Analytical Instrumentation: 8.1 Analyzer Application and Selection 1144

Analytical Instrumentation
8.1 Nuclear Magnetic Resonance 1157

Analyzer Application and Selection 1144 Analyte-Specific Techniques 1157
Introduction 1144 Water 1157
The Selection Process 1144 Oxygen 1157
Problem Definition 1144 Sampling 1157
Information Gathering 1145 Probe Cleaners 1159
Analyzer Location 1161
Technique or Analyzer Selection 1147
Handling the Data 1162
Specificity (Selectivity) 1148
Maintenance 1162
Accuracy and Precision 1148
Cost 1162
Calibration 1148
Summary 1163
Analysis Frequency 1149
References 1168
Kinds of Analyzers 1149
Bibliography 1168
Separation Techniques 1149
Other Separation Techniques 1150
Spectroscopic or Radiant Energy 8.2
Techniques 1150 Analyzer Sampling: Process Samples 1170
Ultraviolet and Visible 1150 Introduction 1171
Fluorescence 1151 General Considerations 1171
Infrared and Near-Infrared 1151 Feasibility Evaluation 1171
Raman 1152 Sample Data Requirements 1171
Microwave and Radio Frequency 1152 Sample Takeoff Point 1172
Refractometry 1153 Sample Transport 1173
Turbidity and Particle Size 1153 Transport Lag 1173
Nuclear Techniques 1153 Sample Disposal 1174
Electrochemical Sensors 1154 Ambient Considerations 1174
Potentiometric 1154 Test and Calibration 1174
Conductive 1156 Components of Sampling Systems 1175
Amperometric 1156 Selecting the System Components 1175
Chemical Techniques 1156 Filter Designs 1175
Miscellaneous Techniques 1156 Separating Liquids from Gases 1175
Quartz Crystal Microbalances 1156 Spargers, Packed Towers, and Strippers 1176
Mass Spectrometry 1157 Separating Two Liquid Phases 1177
1127
2003 by Bla Liptk
1128 Analytical Instrumentation
Removing Gas Bubbles from Liquids 1178 Galvanic and Electrolytic Probes 1201
Slipstream and Bypass Filters 1178 Membrane-Covered Probes 1202
Self-Cleaning and Rotary Disc Filters 1179 Amperometry 1202
Keeping Probes Clean 1179 Solid Electrodes 1203
Homogenizers 1180 Polarography 1204
Sample Conditioning 1180 Advantages 1205
Vaporizing Samples 1182 Coulometry 1205
Entrainment Removal 1182 Controlled Potential Coulometry 1205
Selection of Component Materials 1182 Conclusions 1205
Applications 1183 Limitations 1206
Gas Sampling Probes 1183 Advances 1206
Stack Gas Sampling 1183 Reference 1206
Automatic Stack Sampling 1183 Bibliography 1206
Automatic Liquid Samplers 1184
Sampling of High-Pressure
8.5
Condensate 1184
Air Quality Monitoring 1207
Chemical Reactor Samplers 1184
Duckbill Samplers 1185 Introduction 1207
Solids Sampling 1185 Air Quality Monitoring Systems 1207
Sampling Difficult Processes 1186 Purpose of Monitoring 1208
Trace Analysis Sampling 1186 Impact of Single Sources 1208
Multistream Switching 1187 Research Needs 1209
References 1188 Monitoring in Urban Areas 1209
Bibliography 1188 Sampling Site Selection 1210
Static Methods of Air Monitoring 1210
Dust-Fall Jars 1211
8.3 Lead Peroxide Candles 1211
Analyzer Sampling: Stack Particulates 1189 Other Static Methods 1211
Introduction 1189 Laboratory Analyses 1211
The EPA Particulate Sampling System 1189 Automatic Monitoring 1212
Microprocessor-Controlled Stack Sensors 1212
Sampling 1189 Data Transmission 1212
The Pitot Tube Assembly 1190 Data Processing 1213
Type S Pitot and the Sampling Probe 1190 Averaging Times 1213
Selecting the Sampling Point 1192 Displays 1213
Traversing Point Locations 1192 Audits 1213
Pitot Tube Calculation Form 1192 Automatic Analyzers 1213
Sampling Velocity for Particle Infrared Spectrometers 1213
Collection 1192 Handheld Indoor Air Quality
Isokinetic Sampling 1192 Monitors 1214
Heated Compartment (Hot Box) 1193 Sampling of Ambient Air 1214
Ice-Bath Compartment (Cold Box) 1193 General Air Sampling Problems 1214
Control Unit 1195 Sampling for Gases and Vapors 1216
Automatic Sampling Trains 1195 Absorption 1217
Sampling for Gases and Vapors 1196 Liquid Absorption 1217
References 1196 Impingers 1217
Bibliography 1197 Fritted Absorber 1217
Adsorption 1218
Freeze-Out Sampling 1218
8.4 Sampling of Particulates 1218
Analyzers Operating on Electrochemical Air Filters 1219
Principles 1198 Fiberglass Filters 1219
Introduction 1199 Impingement and Impaction 1219
Voltametric Analysis 1199 Impactors 1219
Current, Voltage, and Time 1200 Electrostatic Precipitation 1220
Potentiometry 1201 Thermal Precipitators 1220
2003 by Bla Liptk

Contents of Chapter 8 1129
Reference 1221 British Thermal Unit 1236

Bibliography 1221 BTU Dry 1236
BTU Saturated 1236
Combustion Air Requirement Index 1236
8.6
Gross Calorific Value 1236
Biometers 1222
Net Calorific Value 1236
Introduction 1222 Wobbe Index 1236
ATP Analysis 1222 Units, Accuracy, and Output Signals 1236
Luminescence Biometer 1223 Design Variations 1238
Reference 1223 Water-Temperature-Rise Calorimeter 1238
Bibliography 1223 Air-Temperature-Rise Calorimeter 1238
Airflow Calorimeter 1238
8.7 Residual Oxygen Calorimeter 1239
Biological Oxygen Demand, Chemical Chromatographic Calorimeter 1240
Oxygen Demand, and Total Oxygen Demand 1224 Expansion Tube Calorimeter 1240
Adiabatic Flame Temperature 1240
Introduction 1224 Thermopile Calorimeter 1240
Oxygen Demand 1225 Applications 1240
The Seed 1225 Sample Conditioning 1241
pH 1225 Conclusion 1241
Temperature 1225 Reference 1241
Toxicity 1225 Bibliography 1241
Incubation Time 1226
Nitrification 1226
Biological Oxygen Demand 1226 8.9
Five-Day BOD Procedure 1226 Carbon Dioxide 1242
DO Determination and Standards 1226 Introduction 1243
Instrumentation 1226 Ambient Air Measurement 1243
Extended BOD Test 1227 Nondispersive Infrared Type 1243
Manometric BOD Test 1227 Gas Filter Correlation Type 1244
Automatic Recording 1228 Source Measurement 1244
BOD Assessment in Minutes 1228 Bibliography 1244
Electrolysis System for BOD 1229
Chemical Oxygen Demand 1229
Standard Dichromate COD Procedure 1229 8.10
COD Detector 1229 Carbon Monoxide 1245
Automatic On-Line Designs 1229 Introduction 1246
Total Oxygen Demand 1231 Calibration Techniques 1246
Sample Valves 1231 Nondispersive Infrared Analyzers 1247
Oxygen Detector 1232 Interferences 1247
Calibration 1232 Gas Filter Correlation 1247
Interferences 1232 Mercury Vapor Analyzer 1248
Applications 1233 Gas Chromatograph 1248
Correlation between Measurement Electrochemical Analyzer 1248
Techniques 1233 Portable Monitors 1249
Variations in Oxygen Demand 1233 Catalytic Analysis 1249
BOD and COD Correlation 1233 Spot Sampling of Ambient Air 1249
BOD and Other Methods 1233 Conclusions 1250
References 1234 References 1250
Bibliography 1234 Bibliography 1250
8.8 8.11
Calorimeters 1235 Chlorine 1251
Introduction 1235 Introduction 1252
Terminology 1236 Residual Chlorine Analyzers 1252
2003 by Bla Liptk

Colorimetric Analyzers 1253 Sample Conditioning 1283

Automatic Colorimetric Analyzer Multistream Analysis 1283
Features 1253 Sample Disposal 1285
Amperometric Analyzers 1254 Installation 1286
Types of Amperometric Analyzers 1254 Summary 1287
Free Residual Chlorine Analysis 1254 Acknowledgment 1287
Membrane Probes 1255 References 1287
Buffers and Reagents 1256 Bibliography 1288
Electrode Cleaners 1256
Conclusions 1256 8.13
Bibliography 1257 Chromatographs: Liquid 1289
Introduction 1289
8.12 Comparison with Gas Chromatographs 1290
Chromatographs: Gas 1258 Carrier Flow 1290
Introduction 1259 The Main Components 1290
Basic Chromatographic Instrumentation 1260 HPLC Column Selectivity and Resolution 1290
Components of a Process Gas Carrier Supply 1291
Chromatograph 1261 Supply Pumps 1291
Analyzer 1262 Pressure and Flow Controls 1291
Oven 1262 Valves 1291
Valves 1263 Columns 1292
Rotary Valve 1263 LiquidPartition Columns 1292
Sliding Plate 1264 LiquidAdsorption Columns 1292
Diaphragm 1265 GelPermeation Columns 1292
Columns 1265 Ion Exchange Columns 1293
Packed Columns 1265 Electrophoresis 1293
WCOT (Capillary) Columns 1266 Detectors 1293
Column and Valve Configurations 1266 Optical Absorbance 1293
Hardware 1267 Refractive Index 1293
Sample Injection 1267 Dielectric Constant 1293
Backflush 1268 Applications 1293
Heart-cutting 1269 Reference 1293
Detectors 1269 Bibliography 1293
Thermal Conductivity Detector 1270
Flame Ionization Detector 1271 8.14
Flame Photometric Detector 1272 Coal Analyzers 1295
Pulsed Flame Photometric Detector 1273 Introduction 1295
Orifice-Capillary Detector 1274 Thermogravimetry 1295
Miscellaneous Detectors 1275 Bituminous Coal Analysis 1295
Photoionization Detector 1275 Gross Calorific Value 1296
Electron Capture Detector 1275 Total Sulfur Analysis 1296
Discharge Ionization Detectors 1276 Ash Analysis 1297
Carrier Gas Flow Control 1277 On-Line Monitors 1297
Programmer-Controller 1277 Gamma-Based Analyzers 1298
Programmer 1278 Recent Developments 1298
Peak Processor 1278 References 1298
Data Acquisition 1278 Bibliography 1298
InputOutput 1278
Communication 1278
Operator Interface 1280 8.15
Alarms and Diagnostics 1281 Colorimeters 1299
Quantitation 1281 Introduction 1300
Sample Handling 1281 Color Measurement 1300
Sample Probe 1282 Absorbance and Transmittance
Sample Transport 1282 Colorimetry 1300
2003 by Bla Liptk

Spectrophotometric Analyzers 1300 Calibration of Conductivity Sensors 1321

Spectrophotometer Design 1301 Maintenance of Conductivity Cells 1322
Tristimulus Method (Reflectance) 1301 Conclusion 1322
The Lab Algorithm of the Textile Industry 1302 References 1322
Continuous Color Monitors 1303 Bibliography 1322
In-Line Liquid Color Measurement 1303
On-Line Shade Monitors 1303
References 1303 8.18
Bibliography 1303 Consistency Analyzers 1323
Introduction 1323
In-Line Consistency Measurement 1324
8.16
Combustibles 1304 Mechanical Devices 1324
Probe Type 1324
Introduction 1305 Blade Types 1325
Selection Considerations 1305 Rotating Sensors 1325
Terminology, Definitions, and Background Optical Sensors 1326
Information 1305
Measuring Woodfree Pulp 1326
Catalytic Combustion on a Heated Filament 1306
Consistency of Pulp Containing Wood 1326
Limitations 1306
Summary 1328
Measuring Circuits 1307
References 1328
Thermocouple Detector 1307
Bibliography 1328
Wheatstone Bridge Detector 1307
Diffusion Head Analyzers 1308
Sampling System 1308 8.19
Accessories 1309 Corrosion Monitoring 1329
Selection of Complete Installation 1309
Introduction 1329
Remote Head System 1309
Corrosion Monitoring Techniques 1329
Multiple Head System 1309
Corrosion Coupon Monitoring 1330
Tube Sampling System 1310
Time of Exposure 1331
Conclusions for Catalytic Detectors 1310
Advantages and Limitations 1332
Flame Ionization and Photoionization
Detectors 1311 Electrical Resistance Monitors 1332
Flame Ionization Detectors 1311 Advantages and Limitations 1332
Photoionization Detectors 1311 Linear Polarization Resistance Monitors 1333
Infrared Combustibles Detectors 1311 Advantages and Limitations 1334
Point Infrared Systems 1312 Bibliography 1334
Area (Open-Path) Infrared Systems 1313
Hydrocarbon Gases in the Atmosphere 1314 8.20
Point Measurement 1315 Differential Vapor Pressure Sensor 1335
Bibliography 1315
Introduction 1335
Design and Operation 1335
8.17 Limitations 1337
Conductivity Analyzers 1316 Reference 1338
Introduction 1316 Bibliography 1338
Theory of Operation 1317
The Cell Constant 1317
8.21
Cell Dimensions 1318
Dioxin Analysis 1339
Two-Electrode Cells 1319
Four-Electrode Measurement 1319 Introduction 1339
Electrodeless Cells 1319 Principle of Operation 1339
Measurement Applications 1320 Sample Recovery 1339
Concentration Measurements 1320 Sample Extraction 1340
High-Purity Water Measurements 1320 Analysis 1340
Corrosive and Fouling Applications 1320 Conclusions 1341
Calibration and Maintenance 1321 Bibliography 1341
2003 by Bla Liptk

8.22 References 1357

Elemental Monitors 1342 Bibliography 1357
Introduction 1342
Atomic Absorption Spectrometer 1342
8.25
Inductively Coupled Plasma Detector 1343
Hydrocarbon Analyzers 1358
Operating Principle 1344
Selecting among AA and ICP 1344 Introduction 1359
X-Ray Fluorescence Spectrometer 1344 Analyzer Types 1359
Instrumentation 1345 Flame Ionization Detectors 1359
Bibliography 1346 Gas Chromatography 1360
Calibration 1361
Nonmethane Hydrocarbons 1361
8.23 Reactive Hydrocarbons 1361
Fiber-Optic Probes 1347 Spectrometric Methods 1361
Introduction 1347 Laser-Induced Doppler Absorption
Principle of Measurement 1347 Radar 1361
Instrumentation 1347 Spectroscopy Perimeter Monitoring 1362
Glass Optical Fiber 1348 Ion Mobility Spectroscopy 1362
Plastic Optical Fiber 1348 Hydrocarbon Dew-Point Meter 1362
Probes 1348 Calibration Methods 1362
Wand Probe 1348 Assessment 1362
Spectra-Caliper Probe 1348 Bibliography 1363
Transmission Probe 1348
Long-Path-Flow Tube 1349
GEM Probe 1349 8.26
Six-to-One Probe 1349 Hydrogen Sulfide 1364
Sample Interfaces 1350 Introduction 1365
Detectors 1350 Electrochemical Cells 1365
Software 1350 Gold-Film and Semiconductor Sensors 1365
Applications 1350 Solid-State Sensors 1366
Absorption 1350 Lead Acetate Tape Staining 1366
Fluorescence 1350 Photometric Analysis 1367
Optrodes 1351 Direct Photometric Analyzer 1367
Oxygen Probe 1351 Gas Chromatography with Flame Photometric
Scattering 1351 Detector 1367
Refractive Index 1352 Tail Gas Analyzer 1367
Bibliography 1352 Reference 1368
Bibliography 1368
8.24
Fluoride Analyzers 1353 8.27
Introduction 1354 Infrared and Near-Infrared Analyzers 1369
Types of Fluoride Compounds 1354 Introduction 1371
Analyzer Types 1355 Principles of IR and NIR Analysis 1371
Gas and Vapor Analyzers 1355 BeerLambert Law 1373
Detector Tubes 1355 Definitions of Terms and Configurations 1374
Electrochemical Cells 1355 IR Instrument Designs 1375
Paper Tape 1356 Single-Beam Configuration 1375
Ion Mobility Spectrometry 1356 Dual-Beam Configuration 1375
Infrared Spectroscopy 1356 Dual-Beam Design for Stacks 1376
Ion-Specific Electrodes 1356 Infrared Analyzers for the Laboratory 1377
Silicon Dioxide Sensors 1356 Grating Spectrophotometers 1377
Laboratory Methods 1356 Filter Spectrometers 1377
Organic Fluoride Analysis 1357 Fourier Transform Spectrometers 1377
Other Methods 1357 Tunable Lasers 1378
2003 by Bla Liptk

