INDEX

Accurate mass assignments,

Aliphatic aldehydes, mass spectra of,
equation, 98
240

ions, 95–96, 174

fragment ions, 240

Accurate mass measurements, 126

fragmentation, 240

AccuTOF GC, 126

general formula, 240

Acetaminophen, 283f
molecular ion, 240

Acetanilide-acetate, 248
Aliphatic amines,

Acetate derivatives, 278

beta cleavage, 251–252

Acid hydrolysis, 278

high-boiling, GC separations of, 249

Acids, 15, 221–230. See also specific acids

low-boiling, GC separations of,

Acridine (Dibenzopyridine), 363–364

249

Actophenone, 349f
Aliphatic diamines, underivatized,

AGC. See Automatic gain control

252–258

Agilent ChemStation Data Analysis

Aliphatic dinitrile, mass spectra,

software, 160f
352–353

Agilent Technologies, 180

fragmentation, 352f, 352–353

Alcohols, 231–237. See also specific alcohols

general formula, 352

ketone groups and, 345

molecular ion, 352

underivatized,
Aliphatic halogenated compounds,
GC conditions for, 231
324–329

GC separations, 231
Aliphatic ions, 346

separation examples, 231

Aliphatic isocyanates, 341

C10 alcohols, TMS derivative of, 231

Aliphatic ketones, 178–179

Aldehydes, 239–242
mass spectra of, 346

mass spectra of, 239

fragment ions, 346–347

underivatized, GC separation of, 239

fragmentation, 346

Alditol acetates, 410

general formula, 346

Aldrin, molecular weight for, structure

sample mass spectrum, 347

and, 374
Aliphatic mononitrile, 351

Aliphatic acids, GC separations, 221

mass spectra, 351

Aliphatic acids-/TMS derivatives, 221

fragmentation, 351

Aliphatic alcohols, 186f, 178–179,

general formula, 351

231
sample mass spectra, 352f, 351

TMS derivatives of, mass spectra of,

Aliphatic thiols, 412

188, 234
Alkane, 332

589
590 Index

n-alkanes, 50–51, 332

GC separations of, 249

Kováts retention index, 50–51

mass spectral interpretation of, 251

separation of, temperature

Amino acids, 15, 265–271

conditions and, 59f

derivatization of, 265

Alkenes, 335
Amino alcohols, 261

Alkyl phosphates, 390

derivatized, GC separation, 261

fragment ion peaks, 390

underivatized, GC separation,

general formula, 390

260–261

Alkyl phosphites, 390

Amino alcohols (aliphatic), 260

fragment ions, 390

Amino sugars, 407

general formulas, 390

Amino sugars (as TMS derivatives)

Alkyl phosphonates, 390

GC separation of, 407

1-Alkyl halides, 325

mass spectra of, 409

Alkylbenzenes, 335, 337

fragmentation, 409

alpha cleavage,
molecular ion, 409

N,N-diethylamine, 254f
Aminophenols, 262, 387

perfluorinated ketones, 316

as acetates, 262

tertiary amines, 253f, 253

GC conditions, 262

Alternate full-spectrum acquisition, 142

underivatized, 262

AM. See Axial modulation

3-aminothiophenol, mass spectrum of,
AMDIS (Automated Mass spectral
414f

Deconvolution and Identification

4-aminothiophenol, 413f

System), 152–153, 191–192, 196

Amirav, A. 71

peak
Ammonia, 109–110

apex of, 197f

as reagent gas, 134

compounds and, 198f

Amphetamine, 120f, 121, 256–257,

pesticide analysis, 380

277

solvents, 401
Analytes, 7, 159, 169–171, 204, 209

Amides, 15, 186f, 243–248. See also

AMDIS Target Analysis, 199f

Capillary column
food safety, 146

derivatization of, 243

nominal mass of, 182

derivatized,
Analyte concentration, calculation of,
GC separation of, 244
with mean RRF, 215–216

mass spectrum of, 248

Analyte retention time, GC/MS, 207

mass spectra of, 244

Analytical spectrum, 117–118

underivatized, GC separation of, 243

Animal steroids, 403

Amines, 15, 186f, 249–263. See also Antioxidants, 387

specific amines GC separation of, 387

derivatization of, 250

m/z values, 387

derivatized, 258
APCI. See Atmospheric pressure

GC separation of, 250

chemical ionization

mass spectral interpretation of, 251

API instrument, See Atmospheric

solvent consideration, 263

pressure ionization instrument

underivatized
Aq. Mode setting selection box, 175–176

Index 591

Aromatic acids, ethyl esters of, 291

mass spectra of, 413–414

Aromatic aldehydes
formula, 413

mass spectra of, 240–241

fragmentation, 413–414

fragmentation, 240–241
molecular ion, 413

general formula, 240

ortho effect, 413–414

molecular ion, 240

Atmospheric pressure chemical ionization

structure for, 242

(APCI), 89–90, 104–105, 112

Aromatic amides, 246

ionization technique, 9–10

derivatization of, 244

Atmospheric pressure ionization (API)

simple, examples of, 246–247

instrument, 00001:0400,

Aromatic amines, 256

Atomic mass, chlorinated pesticides,

GC separations of, 249–250

373–376
Aromatic carboxylic acids, GC
Auto Tune routine, 135–136
separations, 221
Automated background-subtraction
Aromatic compound, M+• peak, 300f,
routines, 196

299
Automated Mass spectral
Aromatic cyanol acids, methyl esters of,
Deconvolution and Identification
292
System. See AMDIS
Aromatic diamines, GC separations of,
Automatic gain control (AGC),
249–250
116–117

