ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

ANALYTICAL INSTRUMENTATION
UNIT III – COMPLETE EXAM NOTES
Industrial Gas Analyzers & Pollution Monitoring Instruments

[Link] 3rd Year | Electronics & Instrumentation Engineering

Reference: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.)

■ Subject Analytical Instrumentation

■ Unit III – Gas Analyzers & Pollution Monitoring

■ Level [Link] 3rd Year | E&I

■ Reference R.S. Khandpur – 3rd Edition

■ Purpose University Exam Preparation (5–10 Mark Answers)

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 1
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ UNIT III – SYLLABUS OVERVIEW

Types of gas analyzers: Oxygen, NO2 and H2S types, IR analyzers, thermal conductivity analyzers, analysis
based on ionization of gases. Air pollution due to carbon monoxide, hydrocarbons, nitrogen oxides, sulphur
dioxide estimation – Dust and smoke measurements.

Topic
Topic Name Marks Weightage
#

1 Oxygen Analyzers (Paramagnetic, Electrochemical) 5–10 marks

2 NO2 Analyzers (Chemiluminescence, Electrochemical) 5–10 marks

3 H2S Analyzers (Electrochemical, Lead Acetate) 5 marks

4 IR (Infrared) Analyzers – NDIR 10 marks

5 Thermal Conductivity Analyzers (TCD) 5–10 marks

6 Ionization-Based Analyzers (FID, PID) 5–10 marks

7 Air Pollution – CO, HC, NOx, SO2 Estimation 10 marks

8 Dust & Smoke Measurement 5–10 marks

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 2
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 1 – OXYGEN ANALYZERS

Oxygen analyzers measure the concentration of O2 in gas mixtures. They are critical in combustion control,
food packaging, medical monitoring, and industrial safety. Two main types are used: Paramagnetic and
Electrochemical.

1.1 Paramagnetic Oxygen Analyzer

■ Principle
Oxygen (O2) is a paramagnetic gas – it is strongly attracted to a magnetic field due to its two unpaired
electrons. Most other gases (N2, CO2, H2) are diamagnetic and are weakly repelled. This property is exploited to
measure O2 selectively.

Key Facts
• Paramagnetic susceptibility of O■ = +3449 × 10■■ (SI units) – highly positive

• NO is also paramagnetic but less so than O■, causing minor interference

• All other common industrial gases are diamagnetic (repelled by magnetic field)

■ Construction & Block Diagram

The analyzer consists of a dumbbell-shaped test body suspended in a non-uniform magnetic field. The dumbbell
contains nitrogen-filled spheres (diamagnetic). It is suspended by a taut quartz fibre with a small mirror attached.

Paramagnetic Oxygen Analyzer – Block Diagram

Sample Flow Magnetic Detector Output

Inlet Controller Field Cell (Dumbbell) Display

N
↑ Magnetic Field ↑

■■ Working
• The dumbbell test body is suspended in a strong non-uniform magnetic field created by shaped pole
pieces.
• When O■-containing sample gas flows around the dumbbell, O■ molecules (being paramagnetic) are
attracted toward the stronger part of the field.
• This creates a force that rotates the dumbbell away from its equilibrium position.
• A light beam reflected off the mirror detects the angular displacement.
• A feedback current through a coil around the dumbbell restores it to null position.
• The restoring current is directly proportional to the O■ concentration – this gives the output.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 3
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

O■ % ∝ Magnetic Susceptibility ∝ Restoring Current (I)

Output current is calibrated in % O■ (0–25%) or ppm

■ Advantages ■ Limitations

Highly selective for O■ Affected by paramagnetic gases like NO

Fast response time (< 10 seconds) Requires vibration-free mounting

No chemical reagents needed Temperature and pressure must be stable

Wide range: 0–100% O■ Expensive to manufacture

Non-consuming – sample not altered Cannot measure O■ in corrosive gas streams

■ Applications
• Combustion control in boilers and furnaces

• Monitoring O■ in flue gases (environmental compliance)

• Medical oxygen monitoring (life support systems)

• Food packaging (Modified Atmosphere Packaging – MAP)

• Chemical plant safety – detecting O■-deficient atmospheres

1.2 Electrochemical Oxygen Analyzer (Galvanic Cell)

■ Principle
Based on electrochemical reduction of O■ at a cathode in an electrolytic cell. O■ diffuses through a
semipermeable membrane, gets reduced at the cathode, and oxidizes the anode material. The resulting current
is proportional to O■ partial pressure.

Cathode: O■ + 2H■O + 4e■ → 4OH■ | Anode: Pb → Pb²■ + 2e■

Overall: O■ + 2Pb + 2H■O → 2Pb(OH)■ | Output Current ∝ [O■]

■■ Working
O■ diffuses through a Teflon/PTFE membrane → reaches gold or platinum cathode → electrochemical
reduction occurs → small current flows through external circuit → current measured by microammeter →
calibrated to give O■ %. The lead (Pb) anode is consumed over time and requires periodic replacement.

■ EXAM IMPORTANT
■ Paramagnetic type uses magnetic susceptibility; Electrochemical type uses redox reactions

■ Galvanic cell = NO external voltage needed. Polarographic cell = External voltage applied

■ Anode material in Galvanic type = Lead (Pb); Cathode = Gold (Au) or Platinum (Pt)

■ Frequently asked: Distinguish between paramagnetic and electrochemical O■ analyzers

■ QUICK REVISION SUMMARY

✓ O■ is paramagnetic due to 2 unpaired electrons → basis of paramagnetic analyzer

✓ Dumbbell test body deflection is proportional to O■ concentration

✓ Electrochemical analyzer: O■ reduced at cathode → current output

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 4
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

✓ Galvanic cell is self-powered; polarographic cell needs bias voltage

✓ Applications: combustion control, food packaging, medical, safety monitoring

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 5
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 2 – NO■ (NITROGEN DIOXIDE) ANALYZERS

NO2 is a toxic reddish-brown gas produced in combustion and industrial processes. It is a major air pollutant
causing respiratory diseases and acid rain. Analyzers measure NO2 in ambient air, stack emissions, and
industrial atmospheres.