Laboratory Instruments in Process Process Applications 1393

Measurement 1378 Types of Electrodes 1393
Infrared Analyzers for Process Glass 1393
Applications 1378 Solid State 1394
Single-Component Analyzers 1378 LiquidIon Exchange 1395
Design Variations 1378 Measurement Range 1395
Gas Filter Correlation Spectrometers 1379 Interferences 1396
Filter Analyzers 1379 Solution Interference 1396
Multiple-Component Fixed Filter Calibration Solutions 1396
Analyzer 1380 Advantages and Disadvantages 1397
Programmed Circular Variable Filter Precision and Accuracy 1398
Analyzer 1380 Conclusions 1398
Infrared Sources 1380 References 1398
Infrared Detectors 1380 Bibliography 1398
NDIR Detectors 1381
Thermal Detectors 1381
Photoconductive Detectors 1381 8.29
Selecting the Cell 1381 Mass Spectrometers 1399
Path Length Selection 1381
Gas Cells 1381 Introduction 1399
Liquid Cells: Transmission Type 1382 Principle of Operation 1400
Liquid Cells: Reflection Type 1382 Sample Input 1400
Solid Samples 1382 Sample Ionization 1400
Calibration: Sources of Analyzer Drift 1382 Ion Separation 1400
Linearity 1383 Magnetic Sectors 1401
Packaging 1383 Quadrupole Filter 1402
Applications and Advances 1383 Ion-Trapping Section 1403
Near-Infrared Analyzers 1384 Time-of-Flight Filter 1403
Interpreting the Absorption Bands 1385 Ion Detection 1403
Sample Temperature Control 1385 Vacuum Environment 1404
Fiber Optics 1385 Data Reduction and Presentation 1404
Types of NIRs 1385 Residual Gas Analyzers 1405
Sources 1386 Conclusions 1405
Gases 1386 Bibliography 1405
Liquids 1386
Solids 1386
Calibration Transfer 1386 8.30
References 1386 Mercury in Ambient Air 1407
Bibliography for Infrared Analyzers 1386
Introduction 1408
Bibliography for Near-Infrared Analyzers 1387
Sample Collection and Concentration 1408
Impinger Collection Methods 1408
Particulate Sampling 1408
8.28 Vapor Sampling 1409
Ion-Selective Electrodes 1388 Amalgamation on Wettable Metals 1409
Introduction 1388 Sampling Tubes 1409
The Nernst Equation 1389 Activated Absorption 1410
The Reference Electrode 1390 Conversion of Mercury Vapors 1410
Concentration and Activity 1391 Methods of Detection 1410
Ionic Strength Adjustment Buffers 1391 Ultraviolet Light Absorption 1410
Temperature Effects 1392 Atomic Absorption Spectrophotometry 1410
The Isopotential Point 1392 Flameless Atomic Absorption
Role of Electrode Internals and Spectroscopy 1410
Calibration 1392 Colorimetric Methods 1411
System Accuracy 1393 Dithizone 1411
Laboratory Devices 1393 Selenium Sulfide and Others 1411
2003 by Bla Liptk

Gas Chromatography for Mercury Cooling Methods 1430

Organics 1411 Automatic Standardization 1431
Atomic Fluorescence Spectroscopy 1411 Limitations 1431
Other Analytical Procedures 1412 Cycled Chilled-Mirror Probe 1432
References 1412 Moisture Indicators 1432
Bibliography 1412 Microprocessor-Based Indicators 1432
Conclusion 1433
References 1433
8.31 Bibliography 1433
Mercury in Water 1413
Introduction 1414
Total Mercury Detection 1414 8.33
Sample Treatment 1414 Moisture in Gases and Liquids 1434
Colorimetric Detection 1414 Introduction 1435
Interference by Copper 1415 Laboratory Analyzers 1435
Analysis Procedure 1415 Process Analyzers 1435
Atomic Absorption Spectrophotometry 1415 Sampling Systems 1435
Analysis Procedure 1416 Electrolytic Hygrometer 1436
On-Line Measurement 1416 Avogadros Law 1436
Organic Mercury Detection 1416 Recombination Effect 1437
Sample Treatment 1416 Cell Limitations 1437
Gas Chromatography 1417 Liquid Samples 1438
Thin-Layer Chromatography 1418 Sampling System 1438
Bibliography 1419 Capacitance Hygrometer 1438
Sampling Systems 1439
Thin-Film Capacitance Probes 1439
8.32 Limitations 1439
Moisture in Air: Humidity and Dew Point 1420 Impedance Hygrometer 1440
Introduction 1421 Installation 1441
Definitions 1422 Sampling System 1441
Relative Humidity Sensors 1422 Limitations 1441
Wet and Dry Bulb Hygrometers 1422 Piezoelectric Hygrometer 1441
Wet-Dry Bulb Hygrometers 1422 Sampling System 1442
Assman Psychrometers 1424 Limitations 1442
Calculation of Relative Humidity 1424 Heat-of-Adsorption Hygrometer 1442
Hair Hygrometers 1424 Sampling System 1443
Cellulose Hygrometers 1425 Limitations 1443
Solution Resistance Elements Infrared Absorption Hygrometer 1443
(Dunmore Cells) 1425 Sampling System 1443
Polystyrene Surface Resistivity Limitation 1444
(Pope Cells) 1425 Microwave Absorption Hygrometer 1444
Thin-Film Capacitance 1425 Limitations 1444
Metal Oxide Sensor 1426 Dipole Polarization Effect
Polymer Sensor 1427 Moisture Sensor 1444
Autocalibration 1427 Sampling System 1445
Dew-Point Hygrometers 1428 Limitations 1445
Solution-Conductivity Type 1428 Cavity Ring-Down Spectroscopy (CRDS)
Installation 1428 Moisture Analysis 1445
Sampling System 1428 Sampling System 1445
Limitations 1429 Limitations 1445
Condensation on a Chilled Surface 1429 Neutron Backscatter Moisture On-Line
Surface Conductivity Type 1429 Analyzer 1445
Sampling System 1429 Sampling System 1446
Limitations 1430 Limitations 1446
Chilled-Mirror Type 1430 Calibration of Moisture Analyzers 1446
2003 by Bla Liptk

Limitations 1448 Advantages and Limitations 1466

Bibliography 1448 Ultracentrifuge 1467
Sedimentation Velocity 1467
Sedimentation Equilibrium 1467
8.34
Instrument Construction 1467
Moisture in Solids 1450
Conclusions 1467
Introduction 1451 Bibliography 1467
Laboratory Analyzers 1451
Karl Fischer Titration 1451
Industrial Detectors 1451 8.36
Nuclear Moisture Gauge 1451 Nitrate, Ammonia, and Total Nitrogen 1469
Theory of Operation 1451 Introduction 1469
The Measuring System 1452 Environmental Significance 1469
Limitations 1452 Nitrification and Denitrification 1470
Infrared Absorption or Reflection 1452 Ammonia Nitrogen 1470
Measurement and Installation 1452 Ammonium and Total Nitrogen Probes 1470
Limitations 1453 Chemiluminescence 1471
Microwave Attenuation 1453 Nitrite Measurement 1471
Basis Weight Compensation 1453 Nitrate Measurement 1471
Moisture in Coal 1453 Total Nitrogen 1472
Sugar Industry Applications 1454 Kjeldahl Method 1472
Capacitance Moisture Gauge 1454 Chemiluminescence Analyzer 1472
Sensor Designs 1454 References 1473
Capacitance Measurement 1455 Bibliography 1473
Limitations 1455
Resistance Moisture Gauge 1455
8.37
Limitations 1455
Nitrogen Oxide Analyzers 1474
Impedance Moisture Gauge 1456
Nuclear Magnetic Resonance 1456 Introduction 1475
Radio Frequency Absorption 1456 Industrial Emission Monitoring 1475
Conclusions 1456 Paramagnetic Analyzers 1475
Bibliography 1456 Thermal Conductivity Analyzers 1475
Nondispersive Infrared Analyzers 1475
Ultraviolet Analyzers 1475
8.35
Chemiluminescent Analyzers 1475
Molecular Weight 1457
Electrochemical Sensors 1475
Introduction 1458 Gas Chromatography 1477
The Average Molecular Weight 1458 Ambient Air Monitoring 1477
Osmometers 1459 Calibration Methods 1477
The Membrane Osmometer 1459 Dynamic Calibration 1477
Automatic Osmometers 1459 Static Calibration 1477
Vapor Pressure Osmometers 1460 NONO2 Combination Analysis 1477
Light-Scattering Photometer 1461 Series Analysis 1478
The Zimm Plot 1461 Colorimetric Determination 1478
The Photometer 1462 The GriessSaltzman Method 1478
Viscometers 1462 The JacobsHochheiser Method 1478
Viscosity vs. Molecular Weight 1463 Portable Monitors 1479
Intrinsic Viscosity 1463 Conclusions 1479
Gel-Permeation Chromatography 1463 References 1479
Differential Refractometer Sensor 1463 Bibliography 1479
The Complete Instrument 1464
Molecular Weight from Chromatograph
Output 1464 8.38
End Group Determination 1466 Odor Detection 1480
Electron Microscope 1466 Introduction 1481
Transmission Electron Microscope 1466 The Measurement of Odor 1481
2003 by Bla Liptk

Sensitivity 1481 Interferometer 1497

Flexibility 1481 Transfer Optics and the Detector 1497
The Gas Chromatograph 1481 Data System/Controller 1497
The Human Olfactory System 1482 Configurations 1497
Sample Preparation 1482 Open Path Ultraviolet Spectrometry 1498
Odor Panels 1482 The OP-UV Spectrometer 1498
Training of an Odor Panel 1483 Open Path Tunable Diode Laser Spectrometry 1499
Tests 1483 Diode Lasers 1501
The Electronic Nose 1483 Applications 1502
Polymeric Film Sensors 1483 Principle of Operation 1502
Metal Oxide Sensors 1484 Wavelength Modulation Spectrometry 1502
Other Sensors 1484 Open Path Detection of Combustibles 1503
Training 1484 OP-HC Detector Design 1504
Applications 1484 Sources and Interference 1504
References 1484 TransmitterReceiver Separation 1504
Bibliography 1484 Advantages and Limitations 1505
References 1505
Bibliography 1505
8.39
Oil in or on Water 1486
Introduction 1486 8.41
Process Industry Measurements 1486 Oxidation-Reduction Potential (ORP) 1506
Capacitance-Type Water-in-Oil Introduction 1507
Detectors 1487 ORP Measurement Principles 1508
Radio-Frequency (Microwave) The ORP Reaction 1508
Sensors 1487 Half-Cell Reactions 1508
Rag Layer and Tank Profiler Half-Reaction 1509
Sensors 1487 Half-Reaction 1509
Water-in-Oil Probes 1487 Overall Reaction 1509
Conductivity and Capacitance Sensors 1488 The Cell Potential 1509
Ultrasonic Sensors 1488 Cell Potential at Equivalence Point 1509
Nuclear Sensors 1489 Chromium Example 1509
Ultraviolet Oil-in-Water Analyzer 1489 Microprocessor-Based Units 1510
Environmental Pollution Sensors 1490 ORP Sensors 1510
On-Off Oil-on-Water Detector 1491 The Nernst Equation 1511
Continuous Oil-on-Water Detector 1491 Electrode Mounting 1511
Oil-Thickness-on-Water Detector 1491 ORP Applications 1512
Oil-in-Water Detector 1491 Chromium Reduction 1512
Conclusions 1492 ORP Maintenance 1512
Reference 1492 ORP Control 1512
Bibliography 1492 Residence Time 1513
References 1513
Bibliography 1513
8.40
Open Path Spectrophotometry
(UV, IR, FT-IR) 1493 8.42
Introduction 1493 Oxygen in Gases 1514
Applications 1494 Introduction 1515
Toxic Sensor Types 1494 Paramagnetic Oxygen Detectors 1515
Instrument Designs 1494 Deflection Analyzer 1516
Blackbody Radiation Interference 1495 Thermal Analyzer 1516
Interferometry 1496 Dual-Gas Analyzer 1517
Beers Law and Path Integrated Catalytic Combustion Oxygen Detectors 1517
Concentrations 1496 Electrochemical Oxygen Detectors 1518
Path Integrated Concentration 1496 High-Temperature Zirconium Oxide
Open Path FTIR Spectrometry 1496 Fuel Cells 1518
2003 by Bla Liptk

Cell Design and Limitations 1519 Ultraviolet Analyzer 1537

Self-Diagnostics and Self-Cleaning 1520 Single-Beam Design 1537
High-Temperature Current-Mode Oxygen Double-Beam Design 1537
Detectors 1520 Amperometric Design 1538
Galvanic Detectors 1520 Calibration 1539
Capillary Systems 1521 Thin-Film Semiconductor Design 1539
Detector Design 1521 References 1539
Advantages and Limitations 1521 Bibliography 1539
Coulometric Sensor 1522
Polarographic Sensor 1522
8.45
Spectroscopic Oxygen Detection 1522
Ozone in Water 1540
Mass Spectroscopy 1522
Near Infrared Spectroscopy 1522 Introduction 1541
TDLAS Designs 1523 Drinking Water Disinfection 1541
Other Oxygen Detection Methods 1524 Amperometric Sensors 1541
Reference 1524 Bare Metal Electrodes 1541
Bibliography 1524 Membrane-Type Designs 1541
Stripping and Gas Phase Monitors 1542
Ultraviolet Absorption 1542
8.43 Colorimetric Method 1542
Oxygen in Liquids (Dissolved Oxygen) 1526 The Indigo Method 1542
Introduction 1527 References 1543
Probe Cleaners and Newer Sensors 1527 Bibliography 1543
Polarographic Cell 1528
Sample Temperature and Flow 1528 8.46
Galvanic Cell 1528 Particulates, Opacity, Dust, and Smoke 1544
Cell Designs 1529 Introduction 1545
Special and Flow-Through Cells 1529 Definitions and Theoretical Concepts 1545
Probe Design 1529 Opacity Measurement 1546
Installation 1530 Units and Definitions 1546
Flow-Through Design 1530 Dust Loading 1546
Coulometric Sensor 1531 Ringelmann Card Numbers 1547
Multiple-Anode Detector 1531 Stack Gas and Particulate Monitoring 1547
Thallium Cells 1531 Particulate Sampling 1547
Thallium Differential Conductivity Stack Gas Monitoring Packages 1547
Analyzer 1531 Light Attenuation and Transmissometers 1547
Fluorescence-Based Sensors 1532 Single-Pass Configuration 1548
Sensor Design and Operation 1532 Double-Pass Configuration 1549
Other Detection Methods 1532 Relative Performance 1550
Operational Considerations for All Optical Divergence 1551
Sensors 1532 Spectral Characteristics 1551
Calibration Methods 1533 Optical Characteristics 1551
Temperature Compensation 1533 Air Purge 1551
Pressure Effects 1534 Manual Stack Samplers 1551
Salinity Effects 1534 Automatic Stack Samplers 1552
Application Considerations 1534 Broken Bag and Runway Visibility
Mounting Considerations 1535 Sensors 1552
Bibliography 1535 Ambient Air Opacity Monitoring 1552
Particulate Concentration 1552
High-Volume Sampler 1553
8.44 EPA Air Quality Goals 1553
Ozone in Gas 1536 Dichotomous Sampler 1553
Introduction 1536 Tape Sampler 1554
Ozone Monitoring 1537 Soiling Index 1555
Monitor Designs 1537 Light Scattering 1555
2003 by Bla Liptk

Nephelometers 1555 Fiber-Optic pH Measurement 1573

Piezoelectric Crystal Mass Balance 1555 Relative Performance of pH Sensors 1573
Impaction Devices 1555 Reference Electrodes 1573
Calibration 1556 Flowing and Double Junctions 1574
Radiometric Devices 1556 Combination Measurement/Reference
Charge Transfer (Triboelectricity) 1556 Electrode 1574
Surface Ionization 1556 Multiple Junction References 1575
Visual Observation 1556 Stiff Gel Reference 1575
Remote Sensing 1557 Differential Reference 1575
Conclusions 1557 Electrode Cleaners 1576
References 1557 Shrouds and Filters 1576
Bibliography 1557 Automatic Cleaners 1576
Ultrasonic Cleaners 1577
Brush Cleaners 1577
8.47 Water-Jet Cleaners 1577
Particle Size and Distribution Monitors 1559 Chemical Cleaners 1577
Introduction 1560 Automatic Retraction 1578
Particle Size and Distribution 1560 Manual Cleaning 1578
Application Objectives 1560 Application Problems 1578
Detectors and Sampling Systems 1560 High Salt Errors 1578
Laboratory Monitors 1561 High Salt Effect on Electrodes 1579
Sensing Small Samples 1561 High Acid Errors 1579
Optical Microscopy 1561 Temperature Errors 1579
Electron Microscopy 1561 Water Concentration Errors 1580
Image Analyzers 1561 Nonaqueous Solutions 1580
Electrical Sensing (Coulter Principle) 1561 Probe Coating and Low Conductivity 1580
Optical Scattering (Single Particle) 1561 Installation Methods 1581
Sensing Intermediate Samples 1561 Submersion Assemblies 1581
Light Scattering (Multiple Particle) 1561 Retractable Units 1581
Sedimentation (Photo and X-Ray) 1561 Median Selector 1582
Sensing Large Samples 1562 Self-Diagnostics 1582
Sieving 1562 Glass Impedance Measurements 1582
Optical Methods 1562 Reference Electrode Impedance 1583
Ultrasonic Attenuation 1562 Sensor Fault Signaling 1583
On-Line Measurement 1562 Calibration 1583
Optical Multiple-Particle Analyzer 1562 Buffer Calibration Errors 1583
Airborne-Particulate Counter 1563 Conclusion 1583
Bibliography 1563 References 1584
Bibliography 1584
8.48
pH Measurement 1565 8.49
Phosphorus Analyzer 1585
Introduction 1566
Measurement Error 1566 Introduction 1585
Measurement Range 1566 Phosphorus in Wastewater 1585
Applications 1566 Colorimetric Analysis 1586
Theoretical Review 1567 Laboratory Methods 1586
Ion Concentrations 1567 Continuous Analyzer 1586
pH Measurement 1568 Total Phosphates 1586
Temperature Effects 1569 Flame Photometric Analysis 1587
pH Electrodes and Sensors 1569 Detector Operation 1587
Flat Glass Electrodes 1569 Gas and Liquid Chromatography 1587
Glasteel 1570 Sample-Handling Systems 1587
Metal Oxide pH Electrodes 1570 References 1588
Ion-Selective Field Effect Transistors 1572 Bibliography 1588
2003 by Bla Liptk