Aromatic diisocyanate, sample mass

Axial modulation (AM), 119

spectra, 343f, 342

Azinphos-methyl, 378–379

Aromatic dinitriles, 353

fragmentation, 353f, 353

Backflush valve, 76

Aromatic fluorine compounds, 315

configuration, 78f, 76

Aromatic halogenated compounds

Background spectrum, 195f, 195

mass spectrum of, 327

Background subtracted spectrum, 194

ortho effect, 327

database search and, 195–196

sample mass spectrum, 328

Background subtraction,

Aromatic isocyanates
chromatographic process, 194

mass spectral interpretation, 341–342

Bacterial fatty acids, 226–227

sample mass spectra, 342f, 342

GC conditions, 226

Aromatic ketones, mass spectrum of, 348

types of, 226–227

formula, 348
Barbiturates, methylation of, 279

fragmentation, 348
Benzaldehyde, 172f

general comments, 348

Benzamide, 246–247

molecular ion, 348

Benzamide-TMS, 248

Aromatic methyl esters, 290–291

Benzanilide, 246–247

Aromatic nitriles, 353

Benzene, epoxide formation and

mass spectra, 353

hydroxylation, 280

fragmentation, 353f, 353

Benzene sulfonic acids, methyl esters

general formula, 353

of, 291

molecular ion, 353

1-ethyl-4-(2-methylpropyl) benzene,

Aromatic thiols, 337f

592 Index

N-ethyl-N,α-dimethyl­ calculation, 215–216

benzeneethanamine, 257f, 256–257

standard additions method, 217f,

1,3-benzimidazole, 367f
217–218

Benzimidazoles, 366–367
Calibration standards, series of, 215

Benzoic acid, 224

Capillary column

Benzoin alkyl ethers, 297–298

C1-C2, 301–305, 302t, 303t, 304t

fragmentation, 297
derivatized nucleosides, 369

general formula, 297

dihydroxybenzenes, 383–384

molecular ion, 297

ethers, 293

Benzoin isopropyl ether, 300f

gases, 317

Benzonitrile, 353f
glycols, 319

Benzpyridine. See Quinoline

halogenated aromatics, 323–324

Benzyl alcohol, 236f, 235

industrial solvent mixtures, 401

Benzyl alcohol-TMS, 387

ketones, 345

Benzyl chloride, 329f, 327

medium-boiling fluorinated

Benzylic carbon atoms, 335

compounds, 305

Benzylic cleavage, 327, 335,

methyl esters, 285–286

366–367
nitriles, 351

Beta cleavage, 287

nitroaromatics, 355

aliphatic amines and, 251–252

nitrogen-containing heterocyclic

Beveled point syringe tip, 32f, 32

compounds, 363

BFB. See Bromofluorobenzene

nucleosides, 369

Bile acids, 225–226

phenols, 383

Biological samples, 211

phosphorus compounds, 389

Boutique databases, 151

plasticizers, 393

Branched alkanes,
saturated halogenated compounds,

mass spectrum of, 333

323

sample mass spectrum of, 333

sulfur compounds, 411

Bromobenzene, 172f
underivatized amides, 243

Bromofluorobenzene (BFB), 137

underivatized glycols, 319

Budde, B., 137–138

unsaturated halogenated

Butyl esters, 285

compounds, 323

Butyl pentyl ether, 299f

Capillary column injectors, 6

M+• peak, 299f

physical characteristics, 55t

n-butylcyclohexane, 335f
SPME sample introduction and,

t Butyldimethylsilyl derivative, 266

41–42

reagents, 266
Carbazole, 364–365

Carbenium ion, 200–201

C1-C2. See Low-boiling fluorinated Carbohydrates, ketone groups and, 345

compounds Carbon, 94

CAD. See Collisionally activated Carbon absorption filter, mechanical

dissociation
pump exhaust and, 101

Caffeine, 277
Carbonyl oxygen, fragmentation

Calibration curve
initiated, 181f

Index 593

Carboxylic acids, 186f Chlorofluorocarbons, 315f, 305–306,

derivatized
314

GC separation of, 221

numbering system for, 302t

mass spectral interpretation, 228

C1-C2, 302t

esters of, GC separation of, 285

cyclic, 304t

underivatized
unsaturated C2, 303t

GC separations of, 221

sample mass spectra of, 314

mass spectral interpretation, 227

Chloronitrotoluenes, 358

C8-C24 carboxylic acids, derivatization

1-chlorooctane, 325f

procedure for, 221

Chlorotoluene, 327

Carrier gas, 18f, 85–86

Chlorpyrifos, 210f, 210–211

considerations, 61
Cholesterol, 404f

flow, linear velocity, 62

Cholesterol-TMS, 405

mobile phase, 15
ChromaLynx software, 126

splitless mode, 20f

Chromatographic peak, 41–42

velocity, 65
SIM, 141

Catechol, 280
Chromatographic process, background

CDS Pyroprobe 5200, schematic for, 46f

subtraction, 194

Centroid data, 90–91

Chrysene, 338f

Centroid mass spectrum, 100f

CI. See Chemical ionization
Centroid mode, 92f
CID. See Collisionally induced
Chemical ionization (CI), 8, 89–90,
dissociation

107, 182, 209

Cinnamic acid, methyl esters of, 291

reactions, 108t
Citraconic acid, 224

Chemical Ionization Mas Spectrometry,

Cleaning, ion source, 107

109–110
Cocaine, 150f, 149, 278

Chemical ionization reagent ions,

metabolites, 277

107–108
Standard Spectrum Tune, 136f

GC/MS Chem Station, 136–137

Cold split injection, 27

Chlordane, 375f, 375

Cold splitless injection, 27

molecular weight for, structure and, Collisionally activated dissociation

374–375 (CAD), 142–143

Chlorinated biphenyls Collisionally induced dissociation
accurate mass value, 323–324 (CID), 142–143
molecular formula, 323–324 Column, 9, 15, 49

