ABSTRACT
Introduction 19 Preparation Phase 19
The Orientation Table 20 Obtaining Preliminary Quotations 26 De ning the Purpose of the Analysis 26 Information Gathering 27
Selection Considerations 27 Speci city 27 Accuracy and Precision 28 Calibration 28 Analysis Frequency 28
Analyzer Types 29 Chromatographs 29 Spectrometers 29 Electrochemical Analyzers 34 Wet Chemistry Analyzers 36 Miscellaneous Techniques 36 Analyte-Speci c Techniques 37 Sampling Techniques 37 Fiber-Optic Probes (FOP) 38 Probe Cleaners 41
Analyzer Location 42 Data Handling 43 Maintenance 44 Cost 44 Conclusions 45 Speci cation Forms 45
Organizations 50 Bibliography 50 Basics 51 Measurement Applications 51
1.2 ANALYZER SAMPLING 53
Introduction 54 General Considerations 54
Feasibility Evaluation 54 Sample System Speci cation 55 Sampling Point Location 56 Sample Transport 56 Transport Lag 57 Sample Disposal 57 Ambient Effects 58 Test and Calibration 58
Sampling System Component Selection 58 Filtering and Separation 59 Separating Liquids from Gases 59 Spargers, Packed Towers, and Strippers 60 Separating Two Liquid Phases 62 Gas Removal from Liquids 62 Bypass Filters 63 Self-Cleaning Filters 63 Automatic Probe Cleaning 65 Homogenizers 65
Sample Conditioning 66 Vaporizing Samples 67 Entrainment Removal 68 Selection of Component Materials 68
Sampling at High Pressure 71 Chemical Reactor Samplers 71 Duckbill Samplers 72
Solids Sampling 72 Dif cult Process Sampling 73
Trace Analysis Sampling 73 Multistream Sampling 74 Sampling for Mass Spectrometers 75 New Sample System Initiative
(NeSSI™) 75 Conclusions 75 Speci cation Forms 75 De nition 78 Abbreviations 78 Organizations 78 Bibliography 78
1.3 ANALYZER SAMPLING 79
Introduction 79 The EPA Particulate Sampling System 80
Microprocessor-Controlled Stack Sampling 80
Pitot Tube Assembly 81 Heated Compartment (Hot Box) 84 Ice-Bath Compartment (Cold Box) 84 Control Unit 84
Automatic Sampling Trains 85 Sampling for Gases and Vapors 86
Speci cation Forms 86 Abbreviations 90 Organizations 90 Bibliography 90
1.4 ANALYZER SAMPLING 91
Introduction 93 Air Quality Monitoring 93
Air Quality Standards 93 Single Source (Stacks) Monitoring 94 Urban Area Monitoring 94 Sampling Site Selection 95
Monitoring Methods 95 Static Monitoring 95 Laboratory Analyses 96
Gas and Vapor Sampling 101 Bag Sampling 101
Particulate Sampling 103 Speci cation Forms 105 De nitions 108 Abbreviations 108 Organizations 108 Bibliography 108
1.5 AMMONIA ANALYZERS 109
Introduction 110 Ammonia Measurement in Liquids 110 Colorimetric Method 110 Ion-Selective Method (ISE) 111 UV Spectrophotometry Method 112 Ammonia in Gases 112 Tunable Diode Laser (TDL) 113 Conclusion 113 Speci cation Forms 114 Abbreviations 116 Bibliography 116
1.6 BIOMETERS TO QUANTIFY MICROORGANISMS 117
Introduction 117 ATP and Living Organisms 118 ATP Analysis 118 Luminescence Biometer 119 Speci cation Forms 120 Abbreviations 122 Organization 122 Bibliography 122
1.7 CARBON DIOXIDE 123
Introduction 124 Role in Global Warming 124 Emissions 125 Ambient Air Measurement 126
Nondispersive Infrared Sensors 126 Gas Filter Correlation Type 127
Source Measurement 127 Speci cation Forms 128 Abbreviations 131 Bibliography 131
1.8
Analyzer Types 134
Nondispersive Infrared (NDIR) 134 Interferences 135 Gas Filter Correlation (GFC) 135 Mercury Vapor Analyzer 135 Gas Chromatograph 136 Electrochemical 137
Portable Monitors 137 Catalytic Analysis 138
Spot Sampling of Ambient Air 138 Conclusions 138 Speci cation Forms 138 Abbreviations 141 Organizations 141 Bibliography 141
1.9 CHLORINE ANALYZERS 142
Introduction 143 Chlorine in Gas and Water 144 Analyzer Types 145
Iodometric 145 Colorimetric 145 Amperometric 146
Regulations 150 Conclusions 150 Speci cation Forms 151 De nitions 153 Organizations 153 Bibliography 153
1.10 CHROMATOGRAPHS 154
Introduction 155 The Separation Process 155 The System Structure 156 The Process Gas Chromatograph (PGC) 157 Components of a PGC 158
Analyzer 158 Oven 159 Valves 160 Rotary Valve 161 Sliding Plate Valve 161 Diaphragm Valve 161
Flame Ionization Detector (FID) 168 Flame Photometric Detector (FPD) 169 Pulsed FPD 170 Ori ce-Capillary Detector (OCD) 172 Miscellaneous Detectors 172 Photoionization Detector (PID) 172 Electron Capture Detector (ECD) 173 Discharge Ionization Detectors 174 Pulsed Discharge Detector
(PDD) 174 Carrier Gas Flow Control 175 Programmer Controller 175