8.50 Flash-Point Tests (ASTM Methods D 5690

Physical Properties AnalyzersASTM and D 9390) 1602
Methods 1589 Low-Temperature Flash-Point Analyzer 1602
Introduction 1590 High-Temperature Flash-Point Analyzer 1603
Advantages of Continuous Analyzers 1590 Calibration and Application 1603
Distillation Analyzers 1590 Octane Analyzers 1603
Laboratory Measurements 1590 Laboratory Tests (ASTM Methods D-2699 and
ASTM Method D 86-IP-123 1590 D-2700) 1603
ASTM Method D 1160 1590 Standard Engine Octane Comparator
ASTM Methods D 288789, D 371088 1592 Analyzer 1603
On-Line Distillation Analyzers 1592 Reactor-Tube Continuous Octane Analyzer 1604
End-Point Distillation Analyzers 1592 Calibration and Application 1604
Near-Infrared Analyzers 1604
Vacuum Distillation Analyzer 1593
Chemometrics 1604
Horizontal Still Distillation Analyzer 1594
Calibration and Application 1604
Simulated Distillation by Gas
Chromatography 1595 Bibliography 1605
Calibration and Sampling 1595
Applications 1595 8.51
Vapor Pressure Analyzer 1595 Raman Analyzers 1606
Reid Method (ASTM Method D 32390) Introduction 1607
Procedure A 1595 Principles of Raman Spectroscopy 1607
Dry Reid Method (ASTM Method Optical Spectroscopy 1607
D 495390) 1596 Principles of Raman Scattering 1607
Liquefied Petroleum Gases (ASTM Raman Scattering and Spectral
Method D 126789) 1596 Information 1607
Air-Saturated Vapor Pressure General Instrumentation 1609
AnalyzerContinuous 1596 Fourier Transform Raman Instrumentation 1610
Air-Saturated Vapor Pressure Dispersive Raman Instrumentation 1610
AnalyzerCyclic 1596 Raman Process Analyzer Instrumentation 1611
Dynamic Vapor Pressure Analyzer 1596 Components of Raman Process Analyzers 1611
Calibration 1597 Laser Excitation Source 1611
Application 1597 Spectrometer 1612
VaporLiquid Ratio Analyzers 1598 Detector 1612
Volatility Test (ASTM Method D Fiber Optic Light Delivery and
253390) 1598 Collection 1612
Continuous Vapor-Liquid Ratio Analyzer 1598 Laser and Raman Filters 1613
Calibration and Application 1598 Sample Interface 1613
Pour-Point Temperature Analyzers 1599 Raman Probes 1613
Pour-Point Test (ASTM Method D Data Analysis, Modeling and Calibration 1614
9787) 1599 Polymerization Application 1614
Pour Point by Differential Pressure 1599 Multivariable Predictive Analysis 1614
Viscous-Drag Pour Pointer 1600 Calibration Model 1614
Calibration 1600 Calibration Transfer 1615
Application 1600 Smart Diagnostics and Analyzer
Cloud-Point Analyzers 1600 Maintenance 1616
Cloud-Point Tests (ASTM Method D Laser Safety 1616
250088) 1600 Outputs and Communication 1616
Optical Cloud-Point Analyzer 1601 Packaging 1616
Calibration and Application 1601 Installation and Maintenance 1616
Freezing-Point Analyzer 1601 Probe Designs 1616
Aviation Fuel Tests (ASTM Advantages and Disadvantages 1617
Method D 238688) 1601 Advantages 1617
Freezing-Point Analyzer for Aviation Fuel 1602 Limitations 1618
Calibration and Application 1602 Applications 1618
Flash-Point Analyzer 1602 Polymer Industry 1618
2003 by Bla Liptk

Conclusion 1618 Tension/Compression and Bending

References 1619 Designs 1635
Bibliography 1619 Extensional Flow Rheometer 1635
Extensional Viscosity Detectors 1636
Capillary Rheometers 1636
8.52 Conclusions 1636
Refractometers 1620 Bibliography 1636
Introduction 1621
RI and Brix Units 1621 8.54
Theory of Operation 1621 Streaming Current or Particle Charge
Critical Angle of Refraction 1622 Analyzer 1637
Differential Refractometer 1623
Single-Pass Design 1623 Introduction 1637
Two-Pass Design 1623 Operating Principles 1637
Temperature Effects 1624 The Streaming Current 1637
Flowing Reference Cell 1624 Calibration 1638
Critical-Angle Refractometer 1624 Applications 1638
Mounting and Compensation 1624 Treatment Chemical Selection 1638
Sampling 1639
Design Variations 1624
Control System 1639
Reflected Light Measurement 1624
Conclusions 1639
Fiber Optic Probe 1625
References 1639
Capabilities and Limitations 1625
Bibliography 1640
Conclusions 1626
Bibliography 1626
8.55
Sulfur-in-Oil Analyzers 1641
8.53
Introduction 1641
Rheometers 1628
X-Ray Absorption Analyzer 1641
Introduction 1628 Method of Operation 1642
Reasons for Using Rheometers 1628 X-Ray Fluorescence 1642
Dynamic Mechanical Analysis 1629 Pulsed UV Fluorescence 1642
Tests to Distinguish Liquids from Solids 1629 Fuel Analysis Spectrometer 1645
Shear-Strain Tests 1629 Bibliography 1645
Stress-Controlled Tests 1630
Nonlinear Shear Flow Properties ( , N1,
N2) 1630 8.56
Rheometer Selection 1630 Sulfur Oxide Analyzers 1646
Rheometer Designs 1630 Introduction 1647
Cone-and-Plate Design 1630 Applications 1647
Shear Flow Properties 1631 Industrial Analyzers 1648
Torque Ranges 1631 Stack Sampling 1648
Rheometer Selection 1632 Nondispersive Infrared 1648
Experimental Difficulties 1632 Ultraviolet 1649
Dynamic Mechanical Analysis 1632 Correlation Spectrometry 1649
Linear Viscoelastic Shear Moduli Thermal Conductivity 1650
G, G 1632 Ambient-Air Analyzers 1650
Molecular Weight Distribution 1633 Ambient-Air Sampling 1650
Time-Temperature Superposition 1633 Calibration 1650
Conversion Among Rheological Colorimetric Analyzers 1650
Properties 1634 Conductimetric Analyzers 1650
Parallel-Disc Design 1634 Coulometric Analyzers 1651
Parallel-Disc Geometry 1634 Flame Photometric Analyzers 1651
Limitation 1634 Electrochemical Analyzers 1652
Rectangular Torsion Design 1634 References 1652
Coaxial-Cylinder Design 1635 Bibliography 1652
2003 by Bla Liptk

8.57 Oxygen Detectors 1671

Thermal Conductivity Detectors 1653 Amperometric Toxic Sensors 1672
Introduction 1653 Number of Electrodes 1672
Thermal Conductivity 1653 Sensor Compensation and Life 1672
Measurement Ranges 1654 Fixed Detectors 1673
The TCD Analyzer 1654 Portable Detectors 1674
Main Components 1654 Discontinuous Dosage Sensors 1674
The Detectors 1654 Color Change Badges 1674
The TCD Cells 1655 Continuous Color-Change Monitor 1674
Bridge Circuits 1656 Color Detector (Dosimeter) Tubes 1674
Temperature Control 1656 Sorption-Type Dosimeters 1675
Operation 1656 Passive Personal Dosimetry 1675
The Reference Filament 1657 Active or Dynamic Sampling 1676
Packaging and Calibration 1657 Liquid and Solid Fillings 1676
Limitations 1657 Calibration 1677
Hydrogen in Hydrocarbons 1657 Dynamic Calibrators 1678
Conclusions 1657 Bubbler/Dilution Calibrator 1678
Bibliography 1657 Electrochemical Calibrating Gas
Generators 1678
References 1678
8.58 Bibliography 1679
Total Carbon Analyzers 1658 Web Links to Government Agencies 1679
Introduction 1659
Advantages and Limitations 1659
8.60
Carbon Measurement Techniques 1659
Turbidity, Sludge, and Suspended Solids 1680
Analyzer Development 1659
Official Methods of TOC Determination 1659 Introduction 1681
Detector Types 1659 Light Absorption and Scattering 1681
Nondispersive Infrared (NDIR) Analyzers 1659 Units of Turbidity 1681
High-Temperature Combustion 1660 Conversion among Turbidity Units 1681
Wet Chemical Oxidation 1660 Turbidity Analyzer Designs 1682
Inorganic Carbon 1661 Forward-Scattering or Transmission Type 1682
Automatic On-Line Design 1661 Dual-Beam Design 1682
Aqueous Conductivity 1662 Laser-Type Meter 1683
On-Line Conductivity 1662 Suspended Solids and Sludge Density
Coulometric Analysis 1662 Sensors 1683
Colorimetric Analysis 1662 Scattered Light Detectors
Flame Ionization Detector 1663 (Nephelometers) 1683
References 1664 Probe Design 1684
Bibliography 1664 Backscatter Turbidity Sensors 1684
In-Line Units 1685
Density-Based Sensors 1685
8.59 Conclusions 1686
Toxic Gas Monitoring 1666 Bibliography 1686
Hazardous and Toxic Atmospheres 1667
Safety Instrument Performance Standards 1667
Types and Levels of Toxicity 1668 8.61
Extreme Toxicity 1668 Ultraviolet and Visible Analyzers 1687
Toxic Gas Measurement 1668 Introduction 1688
Related Sections 1668 UV Absorption 1688
Continuous Sensor Designs 1668 Theoretical Aspects 1689
Chromatography 1670 The Radiation Spectrum 1689
Spectrometers 1671 The BeerLambert Law 1689
Radon Detectors 1671 Calibration 1690
Electrochemical Sensors 1671 UV-Absorbing Compounds 1690
2003 by Bla Liptk

UV Absorption Spectrum 1690 8.63

Applications 1691 ViscometersLaboratory 1708
UV Analyzer Components 1691 Introduction 1709
Radiation Sources 1691 Laboratory Viscometer Designs 1709
Broad and Discrete Line Sources 1692 Bubble-Time Viscometers 1709
Selecting the Measuring Wavelength 1692 Accuracy and Limitations 1711
The Monochromator 1692 Capillary Viscometers 1711
The Measuring Cell 1693 Using the Ostwald Viscometer 1711
Detectors 1693 Accuracy and Limitations 1711
Readouts 1693 Calibration 1711
UV Analyzer Designs 1693 Automatic Capillary Viscometer 1713
Single-Beam Analyzer 1693 Intrinsic Viscosity and Molecular
Split-Beam Analyzer 1694 Weight 1713
Dual-Beam, Single-Detector Analyzer 1695 MarkHouwink Equation 1714
Dual-Beam, Dual-Detector Analyzer 1695 Capillary-Extrusion Viscometer 1714
Flicker Photometer 1695 Design Variations 1715
Photodiode Array Spectrophotometers 1696 Limitations 1715
Scanning Spectrophotometers 1697 Efflux-Cup Viscometers 1715
Retroreflector Probes 1697 Saybolt Viscometer 1715
Visible and NIR Photometers 1698 Ford Cups 1716
Visible Photometers 1698 Zahn Cups 1716
Near-Infrared Photometers 1698 Automatic Efflux Cup 1716
Conclusions 1699 Falling-Ball Viscometers 1717
References 1699 Manual Falling-Ball Unit 1717
Bibliography 1699 Making the Measurement 1717
Calibration and Error Sources 1718
Automatic Falling-Ball Viscometer 1718
8.62 Falling-Needle Viscometer 1718
Rotational Viscometers 1718
ViscometersApplication and Selection 1700
Coaxial-Cylinder Viscometer 1718
Introduction 1700 Non-Newtonian Fluids 1719
Theory of Viscous Behavior 1700 Performance 1720
Stokes Law 1700 Cone-and-Plate Viscometer 1720
HaganPoiseuille Law 1701 The Drive 1720
Kinematic Viscosity 1701 Oscillating Design 1721
Intrinsic Viscosity 1701 Advantages and Precautions 1721
Non-Newtonian Fluids 1701 Oscillating Piston Viscometer 1721
Newtonian Fluids 1702 Bibliography 1721
Pseudoplastics 1702
Dilatant Fluids 1702 8.64
Plastic Solids 1702 ViscometersIndustrial 1723
Thixotropic Materials 1702 Introduction 1724
Rheopectic Substances 1702 Capillary Viscometers 1724
Apparent Viscosity Readings 1702 Sensor for Newtonian Fluids 1724
Conversion among Units of Viscosity 1702 Limitations 1726
Kinematic Viscosity 1703 Calibration 1726
Viscometer Selection and Application 1703 Differential Pressure Type 1726
Selection 1703 In-Line Design 1727
Applications 1705 Dual-Capillary Design 1727
Finished Product Specification 1705 Pipe Section as Viscometer 1727
Routine Laboratory Testing 1705 Backpressure Type 1727
Scientific Research Study 1705 Falling-Piston Viscometer 1728
In-Line Process Control 1705 Process Pressure-Operated Design 1728
Terminology 1705 Precautions 1729
Bibliography 1706 Falling-Slug or Falling-Ball Viscometers 1729
2003 by Bla Liptk

Float Viscometers 1730 pH Measurement 1749

Precautions 1730 Oxidation-Reduction Potential 1749
Single-Float Design 1730 Oxygen Demand Detectors 1749
Two-Float Design 1731 Dissolved Oxygen Sensors 1750
Concentric Design 1731 Total Organic Carbon and Total Carbon
Oscillating Viscometers 1732 Analyzers 1750
Oscillating Blade 1732 Turbidity Meters 1750
Oscillating Piston 1732 Nephelometers 1750
Torsional Oscillation Design 1734 Wet Chemistry and Autotitration 1750
Plastometers 1734 Volatile Organics 1751
Plastic Behavior 1735 VOC Compounds of Interest 1751
Cone-and-Plate Plastometer 1735 Chromatographs 1752
The Unit of Mooney 1735 Sample Obtained by Sparging 1752
Kneader Plastometer 1735 Temperature and Environmental Variables 1752
Capillary Plastometer 1736 Unattended Monitoring Stations 1753
Advantages 1736 References 1753
Limitations 1737 Bibliography 1753
Rotary Viscometers 1737
Rotary Spindle Design 1737
8.66
Installation 1737
Wet Chemistry and Autotitrator Analyzers 1755
Performance 1738
Magnetically Coupled Viscometer 1738 Introduction 1755
Gyrating-Element Viscometer 1738 Automatic Titration 1755
Agitator Power 1739 Types of Reactions and End-Point
Double-Cylinder Viscometer 1739 Detectors 1755
Vibrating-Reed Viscometer 1739 Continuous and Batch Designs 1756
Performance 1740 Volumetric Analyzers 1756
Installation and Calibration 1741 High-Precision Volumetric Analyzer 1756
Coriolis Mass Flow Meter 1741 Operating Sequence 1756
Measuring Tube Torsional Movement 1741 Multiple End Points 1757
Conclusions 1742 Simple Volumetric Analyzer 1757
Bibliography 1742 Applications of Volumetric Analyzers 1758
Colormetric Analyzers 1758
High-Precision Colorimetric Analyzers 1759
8.65 Use of Gas Bubbles 1759
Water Quality Monitoring 1744 Split-Beam Colorimeter 1759
Introduction 1744 Calibration 1759
Categories of Monitors 1744 Simple Colorimetric Analyzers 1760
Monitoring for General Use 1744 Calibration 1760
Regulatory Compliance Monitoring 1745 On/Off Batch Colorimeters 1760
Industrial Monitoring 1745 Applications of Colorimetric Analyzers 1761
Monitoring System Components 1745 Flow Injection Analysis 1761
Sampling Systems 1745 Laboratory FIA 1761
Duckbill Samplers 1745 Industrial FIA 1762
Sample Transport 1746 Application Example 1 1762
Sensors and Analyzers 1747 Application Example 2 1762
Water Quality Parameters 1747 Calibration 1763
Ion-Selective Electrodes 1747 References 1763
Conductivity 1749 Bibliography 1763
2003 by Bla Liptk