2.1 Chemiluminescence NO/NO■ Analyzer

■ Principle
Based on the chemiluminescence reaction between NO and ozone (O3). When NO reacts with O3, it
produces NO2* (excited state) which emits photons (light) as it decays to ground state. The light intensity is
proportional to NO concentration.

NO + O■ → NO■* + O■ → NO■* → NO■ + hν (photons, λ = 600–3000 nm)

Light intensity (hν) ∝ [NO] | For NO■ measurement: NO■ is first converted to NO

■■ Working
• Sample gas enters and is split into two paths: direct NO path and NO■ converter path.
• In the converter path, NO■ is thermally reduced to NO using a molybdenum catalyst at ~315°C.
• Both streams are reacted with excess O■ (generated by UV ozonator) in the reaction chamber.
• Chemiluminescent light (600–3000 nm) is emitted and detected by a photomultiplier tube (PMT).
• Output signal proportional to NO; by subtraction (NOx − NO), NO■ is calculated.
• Range typically 0–500 ppb (ambient) to 0–10,000 ppm (stack gas).

Measurement Channels
• NO channel: sample → reaction chamber + O■ → PMT → NO reading

• NOx channel: sample → Mo converter → reaction chamber + O■ → PMT → NOx reading

• NO■ = NOx − NO (calculated by instrument)

2.2 Electrochemical NO■ Analyzer

■ Principle
NO2 is oxidized/reduced at a working electrode in an electrolytic cell containing an acidic electrolyte. The current
generated is proportional to NO2 concentration.

NO■ + 2H■ + 2e■ → NO + H■O (Reduction at cathode)

Alternatively: NO■ → NO■■ + e■ (Oxidation at anode) | Current ∝ [NO■]

■ Comparison of NO■ Analyzer Types

Analyzer Type Principle Range Sensitivity Main Use

Very high
Chemiluminescence NO + O■ → light ppb–ppm Ambient air monitoring
(sub-ppb)

Electrochemical Redox at electrode ppm range High (ppm) Personal safety monitors

NDIR IR absorption ppm–% Moderate Stack gas analysis

Colorimetric Chemical color reaction ppb–ppm High Lab analysis

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 6
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ EXAM IMPORTANT
■ Chemiluminescence analyzer is the STANDARD method for ambient NO/NO■ monitoring

■ PMT (Photomultiplier Tube) detects light in chemiluminescence analyzer

■ NO■ cannot directly emit chemiluminescence – must first convert to NO via Mo converter

■ Frequently asked: Working principle of chemiluminescence NO■ analyzer (10 marks)

■ QUICK REVISION SUMMARY

✓ NO■ analyzers: Chemiluminescence (most accurate), Electrochemical (portable), NDIR

✓ Chemiluminescence: NO + O■ → excited NO■* → emits photons detected by PMT

✓ For NO■ measurement: NO■ → NO (Mo converter at 315°C) → then chemiluminescence

✓ NOx = NO + NO■; NO■ is computed by subtraction

✓ Electrochemical: redox reaction at electrode → current ∝ [NO■]

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 7
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 3 – H■S (HYDROGEN SULPHIDE) ANALYZERS

Hydrogen sulphide (H2S) is a colorless, highly toxic, flammable gas with a characteristic rotten-egg odor. TLV
(Threshold Limit Value) = 1 ppm. LC50 = 600 ppm. Critical in petroleum refineries, sewage treatment plants, and
mines.

3.1 Electrochemical H■S Analyzer

■ Principle
H2S is oxidized at the sensing electrode of an amperometric electrochemical cell. The resulting anodic current is
proportional to H2S concentration in the sample gas.

Sensing Electrode (Anode): H■S → S + 2H■ + 2e■

Counter Electrode: O■ + 2H■ + 2e■ → H■O | Current ∝ [H■S]

H■S Electrochemical Analyzer – Block Diagram

Sample Filter / Electro- Signal Display /

Inlet Conditioner chem Cell Processor Alarm

Sensing Electrode (Anode) | Electrolyte | Counter Electrode (Cathode)

■■ Working
• Sample gas is filtered to remove particulates and conditioned (humidity control, temperature regulation).
• H■S diffuses through a hydrophobic membrane into the electrolytic cell.
• At the sensing (working) electrode, H■S is oxidized – releasing electrons.
• Current flows proportional to the H■S oxidation rate.
• Signal processor amplifies and conditions the signal for display.
• Alarm relay activates when H■S exceeds preset threshold (typically 5–10 ppm).

3.2 Lead Acetate Tape Method

■ Principle
H2S reacts with lead acetate [Pb(CH3COO)2] impregnated on a paper tape to form lead sulphide (PbS), which is
brown-black. The degree of staining is measured photometrically.