Programmer 176 Peak Processor 176
Microprocessor Operated PGC 176 Input-Output 176 Communication 177
Operator Interface 178 Alarms and Diagnostics 180 Quantitation 180
Sample Handling 180 Sample Probe 180 Sample Transport 181 Sample Conditioning 181 Multistream Analysis 183 Sample Disposal 183
Installation 183 Advances 184 Summary and Acknowledgments 185 Speci cation Forms 185 De nitions 188 Abbreviations 188 Bibliography 189
1.11 CHROMATOGRAPHS 190
Introduction 191 Comparison with Gas
Chromatographs 192 Main Components 192
Carrier Supply 192 Supply Pumps 193 Pressure and Flow Controls 193 Valves 193
Columns 193 Selectivity and Resolution 194 Liquid-Partition Columns 194 Liquid-Adsorption Columns 194 Gel Permeation Columns 195 Ion Exchange Columns 195 Electrophoresis 195
Applications 196 Speci cation Forms 196 De nitions 199 Abbreviations 199 Bibliography 199
1.12 COAL ANALYZERS 200
Introduction 200 Coal Property Measurement 201 Laboratory Techniques 202
Thermogravimetry 202 Bituminous Coal Analysis 202 Gross Calori c Value 202 Total Sulfur 203 Ash Analysis 204
On-Line Monitors 204 Prompt Gamma Neutron Activation
Analyzers (PGNAA) 204 Laser-Induced Breakdown Spectroscopy
(LIBS) 206 Speci cation Forms 206 De nitions 209 Abbreviations 209 Bibliography 209
1.13 COLORIMETERS 210
Introduction 211 Color Measurement 211
Absorbance and Transmittance Colorimetry 211
Spectrophotometric Analyzers 212 Spectrophotometer Design 212
Tristimulus Method (Re°ectance) 213 Lab Algorithm of the Textile
Industry 213 Continuous Color Monitors 214
In-Line Liquid Color Measurement 214 Online Shade Monitors 214 Optical Fluorescence and Luminescence
Sensors 214 New Developments: Multispectral
Analysis 215
Detector Types 221 Catalytic Combustion Type 222
Limitations 222 Measuring Circuits 222 Diffusion Head Design 224 Sampling System 225 Accessories 225 Total System Design 225 Advantages and Disadvantages 227
Flame Ionization and Photo Ionization Types 227 Flame Ionization Detectors 227 Photo-Ionization Detectors 227
Infrared Types 228 Point Monitoring System 228 Open Path System 229 Hydrocarbon Gases in the Atmosphere 230 Point Measurement 231
Speci cation Forms 231 De nitions 234 Abbreviations 234 Bibliography 234
1.15 CONDUCTIVITY MEASUREMENT 235
Introduction 236 Theory of Operation 236 Cell Constant 236 Cell Dimensions 237 Two-Electrode Cells 238 Four-Electrode Measurement 238 Electrodeless Cells 239 Measurement Applications 239 Concentration Measurements 239 High-Purity Water Measurements 239 Corrosive and Fouling Applications 240 Calibration and Maintenance 241
Calibration of Conductivity Sensors 241 Maintenance of Conductivity Cells 241
New Developments 241 Digital Conductivity Sensors 241 New Conductivity Transmitter
Developments 241 Smart Conductivity Transmitters 243 Asset Management 243 Wireless HART™ Transmitters 244
Conclusion 244 Speci cation Forms 245 De nitions 247 Abbreviations 247 Organizations 247
Chemicals 247
1.16 CONSISTENCY MEASUREMENT 248
Introduction 249 Sensor Designs 249
Mechanical Devices 250 Optical Designs 252 Microwave Sensors 254
Conclusions 254 Speci cation Forms 254 De nitions 257 Abbreviations 257 Organization 257 Bibliography 257
1.17 CORROSION MONITORING 258
Introduction 258 Corrosion-Monitoring Techniques 259
Coupon Monitoring 260 Electrical Resistance (ER) Monitors 261 Linear Polarization Resistance (LPR)
Monitors 263 LPR and ER Combination Designs 264 Down-Hole Corrosion Monitoring
(DCMS) 264 Wall Thickness Monitoring 265
Speci cation Forms 265 De nition 268 Abbreviations 268 Bibliography 268
1.18 CYANIDE ANALYZERS: WEAK-ACID DISSOCIABLE (WAD) 269
Introduction 269 Cyanide Species 270 Cyanide Analysis: Laboratory Methods 270 Free Cyanide (CNF) 270
Available Cyanide (CNwad) 271 Total Cyanide (CNT): Manual
Distillation 271 Total Cyanide (CNT): Automated 272
Primary and Alternate Analytical
Bibliography 276 ASTM International Standards 276 U.S. EPA Standards 276 EN ISO Standards 276
1.19 DIFFERENTIAL VAPOR PRESSURE 277
Introduction 277 Applications 277 d/p Vapor Pressure Transmitter 280 Conclusions 280 Speci cation Forms 280 De nitions 283 Abbreviation 283 Bibliography 283
1.20 DIOXIN AND PERSISTENT ORGANIC POLLUTANTS ANALYZERS 284
Introduction 284 Sampling Systems 285
Sample Recovery 286 Sample Extraction 286 Analysis 286
Conclusions 286 Speci cation Forms 286 De nition 289 Abbreviations 289 Bibliography 289