8.1 Analyzer Application and Selection
B. G. LIPTK (1972, 1982, 1995) A. H. ULLMAN (2003) (Sidebar by Georg Erk)
INTRODUCTION The Selection Process
Modern process control requires current information on the The process to follow in selecting the appropriate analyzer
state (composition, temperature, pressure, flow rate, etc.) of for an application involves eight steps:
the material being produced. Modern distributed control sys- 1. Problem definition
tems linked to various control elements (valves, pumps, etc.) 2. Information gathering (to understand the problem fully)
require data much more often than the manual control systems 3. Analyzer selection (making sure to consider and balance
of years gone by. While grab samples taken to a modern lab- these criteria)
oratory will be the gold standard for quality control purposes, Specificity
the effort and time it takes to get a sample, transport it to the Accuracy and precision
lab, and wait for the result can add significantly to the costs Calibration
of the process in process output, energy, etc. For many indus- Analysis frequency
tries, the solution is to move the analysis directly to the process. Kind of analyzer
This need for more and better analyzers does not mean 4. Sampling
that their application is, or ever will be, a simple, routine 5. Analyzer location
task. For an analyzer system to fulfill its expectations, careful 6. Handling of the data
planning and evaluation must precede its purchase, and the 7. Maintenance issues
users must realize that if an expensive analyzer is worth 8. Total cost: hardware, installation, maintenance, etc.
purchasing, it must also be worth calibrating and maintaining.
The operators acceptance, which depends largely on training It is not uncommon to cycle back from one step to
and familiarization, is also crucial. New self-diagnosing and another, as more information is needed to assure that the
self-calibrating analyzers are a major contribution to improved proper decisions are made. Installing the wrong kind of ana-
operator acceptance, but people issues are still more impor- lyzer or putting it in the wrong place will not solve the
tant and should not be discounted. problem, and instead of saving money or improving quality,
In this section, a process for the selection of an analyzer money and effort will be wasted.
is presented. The many issues that must be considered are
covered, as is an overview of kinds of analyzers. The latter PROBLEM DEFINITION
material should be viewed only as introductory. Detailed
discussion of the different instruments is covered elsewhere Defining the problem begins with understanding how the
in this volume and in the references. measurement will be used. Is it for closed-loop process con-
The most important aspect of an analyzer application is trol or for information purposes? Is the measurement really
a clear understanding of why the analyzer is needed, what needed on-line, or could 80% of the benefits be obtained
information is needed, and what will be done with the infor- for 20% of the cost and effort by making the measurement
mation. Put another way, the analyzer problem must be clearly at-line in the control room? What is the benefit of the
defined and understood. Too many analyzer applications have measurement? How will the cost be justified? Is this to reduce
failed because the needed measurement was not the one staffing by moving the measurement from the lab to the pipe?
installed in the process. Is it a yield-improvement project? Answers to these questions
In general, the instrument engineer (analyzer engineer, begin to clarify the needed timescale for the measurement. In
process analytical chemist, etc.) is asked by a process control addition, it is important to understand the process to be mon-
engineer to install an analyzer in a process. It is the analyzer itored. What is the response time of the process? Obviously,
engineers duty to his company to push back and insure that if the process takes 60 min to respond to a temperature change
the application is needed and clearly understood. Merely doing (e.g., distillation column), analyzer requirements are quite
what is asked, in many cases, will lead to unnecessary or even different from those of a process that responds in 6 sec. These
failed installations. issues are important and referred to throughout this chapter.
1144
2003 by Bla Liptk
8.1 Analyzer Application and Selection 1145
Before continuing our discussion of problem definition, INFORMATION GATHERING

it is helpful to define some commonly used terms. In analyt-
ical chemistry, we usually define measurements as laboratory, Reasons for installing process analyzers include the improve-
at-line, on-line, and in-line. In addition, measurements can be ment of safety, as well as of product quality; reduction of
invasive or noninvasive. Process analytical chemistry encom- by-products, decrease in analysis time, tightening of specifica-
passes all of these, except laboratory measurements. tions, and monitoring of contaminants, toxicants, or pollutants.
An at-line measurement is generally a manual measure- Additional requirements and characteristics of the mea-
ment, instrumental or chemical, performed near the process, surement must be understood, including the needed frequency
generally in or adjoining the control room. The method may of analysis, sample availability, cost, and safety considerations.
be identical to the laboratory method, but normally it is Many analyzer experts find filling out a form to be helpful
simpler and faster. The at-line approach is ideal when the in gathering data on needs and desires (Table 8.1a). In select-
resulting information is used to control slow response pro- ing an analysis system, one must ask whether the need for
cesses, or for quality control, or when true real-time mea- the measurement justifies the cost. If the answer is yes, the
surements are prohibitively expensive, compared to the study progresses until several possible types of analyzers are
benefit. An example of an at-line measurement might be a identified, at which time the question of cost is again raised,
caliper measurement of a paper product or a multiphase titra- and some of the more expansive analyzers may be eliminated
tion of a surfactant. In both cases, production samples are from further consideration. After the complete system has
manually taken to the measurement station and tested. A been defined, the estimated costs can be compared with the
typical frequency for an at-line measurement might be hourly. expected benefits and a decision reached.
On-line measurements are those installed on the process With the basic problem defined, the process analytical
such that a sample or slipstream is brought to the measure- chemist must now understand the measurement approach to
ment device, frequently with sample conditioning. In general, be selected. This requires an understanding of the current
this method is used when data are needed very frequently approach, if any, including whether such a measurement is
and the measurement approach is not conducive to in-line made in the plant laboratory. Frequently this information gath-
use. The slipstream approach is needed when the measure- ering step involves discussions with research and development
ment instrument requires sample conditioning, such as filtra- analytical chemists, plant quality control laboratory personnel,
tion. This will be discussed in more detail later. Process gas and library research. In general, for any needed measurement,
chromatographs are examples of instruments that normally there will be several different possible approaches (methods)
use the on-line method and require sample conditioning to that could be taken. While gathering information, the process
allow proper sampling of the small volumes needed for injec- analytical chemist or instrument engineer should be open-
tion. (Of course, chromatographs do not normally provide minded to the methods, while carefully evaluating each one
rapid or continuous data output.) in light of the specific problem at hand. If the results of the
In-line measurements are those in which a probe is measurement will be compared to the laboratorys results, it
inserted directly into the process. No sample conditioning is becomes crucial to understand any differences between the
required. Common examples include pH and other electrode methods. Where possible, similar methods should be used.
measurements. In a gray zone between the on-line and in- However, lab methods are not typically suitable to the process,
line categories, we find approaches in which the instrument so other approaches will probably be needed. The critical
is able to look into the process through a window (for exam- question to be answered during this information gathering
ple, a spectroscopic measurement) or directly on a moving phase is, What is the measurement handle I can employ for
web or conveyor belt. These are real-time approaches, but the process measurement? In other words, What attribute of
not on a slipstream and not really in-line either. the analyte would be easiest to grab (measure) in the process
An invasive measurement is one that in some way pen- environment? For example, if the project request is for an
etrates or changes the process. Any in-line approach would oxygen measurement, the engineer will have learned that it is
be considered invasive, as would an on-line approach that gaseous oxygen, not dissolved oxygen, that is needed, and
modified the process flow with a slipstream. A near-infrared must now determine how to make the measurement, keeping
(NIR) photometer positioned above a web would be nonin- in mind the process conditions. There are several common
vasive since it does not enter or change the process or mate- oxygen measurement approaches, each of which uses a dif-
rial. Similarly, a clamp-on ultrasonic flow or density meter ferent handle or attribute of the oxygen molecule. Depend-
is noninvasive. ing on the process conditions, other components of the matrix,
When an adequate discussion of the measurement need etc., the chemist could select a paramagnetic oxygen analyzer,
has occurred, we can assume that the problem has been which makes use of the fact that elemental oxygen is one of
defined sufficiently, at least in terms of the kind of process the few gases attracted to a magnet, or an electrochemical cell
measurement needed and how it will be used. It may be device, which makes use of oxygens electroactivity. After the
necessary to return to this subject and refine the problem appropriate candidate process method has been selected, the
definition further, based on additional information that will chemist must address these issues: How will the method be
be gathered in the next steps. calibrated? Will it be compared to the lab results? Does it
2003 by Bla Liptk

TABLE 8.1a
Sample Analyzer Specification Form
Project: ................................................................................................... Date: ..................................................................................................................
Specification no.:................................................................................................... Code:...................................................................................................
Information compiled by:.......................................................................................................................................................................................................
A. GENERAL INFORMATION:
1. Plant:................................................................................................... 2. Unit: ..................................................................................................................
3. Process: ..............................................................................................................................................................................................................................
B. CONDITIONS AT PLANNED ANALYZER LOCATION:
1. Ambient temperature range:........................................ to ..................................................... Normal ................................................................................
C F
2. Protected from weather: Yes No
3. Unusual ambient conditions ...............................................................................................................................................................................................
(Corrosive or explosive atmosphere, excessive moisture, dust, etc.)
4. Power available: ........................................................................................... V .......................................................................................................... Hz
(a) Voltage variation: ........................................................................................ to ........................................................................................................ V
(b) Frequency variation: .................................................................................. to ........................................................................................................Hz
(c) Grounding facilities available: Yes No
5. Lighting level: Good Average Poor
(a) Front of instrument ................................................ ..................................................... ...............................................
(b) Back of instrument ................................................ ..................................................... ...............................................
(c) Direct sunlight will strike instrument: Yes No
6. Steam lines near location: ..................................................................................................................................................................................................
7. Instrument air available:
(a) Pressure range: from ........................................................ to ......................................................... Normal ........................................................ PSIA
(b) Temperature range: from ................................................ to .......................................................... Normal .................................................. C F
(c) Contaminants: ..............................................................................................................................................................................................................
3
(d) Size of header: ............................................................................................ Volume: .......................................................................................ft /min.
(Use separate page for each stream to be analyzed.)
C. SAMPLING INFORMATION:
1. Form of sample: Gas Liquid Other ....................................................................................................................................................
2. Temperature range: from ........................................................ to ........................................................... Normal .................................. C F
3. Pressure range: from ............................................................... to ........................................................... Normal .................................................... PSIA
4. Dew point: ...................................................................... C At ............................................................................................................................... PSIG
5. Quantity available: ............................................................................................................................................................................................... per hour
6. Low-pressure return line available:
Yes No Back-pressure .............................................................................................................................................................. PSIG
7. Specific gravity: ..................................................................................................
8. Contaminants in sample:
Oil Wax Solids Particle Size ......................................................................................................................................................................
(Include identity and concentration in list of components below.)
9. Corrosive nature: Acidic Basic Other ................................................................................................................................................
10. Other data (viscosity, unusual surges, etc.): .....................................................................................................................................................................
11. Materials of construction that may be used in contact with sample: .................................................................................................................................
12. Distance from sample tap to analyzer location: ............................................................................................................................................................ ft
2003 by Bla Liptk

TABLE 8.1a Continued

Sample Analyzer Specification Form
13. Size of tap at process line, if any: .....................................................................................................................................................................................
14. Concentration ranges of all components (even if only traces) in stream: (Specify unit of measurement: % by volume, % by weight, or ppm for
each component.)

Components to Be Analyzed Other Components

Maximum Minimum Normal Unit Water (Liquid, Vapor) Maximum Minimum Normal Unit

15. The above stream composition information is considered proprietary:
Yes No
16. Method of lab analysis used to measure sample: ..............................................................................................................................................................
17. Desired response time of analyzer: ...................................................... min ............................................................... sec ...............................................
18. Accuracy required: % of full-scale reading
D. INSTALLATION REQUIREMENTS:
1. Type of installation: Permanent Temporary Portable
2. Type of mounting: None Rack Panel
Other: .....................................................................................................................................................................................................................................
3. Electrical code: Class ......................................................... Group ....................................................... Division ..............................................................
4. Recorder or indicator required: ..........................................................................................................................................................................................
(a) To be supplied with analyzer: Yes No
5. Location of recorder: At analyzer Distance from analyzer ..................................................................................................................... ft
6. Recorder mounting: None Rack Panel
7. Accessories:
(a) Alarms: High Low (b) Controls: .........................................................................................................................................
(c) Others: ......................................................................................................................................................................................................................
8. Date required: ....................................................................................................................................................................................................................
9. Sketch of system indicating sample points and distances to analyzer:
measure the same thing(s)? Of course, the most important TECHNIQUE OR ANALYZER SELECTION
question is, Will this measurement method provide the infor-
mation needed by the process engineer or customer? The most important factors that must be weighed by the
Frequently, while gathering information, one must return instrument engineer are discussed in the remainder of this
to problem definition and seek clarification. This is an itera- chapter and in the chapters that follow. Unfortunately, no
tive process. It is not uncommon for the problem definition single analyzer combines all the desirable features of provid-
to change as you learn more about the possible measurement ing on-stream, specific, continuous, unattended high-sensitivity
approaches and share these learnings with your customer. readings without drift, noise, or need for a sampling system.
Finally, you feel you have enough clarity regarding the Therefore, the selection is always a compromise, which is
problem and can move forward to the technique or analyzer likely to give satisfactory results only if it is preceded by
selection step in the process. careful evaluation.
2003 by Bla Liptk

If the problem has been defined as one requiring the added importance. Often, the terms do not have industry-wide
measurement of one material in the presence of another, it is significance, so the definition should be agreed upon with each
necessary first to look for the handle or unique property of supplier. (Note: With proper calibration, an analyzer will be
the material to be measured. Usually, a first step in determin- accurate.)
ing the suitable methods of analysis is to investigate labora- In general, in process measurement, precision or repeat-
tory methods used to determine the desired property. As ability is more important than accuracy. Since the measure-
previously noted, a meeting with laboratory personnel is a ment is being made continuously or repeatedly, we are much
good first step. Industry methods are another good starting more interested in changes in a value than whether that value
point. For example, the American Society for Testing Mate- is absolutely correct or accurate. Changes in the process are
rials (ASTM) has established certain test methods for the what we are trying to measure and understand (and control).
determination of various properties and materials. Their For the purpose of this discussion, precision is defined
1
methods are widely available in book form and on the web. as the ability of an analyzer to produce the same output each
Other organizations such as the American Oil Chemists Soci- time the sample contains the same quantity of component or
ety (AOCS) and the Technical Association of the Pulp and property being measured. The terms stability, reliability, and
Paper Industry (TAPPI) have also published compendia of reproducibility are sometimes used synonymously with
2,3
analytical methods. Suppliers of the material to be analyzed repeatability. However, reliability is also used to describe the
are possible sources of information for methods of analysis, instruments up time and should not be used as a synonym
as are suppliers of on-line analyzers. for precision. Lack of repeatability may be caused by the
Once prospective methods of analysis have been selected, analyzer, the sampling system, or the effects of temperature,
the search for appropriate hardware begins. Ordinarily, details power supply, composition, pressure, and flow rate. Poor
of the desired measurement are given to the potential analyzer precision or low repeatability can come in two forms: short
suppliers, and estimates of performance are obtained. The term and long term. Short term may mean the measurement
analysis system can often be purchased on a guaranteed- system has lots of randomness (noise). Such random noise
performance basis. For proprietary installations, the user him- degrades the utility of any given reading, but may be tolerable
self must determine how the general analyzer specifications since many data points are collected. Long-term drift can be
apply for the particular application, and since the user is a more significant problem requiring frequent instrument
buying hardware only, the supplier will guarantee only the recalibration or adjustment. Repeatability and inaccuracy are
quality of materials and workmanship. Alternatively, once a normally expressed either as a percentage of the full mea-
single supplier has been selected, a confidentiality agreement surement range or as a percentage of the actual reading.
can be signed allowing information sharing by both par- When discussing specifications for an analyzer, especially
tiesa true partnership to assure a successful installation. with prospective vendors, be very careful to define all tech-
When comparing different analysis approaches, the fol- nical terms and understand exactly what the literature or the
lowing criteria are critical. sales engineer means by terms such as accuracy, drift, preci-
sion, etc. If there is any doubt, ask for a clarifying example with
actual numbers, such as, The refractometer is stable to 1%
Specificity (Selectivity)
of the actual reading over 14 days, without any adjustments.
Specificity is the characteristic of responding only to the prop- That is, it will read 1.102 0.1 for 2 weeks, if the temperature
erty or component of interest. The specificity of the analyzer changes no more than 5C. Sales literature is notorious for
will not exceed that of the analysis. Specificity is often a specifications that are unclear and frequently misleading.
function of the range to be measured, the sample background,
and the process conditions (solid, liquid, or gas; pressure and
Calibration
temperature). The more selective a measurement is, the less
we need be concerned with interferences from other constit- The ability to calibrate an analyzer properly usually depends
uents of the sample matrix. Obtaining a high degree of selec- on the availability of a reliable reference sample, or the ability
tivity frequently means compromising other analytical to perform reliable laboratory analysis on the actual sample
attributes. For example, a gas chromatographic separation that is entering the analyzer. Never lose sight of these inherent
with baseline resolution of the analyte of interest may require difficulties (challenges) in calibration: 1) Samples can change
a longer analysis time than is desired or allowable. after removal from the process and hence are different when
they reach the lab. 2) Highly variable process streams, in which
Accuracy and Precision the lag time between the process measurement point and the
sampling valve cause the sample drawn from the stream and
Frequently, absolute accuracy of a process measurement can- the sample measured in the process to be different. (In some
not be established owing to the lack of a suitable calibration cases, the sample itself may be inhomogeneous, which fur-
standard or the inability to draw an unchanged sample from ther complicates comparison measurements.) 3) The two
the process and analyze it by an official laboratory method. measurement methods may not be measuring the identical
For this reason, other terms, such as repeatability, take on analyte. For example, a near-infrared moisture analyzer may
2003 by Bla Liptk