Chlorinated pesticides, 373–376

conditioning, 54

atomic mass values, 373–376

end, 86–87

extraction procedures, 373

film thickness, 64

GC separations, 373
flow, 62

nominal mass values and, 373–376

GC system, 49

structure of, 373

length, 64

Chlorine atom, 358

performance, 56t

Chlorodinitroanilines, 359f, 359

phase, 21

Chlorofluoroacetones, 316
maintenance of, 52

594 Index

Column (Continued) general formula, 347

physical dimensions and performance, molecular ion, 347–348
54
sample mass spectrum of, 348f, 348
plate numbers, 57f
Cycloakylamines, 256f, 255
temperatures, 59f, 58
Cycloalkanes, 335f, 335
Column bleed, 194f, 275f, 274 Cyclohexane, hydroxylation and
Common neutral-loss analysis, 145 ketone formation, 281
Compounds, 15. See also Eluting 1, 2 cyclohexanediol, 322f
compounds, specific compounds Cyclohexanone, 348f, 402
AMDIS peak, 198f
commonality of, 153 Daidzein, and metabolites, 278
diffusion principle, 87–88 Dark matter, 90, 149, 200–201
molecular ions, 337 Data acquisition, 137
molecular weight and, 255 Data acquisition cycle, 140–141
as reagent gases, 109, 108t Data file, 191–192
retention time and, 159 Data systems, 6, 135–136
RTIC chromatographic peak, 160f requirements, 8
thermal modulators and, 78–79 RRF and, 215–216
thermoconductivity and, 21f Database. See also Boutique databases;
Conical point syringe tip, 32f, 32 Electronic databases
Contaminates, 273–276 background subtracted spectrum,
Contamination, 107, 402 195–196

Continuous measurement of spectra pesticides, 379–380

(Full-spectrum acquisition), 137–138 spectrum selection, 192–193

Continuous-dynode EM, 131f, 130–131 using, 154

Conventional headspace, 39 NIST08 Mass Spectral Database, 120f,

Conventional thermal conductivity 106–107, 119–120, 121
detector, 67 DDT, 376f, 375–376
Coolants, 24 molecular weight for, structure and,
Creatinine-TMS, 367 375
Cresol-TMS, 387 Decafluorotriphenyl phosphine
CTC CombiPalTM, 35, 41–42 (DFTPP), 137
Cyano acids Decanoic acid, 228f
esters of, 292
methyl ester of, 229f
underivatized, mass spectral
TMS derivative of, 229f
interpretation, 228 Deconvolution Reporting Software,
Cyclic alcohols, 233–234 198
Cyclic amines, 255 Default acquisition Threshold,
Cyclic ethers, 296 175–176
fragmentation, 296
Demo Database, 402
general formula, 296
Dempster, J., 105–106
molecular ion, 296
2-deoxyadensine, TMS derivative of,
Cyclic ketones, 347–348 371f, 371
mass spectrum of, 347 Deoxyribose sugars, 369
Index 595

Deprotonated molecules, 107–108 Diethyl(4-methylbenzyl)amine, 249,

Derivatization, 185. See also specific 256–257

chemical Diethylene glycol, 321f

Desorption/ionization techniques,
impurities, 402

112
Diff pump. See Oil diffusion pump

Detectors, 15
Differential pumping, 102–103

Deuterated internal standards, 214

Difficult matrix introduction (DMI), 45

DFTPP, Decafluorotriphenyl
Diffusion principle, compounds and,

phosphine
87–88

Dialkyl-substituted benzenes, 335

Dihydroxybenzenes. See also Capillary

Diamines,
column

derivatization of, 250

derivatization of, 383

GC separation of, 250–251

derivatized, GC separations of,

high-boiling, GC separations of, 249

383–384

Diaminotoluene impurities, 401

underivatized, GC separations of, 383

Diaphragm pumps, 101

Dimethoate, structure of, 377

Diaryl ethers, 296–297

Dimethyl isophthalate, 395

fragmentation, 296
Dimethyl phthalate, 395

general formula, 296

Dimethyl terephthalate (DMT), 395

molecular ion, 296

N,N-dimethylacetamide impurities

Diazepam, 277
(DMAC impurities), 401

Diazinon, 377–378
N,N-dimethylnitroaniline, 357

Diazomethane, 191f
N,N-dimethyl-N­
Dibasic acids,
(trifluoromethylphenyl)-urea, 164f

higher esters of, ethyl and, 290

2, 3-dimethylphenol, 385f, 384–386

methyl esters of, 290

Dimethylpyridines, 363

Dibenzamide, 246–247
Dimethylsiloxanes, 50

Dibenzopyridine. See Acridine

Dimpylate. Diazinon

Dicarboxylic acids, 226

Dinitroanilines, 358

derivatives of, 226

Dinitrobenzenes, 358

GC conditions, 226
GC separation of, 355

3, 4-Dichloroaniline impurities, 402

Dinitrochlorobenzenes, 359

1, 2-dichlorobenzene, 328f
Dinitronaphthalenes, 360f, 360

1, 2-dichlorohexane, 326f, 325

Dinitrophenols, 359

1, 6-dichlorohexane, 326f, 325

Dinitrotoluenes, 358

Dichloromethane, reagent-grade, 402

Dioxin analyses, 127–128

Dichloronitrotoluenes, 359
Dipentyl ether, 299f

2, 6-dichlorophenol, 386f
Diphenyl ether, 300f

4, 5-dichlorophenol, 386f
Direct injection mode, 25–26

Dichlorovos, structure of, 377

Direct insertion probes, 45

Dieldrin, molecular weight for, 375

Direct sample interface (DSI), 44f

Diesters, 285
liquid and solid samples, 43

Di(4-nitrophenyl)ether, GC separation
Direct sample introduction techniques,

of, 355
for GC, 43

596 Index

Direct sampling, into mass ECD. See Electron capture detector

spectrometer, 44
ECNI. See Electron capture negative
Discrete-dynode EM, 129f, 130–131
ionization
Disulfoton, structure of, 378
Edit Scan Parameters dialog box,
DMAC impurities. See
175–176
Dimethylacetamide impurities
EE+. See Odd-electron fragment ion
DMI. See Difficult matrix introduction
Effusion, 87–88
1-dodecene, 336f, 335
EI. See Electron ionization
Double-focusing mass spectrometer,
EI mass spectrum. See Electron
10–11, 127f, 113, 126
ionization mass spectrum
linear m/z scale and, 133–134
EIC. See Extracted ion current
resolution and, 98
chromatograms