1.21 ELECTROCHEMICAL ANALYZERS 290
Introduction 291 Voltammetric Analysis 292
Current, Voltage, and Time 293 Potentiometry 293 Galvanic and Electrolytic
Probes 294 Amperometry 295 Polarography 298 Coulometry 298
Conclusions 299 Limitations 299 Advances 299
Speci cation Forms 299 Abbreviations 302 Bibliography 302
Inductively Coupled Plasma Detector 306
Operating Principle 306 Relative Merits of AA and ICP 307 X-Ray Fluorescence Spectrometer 307
Instrumentation 307 Speci cation Forms 309 Abbreviations 311 Organization 311 Bibliography 311
1.23 FIBER-OPTIC (FO) PROBES AND CABLES 312
Introduction 313 Fiber-Optic Cables 313
Internet Supporting Cables 313 Fiber-Optic Probes 315
System Operation 315 System Components 315 Probe Designs 317 Sealing Techniques 318 Process Interfaces 320
Safety Considerations 322 Fiber-Optic Ignition 322
Environmental Effects 323 Applications 324
Absorption Measurement 324 Scattering 324 Critical Angle and Other Sensors 325
Conclusions 326 Speci cation Form 326 De nitions 328 Abbreviations 328 Organizations 328 Bibliography 328
1.24 FLAME, FIRE, AND SMOKE DETECTORS 330
Introduction 331 Smoke Detectors 331
Ionization Chamber Sensors 331 Photoelectric Sensors 332
Flame and Fire Detectors 332 Thermal Sensors 332 Optical Flame Detectors 332 Fire Detectors 334
Organizations 342 Bibliography 342
1.25 FLUORIDE ANALYZERS 343
Introduction 344 Types of Fluoride Compounds 345 Detector Types 345
Detector Tubes 345 Electrochemical Cells 346 Paper Tape 346 Ion Mobility Spectrometry (IMS) 346 Infrared Spectroscopy 347 Ion-Speci c Electrodes (ISE) 347 Silicon Dioxide Sensors 348 Other Methods 348
Laboratory Methods 348 Speci cation Forms 348 Abbreviations 351 Bibliography 351
1.26 HAZARDOUS AND TOXIC GAS MONITORING 352
Introduction 353 Hazardous Area Classi cation 356
Safety Instrument Performance Standards 357
Levels of Toxicity 357 Exposure Limits 357
Detector Types 360 Electrochemical Sensors 361 Oxygen Detectors 361 Amperometric Sensors 362 Electrodes and Electrolytes 362 Fixed Detectors 363 Portable Detectors 364 Advantages and Limitations 365 Spectrometers 365 Applications 365 Semiconductor Detectors 366 Catalytic Bead Detectors 366 Photo and Flame Ionization
Detectors 366 Open-Path Detectors 366
Dosage Sensors 366 Color-Change Badges 366 Sorption-Type Dosimeters 370
Calibration 371 Dynamic Calibrators 372
De nitions 375 Abbreviations 375 Organizations 375 Bibliography 376 Web Links to Government
Organizations 376
1.27 HEATING VALUE CALORIMETERS 378
Introduction 379 Units and Wobbe Index 381 Design Variations 381
Bomb Calorimeters 381 Water Temperature Rise
Calorimeter 382 Air Temperature Rise Calorimeter 383 Air°ow Calorimeter 383 Residual Oxygen Calorimeter 384 Chromatographic Calorimeter 384 Expansion Tube Calorimeter 384
Temperature-Based Designs 384 Adiabatic Flame Temperature 384 Thermopile 385 Other Temperature-Based Designs 385 Optical Calorimeters 385
Applications 386 Sample Conditioning 386 Conclusion 386 Speci cation Form 386 De nitions 388 Abbreviations 388 Organization 388 Bibliography 388
1.28 HYDROCARBON ANALYZERS 390
Introduction 392 Analyzer Types 393
Flame Ionization Detectors 393 Gas Chromatography 395 Spectrometric Methods 396 Ion Mobility Spectroscopy 398 Hydrocarbon Dew-Point Meter 398
Calibration 399 Conclusions 399
Exposure Limits 404 Detector Designs 405
Fourier-Transform Infrared (FTIR) 405
Performance Standards 406 Conclusion 407 Speci cation Forms 407 De nition 410 Abbreviations 410 Organizations 410 Bibliography 410
1.30 HYDROGEN IN STEAM OR AIR ANALYZERS 411
Introduction 411 Hydrogen and Its Future Role 411
Properties and Safety 412 Detectror Types 413
Thermal Conductivity 413 Solid State 414 Electrochemical 414 Palladium-Based 414 Catalytic Bead (CB) 414 Chromatography 415 Mass Spectrometry 415
Sampling and Installations 415 Specialized Applications 416
Conclusions 417 Speci cation Forms 417 Abbreviations 420 Organizations 420 Bibliography 420
1.31 HYDROGEN SULFIDE DETECTORS 421
Introduction 422 Analyzer Types 422
Electrochemical 422 Gold Film 423 Solid State 423 Lead Acetate Tape 423 Ultraviolet 424 Chromatograph 425
Applications 425 Speci cation Forms 425 Abbreviations 428 Bibliography 428
Principles of Analysis 432
Beer-Lambert Law 434 Laboratory Spectrophotometers 435
Analyzer Design Categories 436 Single-Beam Con guration 436 Dual-Beam Con guration 437