be calibrated against a loss-on-drying lab method, but these the most widely used technique in process analysis, with the
are not identical, and there may be a bias between them caused possible exception of pH.
by other volatile constituents of the sample. In all chromatographic techniques, a small portion of the
Interferences with the analysis can be caused by physical sample stream is injected into a flowing carrier fluid that
or chemical effects that cause a deviation in the analyzer passes through a column in which it contacts a separation
output. If the effect of the interfering substance remains con- medium prior to reaching a detector. In gas chromatography,
stant, a compensation factor can usually be applied in the the sample is vaporized, if it is a liquid, and carried with
calibration procedure. During checkout of the installed sys- helium or nitrogen (most commonly) through the column.
tem, one should verify the effect of interference by calibrating The column may be a tube packed with adsorbent media or
the analyzer for each suspected substance. a thin capillary column coated with an appropriate phase to
When interferences cannot be predetermined, it may be cause a separation. If the sample was a gas to begin with, it
both necessary and practical to send known samples to pro- is carried through the column without the need for vaporiza-
spective suppliers for evaluation. In any case, known and sus- tion. Depending on the analytes to be separated, one chooses
pected interferences and their concentrations should be made the appropriate length of column and coating or packing
known to prospective suppliers when requesting quotations. material. Many different separation materials are available.
Both the method of calibration and the accuracy of the Similarly, many different gas chromatography detectors exist
calibration procedure must be established before one pur- to provide specificity or broad detectabilty. For fixed gases,
chases a process analyzer. the thermal conductivity detector (TCD) is mandatory; for
organic compounds, either the TCD or the flame ionization
detector (FID) is acceptable, but the FID is more sensitive.
Analysis Frequency
Added sensitivity (lower detection limits) comes at a price:
As discussed in the Problem Definition section, one should the FID needs additional gases and extra safety precautions.
first determine whether continuous analysis, automatic-repet- Later chapters will address these subjects in more detail. In
itive batch sampling, or an occasional spot check is required. liquid chromatography, the sample is injected into a flowing
The information from the analyzer and the rate of the stream of solvent (mobile phase), separated, and detected.
dynamic changes in the sample are the main factors to be Common detectors include the refractive index (RI) detector,
considered. which monitors the eluting mobile phase for RI changes;
The need for process control suggests either a continuous absorbance detectors, which monitor the spectral absorbance
analyzer or an analyzer with a continuous output signal, because of the mobile phase at one or more wavelength, commonly
a continuous analyzer provides a better chance for the system in the ultraviolet (UV) or visible (Vis) areas of the spectrum;
to reach and maintain equilibrium with the sample. Also, the and the electrochemical detector, which monitors an electro-
mechanical design of a continuous analyzer ordinarily is less chemical property such as conductance of the mobile phase.
complicated than that of a discontinuous system. However, the Other chromatographic techniques that are available for
discontinuous analyzer may be more attractive if automatic zero process measurement include ion chromatography, which can
checks are frequently needed, if reagents are blended with the measure either the anions or cations of a stream; gel perme-
sample, or if the sample is corrosive. Some analyzers, for exam- ation chromatography, which measures the molecular weight
ple, chromatographs, are inherently discontinuous. distribution, typically of polymer samples; and supercritical
The rate at which the measured variable changes in the fluid chromatography, which operates in the pressure and
process is an important factor in determining the frequency of temperature regime where a carrier fluid, such as carbon
discontinuous analyses. If the sample has to be withdrawn and dioxide, is neither liquid nor vapor.
transported to the analyzer, the time lag factor must also be The disadvantages of the chromatographic techniques are
considered. If several different samples are to share the analyzer the length of time many of the separations take, the fact that
(e.g., stream switching), additional time allowances are required. these are not continuous techniques (samples are injected only
after the previous run is complete and the system has stabi-
Kinds of Analyzers lized), aging of the columns, consumption of gases or sol-
vents, and maintenance of the frequently complex and costly
Analytical techniques suitable for process measurement may sampling systems. In fact, the cost of the chromatograph itself
be organized into several arbitrary categories. No one approach can be less than half of the total installation cost and, if the
is inherently superior to another, although for a specific project, expense of maintenance is also included, the fraction of the
the constraints covered previously will narrow the choice. instruments cost is reduced even further. Some reports indi-
cate that for every successful chromatograph installation in
Separation Techniques the chemical industry, one has failed and been abandoned. For
this reason, some engineers favor simple inexpensive chro-
Separation techniques literally involve the separation of dif- matographs, monitoring one component in a single sample to
ferent components in the sample with appropriate detection. increase reliability. Proponents maintain that an overburdened
Gas chromatography, which dates to the 1950s, is probably chromatograph is more a liability than an asset, and that even
2003 by Bla Liptk

TABLE 8.1b
Absorption/Emission of Electromagnetic Energy Useful for Measurements
Type of Radiation Wavelength Range Characteristic Process Probed
12
Gamma-rays <10 m Nuclear transitions
X-rays 1 nm1 pm Inner-shell electron transitions in atoms
UV 400 nm1 nm n, (valence) electron transitions in molecules
Vis 750 nm400 nm n, (valence) electron transitions in molecules
NIR 2.5 m750 nm Molecular vibrations
IR 25 m2.5 m Molecular vibrations
Microwaves 1 mm25 m Rotations in molecules
a
Radio waves >1 mm Rotations in molecules, electron spin flips
a
NMR uses a magnetic field to split the energy levels and the Rf energy to probe the spin state.
when it is operating, the volume of information generated is respect to light transmission, but linear with absorption and
more likely to swamp than to assist the operator. Therefore, concentration.)
their target is to achieve a degree of standardization and sim-
I0
plicity similar to that found in flow or temperature detectors. A = abc = log 8.1(1)
It is reported that these simple chromatographs can accom- I
modate the majority of present applications. where
New developments in the simplification of sampling sys- A = absorbance
tems may reduce their cost and complexity while increasing a = molar absorption or extinction coefficient (a constant
reliability. Recent developments in the field of sampling sys- for any given compound and wavelength)
tems using a small, industry standard platform of modular b = sample path length
48
components show much potential. Recent research in the c = absorber (sample) concentration
use of chemometrics to extract information from poorly I0 = incident radiation
resolved peaks may provide advantages in analysis time by I = radiation leaving sample
allowing faster run times. Parallel columns of different sep-
aration power combined with chemometrics will provide The region of the spectrum used for the measurement
additional benefits. Chemometrics can help address the issue varies with the kind of compound and information desired
of swamping the operator with information. (Table 8.1b). In addition, the instrument itself will be quite
different in specific components since the properties of the
Other Separation Techniques light vary. Instruments to make these measurements can vary
from single-wavelength photometers to grating instruments
Developments in nonchromatographic separation techniques, to multiplex designs, depending on the spectral region and
such as capillary electrophoresis, in which an applied electric the needs of the measurement.
potential is used to drive the separation of charged species,
are occurring rapidly. The combination or merger of chro- Ultraviolet and Visible
matography and flow injection analysis (FIA) is also on the
horizon. These regions of the spectrum are similar and are generally
grouped together. In fact, most laboratory instruments for this
region include both. The energy of this region corresponds to
Spectroscopic or Radiant Energy Techniques electronic transitions in compounds. In the UV, compounds
with double bonds, such as those in Table 8.1c, are commonly
This family of sensors uses the interaction of electromagnetic measured. Other functional groups with electrons are also
radiation with matter. Most commonly, the technique operates excellent absorbers (Table 8.1d). Vis absorbers are compounds
on either absorption or reflection principles, but fluorescence that are colored to the human eye. Obviously, dyes, inks, etc.
and scattering are also used. are readily measured in the visible portion of the spectrum.
If radiation at different wavelengths is passed through a One major thing to watch out for is that compounds that absorb
process material, the amount of absorption may be an indicator in this region may be such strong absorbers that a short path
of sample identity or composition. The output of such an ana- length is needed to get a good response, and only very low
lyzer is related to the absorption of the light in a linear way, concentrations can be measured. Reducing the path length
as shown in Beers law (more correctly, the LambertBeer may help, but too small a path length in a typical process
law) of radiation absorption. (Transmission is logarithmic with stream will act as a filter and cause the measurement to fail.
2003 by Bla Liptk

Fluorescence
TABLE 8.1c
Partial List of UV-Absorbing Compounds When radiation of one wavelength is absorbed by a molecule
Acetic acid Formic acid with the appropriate molecular structure, it can be remitted at
Acetone Hydrogen peroxide a higher wavelength (lower energy). This process, called fluo-
rescence, is an extremely useful measurement technique, pro-
Ammonia Hydrogen sulfide
vided that the analyte has the appropriate structure. Molecules
Benzene Iodine
with many double bonds, especially conjugated double bonds,
Bromine Isoprene will fluoresce. Many biomolecules, including some vitamins,
Butadiene (1,3) Mercury proteins, cofactors, and the like, fluoresce, allowing the tech-
Carbon disulfide Naphthalene nique to be used in fermentation and other bioprocessing. Crude
Carbon tetrachloride Nitric acid oil also contains fluorescent molecules; low levels of oil on
water are frequently detected using fluorescence. Table 8.1e
Chlorine Ozone
provides a list of some fluorescent compounds along with their
Chlorobenzene Perchloroethane
excitation and fluorescence (emission) wavelengths maxima.
Crotonaldehyde Phenol
Cumene Phosgene Infrared and Near-Infrared
Cyclohexane Styrene
Infrared (IR) instruments were one of the first analyzers to
Cyclohexanol Sulfur be moved from the laboratory to the pipeline, and the tech-
Cyclohexanone Sulfur dioxide nology is available for use with gas, liquid, or solid samples.
1,3-Cyclopentadiene Sulfuric acid In the absorption mode of operation on liquid samples, the
Ethylbenzene Toluene path length has to be very short, though not as short as in the
UV. Noncontacting backscatter designs readily measure mois-
Fluorine Trichlorobenzene
ture in solids (e.g., conveyor belts of flour) or composition
Formaldehyde Xylene (ortho, meta, and para)
with fiber-optic probes (FOPs) in liquids. The probe version
of the IR analyzer eliminates the need for a sampling system
and can be used in both liquid and gas phase processes. NIR
is widely used for moisture measurement. Probably every
paper machine in the world has an IR or NIR analyzer to
TABLE 8.1d
Absorption Bands of Some UV-Vis Absorbing Chromophores (Functional Groups)
Chromophore Structure Wavelength Maximum (nm) Molar Absorptivity [l/(molcm)]
Aldehyde CHO 280300 1118
Amine NH2 195 2800
Bromide Br 208 300
Carbonyl C O 195, 270285 1000, 1830
Disulfide S S 194, 255 5500, 400
Ester COOR 205 50
Ether O 185 1000
Nitrite ONO 220230 10002000
Oxime NOH 190 5000
Thioether S 194, 215 4600, 1600
Carboncarbon double bonds C C 190 8000
(C C)2 210230 21,000
(C C)3 260 35,000
(C C)4 300 52,000
Carbonyl with C C C C C O 210250 10,00020,000
Benzene Aromatic ring 184, 204, 255 46,700, 6900, 170
Diphenyl Linked aromatic rings 246 20,000
Anthracene Fused aromatic rings 252 199,000
2003 by Bla Liptk

TABLE 8.1e
Partial List of Some Fluorescent Compounds and Their Excitation and Fluorescence Wavelength Maxima
Fluorescence Fluorescence
Excitation (Emission) Excitation (Emission)
Compound Maximum (nm) Maximum (nm) Compound Maximum (nm) Maximum (nm)
Adenine 280 375 Proteins 280 313, 350
Adenosine 285 395 p-Terphenyl 284 338
Adrenaline 285 325 Pyrene 330 382
Anilines 280, 290 344, 360 Pyrene, 4-methyl 338 386
Anthracene 420 430 Quinine 250, 350 450
Adenosine triphosphate (ATP) 285 395 Salicylic acid 310 435
Dibenzo[a,e]pyrene 370 400 Terramycin 390 520
Estradiol 285 330 Tetracycline 390 515
Folic acid 365 450 Thymol 265 300
Indole 280 355 Tryptophan 285 365
LSD 325 465 Vitamin A (carotene) 325 470
Neosynephrin 270 305 Vitamin B12 (cobalamine) 275 305
Pentabarbital 265 440 Vitamin B2 (riboflavin) 270, 370, 445 520
Pentothal 315 530 Vitamin B6 (pyridoxine) 340 400
Phenanthrene 252 362 Vitamin E (tocopherol) 285 330
Procaine 275 345
Note: Excitation and fluorescence bands are broad and maxima may shift with pH or solvents.
measure and control drying. NIR instruments can be filter

TABLE 8.1f photometers or spectral instruments using gratings, interfer-
Absorption Bands of Some Raman and Infrared-Absorbing
ometers, or acousto-optic tunable filters (AOTFs) to select
Chromophores
the wavelengths needed for the measurement. Table 8.1f and
Chromophore Intensity Figure 8.1g give some absorption wavelengths for various
1
(Functional Group) Region (cm ) Raman Infrared organic functional groups in the IR and NIR regions.
CC aliphatic chains 250400 Strong Weak
S S 430550 Strong Weak Raman
Si O Si 450550 Strong Weak
In recent years, the Raman spectrometer has moved from the
C Cl 550800 Strong Strong laboratory to the process floor. This has been driven by the
C O C 800970 Medium Weak combination of improved lasers, fiber optics, and compact
O O 845900 Strong Weak spectrometer designs. Raman spectroscopy is complementary
C O C asymmetric 10601150 Weak Strong to IR and provides similar functional group information.
CH3 1380 Medium Strong Raman spectroscopy obtains its information from the scatter-
ing of light from molecules. It is amenable to direct, nonin-
CH2, CH3 asymmetric 14001470 Medium Medium
vasive sampling of solids and liquids. Water and glass are
N N aromatic 14101440 Medium
weak Raman scatters, providing the opportunity to investigate
C C 15001900 Strong Weak samples in aqueous media and through glass site windows,
C N 16101680 Strong Medium or a glass container, or via FOPs. Reports of Raman being
H2O 1640 Weak Strong used to monitor polymerization reactions and distillation pro-
C O 16801820 Medium Strong cesses are among the growing number of published applica-
C C 21002250 Strong Weak
tions. Use of NIR laser diodes has reduced the problem of
background fluorescence. Table 8.1f compares some molec-
C N 22202255 Medium Strong
ular absorption bands in the IR and Raman.
C H 28003000 Strong Strong
O H 31003650 Weak Strong Microwave and Radio Frequency
Note: Intensities and wave number ranges are approximate and may Microwave and radio frequency (Rf) analyzers operate in
vary with exact compounds. both the absorption and reflection modes. Their most common
2003 by Bla Liptk

FIG. 8.1g
Absorption bands of some NIR-absorbing chromophores.
application is in the measurement of moisture in solidswithout is preferred for on-stream applications. In fact, it has practi-
requiring physical contact with the sample. In these wavelength cally replaced the differential refractometer in all but the most
regions, dielectric properties are probed by the radiation; hence demanding applications. It should be noted, though, that the
water, with its high dielectric constant (~78), compared to many critical angle refractometer only measures the RI of that
common organic compounds (<5), is readily determined (e.g., portion of the sample that is in direct contact with the crystal.
moisture in wood). The technique is also used for binary solu- If even a thin coating develops on the surface, the readings
tions. Compared to the previously described spectral regions, will be useless. A variety of cleaning systems may be used
this is a relative newcomer to process measurement. Tables of if this is a problem. Turbulent flow has proven useful in
dielectric constants may be found in References 9 and 10. minimizing fouling. (For a listing of refractive indexes, see
Table 8.1h.)
Refractometry
The RI is a unique property of a chemical compound, based on Turbidity and Particle Size
the fact that light travels at different speeds in different media,
and as such can be used for composition determination in binary As with refractometers, turbidity sensors also work with light,
systems and for various nonspecific concentration measure- but make use of light scattering to measure the suspended solids
ments, e.g., dissolved solids, black liquor, and Brix (sugar). in the liquid. Depending on the concentration of the particles,
Snells law expresses the relationship between RI, the angle of turbidity can be measured at 90, 180, or complete backscatter.
incidence (), and the angle of refraction ( ) as light of a given (Technically, turbidity is the term applied to the straight-
wavelength passes through the interface between two materials. through approach, and nephelometry is used for the scattering
measurement.) In addition to scattered light, some light may
sin be absorbed by the liquid. Since there is a particle size depen-
RI = 8.1(2)
sin dence to light scatter, instruments are also available that use
scattering to measure particle size distribution. Turbidity instru-
Most refractometers use visible light, but at least one uses ments are quite commonly used to monitor filtering systems,
a diode source that emits just beyond the red. Differential centrifuges, etc., for breakthrough, whereas the more expensive
refractometers utilize this relationship by keeping constant; particle size instruments find use monitoring crystallization and
therefore, a measurement of expresses RI. At a critical value polymerization processes.
of , the light is totally reflected; the measurement of this angle
can also be related to RI as follows:
Nuclear Techniques
variable sample RI
critical = arc sin 8.1(3) A variety of techniques utilizing x-rays and other radiation
fixed prism RI
sources are used in process measurements. X-ray fluorescence
Although less sensitive, this latter technique (critical angle (XRF) is widely used to determine metal concentrations in
refractometry) requires no sampling system and, therefore, slurries and to measure silicon coatings on paper. (XRF works
2003 by Bla Liptk