Double-shot mode, 47
EI-only Pegasus, 125

Drebs cycle acids, 222

Electron capture detector (ECD), 70f,

Drugs, 15, 282

15, 69

acetyl derivative of, 279

disadvantages, 70

GC separations, 277
Electron capture negative ionization

LC/MS, and metabolites, 277

(ECNI), 8, 89–90, 110, 141, 209

metabolites of, 277–284

aliphatic halogenated compounds,

TMS derivatives of, 279

324–329

MO-TMS derivative, 279

pesticide analysis, 380

underivatized, fragmentation and

reactions, 111t

elution order, 282t Electron impact, 105–106

Dry glycols,
Electron ionization (EI), 7, 105

derivatization of, 319

source, schematic illustration, 106f

TMS derivatives, GC separation

Electron ionization mass spectrum (EI

of, 319
mass spectrum), reading, 104–105,

DSI. See Direct sample interface

198

Dual column analysis, 73

Electron multiplier (EM), 129–130

Dual detection performing, 74

Electronic databases, 379–380

Dual detector analysis, 73

Electronic flow, 6

Dual-column analysis with splitter, 76

Electronic flow controllers, 61–62

Dual-column systems
Electrons, 69–70

with thermal modulators, 78

Electrophilic analytes, 69

with valves
Electrophilic derivatives, 7

heart-cutting, 77f
Electrospray ionization (ESI), 9–10

heart-cutting and backflushing, 76

Elemental composition, 168

Dual-column/dual-injector systems, ion and, accurate mass assignment

with four-port valve, 76

of, 174

Duty cycle, 117–118

Elements, masses/types/abundances/X

Dynamic headspace (purge and trap),

factors, 170t
39f, 39
Eluting compounds, 22f
Dynamic tune, 137
EM. See Electron multiplier
Dynode, 129f, 128–129
Enhanced Sensitivity Tune, 136–137
Index 597

Environmental Protection Agency

Even-electron protonated molecules

(EPA) Super Fund site, pump oil

(MH+), 112

and, 101
Exhaust, low-vacuum component,

EPA. See Environmental Protection 100f

Agency External ionization quadrupole ion

Equilibration process, liquid samples,

trap, 117f
38
External standard method, 216–217
ESI. See also Electrospray ionization Extracted ion current chromatograms
Esters, 285–292. See also Ethyl esters;
(EIC), 93f, 94f, 91–92, 193

Methyl esters; n-PFP isopropyl

esters; Perfluoropropyl esters;

Fast gas chromatograph, 64

Thioesters; specific ester of

considerations for using, 30

chemical/substance
definitions of, 64t

carboxylic acids, 285

instrumental considerations, 30

mass spectra of, 286

techniques for, 64

C10-C24 monounsaturated methyl Fentanyl, 277

esters, double-bond position in, FI. See Field ionization

288f, 288–289 FID. See Flame ionization detection

C14-C24 methyl esters, 285

Field, F., 107–108

1, 2-di(4-nitrophenyl)ethane, GC
Field ionization (FI), 8, 182

separation of, 355

Filaments, 66–67

1, 2-ethanediol, sample mass spectrum,

Final temperature, 60

321f, 320
Fingerprinting, 46

Ethanol impurities, 402

Finnigan, 116

Ethers, 187f, 293–300. See also Benzoin Flame ionization detection (FID), 15,

alkyl ethers; Benzoin isopropyl 46, 68

ether; Butyl pentyl ether; Cyclic cross section, 68f

ethers; Diaryl ethers; Di(4­ Flame photometric detector (FPD),

nitrophenyl)ether; Dipentyl ether; 15, 70

Diphenyl ether; Glycol ethers; FlowCalc program, 23f, 23

Symmetrical ether; Thioethers; Fluorinated aliphatic compounds,

Unbranched aliphatic ethers 305

GC separation of, 293

mass spectra of, 305

mass spectra of, 293

partially fluorinated, 305–316

1-ethoxybutane, sample mass spectra,

Fluorinated compounds, 301–316.
298f, 298–300
See also Capillary column

7-ethoxycoumarin, o-Dealkylation of,

GC separations, 301

281
mass spectrum, 305

Ethyl esters
Fluorine, 281

aromatic acids, 291

Food, pesticides in, DSI and, 45

of octadecanoic acid, 289f

Food safety, analytes and, 146

Ethylbenzene, 335
Fore pump, 99

Ethyleneimines, 255
Formaldehyde, derivatization of, 239

Even-electron fragment ion (EE+), 200

Formuloa Calculator, 202

598 Index

Forward geometry, 127f

gas sample delivery to, 37f

FPD. See Flame photometric detector

mobile phase, 8

Fragment ions, 255

oven temperature,

aliphatic aldehydes, 240

program rate, 9

aliphatic ketones, 346–347

requirements, 8

alkyl phosphites, 390

phases, structure of, 53f

alkyl phosphonates, 390

probes and, 43

cyclic alcohols, 234

samples,

MO-TMS derivatives, 405

introduction methods, 47, 48t

phenols, 384
introduction process, 15

primary aliphatic alcohols, 232

separation, 265 (See also specific

prostaglandins, 399
chemical)

prostaglandins, MO-TMS
column temperatures, selecting, 58

derivatives, 399
PTH-amino acids, 265

TBDMS derivatives, 271

underivatized, 277–278

TBDMS-derivatized amino acids,

syringes, septum problems and, 31–32
268
system,

underivatized steroids, 405

columns, 49

Free acids, 221, 397–398

components, separation of, 49

Frontal tailing peak, 57f

Gas chromatography/mass
Full-spectrum acquisition. See
spectrometry (GC/MS). See also
Continuous measurement of specific chemicals/hormones/substances
spectra adding versatility to, 73

Full-width at half-maximum analysis, variables, 7

(FWHM), 97f, 96–97 interface, 85–88

Fused silica tubing, 74f, 74 introduction and history, 3–14

FWHM. See Full-width at half- paradox of, 12f, 11

maximum pesticide analysis, 380

quantitation with, 207–218

Gain, 130–131
conclusions on, 218

Galactosamine, 407
schematic, 16f

Gases, 317–318
system, components of, 8f

GC separations, 317
Gas phase, volatile compounds into,
general information, 317
36–37

Gas analysis, common gases and,

Gas sample analysis, 34

317–318
Gas sample delivery, 37f

Gas chromatograph (GC), 3, 15–83.