Laboratory Analyzers 438 Grating Spectrophotometers 438 Filter Spectrometers 440 Fourier Transform Spectrometers 440 Tunable Lasers 440 Process Control Applications 441
Online Applications 441 Single-Component Analyzers 441 Dual-Chamber Luft Detector 442 Design Variations 442 Multiple-Component Fixed Filter
Analyzer 444 Programmed Circular Variable Filter
Analyzer 444 Portable Analyzers 444 Infrared Sources 445 Infrared Detectors 445
NDIR Detectors 445 Thermal Detectors 445 Photoconductive Detectors 446
Selecting the Cell 446 Path Length Selection 446 Gas Cells 446 Liquid Cells: Transmission Type 447 Liquid Cells: Re°ection Type 447 Solid Samples 448
Calibration 448 Linearity 448
Packaging 449 Applications and Advances 449 Near-Infrared Analyzers 451
Interpreting the Absorption Bands 451 Sample Temperature Control 451 Fiber-Optics 451 Types of NIRs 452 Optical Sources 452 Gases 452 Liquids 453 Solids 453 Calibration Transfer 453
Speci cation Forms 453 De nitions 456
Reference Electrode 460 Concentration and Activity 461 Ionic Strength Adjustment,
Buffers 462 Temperature Effects 463 System Accuracy 464
Electrode Types 464 Glass 464 Solid State 465 Liquid Ion Exchange 466
Measurement Range 467 Interferences 467
Solution Interferences 467 Calibration 468
Multiple Electrode Heads 469 Advantages 469 Potential Disadvantages 469 Speci cation Forms 470 De nitions 473 Abbreviations 473 Bibliography 473
1.34 LEAK DETECTORS 474
Introduction 475 Above Ground Detection 476
Pressure-and Vacuum-Based Testing 476
Combustible or Toxic Leaks 476 Personal Alarms 477
Detector Types 477 Ultrasonic Detectors 477 Thermal Conductivity
Detectors 478 Halogen Detectors 478 Thermography 479 Mass Spectrometry 479
Underground Detection 479 Level Monitoring 479 Soil Concentration
Detection 480 Aspirated Sensors 481 Standpipe Detector 481
New Developments 481 Speci cation Forms 482 Abbreviations 485 Organizations 485 Bibliography 485
1.35
Sample Input 487 Sample Ionization 487 Ion Separation 489 Ion Detection 491 Vacuum Environment 491 Data Reduction and Presentation 492
Residual Gas Analyzers 492 Conclusions 493 Speci cation Forms 493 Bibliography 496
1.36 MERCURY IN AMBIENT AIR 497
Introduction 498 Sampling and Concentration 498
Impinger Collection Methods 498 Amalgamation on Wettable Metals 500 Activated Absorption 500 Conversion of Mercury Vapors 501
Detection Methods 501 Ultraviolet Absorption 501 Colorimetric Methods 502 Gas Chromatography for Mercury Organics 503 Atomic Fluorescence Spectroscopy 503 Other Analytical Procedures 503
Regulations 503 Speci cation Forms 504 De nitions 506 Abbreviations 506 Organizations 506 Bibliography 506
1.37 MERCURY IN WATER 507
Introduction 508 Total Mercury Detection 508
Sample Treatment 508 Colorimetric Detection 509 Atomic Absorption Spectrophotometry 509 Online Measurement 511
Organic Mercury Detection 513 Sample Treatment 513 Gas Chromatography 513 Thin-Layer Chromatography 514
Direct (Thermal) Decomposition 515
Enthalpy in the Air 522 Applications 523
Using the Psychrometric Chart 523 HVAC: Heating, Ventilating, and Air
Conditioning 523 Clean Rooms, Incubators,
Microenvironments, Respiration Therapy 524
Breathing Air 524 Airline Environment 524 Humidity Effect of Combustion 524 Calculation of Relative Humidity
from First Thermodynamic Principles 524
Internet Options for the Calculation of Relative Humidity 525
Sensor Technology 525 Spectroscopic Absorption 526 Electrolytic Cells 526
Thin-Film Capacitance Probes 527 Chilled Mirror 528 Cooling Methods 528 Legacy Designs: Historical Perspective 529
Additional Considerations 531 Installation 531 Condensing Atmospheres 531
Calibration 532 Autocalibration 532 Handheld Calibration 532 Reference to Standards 533 Two-Pressure Humidity Generator 533
Calibration Method 534 Conclusions 535 Selection Criteria 535 Speci cation Forms 535 De nitions 538 Abbreviations 538 Standards Agencies 538 Bibliography 538
1.39 MOISTURE IN GASES AND LIQUIDS 540
Introduction 542 Laboratory Analyzers 542 Process Analyzers 542
Sampling Systems 543 Electrolytic Hygrometer 543 Capacitance Hygrometer 545 Impedance Hygrometer 548 Piezoelectric Hygrometer 549
Sensor 553 Cavity Ring-Down Spectroscopy (CRDS):
Moisture Analysis 554 Neutron Backscatter Moisture Online
Analyzer 554 Refraction-Based Moisture Analyzer 555 Calibration of Moisture Analyzers 555