ELECTROCHEMICAL SENSORS
TABLE 8.1h
Refractive Index Table
Several kinds of measurements make direct use of electricity
Compound RI Compound RI in the measurement. These are potentiometric, wherein an
Acetic acid 1.3718 Formic acid 1.3714 electric potential is measured and the solution remains
Acetone 1.3588 Glycerol 1.4729 unchanged; conductive, in which a minute current is mea-
Acrylic acid 1.4224 Glycol 1.4318 sured, but the system is essentially unchanged; and ampero-
Amyl acetate 1.4012 Heptane 1.3876
metric, in which a chemical reaction occurs during the course
of the measurement.
Benzene 1.5011 Hexane 1.3749
The basic principle of their operation for a system in which
Butyl acetate 1.3951 Hexanol 1.4135 a reactant, R, goes to a product, P, is the Nernst equation:
Butyl alcohol 1.3993 Hydrazine 1.470
RT CP0
Butylene 1.3962 Hydrogen chloride 1.256 E = E0 ln 8.1(4)
Carbon disulfide 1.6295 Lead tetraethyl 1.5198 nF CR0
Carbon 1.4631 Menthol 1.458 where
tetrachloride E = applied potential
0
Chlorobenzene 1.5248 Methyl alcohol 1.3288 E = standard potential for the system (the chemistry of
Chloroform 1.4464 Methyl-ethyl ketone 1.3807 the reaction being measured)
R = the molar gas constant
Cycloheptane 1.4440 Nitric acid 1.397
T = the absolute temperature (K)
Cyclohexane 1.4262 Nonane 1.4055
n = the number of electrons involved in the reaction
Cyclohexanone 1.4503 Octane 1.3975 F = Faraday constant
Cyclopentane 1.4065 Pentane 1.3575 CP0 = the concentration of product at the electrode surface
Decane 1.41203 Perchloroethylene 1.5053 CR0 = the concentration of reactant at the electrode surface
Di-ethyl benzene 1.4955 Phenol 1.5425
Di-ethyl ether 1.3497 Propanol(iso) 1.3776
Potentiometric
Di-methyl 1.4972 Propanol(n) 1.3851 The family of analytical sensors that detect the electrical
benzene potential generated in response to the presence of dissolved,
Ethyl acetate 1.3722 Styrene 1.5434 ionized solids in a solution include pH, oxidationreduction
Ethyl alcohol 1.3624 Toluene 1.4969 potential (ORP), and ion-selective electrodes (ISEs) or
Ethylbenzene 1.4952 Water 1.3330 probes. In potentiometric analysis, the potential difference
between two electrodes (reference and measurement) is
Note: All data based on 68F (20C). determined. As these two electrodes must be electrically con-
nected, another potential, the junction potential, is also inher-
ent to the measurement. (In fact, most of the problems of
by exciting an inner-shell electron of an element, causing an process pH measurement occur because of fouling of the
x-ray to be emitted. The energy (wavelength) of the emitted junction.)
x-ray is indicative of the element, and the number of x-rays For these measurements, the Nernst equation can be
is proportional to concentration. The excitation radiation can rewritten to:
come from an x-ray tube or a radioactive source.)
The absorption or backscatter of neutron or gamma radi-
z
i
RT z
ation can also be correlated to composition in some systems. E cell = K + ln ai + kij a j j + E LJ 8.1(5)
zi F

Neutrons have been used to measure the moisture content of
solids in processes in which hydrogen is present only in the where
free water and is not bonded to the other molecules (or is Ecell = the measured potential
relatively constant in the nonwater part of the matrix). For K = is a constant for the measurement system (elec-
example, the moisture of wood chips in pulping has been trode, etc.)
determined by this technique. Gamma rays, which are R = the molar gas constant
extremely energetic, are absorbed nonspecifically, and their T = the absolute temperature (K)
attenuation can be used as a measure of density. Since gamma F = Faraday constant
rays can penetrate metallic walls, they can give composition ai = the activity of the analyte ion, i
data for binary systems without contacting the process aj = the activity of an interfering ion, j
stream. These techniques are also used extensively as a non- kij = selectivity coefficient
invasive way to measure tank or pipe level, density within a zi and zj = the charges of ions i and j, respectively
pipe, and the like. ELJ = the liquid junction potential
2003 by Bla Liptk

It can be further simplified in dilute solutions (where determined by the measurement of activity (activity = c,
activity and concentration are approximately equal) to where is the activity coefficient of the ion) only if the other
variables of the equation are constant. To achieve this involves
0.0592 log c scrupulous design; occasionally, it also requires sample prep-
E cell = K + 8.1(6)
n aration. Frequently, in real-world applications, calibration of
the electrode in the matrix, over a limited analyte range, can
where be used to minimize concerns over activityconcentration dis-
c = the concentration of analyte crepancies.
n = charge of the analyte ion Unless the interferences to which ion-selective measure-
0.0592 = the combination of the RT/F at 25C ments are subject can be recognized and eliminated in the
potential installations, misapplications are likely. The avail-
ORP sensors are available in probe designs to detect the able ISEs are listed in Table 8.1i, where they are also grouped
ratio of reducing agent to oxidizing agentan important para- by the type of membrane utilized. Coating or material buildup
meter in effluent treatment controls, for example. on the membranes calls for the same degree of maintenance
ISEs are also based on the Nernst law. If total ionized as required for pH electrodes.
solids (conductivity) are constant, a correlation can be drawn pH sensors are ISEs, sensitive to the activity of hydrogen
between the activity of a specific ion and its concentration ions in the process stream, and as such, reflect the acidity or
in the process stream. The ideal reference electrode pro- alkalinity of the sample. pH is one of the most commonly
duces a constant potential that is independent of the com- made measurements in industry. On the surface, it appears to
position of the solution. A perfect measuring electrode gives be easy to measure pH, since all that is needed is the insertion
a 59-mV change in potential for each tenfold change in the of the probe into the process, but in practice, it is not so simple.
activity of a monovalent ion. It is important to emphasize that Probes may become fouled on the sensing surface; most are
it is the activity of free ions that the electrodes respond to and made of glass and quite fragile; concentrated solutions, or ones
not the concentration. It is important to understand that that are not aqueous, stretch the definition of pH (which is for
according to the Nernst equation, concentration, c, can be dilute aqueous solutions), and high purity water (e.g., boilers)
TABLE 8.1i
Ion-Selective Electrodes: Types and Applications
Type of Lower Detectable
Ion Electrode Limit (ppm) Principal Interferences

Bromide Solid state 0.4 CN , I , S
+ ++ ++ ++ ++
Cadmium Solid state 0.01 Ag , Hg , Cu , Fe , Pb
++ ++ ++ ++ ++ ++ ++ ++
Calcium Liquidion exchange 0.4 Zn , Fe , Pb , Cu , Ni , Sr , Mg , Ba

Chloride Liquidion exchange 0.4 ClO4 , I , OH , NO3 , Br , OAc , HCO3 , F , SO4

Chloride Solid state 1.8 Br , CN , SCN , I , NH3, S
+ ++ +++
Copper (II) Solid state 0.006 Ag , Hg , Fe

Cyanide Solid state 0.3 S,I

Fluoride Solid state 0.02 OH

Fluoroborate (boron) Liquidion exchange 0.11 I , HCO3 , NO2 , NO3 , F , Br , OAc , OH , Cl , SO4

Iodide Solid state 0.007 S , CN , S2O3
+ ++ ++ ++ ++
Lead Solid state 0.02 Ag , Hg , Cu , Cd , Fe

Nitrate Liquidion exchange 0.6 ClO4 , I , ClO3 , S , Br , NO2 , CN , HCO3

Perchlorate Liquidion exchange 1.0 OH , I , NO3 , MnO4 , IO4 , Cr2O
+ + + + + +
Potassium Liquidion exchange 2.0 H , NH4 , Ag , Na , Li , Cs
Redox Solid state Varies All redox systems
++
Silver Solid state 0.01 Hg
+ + + +
Sodium Solid state 0.02 Ag , H , Li , K
Sulfide Solid state 0.003

Thiocyanate Solid state 0.6 I , S2O3 , Br , CI , NH3
++ ++ ++ ++ ++ ++
Water hardness Liquidion exchange 0.001 Zn , Fe , Cu , Ni , Ba , Sr
2003 by Bla Liptk

requires specially designed probes, if it is to work at all. Recent of process measurements, such instruments are commonly
improvements in electronics have reduced drift, instability, and used to measure oxygen, including both dissolved oxygen in
transmission distance limitations. Combination electrodes liquids and vapor phase oxygen in gas samples. Membrane-
(measurement and reference), gel fill solutions, and the devel- separated amperometric sensors are also used for other gases,
opment of various electrode-cleaning devices, such as air and such as CO, H2S, and Cl2. Sensors using this concept are also
water jets, and mechanical and ultrasonic cleaners have being developed for bioanalytes such as glucose, where a
reduced many of the problems. New nonglass electrodes based specific enzyme is part of the measurement system.
on ion-sensitive field effect transistors (ISFETs) have opened
up new applications where glass has been problematic (e.g.,
food and beverage processes). Automation of the removal, Chemical Techniques
cleaning, and reinsertion of pH probes is now available off-
the-shelf for those applications that require nearly continuous In-process measurement using wet chemical methods can be
pH measurement and cannot tolerate downtime for mainte- performed in two different ways: batch, or discontinuous and
nance. Nevertheless, despite all this activity, pH remains a continuous.
difficult measurement for which installation of standby spare Process autotitrators draw a sample from the process at
sensors and scheduled periodic maintenance are likely to be a regular interval and deliver the sample to a titration vessel.
necessary. Once in the vessel, the sample may be diluted or prepared in
other ways for a titration, very similar to a titration performed
in the lab. An autoburet delivers the titrant until an end point
Conductive is sensed. The titration cell is then drained and rinsed, and a
Conductivity sensors measure a solutions ability to conduct new sample is drawn. Cycle times depend on the chemistry,
electricity, which is a function of all dissolved ionized solids but are typically 5 to 15 min. The end point may be deter-
in the solution. Two basic kinds of conductance measurement mined potentiometrically, conductimetrically, or photometri-
instrument are available: direct contact and inductive. The cally. Methods to measure acid value (number) are common
direct device makes direct, electrical contact with the process examples.
solution with two (or sometimes four) electrodes and mea- In continuously flowing wet chemistry methods, a very
sures the flow of electricity from one electrode to the other. small sample is injected into a flowing stream that can be
Any fouling of the probes, which affects electric contact, a solvent or a reagent. (In some applications, a small por-
requires cleaning of the probes. The inductive type is less tion of the process stream is the carrier and reagent is
sensitive to fouling because it does not make electrical con- injected into it.) Additional reagent(s) can be added, as can
tact with the process fluid. Toroidal (donut shapes are com- heat, mixing, time to allow a reaction, etc., until the reacted
mon) probes use several electric coils to probe the electric sample reaches a detector. Detectors are most commonly
properties of the fluid. The probe is coated with an inert photometers, but flow-through pH and other electrochem-
material such as a fluorocarbon. Another design builds the ical detectors are also available. The flowing system can
inductive probe directly into a pipe spool piece. Inductive be continuous (flow injection analysis), bubble segmented
conductance probes are widely used to measure the concen- (as in autoanalyzers), or a variant of FIA, sequential injec-
tration of strong acid and base solutions. Plots of conduc- tion, in which a rotary valve takes the place of much of the
12
tivity vs. concentration of various electrolytes are used to tubing.
determine if an application is suitable for these devices.
Conductance data for various compounds are available in
various chemical handbooks and an excellent compilation Miscellaneous Techniques
911
from a vendor.
Quartz Crystal Microbalances Certain crystals are known
to generate an electric signal when they are deformed; con-
versely, these crystals can be caused to move when a voltage
Amperometric
is applied. These phenomena are known as the piezoelectric
Amperometric, also known as galvanic and polarographic, effect, and it has been used to create sensors. The former
cells induce a reaction in the sample by applying a high effect has been used to detect pressure, acceleration, temper-
enough voltage. The resulting current is measured and is ature, force, and thickness; the latter effect has been applied
proportional to the concentration of the species reacting. The to measure various analytes, including moisture, in gases. The
electrolyte and electrodes are separated from the process frequency of crystal oscillation is affected by the mass of
stream by a membrane, a feature that eliminates the need material on the crystal, so that a crystal coated with an absor-
for a sample system and can perform well if the membrane bent material will vibrate differently when the coating absorbs
is kept clean. (Of course, the analyte molecules must diffuse more or less analyte. If the specificity of the coating is high,
through the membrane into the electrolyte to the electrodes a sensitive and specific analytical sensor can be developed.
if there is to be a reaction and resulting signal.) In the world Surface acoustic wave (SAW) sensors, in which the speed of
2003 by Bla Liptk

sound transmission through the coating is affected by the Several chapters of this book are devoted to water mea-
absorbed analyte, can be even more sensitive. surement in more detail.
Mass Spectrometry Previously only available for gas streams, Oxygen Oxygen is an important and unique analyte in
mass spectrometry (MS) is becoming available for liquids as industry. It is measured as the element in both gas and liquid
well. Various approaches to the method are used, but all samples. In the gas phase, it is important for breathing (envi-
require a gaseous sample (vaporized, if necessary) that is ronmental sensing), combustion control, and chemical stabil-
injected into a vacuum and ionized (usually by an electron ity. As mentioned previously, oxygen is paramagnetic and can
beam). The ionized sample molecules and the charged frag- be measured using this property. Such instruments operate
ments of their decomposition are then sorted and measured best in relatively clean, noncondensing environments with
by their mass-to-charge ratio. This last process can be accom- oxygen levels from ~0.5% to ambient levels. Oxygen can also
plished by the time of flight of the ions down an evacuated be measured electrochemically, and several varieties of instru-
tube, their trajectory through a magnetic field, or selection by ments are available using different electrochemical tech-
an electrostatic field. Detection is by electron multipliers or niques. High-temperature catalytic instruments are most
other devices. The most common application of process MS commonly used in combustion control applications where the
is in gas plants, where many gases can be detected simulta- gas stream is already hot and the oxygen level is low. Fuel
neously, or multiple streams can be examined sequentially. cell (amperometric) devices are also available. They require
periodic replacement of the fuel cell, as it is a consumable
Nuclear Magnetic Resonance Nuclear magnetic resonance part of the measurement.
(NMR) is an excellent technique for compositional informa- Oxygen dissolved in water (and other liquids) can also
tion. In the laboratory, it is widely used to identify unknown be measured with an electrochemical probe. The oxygen
materials. Its use in process analysis is a relatively recent diffuses through a membrane to the active electrode.
occurrence. NMR makes use of a fundamental property of all One of the parameters of interest in pollution control is
matterits nuclear structure. (Despite the fears of the public, the oxygen demand of the effluent. This is a measure of the
NMR is not a technique involving radiation. If an application organic load in the system, which will potentially use oxy-
is contemplated using NMR, this will need to be explained gen as it is consumed by microorganisms (biological oxygen
to plant personnel.) NMR probes the molecules by applying demand (BOD)) or reacts chemically (chemical oxygen
both a magnetic and Rf field. Depending on the instrument, demand (COD)). Laboratory measurement of BOD takes sev-
this can yield a simple number or a relatively high resolution eral days of incubation and requires the sample to be inocu-
spectrum. NMR can only measure nuclei of atoms with a lated with the appropriate organisms. Instruments are
magnetic moment (caused by an odd number of neutrons or available that can reduce this time. Total organic carbon
protons). Therefore, the technique can only be used to mea- (TOC) analyzers give a close correlation to COD. Several
1 13 14 19 31
sure species containing H, C, N, F, and P. From a different approaches are taken by the commercially available
practical standpoint, process instruments have not yet been instruments. However, in all cases, the sample stream is first
built that are sensitive enough to be used with anything other digested, and then the carbon dioxide formed from this com-
than proton NMR. Low-resolution (wide-band or pulsed) bustion step is measured. The digestion may be strictly chem-
NMR units are useful for the measurement of free (unbound) ical or UV light induced (with catalyst). The resulting CO2
proton-rich compounds such as water or oil. is measured either directly by infrared photometry or by the
change in conductivity of water into which the CO2 is dis-
Analyte-Specific Techniques solved. The entire cycle is completed in a few minutes.
Many analytes have unique characteristics that have led to

instruments designed specifically for their measurement. SAMPLING
13
Water and oxygen stand out as examples.
Perhaps the most critical aspect of any analyzer installation
Water The measurement of water in the gas phase (humid- is the sampling mechanism. The data an instrument gener-
ity) is one of the most common. There may be more patents ates can be no better than the sample it has been presented
for humidity sensors than any other measurement. With so for analysis. Sampling is such an important area that entire
1416
many different approaches for the measurement, selection of books have been published on that subject alone. In this
the appropriate one for a given application is both complicated volume, there are several chapters on sampling.
and critical. In the discussion above, mention has been made of
In the liquid or solid phase, moisture measurement can analyzers, such as chromatographs, that require the sample
also be made with a wide variety of techniques. Already to be withdrawn from the process and delivered to the
mentioned in this chapter were IR and NIR, microwave and instrument. For such instruments, there is no option, but for
Rf, and neutron techniques. In addition, there are techniques many of the spectroscopic and electrochemical analyzers,
based on capacitance, impedance, and electrical resistance. the option of using directly inserted probes is available.
2003 by Bla Liptk