Gas sample loop, 35f

See also specific chemicals/hormones Gas sample valves, 35f, 36

analysis time, total analytic points on, 36

procedure, 66
six-port, 37f, 36

column bleed, 194f

Gasoline, GC separation of, 332

direct sample introduction

Gas-phase eluate, 89

techniques, 43
Gas-sampling valves, 35f, 35

features, 16f, 22
Gas-tight syringes, 35

Index 599

Gaussian peak, 57f Helium, 87–89

GC. See Gas chromatograph Van Deemter plot, 63f, 63
GC/MS/MS. See Tandem mass HEPT. See Height equivalent to
spectrometry theoretical plate

GC-nitrogen-phosphorous detector, Heroin, 278

204
Heteroatoms, 198–200

General databases of mass spectra, 151

Heterolytic cleavage, 253f, 346

GERSTEL Cooled Injection System

Hexachlorobenzene, 106–107

(CIS), 43
Hexamethyleneimines, 255

GERSTEL TDU, 43
Hexamethylphosphoramide, 283f, 278

GERSTELTwisterTM device, 43
and metabolites, 278

Glass connector, 25f, 25

Hexanal, 241f, 241

Glass liners, 23–24

Hexanamide, 248f, 247

Glass Y-shaped connectors, 74f, 75f

Hexanedinitrile, 352f

Glucosamine, amino sugars and, 407

Hexanenitrile, 352f

Glycol ethers
2-ethyl-1-hexanol, 183f, 182–183

derivatization of, 319

2-hexanone, 347f, 347

TMS derivatives, 319

High resolution, 96

GC separation of, 319

High resolving power, 96

underivatized, mass spectral

High vacuum component, 101

interpretation, 320
Higher-boiling fluorinated

Glycol methacrylates, 286

compounds, GC separations, 305

Glycols, 319–322. See also Capillary

High-purity solvents, 402

column
High-vacuum valves, 36

GC separations, 319
Hit list, 161–164

underivatized, 319–320
of search results,
Gohlke, R., 5
reverse Match Factor column and,
162f
Halogenated aromatics, 323–324. sample spectrum v., 163f

See also Capillary column Hold times, 61

Halogenated compounds (other than Holmes, J., 5

fluorinated compounds), 323–329. Homolytic cleavage, 346

See also Capillary column Hormones, 397

GC separations, 323
Hot splitless injection, injection speed, 30

mass spectra of, 324

Hunt, D., 110–111

Handbook of Mass Spectra of Environmental Hydride-shift rearrangement

Contaminates, 379–380
fragmentation, 253f, 296

Hazardous waste, 101

example, 297

HCN. See Hydrogen cyanide

Hydrocarbon compounds, 332

Headspace sampling, 38
Hydrocarbon emission profiles, from

Heart-cutting applications, dual-

PFPD, 72f

column systems, 77f, 76

Hydrocarbon fuels, 15

Height equivalent to theoretical plate

Hydrocarbons, 331–339

(HEPT), 62
GC separation of, 331

600 Index

Hydrogen, 94
Ion source fouling, 109–110, 182

Van Deemter plot, 63f, 63

Ionization,

Hydrogen cyanide (HCN), 68–69

technique, 9–10, 89

α-Hydrogen shift, 253f

types, 104

Hydroquinone, 280
Ion/molecule reaction, 107–108,
Hydroxyl group, 189f
119–120
Hydroxyl oxygen, fragmentation
Ion-optics fouling, 109–110
initiated, 181f
Ions kinetic energy, 128–129
Hydroxylated phenol group, 387
Isocyanates, 341–343
GC separations, 341

Imidazoles, 366–367 o-ethylphenyl isocyanate, 344f

Indoles, 364–365 p-ethylphenyl isocyanate, 344f

Industrial solvent mixtures. See also Isophthalates, 394

Capillary column
Isopropyl alcohol impurities, 402

GC separations, 401
N-PFP isopropyl ester derivative, 265,

impurities in, GC separations of, 401

271

Initial temperature (of analytical run),

N-PFP isopropyl esters, GC separation

60
of, 267f

Injection mode,
Isothermal analysis, 59f, 58

liquid sample and, 29t

Isothiocyanates, 414

sample and, 28
Isotope peaks, relative intensity of, 173,

Injection speed, 30
168

hot splitless injection, 30

Isotope-Peak Calculator/Comparator,

Injection techniques, 29
202f, 202

Injector(s),
Itaconic acid, 224

settings, 9

types of, 9
JadeTM inlet, 34f, 33

In-line rotary vane pump, 101

JEOL instrument, 126

Instrumental variables, 7, 8
Jet separator, 87f, 85, 87

Internal ionization quadrupole ion

disadvantages, 88

trap, 117f, 134, 209

Internal standard calibration curve, for

α-Keto acids-MO-TMS derivatives,
phencyclidine, 216f
222–224
Internal standard method, 214
derivatives, 222

Ions, 89–90. See also specific ions

α-Keto-β-methylvaleric acid, 223

accurate mass assignment, 95–96, α-Ketobutyric acid, 222

174
α-Ketoisocaproic acid, 223

detection, 128
Ketone groups, carbohydrates, 345

monitoring, selecting, 140

Ketones, 345–349. See also Capillary

for pesticide identification, 380t

column; Cyclic ketones

time, 116–117
derivatives of, 345

volume, 105–106
reduction and preparation of, 345

Ion optic system, 127f

GC separation of, 345

Ion source, cleaning, 107

methoxime derivatives of, 345

Index 601

Kováts retention index, 51f

M+•. See Molecular ions
equation for, 51
Mainlib spectrum, 158f
n-alkanes and, 50–51
Malathion, structure of, 378

Mass accuracy, 92

Large-volume injection, 28f, 27 Mass chromatograms, 93f, 94f, 91–92,

LC/MS. See Liquid chromatography/ 141–142

mass spectrometry use of, 193

Lindane, molecular weight for, Mass discrimination, 128–129

373–376 Mass spectra, 90. See also Mass
structure and, 373–376 spectrometry; specific chemicals/
Linear analyte response, 217–218 hormones
Linear m/z scale, double-focusing mass Mass spectral data interpretation,
spectrometer, 133–134 149–205
Linear regression data, calculation, Mass spectral database, 151