Speci cation Forms 558 Abbreviations 560 Bibliography 560
1.40 MOISTURE IN SOLIDS 561
Introduction 563 Chemical Methods 563 Gravimetric Methods 563
Oven Drying (Loss on Drying) 563 Desiccants 565 Thermogravimetry 565 Lyophilization 565 Absorption and Condensation 566
Fast Neutron Moderation 566 Neutron Probe 566
Combined Neutron/Gamma Probes 567 Infrared Absorption and Re°ection 569 Time Domain Re°ectometry 570 Microwave Attenuation 571
Basis Weight Compensation 571 Moisture in Coal 571 Sugar Industry Applications 572
Capacitance Moisture Gauge 572 Sensor Designs 572
Capacitance Measurement 573 Limitations 573
Resistance Moisture Gauge 573 Limitations 573
Impedance Moisture Gauge 574 Nuclear Magnetic Resonance 574 Radio Frequency Absorption 575 Conclusions 575 Speci cation Forms 575 De nitions 578 Abbreviations and Symbols 578 Bibliography 578
1.41 MOLECULAR WEIGHT OF LIQUIDS 580
End Group Determination 591 Electron Microscope 591 Ultracentrifuge 592
Conclusions 592 Speci cation Forms 593 De nitions 595 Abbreviations 595 Bibliography 595
1.42 NATURAL GAS MEASUREMENTS 597
Introduction 597 Natural Gas Instrumentation 597
Flow Measurement 597 Analyzers 600
Speci cation Forms 603 Abbreviations 605 Organizations 605 Bibliography 605
1.43 NITROGEN, AMMONIA, NITRITE AND NITRATE 606
Introduction 607 Nitrogen and the Environment 607
Nitri cation and Denitri cation 608 Analysis Goals 608
Ammonium Detectors 608 Nitrite Measurement 609 Nitrate Measurement 609 Total Nitrogen 610
Summary 611 Speci cation Forms 611 De nitions 614 Abbreviations 614 Organizations 614 Bibliography 614
1.44 NITROGEN OXIDE (NOX) ANALYZERS 615
Introduction 616 Designs For Industrial Emission
Applications 616 Paramagnetic Analyzers 616 Thermal Conductivity Analyzers 616 Nondispersive Infrared Analyzers 617 Ultraviolet Analyzers 617 Electrochemical Sensors 618 Gas Chromatographs 618
Portable Monitors 620 Conclusions 620 Speci cation Forms 621 De nitions 624 Abbreviations 624 Bibliography 624
1.45 ODOR DETECTION 625
Introduction 625 Odor Measurement 626
Human Olfactory System 626 Odor Testing 626
Odor Panels 627 Odor Detectors 627
Gas Chromatography 627 Electronic Nose 628 Polymeric Film Sensors 629 Metal Oxide Sensors 629 Other Sensors 629
Applications 630 E-Nose Applications 630
Speci cation Forms 630 De nitions 633 Abbreviations 633 Organization 633 Bibliography 633
1.46 OIL IN OR ON WATER 634
Introduction 635 Environmental Pollution Sensors 635 Water-in-Oil Measurements 635
Capacitance 635 Radio Frequency (Microwave) 636 Conductivity-Based Interface 638 Ultrasonic Pipeline Interface 638 Nuclear 638 Near Infrared 639
Oil-in-Water Measurements 640 Ultraviolet 640
Oil-on-Water Measurements 641 Nephelometers Using Lasers 641 Oil Slick Thickness Detection 642
Conclusions 642
ORP 654 ORP Scales 654 Oxidation and Reduction 655 Redox Couples and Reversibility 655 ORP Reaction 655 Practical Measurements 656
ORP Sensors 657 Nernst Equation 657 Electrode Mounting 657
ORP Applications 658 Chromium Reduction 658 Corrosion Protection 659
ORP Maintenance and Calibration 660 Maintenance 660 Calibration 660
ORP Control 660 Residence Time 661
Recent Developments 661 Speci cation Forms 661 Abbreviations 664 Organizations 664 Bibliography 664
1.48 OXYGEN DEMANDS (BOD, COD, TOD) 665
Introduction 666 Oxygen Demand Testing 666
Seed 666 pH 666 Temperature 667 Toxicity 667 Incubation Time 667 Nitri cation 667
BOD Tests 667 Five-Day BOD Tests 667 Extended BOD Test 669 Manometric BOD Test 669 BOD Determination in Minutes 670
COD Measurement 671 Dichromate COD Test 671 Automatic On-Line Measurement 672
TOD Measurement 673 Sampling Valves 674 TOD Oxygen Detector 675 Calibration 675 Interferences 676 On-Line Monitoring 676 Applications 676
Correlation among BOD, COD, AND TOD 677 BOD and COD Correlation 677
Bibliography 681
1.49 OXYGEN IN GASES 682
Introduction 683 Paramagnetic Oxygen Sensors 684
De°ection Analyzer 684 Thermal Analyzer 685 Dual-Gas Analyzer 686
Catalytic Combustion Oxygen Sensors 686
Electrochemical Oxygen Sensors 686 High-Temperature Zirconium Dioxide Fuel
Cells 687 High-Temperature Current-Mode Oxygen
Sensors 689 Galvanic Sensors (Fuel Cells) 689 Coulometric Sensor 692 Polarographic Sensor 692
Spectroscopic Oxygen Detection 692 Mass Spectroscopy 693 Near-Infrared Spectroscopy 693
Other Oxygen Detection Methods 695 Developments Over the Last Decade 695 Speci cation Forms 695 Abbreviations 699 Bibliography 699