Dual-Fiber Absorbance with SMA Connector
Optical Transmission Set-Up

(Single Optical Waveguide, Single Beam)
Section
Reflected Light
Bundle Spectrophotometer
for Analysis
Section Transmitted
SMA Connector
Section Light
Six-To-One Probe (Single-Fiber to Annulus Configuration)
Reflective
Fiber-Optic
Probe
Diffuse Reflectance Absorbance

(No Tip)
Fluorescence Fluid
FIG. 8.1j
Fiber-optic probes can provide data on absorbance, diffuse reflectance, fluorescence, and scattering. (Courtesy of Guided Wave, Inc.,
http://www.guided-wave.com.)
Probe-type analyzers have been used for a long time to

measure pH, conductivity, selective ion, dissolved oxygen,
relative humidity, residual chlorine, oxidationreduction
potential, differential vapor pressure, corrosion, and many Temperature
other variables. Improvements in quality and cost of fiber- Probe
optic probes have made them widely available for in-line
Process
measurement.
Fiber-optic probes use waveguides made of glass or R.I. Probe
quartz or other more esoteric material to deliver and return
the process-modified light from the probe to the instrument
located some distance away, frequently in a control room
(Figure 8.1j). FOPs can acquire data on spectral absor-
bance, diffuse reflectance, fluorescence, or scattering, and Coupling
several FOPs can be multiplexed to the same computer- Pipe to Tubing Connector
controlled analyzer. Performing spectroscopic measurements
FIG. 8.1k
over FOPs first became popular with near-infrared instru- Temperature-compensated RI-detecting fiber-optic probe. (Courtesy
ments, but their use in the UV-Vis and IR regions has grown of NetTest Photonics Division, formerly MetriCor, http://www.nettest.
as well. com.)
Insertion probe critical angle refractometers are avail-
able. RI units are also available with fiber-optic sensing locationsand they are unaffected by electromagnetic
and transmission (Figure 8.1k). They claim the same interference, dust, humidity, or hazardous environments.
advantages of all FOP instrumentsminimal consumption Measurements can be transmitted over large distances, up
of space on the pipe and ease of access to hard-to-reach to 1 km (0.625 mi).
2003 by Bla Liptk

once every 15 sec. This action serves to refresh the sample

while at the same time eliminating deposits and wiping the
N.O. Switch optical surfaces clean of dirt or slime. The result is a low-
Closes When
Probe Tilted
maintenance installation that provides reliable measurements
or Removed of suspended solids concentration.
Handrail In-line, probe-type analyzers are also used in stack gas
Pivot composition measurement. Some of the microprocessor-
based designs also provide self-calibration for both zero and
span. In addition, they can provide automatic cleaning and
drying to accommodate wet-scrubber applications, in which
Liquid it is necessary to periodically force hot and pressurized instru-
ment air into the probe cavity to thoroughly dry the diffuser.
Probe The measurement is made by analyzing the measurement
Falls Back Travelling
to Normal Scraper
beam as it is returned by the retroreflector within the probes
Position When Tips Up Probe gas measurement cavity (Figure 8.1n). These probe-type
Scraper stack gas analyzers can operate in locations with high water
Passes vapor and particulate loadings and at temperatures up to
Sludge
800F (427C).
Travelling Scraper A relatively new development in the area of in-stack
analyzers is the introduction of acousto-optic tunable fil-
FIG. 8.1l ters. Their main advantage is speed and the elimination of
Probe-type sensors are used to detect the location and density of
maintenance-prone mechanical elements such as filter
sludge and slurry layers in clarifiers. (Courtesy of Markland Spe-
cialty Engineering, Ltd., http://www.sludgecontrols.com.)
wheels, moving gas cells and mirrors, diffraction gratings,
and mechanical light choppers. The AOTF acts as an elec-
tronically controllable narrow-band filter that can be tuned
to any desired frequency in milliseconds. As shown in
Reciprocating
Piston
Figure 8.1o, the resulting beam at the selected wavelength
Photocell
is directed across the stack and can simultaneously mea-
sure the concentrations of CO, CO2, C2H6, CH4, NO, NO2,
H2O, etc. This is achieved by the computer selecting the
frequencies required for the measurement of the concen-
tration of each component and the AOTF being tuned to
Sampling each of the selected frequencies one at a time, but at a high
Chamber Optical
Glass Tube speed. This results in a scanning spectrometer without
Surface
moving parts.
Probe Cleaners
While probe-type in-line analyzers can eliminate the transpor-

Wiping tation lag and sample deterioration problems associated with
Light
Seal on-line analysis, they are not without problems of their own,
Source
(Patented) the largest of which is fouling. Various mechanisms are avail-
FIG. 8.1m able to clean the probe automatically. It is recommended that
Probe-type self-cleaning suspended solids detector. (Courtesy of when a probe cleaner is used, it be placed inside a sight glass
Monitek Technologies, Inc., a Metrisa Company, http://www.monitek. so that the operator can continuously observe the performance
com.) of the cleaner (Figure 8.1p). Wide varieties of probe-cleaning
devices are available on the market. Their features and capa-
bilities for various types of coatings, and a list of their suppliers
Probe-type sensors have also been developed for sludge are given in Table 8.1q. Probe cleaners for pH and other elec-
and slurry measurement applications. These include the trodes have been available for many years.
detection of sludge levels, interfaces, and densities in clari- If there is no sampling system, the integrity of the sample
fiers and digesters (Figure 8.1l). is automatically guaranteed, and preference should be given
Figure 8.1m illustrates a mechanically self-cleaning to sensors that penetrate the process pipe with a retractable,
probe design used to measure the suspended solids concen- cleanable probe. Probe sensors, either solid or membrane,
tration in biological sludge. In this design, a motor-driven require periodic cleaning, which can be done manually, by
reciprocating piston located within a glass tube is stroked withdrawing the probe through an isolating valve so that the
2003 by Bla Liptk

Scanner
Light Source Ceramic

Filter
Gas Measurement
Cavity
Retroreflector
Detector
Stack Gas
Monochromator Shutter Flow
FIG. 8.1n
Probe-type stack gas analyzer. (Courtesy of Monitor Labs, Inc., a subsidiary of Spirent plc, formerly Lear Siegler, Inc., http://www.moni-
torlabs.com.)
Stack
Detector AOTF Source
Detector R.F. Amplifier

Amplifier
Gate
Detector
Integrator
Frequency
A/D Converter Synthesizer
Microcomputer SYNC Microcomputer
1/4" NPT (6.4 mm)

Stack Mounted Elements Spray Nozzle
(Optional)
Control Room Elements
LCD Display
Calculator Display
Keyboard
Microcomputer Microcomputer
Strip Printer
Panel Mounted
Optional IBM Control Room
RS232 Computer for Module
Logging and
Graphic Display
FIG. 8.1o FIG. 8.1p

AOTFs can enhance the speed and increase the reliability of mul- Probe cleaners should be mounted in sight-flow glasses for good
ticomponent analysis in stack gases. visibility. (Courtesy of Aimco Instruments, Inc.)
2003 by Bla Liptk

TABLE 8.1q
a
Selection of Automatic Probe Cleaners
Applicable Choice of Probe Cleaner
Mechanical Chemical
Hydrodynamic Acoustical
Brush Rotary Scraper Acid Base Emulsifier (Self-Cleaning) Ultrasonic
Service
Oils, fats
Resins (wood, pulp)
Emulsion of latex
Fibers (paper, textile)
Solid suspensions
Crystalline precipitation
(carbonates)
Amorphous precipitations
(hydroxide)
Material of construction Stainless Stainless steel PVC PVC PVC Stainless steel Polypropylene,
steel (brush stainless steel
pH 714)
Temperature F 40140 40140 40140 40140 40140 40250 40195
C 460 460 460 460 460 4120 490
a
Probe cleaner suppliers:
ThermoAnderson (Teflon brush, http://www.andersoninstruments.com)
Branson Cleaning, a subsidiary of Emerson (ultrasonic cleaners, http://www.bransoncleaning.com/ppg/index.html)
Fetterolf Corp. (spray rinse valve, http://www.fetterolfvalves.com)
Helios Research Corp. (tank spray washers, http://www.heliojet.com)
Polymetron, Division of Danaher Corp. (probe cleaners, http://www.polymetron.com)
Spraying Systems Co. (tank spray washers, http://www.spray.com)
Toftejorg Inc. (tank spray washers, http://www.toftejorg.com)
Gamajet Cleaning Systems (tank spray washers, http://www.gamajet.com)
Many or most vendors of electrodes can provide self-cleaning or auto-cleaning capability for their systems. Many operate on a timer, cleaning the
electrode periodically. Some can automatically extract a probe from the process, clean, and even recalibrate before reinserting it into the line. For
example, pH, ORP, and ISE probe vendors GLI (Great Lakes, http://www.gliint.com) and Foxboro (http://www.foxboro.com/index.htm) have a
variety of systems to clean electrodes, including ultrasonic, brushes, and Teflon balls.
process is not opened when the electrode is cleaned, or auto- of the measured value, or of diagnostic information should
matically. Automatic probe-cleaning devices may be pressur- be considered. Quality of the electrical power can be critical,
ized liquid or gas jets, or thermal, mechanical, or ultrasonic as many microprocessors in analyzers can be reset or dam-
cleaning and scraping devices. aged by voltage spikes.
If a sampling system is used, variation in pressure in
ANALYZER LOCATION vents and drains, and oil or moisture, or both, in air lines can
wreak havoc on the system. The temperature and humidity
The location of the analyzer can be critical to the success of of the atmosphere surrounding the analyzer may also con-
the installation. If the instrument is to be installed at some tribute to unreliable performance.
distance from the process, the lines bringing the sample to Fire and explosion are the major safety hazards of analyzer
the instrument must be considered. Many questions will need installations (See Table 8.1r). The safety of analyzer houses
to be answered. For example, what is the lag time to reach is also a consideration. (See Sidebar 8.1s by Georg Erk.) The
the instrument? Do the lines need heat tracing? Will the sam- inability of most laboratory instruments to meet electrical
ple be returned to the process? requirements limits their use in on-line applications. Often,
Ambient conditions for the analyzer must be considered. however, purging an analyzer that is not explosion-proof
Should the instrument or several instruments be housed in allows it to be used in hazardous areas. Samples or stored
an analyzer house or shelter? Instruments require power and reagents containing toxic, flammable, or noxious substances
other utilities that must be included in the planning. Access are also safety hazards. This can be a major issue when con-
to the instrument for maintenance, local readout or display sidering liquid chromatography analyzers, for example.
2003 by Bla Liptk

The second calibration is more of an adjustment. The output

TABLE 8.1r of the analog signal must be set. In other words, the low and
Electrical Area Classifications
high output must be made to read correctly. Frequently this
Flammable Gas Combustible Dust Ignitable Fibers must also be matched to the input on the control system. For
Class I Class II Class III
example, an NIR calibrated to read percent moisture of wheat
Group A: acetylene Group E: metal No groups listed flour from 0 to 25% might have its 4 to 20 mA output set so
dust, aluminum, that 4 mA equals 10% moisture and 20 mA equals 25%, thus
magnesium, etc.
providing higher resolution for the output.
Group B: hydrogen or Group F: carbon Newer-style analyzers provide digital outputs. These may
manufactured gas black, coal or be a relatively simple ASCII output using an RS232 connec-
coke dust
tion or Ethernet, TCPIP, etc. If an analyzer provides a single
Group C: ethyl-ether, Group G: flour, piece of information, such as moisture, the issue is quite
ethylene, cyclopropane starch, grain dust different from another analyzer that measures a process
Group D: gasoline, hexane, stream and transmits the concentrations of five different con-
naphtha, benzene, stituents, e.g., a gas chromatograph measuring three alkanes,
propane, butane, alcohol, two alkenes, and several aromatic compounds.
acetone, benzol, lacquer
Even more complex is the question of chemometric mod-
solvent, natural gas
els that are used by some spectral techniques (IR, NIR, for
Division 1 Division 2 Division 1 Division 2 Division 1 Division 2
example) and are beginning to be used in chromatography
as well.
Class I Flammable Gases
When selecting the analyzer for an installation, the data
Division 1 Locations Division 2 Locations handling must be considered. What inputs are available on the
Locations in which: Locations in which: control system? Will chemometric calculations be done on the
(1) Hazardous concentrations (1) Gases are handled, processed, or analyzer system or a separate computer system or by the con-
exist continuously, used, but will normally be confined trol system? What kind of cable is needed for the data trans-
intermittently, or to closed containers or systems from mission, and over what distance can it be used without
periodically under which they can escape only in degrading the signal? How does that affect installation cost?
normal operating accidental rupture or abnormal
conditions. operation of equipment.
MAINTENANCE
(2) Gases exist frequently (2) Gases are normally prevented by
because of repair, positive ventilation, but might
maintenance, operations, become hazardous through failure of
Analyzer hardware is likely to receive better care if it is acces-
or leakage. ventilating equipment. sible and housed in pleasant surroundings, such as in air-con-
ditioned buildings. Spare parts and special testing components
(3) Breakdown or faulty (3) Adjacent to Class I, Division I
operation might release locations in which gases might
should be ordered at the same time as the system to avoid future
gases that might cause occasionally be communicated. delays; the availability and most effective use of qualified main-
simultaneous failure of tenance personnel are also factors of major importance.
electrical equipment. Analyzers already used in the plant are helpful in deter-
mining maintenance and spare parts requirements. Major sub-
assemblies not stocked as spare parts can also be interchanged
HANDLING THE DATA and can help to obviate waiting for parts for the duplicated
system. Standardizing on one model of a particular analyzer
Another issue that must be considered during the analyzer within a site will reduce training and spare parts costs.
selection process regards the data. How will the valuable data
your instrument and sampling system have generated be trans- COST
ferred from the analyzer to the people and control system
computer that can make use of it? What kind of output is For the approximate cost ranges of the various analyzer cat-
there? Will there be a local display? egories, refer to Table 8.1t, and for more accurate costs of the
For years, most analyzers provided only an analog output various analyzers, refer to the feature summaries at the begin-
of current (most common, and typically 4 to 20 mA) or volt- ning of each section in this chapter. The cost elements of an
age. In recent years, this has changed so that more and more analyzer installation include the following:
analyzers provide a digital output, as well as, or instead of,
the analog output. In the case of the analog output, analyzers Engineering study
generally need to be calibrated in two ways. First, as already Analyzer
mentioned, calibration standards (knowns or samples that are Recorder or other display hardware
independently measured by the lab) are determined and used Sample system
to set the instrument, frequently just a zero and span setting. Startup and checkout in the laboratory
2003 by Bla Liptk

Sidebar 8.1s
Safety of Analyzer Houses (by Georg Erk)
With major input from the U.S. National Delegation and under its leadership, the International Technical Commission issued the document Safety
of Analyser Houses, IEC 61285 Ed. 1.0.b: 1994.
This document discusses all aspects of the safety of analyzer houses. It is recommended that the reader obtain the full document for detailed
information, specifications, and documentation for the design and installation of analyzer houses and their components. It is available from:
Customer Service
American National Standards Institute
25 West 43rd Street
New York, NY 19936
Telephone: 212 642-4980
Fax: 212 302-1286
www.ansi.org and their Information Handling ServiceGlobal Engineering Documents

Hard copy: U.S. $96
Electronic: U.S. $89
The major concepts of this international standard are:

Analyzers and analyzer sampling system require varying degrees of protection. In some cases, the instrument itself may require additional
protection, such as an analyzer case, analyzer cabinet, a shelter, or a house. The selection of the housing may be determined by the minimal
protection requirement.
The highest cost installation is the house, but it is generally justified when regular attention is needed and a high service factor is expected. For
installation in extreme conditions, the house may need a natural or a forced ventilation system.
The electrical area classification for the location of the house should be in accordance with IEC 60079-10.
If toxic materials are introduced into the house, the ventilation system must ensure that the occupational exposure limit (OEL) is not exceeded
under normal or any likely fault condition.
Safety monitoring and alarm systems can vary considerably from simple alarms direct from the analyzer to announce, for example, purge failure;
to interactive systems taking inputs from gas detectors, fire detectors, and ventilation monitors; to initiate alarms, automatic shutdowns,
extinguisher release, and interlocks on ventilation systems control.
Types of failure in the system that require monitoring, alarming, or shutdown systems are ventilation failures, flammable gas or vapor detection,
toxic gas detection, oxygen deficiency detection, fire detection and protection, and purge failure.
Alarms generated and displayed may be local audible and visual systems, but in most cases, they will also require transmittal to the plant operator
and into the central control room.
On a more general note, IEC Technical Report IEC/TR 61831: 1999, On-Line Analyzer Systems: Guide to Design and Installation, an 84-page
document, defines many more items for consideration when dealing with design, installation, and documentation of analyzer systems. The first
edition of this document was printed in July 1999 and may be available directly from IEC as follows:
International Electrotechnical Commission
3, rue de Varembe
Geneva, Switzerland
Fax: +41 22 919 0300
E-mail: inmail@iec.ch
http://www.iec.ch
Calibration standard are right or wrong; as in most of life, compromise is the