H■S + Pb(CH■COO)■ → PbS (brown-black) + 2CH■COOH

Optical density of PbS stain ∝ [H■S] | Measured by reflectance photometry

Lead Acetate Tape System Details

• Sample pump draws gas at fixed flow rate (typically 1–2 L/min) across tape

• Tape advances at fixed rate; each spot represents one time interval

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 8
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

• Reflectometer measures optical density of stain on tape

• Range: 0–50 ppm or 0–100 ppm H■S

• Suitable for continuous monitoring with automatic tape advance

Feature Electrochemical Lead Acetate Tape

Principle Electrooxidation Chemical staining + photometry

Response Time < 30 sec 1–5 minutes

Range 0–500 ppm 0–100 ppm

Consumables Cell (replace ~1 yr) Tape cassette (replace monthly)

Portability Portable/fixed Fixed installation

Selectivity Moderate High for H■S

■ EXAM IMPORTANT
■ H■S TLV = 1 ppm | IDLH (Immediately Dangerous to Life) = 100 ppm

■ Lead acetate tape method uses chemical color reaction – photometric detection

■ Electrochemical sensor uses amperometric principle – current output

■ Cross-sensitivity: SO■, mercaptans may interfere with electrochemical H■S sensors

■ QUICK REVISION SUMMARY

✓ H■S is highly toxic (TLV 1 ppm) – detected by electrochemical or tape methods

✓ Electrochemical: H■S oxidized at anode → current ∝ [H■S]

✓ Lead acetate tape: H■S + Pb(CH■COO)■ → PbS (brown) → reflectance measured

✓ Applications: petroleum refining, sewage, mines, chemical plants

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 9
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 4 – INFRARED (IR) ANALYZERS

Infrared analyzers exploit the fact that polyatomic gas molecules absorb IR radiation at specific
wavelengths corresponding to their molecular vibration frequencies. By measuring IR absorption, gas
concentration can be determined with high specificity.

■ Fundamental Laws
• Beer-Lambert Law: A = ε × c × L (A = absorbance, ε = molar absorptivity, c = concentration, L = path length)

• Transmittance: T = I/I■ | Absorbance: A = log(I■/I) = ε·c·L

• Homonuclear diatomics (N■, O■, H■, Cl■) do NOT absorb IR – no dipole moment change

• Polyatomic molecules (CO, CO■, SO■, NO, CH■, H■O) absorb IR strongly

Beer-Lambert Law: A = log(I■/I) = ε · c · L

I■ = incident intensity | I = transmitted intensity | ε = absorptivity | c = concentration | L = path length

4.1 Non-Dispersive Infrared (NDIR) Analyzer

■ Principle
In NDIR, no dispersive element (prism/grating) is used. Instead, the entire broadband IR from the source
passes through the sample. The detector is filled with the target gas (or uses a narrow-band optical filter),
making it selectively sensitive to only that gas's absorption wavelengths.

■ Block Diagram
Non-Dispersive Infrared (NDIR) Analyzer – Block Diagram

Reference Cell

(N■ / CO■-free air)

IR Motor Detector Amp &

Source Chopper (Luft/Pneumatic) Display

Sample Cell

(Gas Sample)

■■ Working (Dual Beam Type)

• Two identical IR sources (Globar/Nernst glower, ~700–1000°C) emit broadband IR radiation.
• A rotating sector mirror (chopper, ~10 Hz) alternately interrupts both beams to create AC signal.
• The reference beam passes through a sealed cell filled with non-absorbing gas (N■ or CO■-free air).
• The sample beam passes through the sample cell where target gas absorbs IR at specific wavelengths.
• Both beams reach the Luft detector (two-chamber capacitor microphone type).
• Unequal heating of the two detector chambers creates a pressure difference → diaphragm vibrates.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 10
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

• Vibrating diaphragm changes capacitance → AC electrical signal → amplified and displayed.

• Output signal = difference in absorption → proportional to concentration of target gas.

4.2 NDIR Detector Types

Detector Type Working Principle Selectivity Application

Luft Detector Pressure difference from IR heating

Very high (gas-filled) Classic NDIR for CO, CO■
(Pneumatic) → diaphragm capacitance change

Solid-State Photoconductivity: IR changes Moderate (filter

Modern NDIR analyzers
(PbSe, MCT) resistance needed)

Thermopile Seebeck effect: IR heat → voltage Low (broadband) General IR power measurement

Pyroelectric Polarization change with

Moderate FT-IR, portable analyzers
(DTGS, LiTaO■) temperature

4.3 IR Absorption Bands of Common Gases

Gas Primary IR Absorption Band (µm) Typical Concentration Range

CO (Carbon Monoxide) 4.67 µm 0–5000 ppm

CO■ 4.26 µm, 15 µm 0–5%, 400 ppm (ambient)

SO■ 7.35 µm, 8.7 µm 0–5000 ppm

NO 5.3 µm 0–1000 ppm

CH■ (Methane) 3.3 µm, 7.7 µm 0–100% LEL

H■O 2.7 µm, 6.3 µm Interference gas – removed

■ Advantages of NDIR ■ Limitations of NDIR

Highly selective – species-specific Cannot analyze homonuclear diatomics (O■, N■)

Continuous, real-time measurement Water vapor causes interference (must remove)

Wide dynamic range (ppb to %) Temperature and pressure affect readings

Low maintenance, robust Complex optical alignment required

Non-destructive – sample unchanged Cross-sensitivity with overlapping IR bands

Suitable for stack gas, process gas Initial cost is high

■ EXAM IMPORTANT
■ NDIR is the most widely used method for CO, CO■, SO■, CH■, NOx measurement

■ Luft detector = pneumatic detector using gas-filled capacitor microphone principle

■ Beer-Lambert Law is the mathematical basis for all IR analyzers

■ N■ and O■ CANNOT be measured by IR – no IR absorption (homonuclear)