1.50 OXYGEN IN LIQUIDS (DISSOLVED OXYGEN) 700
Introduction 701 Electrochemical Detectors 702
Polarographic (Voltametric) Cells 703 Galvanic Cells 704 Thallium Cells 707
Fluorescence Sensors 708 Wet Chemistry Analyzers 709 Considerations Applicable to All
Sensors 709 Calibration Methods 709 Temperature Compensation 709 Pressure Effects 710 Salinity Effects 711
Applications 711 Installations 711
Monitor Designs 716
Ultraviolet Analyzer 716 Single-Beam Design 717 Double-Beam Design 718
Amperometric Design 719 Calibration 719
Thin-Film Semiconductor Design 719 Chemiluminescence Design 720 Speci cation Forms 721 Abbreviations 723 Organizations 723 Bibliography 723
1.52 OZONE IN WATER 724
Introduction 725 Drinking Water Disinfection 725
Amperometric Sensors 725 Bare Metal Electrodes 725 Membrane-Type Designs 726
Stripping and Gas Phase Monitors 727 Ultraviolet Absorption 727 Colorimetric Method 727 The Indigo Method 727 Speci cation Forms 727 Abbreviations 730 Organizations 730 Bibliography 730
1.53 PARTICLE SIZE DISTRIBUTION (PSD) MONITORS 731
Introduction 732 Application Objectives 733
Particle Characteristics and Sampling 734 Laboratory Measurements 734
Small Samples 734 Medium Size Samples 735 Large Samples 735
Online Measurement 736 Optical Analyzer 736 Airborne-Particulate Counter 737
Particle Distribution Monitors 737 Laser Diffraction 737
Speci cation Forms 738 De nitions 741 Abbreviations 741 Organizations 741 Bibliography 741
1.54
Theory 744
Opacity Measurement 744 Units and De nitions 745
Stack Emission Monitoring 746 Particulate Sampling 746 Stack Gas Analysis and Sampling 747
Light Attenuation and Transmissometers 748
Single-Pass Con guration 749 Double-Pass Con guration 749 Relative Performance Factors 750
Light Scattering Designs 751 Laser-based Designs 751
Stack Samplers 752 Manual Stack Samplers 752 Automatic Stack Samplers 753 Broken Bag Monitors 753
Ambient Air Opacity Monitoring 754 Particulate Concentration 754 Ambient Air Sampling 754 Soiling Index 757 Nephelometers 757 Piezoelectric Crystal Mass
Balance 757 Impaction Devices 757 Radiometric Devices 758 Charge Transfer (Triboelectricity) 758 Surface Ionization 759 Visual Observation 759 Remote Sensing 759
Conclusions 759 Speci cation Forms 760 De nitions 762 Abbreviations 762 Organizations 762 Standards 762 Bibliography 763
1.55 pH MEASUREMENT 764
Introduction 765 Measurement Error 765 Measurement Range 766 Applications 766
Theoretical Review 766 Ion Concentrations 767
High Salt Errors 778 High Acid Errors 779 Solution Temperature Effects 779 Water Concentration Errors 779 Nonaqueous Solutions 780 Probe Coating and Low Conductivity 780
Installation Methods 781 Submersion Assemblies 781 Retractable Units 782 Median Selector 783 Self-Diagnostics 783
Calibration 783 Buffer Calibration Errors 784 Cleaning and Calibration Systems 784
Conclusion 788 Speci cation Forms 788 De nitions 791 Abbreviations 791 Organizations 791 Bibliography 791
1.56 PHOSPHATE ANALYZER 792
Introduction 793 Phosphorus in Wastewater 793 Laboratory Analysis 793 Continuous Colorimeter 793
Pumpless Design 794 Total Phosphate Analysis 795 Flame Photometric Analysis 795
Operation 795 Chromatography 796 Sample Handling Systems 796 Speci cation Forms 796 De nitions 799 Abbreviation 799 Organizations 799 Bibliography 799
1.57 PHYSICAL PROPERTIES ANALYZERS FOR PETROLEUM PRODUCTS 800
Introduction 801 Advantages of Continuous Analyzers 803 Distillation Analyzers 803
Laboratory Measurement Standards 803 Online Distillation Analyzers 804
Vapor Pressure Analyzers 808 Reid Method (ASTM Method D 323-90) 808
Air-Saturated Vapor Pressure Analyzer-Continuous 809
Air-Saturated Vapor Pressure Analyzer-Cyclic 810
Dynamic Vapor Pressure Analyzer 810 Calibration 811 Applications 811
Vapor-Liquid Ratio Analyzers 811 Volatility Test (ASTM Method D
2533-90) 812 Continuous Vapor-Liquid Ratio
Analyzer 812 Calibration and Applications 813
Pour-Point Temperature Analyzers 813 Pour-Point Test (ASTM Method D 97-87) 813 Pour Point by Differential Pressure 813 Viscous-Drag Pour Pointer 814 Calibration 814 Applications 814
Cloud-Point Analyzers 814 Cloud-Point Tests (ASTM Method
D 2500-88) 814 Optical Cloud-Point Analyzer 815 Calibration and Applications 816
Freezing-Point Analyzer 816 Aviation Fuel Tests (ASTM Method D
