNO3 Gel
Reference Electrode
Sample Solution

Glass Electrode

Temperature Compensator

Liquid Junction
CONDUCTIVITY
What is conductivity?
Conductivity measures the ability of a solution to conduct electric
current between two electrodes.
It is also referred to as specific conductance or simply conductivity
Aqueous solutions of acids, bases or salts are known as electrolytes
and are direct conductors of electricity
The degree of electrical conductivity of such solutions is affected by
three factors : nature of the electrolyte, concentration & temperature
A measurement of conductivity at a fixed temperature can be a
measurement of the solution’s concentration which can be
expressed in % by weight, ppm etc.
If the number of ions in a liquid is very small, the solution will be
“resistive” to current flow.
In a solution, current travels by ion
transport.Therefore with an increasing amount
of ions present in the liquid, the liquid will have a
higher conductivity, _Current
+
Source
__ +
__ +
__ +
+ - + +
- -
- +
The primary element in an electrical
conductivity system is the conductivity cell
To wheatstone
Bridge circuit

A
C
L

Area A=Area of electrodes (cm2)

L= Distance betn. Electrodes (cm)
L
 Electrodeless Measurement

In applications where the

measured solution tends to coat
,plug or abrade the sensor a
toroidal element can be used.
It uses the principles of Induced
current in two close coupled coils
The coil (Toroid) ‘A’ induces a
current in the fluid which inturn
induces a current in coil ‘B’, the
output current amplitude is
attenuated by the resistance
(hence conductance) of the
solution.
 ANALYZERS PRESENT IN PLANT
Tag No: Service Range Background composition Zero gas Span Gas
01-AR-01 OXYGEN 0-0.08% CO2 - 97.25%, N2 - 1.63% C02 0.08% of
O2 in CO2
02-AR-002 METHANE CO2 - 5.15%, H2 - 36.17%, 0.8% CH4 in N2
0-1%
N2 - 15.55%, CO - 7.92%, N2
AR - 0.19%, H2O - 34.63%
02-AR-003 FLUE GAS CO2 - 13.01%, H2 - CO N2
36.17%, N2 - 15.55%, CO -
7.92%, AR - 0.19%, H2O -
34.63%
02-AR-001 FLUE GAS Flue Gas
03-AR-002 H2 (60-80%) H2 - 72.16%, N2 - 25.58%, 80% H2, 60% H2, Balance
CO - 0.44%, AR - 0.3%, Balance N2 N2
CH4 - 0.63%, H20 - 0.79%
03-AR-001 C02 0-5000ppm Flue Gas 4000 ppm N2
CO2 in N2
03-AR-003 CH4 0-2% OR 0- H2O - 0.32%, N2 16% CH4 in N2, N2
10% - 26.15%, CH4 - 8% CH4 in N2
1.2%, AR -
0.31%
03-AR-004 CO+CO2 0-25PPM AR - 0.31%, N2 - CO + CO2 must N2
26.15%, H2 - be 80 - 90% of
72.02%, H2O - Operating Range
0.32%

03-AR-006 PROCESS Buffer Solution, Buffer

CONDENSATE pH - 4.0 (Acidic), Solution, pH -
pH - 9.22 (Basic) 6.88 at 20 Deg
at 20 Deg C C
05-AR-001 H2 40-80% N2 - 19.04%, 80% H2, Balance 40% H2,
CH4 - 7.01%, AR N2 Balance N2
- 2.16%, NH3 -
14.67%
05-AR-002 CH4 N2 - 19.04%, 8% CH4 in N2 4% CH4 in N2
4-8% CH4 - 7.01%, AR
- 2.16%, NH3 -
14.67%

05-AR-101 NH3 0-80 PPM H2 - 61.66%, N2 800 ppm NH3, N2

- 20.54%, AR - Balance N2
2.34%, CH4 -
7.55%