■ Dispersive IR = uses prism/grating; Non-dispersive IR = uses optical filter/gas-filled detector

■ QUICK REVISION SUMMARY

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 11
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

✓ IR analyzer: polyatomic gas absorbs IR at specific λ → concentration from Beer-Lambert law

✓ NDIR uses no dispersive element; detector filled with target gas ensures selectivity

✓ Two beams: reference (N■) and sample; difference signal → concentration

✓ Luft detector: gas-heated pressure difference → vibrating diaphragm → capacitance change

✓ Cannot measure homonuclear diatomics (N■, O■, H■) – no IR absorption

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 12
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 5 – THERMAL CONDUCTIVITY ANALYZERS (TCD)

A Thermal Conductivity Detector (TCD) measures gas concentration based on the difference in thermal
conductivity between the sample gas mixture and a reference gas. Each gas has a unique thermal conductivity
value.

Thermal Conductivity Values (κ) at 25°C

• H■: κ = 0.172 W/m·K (highest among common gases – ~6× air)

• He: κ = 0.142 W/m·K

• Air (N■): κ = 0.026 W/m·K (reference)

• CO■: κ = 0.016 W/m·K

• Higher thermal conductivity → more heat dissipated from hot wire → lower wire temperature → lower
resistance

■ Principle
A tungsten or platinum filament (hot wire) is heated by a constant current in a cell through which gas flows.
The filament temperature depends on how efficiently the surrounding gas conducts heat away. When gas
thermal conductivity changes (due to sample gas presence), the filament temperature changes → resistance
changes → bridge imbalance signal → concentration output.

■ Construction – Wheatstone Bridge

Thermal Conductivity Detector (TCD) – Wheatstone Bridge Circuit

R4 R1
(Sample) (Ref)

R3 R2 Output
(Ref) (Sample)

Battery (Vb)

■■ Working
• Four identical metal filaments (W or Pt) form the four arms of a Wheatstone bridge.
• R1, R3 (reference cells) carry pure carrier/reference gas; R2, R4 (measuring cells) carry sample gas.
• All filaments are heated by a constant DC current to ~100–200°C above ambient.
• Reference filaments and sample filaments are in thermal equilibrium with their respective gas streams.
• When sample gas with different thermal conductivity enters R2/R4, their temperature changes.
• Temperature change → resistance change → bridge imbalance → output voltage ∆V.
• ∆V is proportional to the difference in thermal conductivity → proportional to concentration.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 13
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

∆V ∝ ∆κ = κ(sample mixture) − κ(reference gas) → ∆V ∝ concentration

Bridge output: ∆V = Vs × [∆R/(2R+∆R)] | ∆R ∝ ∆T ∝ ∆κ

5.1 Katharometer (TCD for H■ Detection)

A Katharometer is a specialized TCD used to detect H2 (and He) in gas mixtures. H2 has extremely high
thermal conductivity (~6× air), making it easy to detect. Used in synthesis gas analysis, fuel cell monitoring, and
gas chromatography.

■ Advantages ■ Limitations

Simple construction, robust Non-selective – measures bulk thermal conductivity

Responds to all gases (universal) Not suitable for trace analysis (ppb level)

Low cost, easy maintenance H■O vapor interferes strongly

Wide concentration range (ppm to %) Temperature sensitive – needs thermostating

Used as GC detector universally Cannot work if sample κ ≈ reference κ

■ Applications of TCD
• Gas chromatography (GC) – universal detector for all eluted compounds

• Hydrogen purity measurement in power station generators

• Helium purity analysis in industrial cylinders

• Binary gas mixture analysis (H■ in N■, CO■ in air)

• Blast furnace gas analysis (CO, CO■, H■, N■)

■ EXAM IMPORTANT
■ TCD is the most UNIVERSAL gas detector – responds to ALL gases

■ Wheatstone bridge with 4 filaments: 2 reference + 2 sample arms

■ Katharometer = specialized TCD; hot wire = W or Pt filament

■ Frequently asked: Explain working of TCD with Wheatstone bridge circuit (10 marks)

■ H■ has κ ≈ 6× air – hence H■ causes maximum deflection in TCD

■ QUICK REVISION SUMMARY

✓ TCD measures gas concentration based on thermal conductivity difference

✓ Wheatstone bridge: 4 filaments (R1–R4); R1,R3 = reference; R2,R4 = sample

✓ Bridge imbalance ∆V ∝ ∆κ ∝ concentration of sample gas

✓ Katharometer = TCD for H■/He detection (very high κ)

✓ Universal – detects any gas that differs in κ from carrier gas

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 14
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 6 – ANALYSIS BASED ON IONIZATION OF GASES

Ionization detectors measure gases by ionizing gas molecules and collecting the resulting ions/electrons as an
electric current. Particularly sensitive for organic compounds and hydrocarbons.

6.1 Flame Ionization Detector (FID)

■ Principle
When organic compounds (hydrocarbons) are burned in a H2/air flame, they produce ions and electrons (a
process called chemi-ionization). A polarizing voltage collects these ions as a current proportional to the
number of carbon atoms in the compound.

C■H■■■■ + O■ (H■/air flame) → CO■ + H■O + ions + electrons → current I

Signal current I ∝ number of carbon atoms × concentration | Detection limit: ~1 ppb for hydrocarbons

■■ Working
• Carrier gas (N■ or He) carries sample through the chromatographic column into FID.
• H■/air mixture burns in the detector jet, creating a hot (>2000°C) diffusion flame.
• Organic compounds entering the flame are pyrolyzed and ionized (chemi-ionization).
• Electrodes with polarizing voltage (+ve collector, −ve jet) collect ions/electrons.
• Resulting picoampere-level current is amplified by electrometer amplifier.
• Output current proportional to number of carbon-hydrogen bonds in the compound.