215–216
pesticide analysis, 380

Linear velocity, carrier gas flow, 62

search algorithms, 154–155

Lipid compounds, 397

Mass spectral interpretation, 227, 232,

Liquid chromatography Resources,

280

204
cyclic alcohols, 233–234

Liquid chromatography/mass
metabolites, 280

spectrometry (LC/MS), 9–10

primary aliphatic alcohols, 232

drugs, and metabolites, 277

TBDMS-derivatized amino acids,

Liquid samples
268

direct sample interface, 43

underivatized glycol ethers, 320

equilibration process, 38f, 38

underivatized glycols, 320

inlets for, 16
Mass spectral ionization, type of, 8

Liquids, volatile compounds in, Mass spectral peaks, 91f, 97f, 90, 95–96
solvent-free determination, 36
in profile mode, 100f
Logical losses, 200
Mass spectrometer, 3, 15, 89

Low resolution, 96
direct sampling into, 44

Low-boiling aromatic hydrocarbon

tuning, 134

compounds, GC separation of, 331

Mass spectrometer instrumentation,
Low-boiling fluorinated compounds
89–148
(C1-C2), GC separations, 301
Mass spectrometrists, 204

capillary columns, 301–305, 302t,

Mass spectrometry, nominal mass and,
303t, 304t
373–376
Low-molecular-weight aliphatic acids,
Mass Spectrometry of Pesticides and
derivatization procedure for, 221
Pollutants, 379–380
Low-molecular-weight compounds,
Mass Works software, 175

335
Mass-to-charge ratios. See m/z value
Low-vacuum component, 100f, 99
MassWorks, 98–99
exhaust and, 100f
McLafferty, F., 5

Low-vacuum pump, components, 100f

McLafferty rearrangement

Lutidines, 363
fragmentation, 287, 327, 346–347

602 Index

McReynolds constant, 52
Microchannel plate electron multiplier,

Mechanical pump exhaust, filtering, 101

132f, 132

Medium-boiling fluorinated
Microcomputer, 6

compounds, GC separations, 305

Microfurnaces, 18

MerlinTM microseal, 33f, 33

Minicomputer, 6

Mesaconic acid, 224

Mixed derivatizing reagents, using,

Metabolites,
189–190

of drugs, 277–284
Molecular ions (M+•), 90, 112, 149

LC/MS, 277
aliphatic dinitriles, 352

mass spectral interpretation, 280

aromatic ketones, 348

Meta-isomer, 413–414
benzoin alkyl ethers, 297

Methadone, 278
composition, after determination,

Methadone metabolites, 278

176

Methane, 108f, 109–110, 183f, 182–183

compounds, 337

Method of standard additions. See

cyclic alcohols, 233

Standard additions method

cyclic ethers, 296

Methoxychlor, molecular weight for,

cyclic ketones, 347–348

structure and, 376

diaryl ethers, 296

Methyl esters. See also Capillary column

fragmentation, of xylene, 335

of aliphatic acids, 286–288

nitroaromatics, 355

of aromatic cyano acids, 292

phenols, 384

of benzene sulfonic acids, 291

prostaglandins, 399

of cinnamic acid, 291

steroids, underivatized, 404

of cyano acids, 286

unbranched aliphatic ethers, 294

of dibasic acids, 290

Molecular ions (M+•) peak, 165, 166t,

pyrrolidine derivatives of, 288f

255

of straight-chain fatty acid, 190f

absence of, 178

Methyl ketone, 200–201

aliphatic halogenated compounds,

Methyl parathion, structure of, 378

324–329

Methyl stearate, 211f, 211

aromatic dinitriles, 353

4-methyl-4hydroxy-2-pentanone,
aromatic fluorine compounds, 315

195f, 178–179
aromatic hologenated compounds,

Methylated barbiturates, 278

327

Methylation,
aromatic nitriles, 353

of barbiturates, 279
benzimidazoles, 366

of sedatives, 279
butyl pentyl ether, 299f

2-methylbenzaldehyde, 242f, 241

chlordane, 375

Methylglutaronitrile, 352–353
chlorofluoroacetones, 316

Methylpyridines, 363
chlorofluorocarbons, 305–306

Methyl-substituted straight-chain
cyclic ketones, 347–348

alkane, 334f, 333

DDT, 375–376

MH+. See Even-electron protonated

dinitroanilines, 358

molecules
dinitrophenols, 359

Microchannel plate, 132

dinitrotoluenes, 358

Index 603

fluorinated aliphatic compounds, 305

MS Interpreter, 202

free acid form PGA1, 397–398

MS SIM/Scan Parameters dialogue

imidazoles, 366
box, 176f, 175–176

low-molecular-weight compounds
MSTFA reagent, 261, 383

and, 335
MTBSTFA reagent, 250

nitroanilines, 356
Multicolumn systems, 76

nitroaromatic compound, 357f, 361

Multifunction PTV injectors, 25

perfluorinated acids, 315

Multilevel temperature programs, 60

perfluorinated ketones, 316

Multiple acquisition time segments,

perfluorinated olefins, 315

141–142

pesticides, 379
Multiple-peak mass spectra, 104–105

phosphoramides, 390
Multistep pyrolysis, 47

phthalates, 394
Munson, B., 107–108

polynuclear aromatic hydrocarbon

m/z analyzer, 8–11, 99, 185–187, 207

compounds, 337
types, 113

primary aliphatic alcohols, 232

m/z range, 9

pyrrolidine moiety, 288

m/z scale, 153

steroids, underivatized, 405

DC:RF amplitudes, 115

unsymmetrical ether, 299f, 298–299

m/z scale calibration, 9, 113, 132

Molecular weight,
m/z shift, 253f

aldrin, 374
m/z value (Mass-to-charge ratios), 5,

chlordane, 374–375
90, 95, 137–138, 145, 305–306,

compounds and, 255

306t

DDT, 375
antioxidants, 387

dieldrin, 375
for molecular ion, steps taken, 166t

heptachlor, 374
organophosphorus pesticides,

lindane, 373–376
377–379
methoxychlor, 376
m/z value ion, chlorofluorocarbons,
TMS derivatives of sugars, 408
305–306
unknown glycols and, 320