2386-88) 816 Freezing-Point Analyzer for Aviation
Fuel 816 Calibration and Applications 816
Flash-Point Analyzer 816 Flash-Point Tests (ASTM Methods D
56-90 and D 93-90) 817 Low-Temperature Flash-Point
Analyzer 817 High-Temperature Flash-Point
Analyzer 818 Calibration and Applications 818
Octane Analyzers 818 Octane Tests (ASTM Methods D 2699 and
D 2700) 818 Octane Comparator Analyzer (ASTM
Method D-2885) 818 Reactor-Tube Continuous Octane
Analyzer 819 Calibration and Applications 819
Near-Infrared Analyzers 819 Chemometrics 820
Bibliography 824
1.58 RAMAN ANALYZERS 825
Introduction 826 Principles of Raman Spectroscopy 827
Optical Spectroscopy 827 Raman Scattering 827 Spectral Information 829
Instrumentation 830 Fourier Transform Raman
Instrumentation 831 Dispersive Raman Instrumentation 832
Raman Process Analyzers 833 Components 833 Data Analysis 838 Diagnostics and Maintenance 840 Laser Safety 840 Outputs and Communication 840 Packaging 840 Installation and Maintenance 841 Probe Designs 842
Advantages and Disadvantages 842 Advantages 843 Limitations 843
Applications 843 Conclusion 844 Speci cation Forms 844 De nitions 847 Abbreviations 847 Organization 847 Bibliography 847
1.59 REFRACTOMETERS 849
Introduction 850 UNITS (RI and BRIX) 851
Theory of Operation 852 Critical Angle of Refraction 852
Refractometer Designs 853 Differential 853 Critical-Angle 854 Automatic 855 Design Variations 856 Re°ected Light Measurement 859
Conclusions 860 Speci cation Forms 860 De nitions 863 Abbreviation 863 Bibliography 863
1.60
Solid Polymer Measurements 865 Tests to Distinguish Liquids from Solids 866
Shear-Strain Tests 866 Shear Creep Tests 867 Nonlinear Shear Flow 867
Selection 867 Detector Designs 868
Cone and Plate 868 Shear Flow Properties 868 Parallel Disk 871 Rectangular Torsion 872 Coaxial Cylinder 873 Tension/Compression and Bending 873 Extensional Flow 873 Capillary 874
Conclusions 874 Speci cation Forms 875 De nitions 877 Abbreviations 877 Organization 877 Bibliography 877
1.61 SAND CONCENTRATION AND SUBSEA PIPELINE EROSION DETECTORS 878
Introduction 878 Background 878 Passive Acoustic Sand Detector 879
Principle of Operation 879 Advantages 879 Limitations 879
Intrusive and Erosion Based Sand Detector 880 Principle of Operation 880
Typical Sand Monitoring System/Data Flow 882
Conclusion 882 Speci cation Forms 883 De nitions 885 Abbreviations 885 Organizations 885
1.62 SPECTROMETERS, OPEN PATH (OP) 886
Introduction 887 Types of Designs 887
Sample Cell 891 Transfer Optics and the Detector
Types 892 Sample Cell 893 Data System/Controller 893 Instrument Con gurations 893
OP-UV Spectrometry 897 The Spectrometer 897
OP-TDLAS Spectrometry 898 Diode Lasers 899 Applications 900 Principle of Operation 900 OP-CRDC Spectroscopy 902
Applications 902 Toxic Gas Measurement 903 Combustible Vapor Measurement 903
Speci cation Forms 904 De nitions 907 Abbreviations 907 Organizations 907 Government Agencies 907 Bibliography 908
1.63 STREAMING CURRENT PARTICLE CHARGE ANALYZER 909
Introduction 910 Operating Principle 910
The Streaming Current 910 Treatment Chemical Selection 912
Calibration 912 Applications 913
Sampling 913 Control System 914
Speci cation Forms 915 De nitions 918 Abbreviations 918 Organization 918 Bibliography 918
1.64 SULFUR DIOXIDE AND TRIOXIDE 920
Introduction 921 Applications 922
Industrial Analyzer Types 923 Nondispersive Infrared (NDIR) 923 Ultraviolet 924 Correlation Spectrometry 925 Thermal Conductivity 925
Coulometric Analyzers 927 Flame Photometric Analyzers 927 Electrochemical Analyzers 927
Speci cation Forms 928 Abbreviations 930 Bibliography 930
1.65 SULFUR IN OIL AND GAS 931
Introduction 932 Gas Chromatography with Flame Photometric
Detection 932 Hydrogenolysis and Rateometric
Colorimetry 933 Sulfur Chemiluminescence 934 Pyrolysis and Ultraviolet Fluorescence 935 X-Ray Fluorescence 936
Sampling and Calibration 937 New Developments 937
Conclusions 937 Speci cation Forms 937 Abbreviations 940 Organizations 940 Bibliography 940
1.66 THERMAL CONDUCTIVITY DETECTORS 941
Introduction 942 Thermal Conductivity 942
Measurement Ranges 942 TCD Analyzer 943
Detectors 943 TCD Cells 944 Bridge Circuits 944 Operation 946 Packaging and Calibration 946
Conclusions 947 Speci cation Forms 947 De nitions 950 Abbreviations 950 Bibliography 950
1.67 TOTAL CARBON AND TOTAL ORGANIC CARBON (TOC) ANALYZERS 951