FID Key Characteristics

• FID does NOT respond to: CO■, H■O, O■, N■, SO■, NO■ (inorganic gases)

• FID responds to: ALL organic compounds containing C-H bonds

• Carbon number response: CH■=1, C■H■=2, C■H■=3, etc. (additive response)

• Used in GC for hydrocarbons; also in Total Hydrocarbon Analyzers (THC)

• Selectivity: Organic compounds >> Inorganic gases

6.2 Photoionization Detector (PID)

■ Principle
Uses UV photons to ionize gas molecules. If the photon energy (eV) exceeds the ionization potential (IP) of the
molecule, an electron is ejected. The resulting ion current is measured.

M + hν → M■ + e■ (if photon energy hν > ionization potential IP of M)

UV lamp energy: 10.6 eV (krypton), 11.7 eV (argon) | Ion current ∝ [M]

■ FID vs PID Comparison

Feature FID PID

Ionization Method Hydrogen flame (thermal) UV photons (non-destructive)

Gases Detected All C-H organics Organics with IP < lamp energy

H■ fuel required Yes No

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 15
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

Response to Inorganics No NH■, H■S (if IP < lamp)

Sensitivity ppb–ppm ppb–sub-ppb

Portability Limited (H■ gas needed) Highly portable

Main Application GC, THC analyzer VOC surveys, field monitoring

■ EXAM IMPORTANT
■ FID is the STANDARD detector for hydrocarbon (HC) analysis in ambient air monitoring

■ FID signal ∝ number of C-H bonds – responds to carbon atoms, not molecular weight

■ PID uses UV ionization – no flame needed – ideal for field/portable VOC detection

■ Neither FID nor PID can detect homonuclear diatomics or fully oxidized species

■ QUICK REVISION SUMMARY

✓ FID: organic compounds burned in H■/air flame → ions → current ∝ carbon atoms

✓ PID: UV photons ionize molecules with IP < photon energy → ion current output

✓ FID: used in GC, Total Hydrocarbon (THC) analyzers for ambient HC monitoring

✓ PID: highly portable, sensitive, no H■ required – field VOC detection

✓ Both are selective for organics; insensitive to CO■, H■O, N■, O■

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 16
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 7 – AIR POLLUTION MONITORING

Air pollution monitoring involves continuous measurement of pollutant concentrations to ensure compliance with
ambient air quality standards (NAAQS – National Ambient Air Quality Standards). Key pollutants include CO,
hydrocarbons (HC), NOx, and SO2.

Air Pollution Monitoring – Continuous Ambient Air Quality Monitor

Sample Sample Analyzer Data Display /

Pump Conditioner Module Logger Transmitter

CO NOx SO■ HC O■ PM

Target Pollutants

■ NAAQS – National Ambient Air Quality Standards (India)

NAAQS Standard Averaging
Pollutant Measurement Method
(India) Time

SO■ 80 µg/m³ 24-hour UV Fluorescence / NDIR

NO■ 80 µg/m³ 24-hour Chemiluminescence

CO 4 mg/m³ 8-hour NDIR / Electrochemical

O■ 180 µg/m³ 1-hour UV Photometry

PM10 100 µg/m³ 24-hour Gravimetric / Beta Attenuation

PM2.5 60 µg/m³ 24-hour Gravimetric / TEOM

Pb 0.5 µg/m³ Annual AAS after filter collection

7.1 Carbon Monoxide (CO) Estimation

CO is a colorless, odorless, toxic gas produced by incomplete combustion. It binds to hemoglobin (230× more
strongly than O2), causing asphyxiation.

Method Principle Range Notes

NDIR Analyzer IR absorption at 4.67 µm 0–1000 ppm Most common; reference method

Electrochemical Oxidation at Pt electrode 0–1000 ppm Portable monitors

CO→CO■ with catalyst; heat

Catalytic Oxidation ppm–% Simple, robust
measured

GC-FID Separation + FID detection ppb Lab standard method

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 17
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ Sources of CO: Motor vehicle exhaust (main source), incomplete combustion in boilers/furnaces, cigarette
smoke. In urban areas, CO from vehicles contributes >90% of ambient CO.

7.2 Hydrocarbon (HC) Estimation

Hydrocarbons include methane (CH4) and Non-Methane Hydrocarbons (NMHC). NMHC are precursors to
photochemical smog. Measurement is done as Total Hydrocarbons (THC) using FID.

THC Analyzer System

• THC Analyzer uses FID (Flame Ionization Detector) as the sensing element

• CH■ column + FID measures methane specifically; THC − CH■ = NMHC

• FID flame gas: H■ (40 mL/min) + air (400 mL/min); carrier: N■ or He

• Range: 0–100 ppm C (expressed as equivalent carbon atoms)

• Key sources: unburned fuel from engines, solvent evaporation, petroleum operations

7.3 Nitrogen Oxides (NOx) Estimation

NOx = NO + NO2. Primary pollutant from high-temperature combustion. In atmosphere, NO oxidizes to NO2
which causes photochemical smog, acid rain, and respiratory damage.