Installation costs order of the day. We must balance the cost, complexity,
Spare parts maintainability, etc., against the value of the measurement
Startup and checkout in the plant data to the process and make our choices. Tables 8.1t to 8.1v
Utilities and reagents provide some summary and comparison information that
Training repairmen may help clarify the different techniques and which one
Maintenance might be best for a given analyzer project. Table 8.1t com-
pares key attributes (cost, complexity, type of sample, etc.)
SUMMARY for many of the techniques covered in this section.
Table 8.1u provides analyzer suggestions for some com-
In an analyzer project, there are many different options and monly measured analytes. Finally, Table 8.1v provides sug-
choices to be made. The skilled analyzer engineer or chemist gestions for analysis techniques for some common analyzer
must make many decisions and, in general, none of them applications. All three tables should be taken (and used) with
2003 by Bla Liptk

TABLE 8.1t
Summary of Some Attributes of Major Analyzer Approaches
Use this table as a basic guide. It provides you with a starting point, to help you think about the analytes measurable attribute. Usually, several methods
will be applicable to any given analyte, depending on concentration, matrix, etc.
Sample Sampling
Technique Cost Complexity Calibration Phase System Selectivity Mode Range
Gas chromatography 2, 3 2, 3 1 1, 2 3 1 1a, 3 1, 2, 3
Liquid chromatography 3 3 1 2 3 1 1a, 3 1, 2, 3
IC 3 3 1 2 3 1 1a, 3 1, 2, 3
UV-Vis
Filters (12 wavelengths) 1 1 1 1, 2 1 1, 2, 3 1a, 2 1, 2, 3
Full spectrum 2, 3 1 2, 3 1, 2, 3 1 1, 2, 3 1a, 2 1, 2, 3
Fluorescence (filter) 2 1 2 2, 3 1 1, 2 1a 1, 2
NIR
Filters (26 wavelengths) 2 1 2 2, 3 1, 2 2 1a, 2 2, 3
Full spectrum 3 2, 3 3 2, 3 1, 2 2 1a, 1b, 2 2, 3
IR
Filters (26 wavelengths) 2 1 2 1, 2, 3 1, 2 1, 2 1a, 1b, 2 2, 3
Full spectrum 3 2, 3 3 1, 2 1, 2 1, 2 1a, 1b, 2 2, 3
Raman, with fiber optics 3 2, 3 2, 3 2 2 2 1b, 2 2, 3
Microwave/Rf 2, 3 2 2 2, 3 2 3 1a, 1b, 2 2, 3
RI 1, 2 1 1 2 1 3 1b, 3 2, 3
Turbidity 1, 2 2 1 2 1 3 1b, 2 2, 3
Particle size 3 2 1 1, 2, 3 1, 2 3 1b, 2, 3 N/A
XRF 3 3 1 2, 3 1, 2 1 1a, 1b, 2 2, 3
Potentiometric (pH/ISE/ORP) 1 1 1 2 1, 2 1, 2 1b, 2 1, 2, 3
Conductance 1 1 1 2 1 3 1a, 1b, 2 2, 3
Amperometric (fuel cell, 1 1 1 1, 2 1 1, 2 1b, 2 1a, 2, 3
galvanic/polarographic)
Autotitration 2, 3 2 2 2 2 2 3 1, 2, 3
FIA 3 3 2 2 2 2 2, 3 1, 2, 3
MS 3 2 2 1 2 1 2 1, 2, 3
NMR 3 3 2 2 2 2 3 3
Explanation of Codes:
Attribute Code 1 Code 2 Code 3
Cost <$5000 $500020,000 >$20,000
Complexity Low Moderate High
Calibration 2 points (or does Several points Chemometrics
not need)
Sample Phase Gas Liquid Solid
Sampling System None Simple Complex
Selectivity Specific Varies with Nonspecific
system
Mode Noninvasive (a); Continuous Intermittent
invasive (b)
Range Trace (<0.1%) 0.15% >5%
Note: N/A = not applicable. As with all generalizations, these comparisons should be taken as a guide. Different installation schemes, different
analytes, etc., can dramatically change costs, complexity, and the other attributes in the above table. The addition of fiber optics to any of the
optical techniques will provide increased accessibility to the process from remote locations and eliminate the need for a sampling system, but the
cost of the fiber, especially in the mid-infrared region, is considerable.
2003 by Bla Liptk

TABLE 8.1u
Analyzer Selection Guide for Some Common Analytes
The analyzers suggested here make use of the main measurement attributes of each analyte, so that, for example, a UV analyzer is suggested for
nitrobenzene, a strong UV absorber. Most organic compounds can be measured using gas or liquid chromatography, so those techniques are not noted
for every analyte in the table. Many additional factors will affect the final analyzer choice, especially concentration and matrix. See the text.
Acetaldehyde 9 Furfural 9
Acetic anhydride 9 Hazardous gases 1
Acetone 9 Hexane 3
Acrylonitrile 9 Hydrazine, ppb 17
Aldehydes 3, 9 Hydrogen chloride 1, 6
Alkyl chloride 1 Hydrogen cyanide 1
Aluminum 6 Hydrogen fluoride 1
Amines, ppm 17 Methane 3
Ammonia 1, 3, 5, 6, 11 Methyl bromide 1
Aniline 9 Methyl chloride 1
Argon 11, 14, 15 Methylene chloride 1, 3

Bromine 9 Nitrogen compounds (e.g., NH3, NO3 , NO2, amines) 6
Butadiene 9, 10 Nitrogen peroxide 9
Butane 2, 7, 8 Nitrous fumes 1
Caffeine 4, 9 Potassium dichromate 9
Carbon disulfide 1, 9 Propylene dichloride 1
Chlorine 1, 5, 6, 9, 12 Proteins 6, 9
Chlorine, residual 1, 5, 6 Residual chlorine 1, 5, 6
Chlorine, ppm 1 Sulfuric acid 2, 5, 6, 19
Chlorobenzene 1 Tetraethyl lead, ppb 17
Chloroform 1 Trichloroethylene 1, 3
Color 9 Trichloroethylene, ppm 17
Cyclohexane 6, 10 Ketones 9
Diolefin vapors 9 Methanol 3
Ethane 3 Nitrobenzene 9
Ethyl bromide 1 Nitrogen dioxide, ppm 14, 15
Ethyl chloride 1 Nitrous oxide 3
Ethylene bromide, ppm 17 Oxygen 1, 6, 11, 13, 16
Ethylene chloride, ppm 17 Propane 3, 14, 15
Ethylene glycol 10 Pyridine 9, 14, 15
Ethylene in % 3, 14, 15 Silicon 18
Ethylene oxide 3, 11 Sulfur dioxide 1, 3, 6, 9, 11
Freon 3, 11 Tetrachloroethylene, ppm 17
Vinyl chloride 1, 3
Code numbers used:
1. Electrochemical (polarographic, amperometric, fuel cell, etc.) 11. Thermal conductivity
2. Conductance 12. Phototape
3. IR 13. Zirconium oxide
4. NIR 14. Mass spectrometer
5. pH, ORP, ISE 15. Chromatography (gas or liquid)
6. Wet chemistry (FIA, autotitration, etc.) 16. Paramagnetic
7. Electrolytic hygrometer 17. Flame ionization
8. Capacitance 18. XRF
9. UV-Vis 19. Density
10. Refractometers 20. Miscellaneous analyte-specific techniques
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TABLE 8.1v
Analyzer Selection Guide for Some Common Applications
Use this table as a basic guide. It provides you with a starting point, to help you think about the analytes measurable attribute. Usually, several methods
will be applicable to any given analyte, depending on concentration, matrix, etc.
Acidity (of aqueous solutions) 5, 6 Ethylene in C1C8, H2, CO2 15
Acids in water 2, 5, 6, 10,19 Ethylene oxide in methane, ethane, propane 14, 15
Alcohol in water 10, 19 Fluoride in water 5, 6
Alkalinity of water 6 Freon moisture content 7, 20
Ammonium ions in water 5, 6 Glycerine and salts in water 10, 19
Aromatics in vapors or in water 9 Green, white, or black liquor concentration 10
Benzene in ethanol or cyclohexane 9, 10 Hardness (total) in water 6
Benzene in raffinate or in ethyl alcohol 9 Helium in oxygen, nitrogen 11
Benzene moisture content 4, 8 Helium moisture content 7, 20
Benzotriazole in water, ppm 9 Hexane moisture content 7, 20
Brine concentration 2, 10, 19 Hexavalent chromium 6
Bromide ions in water 5 Humidity (air) 7, 20
Butadiene in butanes and butylenes 9, 15 Hydrazine in water 6
Butadiene in styrene 10, 15 Hydrocarbon in H2S, CO2, air 1, 14, 15
Cadmium ions in water 5, 6 Hydrocarbon vapors in ambient air 17, 11
Caffeine in coffee 4 Hydrogen impurities (in O2, N2, CO, H2O) 14, 15
Caffeine in water or ethylaetate or CH2Cl2 9 Hydrogen in chlorine 9, 11
Calcium ions in water 5, 6 Hydrogen in nitrogen, oxygen, inert gases 11, 15
Carbon dioxide in carbonated beverages 3 Hydrogen sulfide in air 1, 9, 12
Carbon dioxide in gases 1, 3, 6 Hydrogen sulfide in hydrocarbon liquids 6
Carbon dioxide moisture content 7, 20 Hydrogen sulfide in natural gas or in stack gas 1, 9
Carbon monoxide in gases 1, 3 Iodide ions in water 5, 6
Carbon monoxide moisture content 7, 20 Iron (total) in water 6
Carbon tetrachloride in air 1 Isobutane in C5, n-C6, i-C7 hydrocarbons 15
Catsup and tomato paste (solids content) 10, 19 Isobutane in n-butane (liquid) 10
Caustic concentration 2, 6, 10, 19 Isoprene in solvents 9
Chemical oxidation demand 6 Jams, jellies, juices for sugar content (Brix) 10
Chloride ion in aqueous solution 5, 6 Kerosene moisture content 4, 8
Chlorine in air 1, 11 Lead ions in water 5, 6
Chlorine in ethylene dichloride 9 Methane in other gases 3, 11, 14, 15
Chlorine, ppm, in off-gas or phosgene 9 Methane moisture content 4, 7, 20
Chromium in water (hexavalent or total) 6 Methanol in water 10, 19
Citrus juice (Brix, sugar concentration) 10, 19 Natural gas moisture content 3, 7, 8, 20
Combustibles in air 17 Neon moisture content 3, 7, 20
Copper in water 5, 6 Nitrate and nitrite in water 6
Cyanide in water 5, 6 Nitric acid in water 2, 5, 6, 10
Cyclohexane in n-hexane/methylcyclopentane 10 Nitric oxide in air 1

Divalent ions in water 5, 6 Nitrogen (NH3, NO3, NO2, total, etc.) in water 6
Divinyl acetylene in acrylonitrile 9 Nitrogen in argon 14, 15
Ethane moisture content 7, 20 Nitrogen moisture content 3, 7, 20
Ethanol in benzene or in water 10, 19 Octane rating of gasoline 4
Ethyl chloride moisture content 7, 20 Oil (triglyceride) in milk and other foods 4
Ethylene glycol in water 10, 19 Oil in liquid Freon 3, 4
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TABLE 8.1v Continued

Analyzer Selection Guide for Some Common Applications
Oil in wax 10, 19 Starch in water 10, 19
Ortho- and meta-xylene in para-xylene 10, 14, 20 Steam in air 3, 20
Ortho-phosphate in water 6 Styrene in ethyl benzene 10, 20
Oxygen (dissolved) in water 1 Sucrose in water 3, 6, 10, 19
Oxygen in argon, hydrogen 11, 13, 14, 15, Sugars in water, syrups 3, 6, 10, 19
16
Oxygen in ethylene 11, 13, 14, 15, Sulfate and sulfite in water 6
16
Oxygen in stack gases 13, 16 Sulfur dioxide in stack gas 3, 9
Oxygen moisture content 3, 7, 20 Sulfur dioxide moisture content 3, 7, 20
Ozone in air 9 Sulfuric acid in water 5, 6, 10, 19
Paper moisture 3, 4, 20 Tetranitromethane in air 3
Phenol in water 6, 9 TiO2 in paint or paper 18
Phosgene in air 1, 9, 12 Toluene in hydrocarbons 9
Phosphoric acid concentration in water 5, 6, 10, 19 Trans-unsaturation of vegetable oils, detergents 3, 4
Phosphorus (total or o-phosphate) in water 6 Vinyl acetate in polymer vapor 3
Polymersolvent mixtures 10, 19 Water (moisture) in liquids 3, 4, 20
Potassium dichromate in water 5, 6, 9 Water (moisture) in solids 4, 8, 20
Potassium ions in water 5, 6 Water (moisture, humidity) in gases 3, 7, 20
Propane moisture content 3, 7, 8, 20 Water hardness 5, 6
Propylene glycol in water 3, 10, 19 Water in liquid SO2 3, 4
Propylene moisture content 3, 7, 8, 20 Water in methylene chloride liquid 3, 4
Silicates in water and in seawater 6 Water in organic liquids 3, 4
Silicon in paper 18 Water vapor in air 3, 7, 20
Sodium carbonate in water 2, 3, 5, 6 Wax in oil 10, 20
Sodium chloride in water 2, 10, 19 Wine, ethanol 10, 19
Sodium hydroxide in water 2, 4, 5, 6, 19 Xylenes in hydrocarbon 9
Sodium ions in water 5
Code numbers used:

1. Electrochemical (polarographic, amperometric, fuel cell, etc.) 11. Thermal conductivity
2. Conductance 12. Phototape
3. IR 13. Zirconium oxide
4. NIR 14. Mass spectrometer
5. pH, ORP, ISE 15. Chromatography (gas or liquid)
6. Wet chemistry (FIA, autotitration, etc.) 16. Paramagnetic
7. Electrolytic hygrometer 17. Flame ionization
8. Capacitance 18. XRF
9. UV-Vis 19. Density
10. Refractometers 20. Miscellaneous analyte-specific techniques
Note: Careful study of this table will show some apparent inconsistencies, but also some patterns. The inconsistencies are not real; they occur when
several techniques are listed because the concentration and details of the application are missing. For example, the concentration vs. conductance
curve for sulfuric acid increases with concentration and then rolls over and decreases. The use of conductance is fine in some ranges, but not in
others. An example of one of the patterns that emerge from the table is the apparent similar utility of three inferential methods of analysis: conductance,
refractive index, and density. As the concentration of some analytes increases, the conductivity, refractive index, and density all change, providing
three relatively simple measurements to consider.
2003 by Bla Liptk

the proverbial grain of salt. Analyzers are constantly chang- Dean, J. A., Ed., Analytical Chemistry Handbook, New York: McGraw-Hill,
ing; developments in electronics, sensing transducers, and 1995.
Ewing, G., Analytical Instrumentation Handbook, New York: Marcel Dekker,
all aspects of measurement science improve almost daily. In 1990.
addition, very few applications are exactly the same. There- Galster, H., pH Measurement, New York: VCH, 1991.
fore, use these tables as a starting point, and carefully eval- Guiochon, G. and Guillemin, C. L., Quantitative Gas Chromatography for
uate all the criteria discussed in this section and the rest of Laboratory Analyses and On-Line Process Control (Journal of Chro-
this volume. matography Library, No. 42), Amsterdam: Elsevier, 1988.
Koch, K. H., Process Analytical Chemistry: Control, Optimization, Quality,
Economy, New York: Springer-Verlag, 1997.
Lin-Vien, D., Colthup, N. B., Fateley, W. G., and Grasselli, J. G., The
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Manka, D. P., Ed., Automated Stream Analysis for Process Control, Vols. 1 Miscellaneous
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2003 by Bla Liptk

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8.1 Nuclear Magnetic Resonance 1157

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Reference 1221 British Thermal Unit 1236

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Colorimetric Analyzers 1253 Sample Conditioning 1283

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Spectrophotometric Analyzers 1300 Calibration of Conductivity Sensors 1321

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8.22 References 1357

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Laboratory Instruments in Process Process Applications 1393

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Gas Chromatography for Mercury Cooling Methods 1430

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Limitations 1448 Advantages and Limitations 1466

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Sensitivity 1481 Interferometer 1497

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Cell Design and Limitations 1519 Ultraviolet Analyzer 1537

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Nephelometers 1555 Fiber-Optic pH Measurement 1573

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8.50 Flash-Point Tests (ASTM Methods D 5690

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Conclusion 1618 Tension/Compression and Bending

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8.57 Oxygen Detectors 1671

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UV Absorption Spectrum 1690 8.63

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Float Viscometers 1730 pH Measurement 1749

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INTRODUCTION The Selection Process

Before continuing our discussion of problem definition, INFORMATION GATHERING

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TABLE 8.1a Continued

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measure and control drying. NIR instruments can be filter

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Many analytes have unique characteristics that have led to

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Dual-Fiber Absorbance with SMA Connector

Optical Transmission Set-Up

Diffuse Reflectance Absorbance

Probe-type analyzers have been used for a long time to

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once every 15 sec. This action serves to refresh the sample

While probe-type in-line analyzers can eliminate the transpor-

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Light Source Ceramic

Detector R.F. Amplifier

Microcomputer SYNC Microcomputer

1/4" NPT (6.4 mm)