Oxidation Methods 955 Aqueous Conductivity 958 Coulometric Analysis 961 Colorimetric Analysis 961 Flame Ionization Detector 961
Conclusion 962 Speci cation Forms 962 Abbreviations 965 Organizations 965 Bibliography 965
1.68 TURBIDITY, SLUDGE AND SUSPENDED SOLIDS 966
Introduction 967 Light Absorption and Scattering 967 Units of Turbidity 967
Turbidity Analyzer Designs 969 Forward Scattering or Transmission Type 969 Scattered Light Detectors
(Nephelometers) 974 Backscatter Turbidity Sensors 976 Density-Based Sensors 976
Conclusions 976 Speci cation Forms 977 De nitions 980 Abbreviations 980 Organizations 980 Bibliography 980
1.69 ULTRAVIOLET AND VISIBLE ANALYZERS 981
Introduction 982 UV Theory 983
UV Absorption 983 Radiation Spectrum 984 Beer-Lambert Law 985 UV-Absorbing Compounds 986 UV Absorption Spectrum 987 Applications 987
UV Analyzer Components 987 Radiation Sources 988 Emission Types 988 Selecting the Wavelength 989 Monochromator 989 Optical Dispersion 990 Measuring Cell 990 Detectors 990 Readouts 991
Dual-Beam, Dual-Detector 993 Flicker Photometer 993 Photodiode Array (PDA)
Spectrophotometers 994 Scanning Spectrophotometers 995 Retrore°ector Probes 996
Visible and Nir Analyzers 997 Visible Light Photometers 997 Near-Infrared Photometers 997
Conclusions 997 Speci cation Forms 998 De nitions 1001 Abbreviations 1001 Organizations 1001 Bibliography 1001
1.70 VISCOMETERS 1002
Introduction 1002 Theory of Viscous Behavior 1002
Stokes’ Law 1003 Hagen-Poiseuille Law 1003 Intrinsic Viscosity 1004 Newtonian and Non-Newtonian
Fluids 1004 Typical Viscosities and Conversion among
Units 1006 Viscometer Selection and
Application 1008 Selection 1010 Applications 1010
Speci cation Forms 1011 De nitions 1014 Abbreviations 1014 Organizations 1014 Bibliography 1014
1.71 VISCOMETERS 1016
Introduction 1018 Capillary Viscometers 1020
Limitations 1020 Calibration 1020 Differential Pressure Type 1021 Backpressure Type 1023
Concentric Design 1027
Plastometers 1028 Plastic Behavior 1028 Cone-and-Plate Plastometer 1028 Kneader Plastometer 1029 Capillary Plastometer 1029
Rotational Element Viscometers 1030 Rotary Spindle Design 1030 Gyrating-Element Viscometer 1032 Agitator Power 1032 Dynamic Liquid Pressure 1033
Oscillating Viscometers 1034 Oscillating Blade 1034 Oscillating Piston 1035
Vibrational Viscometers 1036 Torsional Oscillation Design 1036 Vibrating-Reed/Rod Viscometer 1037
Coriolis Mass Flowmeter 1038 Measuring Tube Torsional
Movement 1038 New Developments 1039
Trends 1039 Conclusions 1040 Speci cation Forms 1040 De nitions 1043 Abbreviations 1043 Organizations 1043 Bibliography 1043
1.72 VISCOMETERS 1045
Introduction 1046 Laboratory Viscometer Designs 1048
Bubble-Time Viscometers 1048 Capillary Viscometers 1048 Falling/Rolling Element Viscometers 1053 Ori ce/Ef°ux Cup Viscometers 1055 Oscillating Piston Viscometer 1057 Rotational Viscometers 1057 Vibrational Viscometers 1063
Trends 1063 Automation 1063 Lab Management Systems 1063 Adaptability 1064 Smart User Interfaces 1064 Smart Accessories 1064
Speci cation Forms 1064 De nitions 1067 Abbreviation 1067 Organizations 1067 Bibliography 1067
Regulations 1071
Monitoring System Components 1071 Sampling Systems 1071 Analyzer Types 1073 Ion-Selective Electrodes 1073 Chromatographs 1079 Portable Spectrophotometer 1081
Conclusions 1082 Speci cation Forms 1083 De nitions 1086 Abbreviations 1086 Organizations 1086 Bibliography 1086
1.74 WET CHEMISTRY AND AUTOTITRATOR ANALYZERS 1087
Introduction 1087 Titration End Points 1088
End Point Detectors 1089 Continuous and Batch Designs 1089
Colorimetric Analyzers 1092 High Precision Designs 1092 Simpler Design 1094 On-Off Batch Design 1094 Applications 1095
Flow Injection Analyzers (FIA) 1095 Laboratory Design 1096 Industrial Designs 1096 Application Example 1 1096 Application Example 2 1097 Calibration 1097
Conclusions 1097 Speci cation Form 1098 De nitions 1100 Abbreviations 1100 Organizations 1100 Bibliography 1100
INTRODUCTION
The role of analyzers in our everyday life is becoming more and more important and their capabilities and sophistication are exploding. Here, I will give just one practical example, involving the monitoring of methane emitted into the atmosphere by fracking for natural gas. I could have picked dozens of other examples, but this one combines some very important new ideas and solutions, which illustrate how the analyzer technology is evolving.