■■ Chemiluminescence NOx Analyzer – Process Flow:

• Ambient sample enters → split into two streams
• Stream 1 (NO): directly to chemiluminescence reaction chamber
• Stream 2 (NOx): passes through Mo converter (315°C) → NO■ converted to NO → reaction chamber
• Both react with O■ from UV ozonator → light emission detected by PMT
• NO signal from stream 1 directly; NOx from stream 2; NO■ = NOx − NO

NO + O■ → NO■* + O■ → NO■ + hν | Light ∝ [NO] | NO■ = NOx − NO

PMT detects 600–3000 nm emission | O■ generated from air by UV lamp at 185 nm

7.4 Sulphur Dioxide (SO■) Estimation

SO2 is a colorless, pungent toxic gas from combustion of sulphur-containing fuels (coal, oil). Major cause of acid
rain. NAAQS: 80 µg/m3 (24-hr).

Method Principle Details

UV Fluorescence SO■ absorbs UV at 214 nm → re-emits fluorescence Most sensitive; range: ppb to ppm;
(Primary/Reference) at ~330 nm Fluorescence intensity ∝ [SO■] EPA reference method

Less sensitive; used in stack

NDIR IR absorption at 7.35 µm and 8.7 µm
monitoring

Pulsed UV excitation reduces photodecomposition Standard method in CAAQMS

Pulsed Fluorescence
Improved sensitivity and stability networks

Conductometric SO■ absorbed in K■S■O■ → colored compound

Wet chemical reference method
(West-Gaeke) Measured photometrically

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 18
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

UV Fluorescence: SO■ + hν (214nm) → SO■* → SO■ + hν' (fluorescence ~330nm)

Fluorescence intensity F ∝ [SO■] | Interferences: aromatic HCs quench fluorescence (use HC scrubber)

■ EXAM IMPORTANT
■ UV fluorescence is the EPA/CPCB reference method for ambient SO■ monitoring

■ Chemiluminescence is the reference method for NOx; NDIR for CO

■ FID is used for Total Hydrocarbon (THC) measurement

■ NOx = NO + NO■; measured by chemiluminescence with Mo converter for NO■

■ NAAQS values must be memorized for SO■, NO■, CO, O■, PM10, PM2.5

■ QUICK REVISION SUMMARY

✓ CO: measured by NDIR at 4.67 µm – most common method

✓ HC: measured by FID as THC; NMHC = THC − CH■

✓ NOx: chemiluminescence – NO + O■ → light; NO■ via Mo converter

✓ SO■: UV fluorescence at 214 nm excitation, ~330 nm emission

✓ CAAQMS (Continuous Ambient Air Quality Monitoring Station) uses all above methods

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 19
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

SECTION 8 – DUST AND SMOKE MEASUREMENTS

Particulate matter (dust and smoke) consists of solid/liquid particles suspended in air. Classified by aerodynamic
diameter: TSP (Total Suspended Particles), PM10 (≤10 µm), PM2.5 (≤2.5 µm), PM1.0. Fine particles (PM2.5)
penetrate deep into lungs and are most harmful.

Particle Type Size Range Health Effect Measurement

TSP > 10 µm Settles in nose/throat High Volume Sampler

PM10 (Inhalable) ≤ 10 µm Penetrates bronchi Impactor + filter

PM2.5 (Fine) ≤ 2.5 µm Reaches alveoli PM2.5 impactor, TEOM

PM1.0 (Ultrafine) ≤ 1.0 µm Enters bloodstream OPC, CPC

Smoke 0.1–1 µm Toxic combustion products Ringelmann/opacity

8.1 Optical Methods – Light Scattering

■ Principle
When a beam of light passes through a medium containing suspended particles, the particles scatter light in all
directions (Mie or Rayleigh scattering). The intensity of scattered light is proportional to the particle
concentration.

Mie Scattering: I_scatter ∝ N × d■ / λ■ (for d << λ, Rayleigh regime)

N = number of particles | d = particle diameter | λ = wavelength of light

Optical Dust Monitor – Light Scattering Principle

Laser/LED Sensing Beam Signal

Source Zone Trap Processor

↓ Scattered Light

Photo-

Detector

■■ Working
• Laser or LED source emits a focused beam through the sensing zone.
• Dust-laden air sample is drawn through the sensing zone by a pump.
• Particles in the sensing zone scatter light at 90° (or forward scatter).
• Photodetector (avalanche photodiode or PIN diode) positioned at 90° detects scattered light.
• Pulse counting mode: each particle pulse counted to give number concentration.
• Analog mode: scattered light intensity proportional to mass concentration (µg/m³).
• Beam trap on the far side absorbs direct beam to prevent detector saturation.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 20
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

8.2 Beta Ray Attenuation Monitor (BAM)

■ Principle
Beta (β) particles (electrons from radioactive source ¹■C) are attenuated when passing through a
particulate-laden filter tape. The degree of attenuation is proportional to the collected particle mass.

I = I■ × e^(−µm) (Beer-Lambert for beta rays)

I = transmitted beta intensity | I■ = incident intensity | µ = mass attenuation coefficient | m = areal mass (µg/cm²)

BAM System Details

• Sample is collected on filter tape (glass fiber) for a fixed time interval

• Beta source: ¹■C (half-life 5730 years) – low-energy, safe

• Geiger-Müller or scintillation detector measures beta intensity before/after collection

• Mass = calculated from attenuation using calibration equation

• Suitable for PM10 and PM2.5 (with appropriate size-selective inlet)

• EPA Federal Reference Method (FRM) equivalent – widely used in CAAQMS

8.3 Gravimetric Method (Reference Method)

■ Principle: Air is drawn through a pre-weighed filter at controlled flow rate. The filter is re-weighed after
collection. The mass increase divided by the total air volume gives PM concentration in µg/m3.