Molecular weight discrimination, 21

N. See Number of theoretical plates

C6-C24 monocarboxylic acids, 226

Nalbuphine, 277

derivatives of, 226

Nalbuphine-TMS, 278

GC conditions, 226
Naloxone, 277

Monoisotopic composition, 97f

Naloxone-TMS, 278

Monoisotopic ion, 94
NCI. See Negative chemical ion

Monoisotopic peak, 95
N-Dealkylation, 281

Monosaccharides, 407
Negative chemical ion (NCI),

Morphine, 278
110–111

Morrel, F., 5
netCDF format, 191–192

MO-TMS derivatives,
Neutral losses, 167t

of drugs, 279
Nicotinamide, 246–247

fragment ions, 405

Nicotine, 277

molecular ion, 405

NIST AMDIS, 126

604 Index

NIST MS Search Program, 156f, 158f, N,N-diethylamine, 254f

154–155, 196, 201–202 N,N-Diethylnicotinamide, 246–247

NIST08 Mass Spectral Database, 203f, N,N-dipropyl-1-butamine, 254f

197, 203–204, 384–386

Noise spikes, 152

pesticides, 379–380
Nominal mass, 373–376

solvents, and impurities of, 402

Nominal mass ion, 93–94

NIST/EPA/NIH Mass Spectral

Nominal mass molecular ion peak,

Database, 155–156, 165

93–94
Nitriles, 351–353. See also Capillary
Nominal mass values, chlorinated
column
pesticides, 373–376

GC separation of, 351

Normal identity search, 155

Nitroaminotoluenes, 357
Normal presearch algorithm, 155

2-chloro-4-nitroananilines, 359f, 359

NPD. See Nitrogen-phosphorus

m-nitroaniline isomer, 357f, 356

Nucleosides. See also Capillary column

Nitroanilines, 355–356
derivatized, GC separation of, 369

Nitroaromatics, 355–361. See also

Nucleosides (TMS derivatives), 369–371,

Capillary column
371f

fragmentation, 355–356
biologically active, structures of,

GC separation of, 355

370f, 369

general formula, 355

derivatization, 369

m+• peak, 357f, 361

Number of theoretical plates (N),

molecular ion, 355

54–55

sample mass spectra, 357f, 360

Nitrodiphenylamines,
o-chloroaniline, acetyl derivative of,
GC separation of, 355
mass spectrum, 259f
mass spectra of, 359
Octadecanoic acid, ethyl ester of, 289f
o-nitrodiphenyl amine, 360f, 360
1-octanethiol, 412f
Nitrogen, 94
1-octanol, 234f, 234–235
Nitrogen carrier gases, Van Deemter
TMS derivative of, 235f, 235

plot, 63f, 63
n-octylamine, 252f, 260

Nitrogen ions, 255

di-n-butylphthalate, 395

Nitrogen Rule, 120–121, 167–168,

di-n-octylphthalate, 394f, 395

188, 200
di-n-propylphthalate, 395

Nitrogen-containing heterocyclic Odd-electron fragment ion (EE+),

compounds, 363–367. See also 178–179, 200, 166t, 346–347

Capillary column o-dichlorobenzene, 329f
GC separations, 363
Oil diffusion pump (Diff pump), 103f,
mass spectra of, 363
101–102

Nitrogen-phosphorus (NPD), 15
Oil rotary pump, 100f

Nitronaphthalenes, 358
On-column injectors, 26f, 27f, 26, 24

Nitrophenol, 356, 361

OPD metabolites. See

3-nitrophenol, 357f
o-Phenylenediamine metabolites

o-nitrotoluene isomer, 356f, 356

Open-split interface, 86f, 85

Nitrotoluenes, 356
Operational variables, 7, 9

Index 605

o-Phenylenediamine (OPD) PFK. See Perfluorokerosene

metabolites, 278
PFP esters. See Perfluoropropyl esters
Organic acids, in urine, 224–225
PFPD. See Pulsed-flame photometric
Organophosphorus pesticides, 377–379
detector
Ortho effect, 260f, 258, 262–263, 335
PFTBA. See Perfluorotributylamine
aromatic hologenated compounds, PGE2-methoxime-di-TMS, 400f
327
PGF2-methyl-triTMS, 400f
aromatic thiols, 413–414
Pharmaceuticals, thermal modulators
substituted phenols and, spectra of,
and, 78–79
386–387
Phenazines, 365–366
Oxazepam, 277
Phencyclidine, internal standard
calibration curve for, 216f
Packed column injectors, physical Phenols, 186f, 280, 383–388. See also
characteristics, 55t
Capillary column

Packed columns, 249–250

derivatization of, 383

Parathion, 378
derivatized, GC separations of,

Parts per million (ppm), 92–93

383–384

p-chloroaniline, acetyl derivative of,

mass spectra of, 384

259f
as TMS derivatives, 387

Pentobarbital, 184f, 277

underivatized,

Perfluorinated acids, 315

GC separations of, 383

Perfluorinated ketones, 316

mass spectra of, 384

Perfluorinated olefins, 315

fragment ions, 384

Perfluorokerosene (PFK), 134f,

molecular ion, 384

133–134, 188
sample mass spectra of, 385f, 384

Perfluoropropyl (PFP) esters, 211

Phenol-TMS, 387

Perfluorotributylamine (PFTBA), 133f,

Phenyl dimethylsiloxane, 50

133–134, 175, 275f, 275

4-phenyl-n-butanol, 236f, 235–237

examination points for, 134–135

8-phenyl-n-octanol, 237f, 235–237

structure of, 133f

Phenylacetic acids, 224

Pesticides, 15, 69, 373–381. See also

N-Phenyldibenzamide, 246–247

Chlorinated pesticides;
1-phenylethanol, 385f, 384–386

Organophosphorus pesticides;
Phosphoramides

Phosphorus pesticides; specific

(Hexamethylphosphoramide),

pesticides
391f, 390

analysis, mass spectral data base, 380

Phosphorus compounds, 68–69,
chlorinated biphenyls, 323–324
389–390. See also Capillary
database, 379–380
column
in food, DSI and, 45
GC separations, 389