PM Concentration (µg/m³) = (Mass gain of filter, µg) / (Volume of air sampled, m³)
Filter must be conditioned at 20±1°C, 50±5% RH for 24 hrs before weighing

8.4 Smoke Density Measurement – Ringelmann Chart

■ Principle: The Ringelmann Chart is a visual method for estimating smoke density from chimneys. It consists
of 5 cards numbered 0–5, each with a grid pattern of increasing blackness (0 = clear to 5 = totally black).

Ringelmann
% Blackness Description Permissible?
Number

0 0% Clear sky / no smoke ■ Yes

1 20% Light grey smoke ■ Yes

2 40% Grey smoke ■■ Marginal

3 60% Dark grey smoke ■ No

4 80% Very dark smoke ■ No

5 100% Dense black smoke ■ No (banned)

■ Note: In India, Ringelmann 1 or less is generally permitted from industrial stacks. Stack opacity > Ringelmann
2 is a violation. Electronic opacity meters (transmissometers) are now used for continuous monitoring.

8.5 TEOM (Tapered Element Oscillating Microbalance)

■ Principle: A tapered glass element coated with a filter oscillates at its natural resonant frequency. As particles
deposit on the filter, the mass increases → resonant frequency decreases. Change in frequency is proportional

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 21
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

to mass deposited.

∆m = K■ × f■² × (1/f■² − 1/f■²)

∆m = mass change | f■ = initial frequency | f■ = frequency after collection | K■ = instrument constant

■ Comparison of Dust/Smoke Measurement Methods

Method Principle Real-time? PM Size Key Feature

TSP/PM10/P
Gravimetric Filter + weighing No (offline) Gold standard / reference
M2.5

Beta Attenuation
β-ray attenuation by filter Yes (hourly) PM10/PM2.5 FRM equivalent
(BAM)

Light Scattering
Mie/Rayleigh scattering Yes (1 min) PM1–PM10 Size-resolved, portable
(OPC)

TEOM Oscillating microbalance Yes (1 hr) PM2.5/PM10 Continuous mass

Smoke
Ringelmann Chart Visual opacity comparison Manual only Simple, regulatory use
opacity

■ EXAM IMPORTANT
■ Gravimetric method is the PRIMARY/REFERENCE method for PM measurement

■ BAM (Beta Attenuation Monitor) uses ¹■C beta source – most used in CAAQMS

■ Ringelmann Chart: 0 (clear) to 5 (black) – 6 levels; measures stack smoke opacity

■ TEOM: frequency change ∝ mass deposited – continuous real-time PM monitor

■ Light scattering (OPC): measures scattered light at 90° – gives particle count & size

■ QUICK REVISION SUMMARY

✓ Dust: solid/liquid particles classified as TSP, PM10, PM2.5, PM1.0 by aerodynamic diameter

✓ Light scattering: laser/LED → 90° scatter from particles → photodetector → concentration

✓ BAM: beta rays attenuated by collected filter mass → I = I■·e^(−µm) → PM mass

✓ Gravimetric: filter mass difference / air volume = PM concentration (µg/m³)

✓ Ringelmann: visual smoke opacity scale 0–5 (0=clear, 5=dense black)

✓ TEOM: oscillating element frequency decreases as PM mass accumulates

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 22
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ MASTER COMPARISON TABLE – ALL GAS ANALYZERS

Gas Mea
Analyzer Principle Detector Range Key Application
sured

Magnetic
Paramagnetic Null-balance 0–100% Combustion
O■ susceptibility (O■ is
O■ Analyzer dumbbell O■ control
paramagnetic)

Electrochemical Galvanic cell (O■ Pb anode, 0–25% Medical, food

O■
O■ Analyzer reduction) Au cathode O■ packaging

Chemiluminesce NO,
NO + O■ → NO■* → PMT (photo ppb–ppm Ambient air
nce NO■ NO■,
photon emission multiplier) NO/NO■ monitoring
Analyzer NOx

Electrochemical Redox at working Amperometr

NO■ ppm Safety monitors
NO■ Analyzer electrode ic cell

H■S
Oxidation of H■S at Amperometr 0–500 Petroleum,
Electrochemical H■S
anode ic cell ppm sewage
Analyzer

Lead Acetate H■S + Pb acetate → Reflectance 0–100 Continuous H■S

H■S
Tape Method PbS stain photometer ppm monitoring

CO,
Luft
CO■,
IR absorption at (pneumatic) Process gas,
NDIR Analyzer SO■, ppb–%
specific λ or stack, ambient
NOx,
solid-state
CH■

H■, He,
Wheatstone
TCD / binary Thermal conductivity GC detector, H■
bridge (hot ppm–%
Katharometer gas difference purity
wire)
mixtures

Total HC Ion
Chemi-ionization in THC monitor, GC
FID (organics collection (el ppb–% C
H■/air flame detector
) ectrometer)

Ion
VOCs, UV photoionization Field VOC
PID collection ppb–ppm
organics (IP < hν) surveys
chamber

UV UV excitation
PMT or ppb–ppm Ambient SO■
Fluorescence SO■ (214nm) →
photodiode SO■ monitoring
(SO■) fluorescence (330nm)

PM10/P Beta ray attenuation Geiger-Müll CAAQMS PM

BAM (Dust) µg/m³
M2.5 by collected filter er detector monitoring

Light Scatter PM1–PM Mie/Rayleigh Photodiode/ µg/m³ or Real-time PM,

(Dust) 10 scattering at 90° APD #/cm³ portable

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 23
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ KEY FORMULAS AND DEFINITIONS

Beer-Lambert Law:

A = ε · c · L = log(I■/I)
A=absorbance, ε=molar absorptivity (L/mol·cm), c=concentration (mol/L), L=path length (cm)

Transmittance:

T = I/I■ and A = −log(T)

T=fraction of light transmitted; A and T are inversely related

TCD Bridge Output:

∆V = f(∆κ) = f(κ_sample − κ_reference)

∆V proportional to difference in thermal conductivity

Beta Attenuation:

I = I■ · e^(−µm)
µ=mass attenuation coefficient (~0.3 cm²/mg); m=areal mass density (mg/cm²)

PM Concentration (Gravimetric):

C (µg/m³) = ∆m / V
∆m = mass gain of filter (µg); V = volume of air sampled (m³)

TEOM Mass:

∆m = K■ · f■² · (1/f■² − 1/f■²)

K■=instrument spring constant; f■=baseline frequency; f■=measurement frequency

Chemiluminescence:

I_light ∝ [NO] × [O■]

Light intensity proportional to NO and O■ concentrations; excess O■ used

FID Response:

Signal ∝ Σ(n■ × C■)

n■ = effective carbon number of compound i; C■ = concentration of compound i

Key Definitions
Paramagnetism:
Property of materials with unpaired electrons that are attracted to a magnetic field. O■ has 2 unpaired electrons
→ strongly paramagnetic.

Chemiluminescence:
Emission of light as a result of a chemical reaction (not heat). Used in NO/NO■ analysis (NO + O■ reaction).

NDIR (Non-Dispersive IR):

IR analyzer that uses no dispersive element (prism/grating). Selectivity achieved by detector filled with target
gas or narrow-band optical filter.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 24
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

Thermal Conductivity (κ):

Rate of heat conduction through a gas (W/m·K). Different for each gas – basis of TCD/Katharometer
measurement.

Luft Detector:
Pneumatic IR detector named after inventor. Uses two gas-filled chambers separated by flexible diaphragm.
Differential IR absorption creates pressure difference → capacitance change.

CAAQMS:
Continuous Ambient Air Quality Monitoring Station. Automated station measuring SO■, NO■, CO, O■, PM10,
PM2.5 continuously.

Ringelmann Number:
Visual scale (0–5) for smoke opacity from chimneys. 0=clear, 5=totally black (100% opaque).

TLV (Threshold Limit Value):

Maximum allowable concentration of a chemical in workplace air for 8 hrs/day, 5 days/week without health
effects.

PMT (Photomultiplier Tube):

Highly sensitive light detector. Used in chemiluminescence analyzers. Converts photons to electron cascade →
amplified current.

Ionization Potential (IP):

Minimum energy required to remove an electron from a neutral gas molecule. PID lamp must exceed IP of target
compound.

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 25
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

■ FREQUENTLY ASKED EXAM QUESTIONS

10-Mark Questions
1. Explain the construction and working principle of a Non-Dispersive Infrared (NDIR) Analyzer with a neat block
diagram. What is the role of the Luft detector?

2. Describe the working of a Chemiluminescence NOx Analyzer with block diagram. How is NO■ measured
separately?

3. With a neat diagram, explain the Thermal Conductivity Detector (TCD). Draw and explain the Wheatstone
bridge circuit used.

4. Explain in detail how air pollution due to SO■ is estimated using UV fluorescence method. Give the reaction,
block diagram, and NAAQS standard.

5. Write a detailed note on Dust and Smoke Measurement methods: (a) Light Scattering (b) Beta Attenuation
Monitor (c) Gravimetric method.

5-Mark Questions
1. What is the principle of paramagnetic oxygen analyzer? Why is O■ paramagnetic?

2. Explain the Lead Acetate Tape Method for H■S detection with chemical reaction.

3. Compare FID and PID gas analyzers with respect to principle, sensitivity, and application.

4. What is Beer-Lambert Law? How is it applied in IR gas analysis?

5. Explain the working of a Galvanic Cell type O■ analyzer. Give electrode reactions.

6. What is the Ringelmann Chart? List the 6 numbers with their % blackness.

7. Explain TEOM principle for PM measurement. Give the formula used.

8. Describe the electrochemical H■S analyzer with construction and working.

Short Notes (2–3 marks)

1. Katharometer | 2. Luft Detector | 3. PMT in analyzers | 4. NAAQS standards

5. Mie Scattering | 6. Chemiluminescence reaction | 7. BAM (Beta Attenuation Monitor)

8. UV Fluorescence SO■ method | 9. Ionization potential in PID | 10. Mo Converter in NOx analyzers

■ EXAM STRATEGY TIPS

✓ Always draw a labeled block diagram for 10-mark instrument questions

✓ Include: Principle → Construction → Working → Advantages → Limitations → Applications

✓ For working principles, write chemical equations wherever applicable

✓ Memorize NAAQS values for SO■, NO■, CO, O■, PM10, PM2.5

✓ Know the reference methods: CO→NDIR, NOx→Chemiluminescence, SO■→UV Fluorescence,

PM→Gravimetric/BAM

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 26
ANALYTICAL INSTRUMENTATION – UNIT III Industrial Gas Analyzers & Pollution Monitoring

✓ Compare at least 2 analyzer types in comparison questions (use a table)

✓ Beer-Lambert law formula must be written with all symbol definitions

■ All the Best for Your Exams!

Reference: Handbook of Analytical Instruments – R.S. Khandpur (3rd Edition) | Prepared for [Link] 3rd Year
Electronics & Instrumentation Engineering

[Link] E&I | Ref: Handbook of Analytical Instruments – R.S. Khandpur (3rd Ed.) Page 27