identification of, 380t

structure, 389

mass spectra of, 379

Phosphorus pesticides, 389

NIST08 Mass Spectral Database,

Photomultiplier, 71

379–380 Photomultiplier ion detector, 130f

Wiley Registry, 9th ed., 379–380 Phthalates, 292, 393–395

606 Index

Picolines, 363 10-ethyl-10-propyldocosane, 334f,

Piperidines, 255 333
Plant steroids, 403 Propylene glycol,
Plasticizers, 393–395. See also Capillary library search and, 320
column mass spectrum of, 321f
GC separations, 393 Prostaglandins,
Plate numbers, 57f derivatized, GC separation of, 398
PLOT column. See Porous-layer MO-TMS derivatives, 397–400
open-tubular column derivatization of, 398
Polar stationary phases, 52–54 Prostaglandin A’s (PGAs), 397–398
Polymer additives, 393–395 Prostaglandin B’s (PGBs), 397–398
Polymers, 47 Prostate gland, 397
Polynuclear aromatic hydrocarbon Protonated molecules, 107–108,
compounds, 337 182–183
GC separation of, 331 Protonation reaction, 107–108
Porate, 377 PTH-amino acids,
Porous-layer open-tubular column derivatization of, 265
(PLOT column), 49–50 GC separation, 265
Postacceleration device, 129f, SIM of, 270t
128–129 TBDMS derivatives of, mass spectra
ppm. See Parts per million of, 269
Precursor ions, 142–143 underivatized, mass spectra of, 269
Precursor-ion mass spectrum, 145 PTV injectors. See Programmable-
Prefilter, 107 temperature vaporizing injectors
Pressure control, 6 Pulsed-flame photometric detector
Pressure-pulsed injection, 31 (PFPD), 70
Primary aliphatic alcohols, 232 hydrocarbon emission profiles from,
fragment ions, 232
72f
fragmentation, 232
operational steps for, 72f
general formula, 232
sulfur emission profiles from, 72f
molecular ion peak, 232
Pump oil, EPA Super Fund site, 101
Primary amides, 244–245 Pumping speeds, manufacturers and,
derivatization of, 243 102–103
Primary amines, 252 Purge activation time, 20f, 21f, 19
Primary immonium ion, 253f Purge gas, 86f, 85–86
Probability value, 161–164 Pyrazines, 365–366
Probes, for GC, 43 examples, 365–366
Product ion analysis, 145 Pyridines, 363–364
Product-ion mass spectrum, 145 Pyrolizers, 45
Profile data, 92f, 90–91 commercial, automated analysis, 47
Profile mass spectrum, 100f Pyrolysis GC, 45
Profile mode, 92f, 100f, 175 Pyrolysis temperature, 46–47
Programmable-temperature vaporizing Pyrroles, 364–365
injectors (PTV injectors), 24 Pyrrolidines, 255
Index 607

Pyrrolidine derivatives, of methyl

Reagent gases; see also
esters, 288f, 288
Trimethylsilyl reagents; TRI-SIL
Pyruvic acid, 222
Z reagent; specific reagent
chemicals/gases
QIT. See Quadrupole ion trap Rear tailing peak, 57f
QMF. See Quadrupole mass filter Reconstructed total ion current (RTIC),

Quadrupole ion trap (QIT), 9–10, 93f, 121–122, 151f, 150–151

65–66, 113, 116

chromatogram, 100f

disadvantage, 118–119
of data, 157f

GC/MS instruments, multiple scan

selecting spectrum, 191

segments, 118f
chromatographic peak, 158f, 152

Quadrupole ion trap (QIT) mass

compounds and, 160f

spectrometers, 208
diazomethane and, 191f

operational pressure of, 144

Reduced sugars (as acetates), GC
Quadrupole mass filter (QMF), 10–11,
separation of, 407–408
114f, 113–115
Relative response factor (RRF),

Quadrupole Mass Spectrometry and its

equation, 215

Applications, 113–114
Replicate Database, 155–156
Quant ion, 207, 209–210
Resolution, 95f, 92, 124

Quantitation methods, 212

double-focusing mass spectrometer,

Quantitative analysis, GC/MS, 207

98

Quantitative Chemical Analysis, 218

TOF mass spectrometer, 98

Quantitative data, commercial GC/

Resolving power, 92

MS data systems and, 218

Resorcinol, 280

Quantitative response factor (RF), 211,

Retention index (RI), 149

213–214
Reverse geometry system, 127f
Quantitiation ion, 207
Reverse Match Factor column, 159–161
selection of, 209
hit list search, 162f
Quick presearch algorithm, 155
RI. See Retention index
Quinoline (Benzpyridine), 364
Ribose sugars, 369

Quinoxalines, 365–366
Rings plus double bonds (R+db),
calculating, 176–178
R Match Factor value, 196
Root pumps, 101

Radioactive foil, 69–70

RRF. See Relative response factor
Rapid data acquisitions, 125
RTIC. See Reconstructed total ion
R+db. See Rings plus double bonds
current
Reagent gases, 107–108. See also specific
Rule of loss of largest moiety, 295

reagent gases/chemicals
ammonia, 134
Samples, 121–122, 149–150, 216–217.

characteristics of, 109t

See also Biological samples; Liquid

compounds, 109, 108t

samples; Solid samples; Trace

Reagent ions, 107–108 analysis samples; Unknown

Reagents, 7. See also Mixed sample; Unspiked samples

derivatizing reagents; MSTFA injection mode and, 28, 29t

reagent; MTBSTFA reagent; introduction process, 15

608 Index

Samples (Continued) Selectivity and retention indices, 50

preparation, 278
Self-aligning continuous-dynode
solid-phase extraction, 279
electron multiplier replacement,
solvent extraction, 278
131f
underivatized, contaminates after, 274
Semivolatiles, 137

Sample mass spectra TBDMS­ Septum problems,

derivatized amino acids, 271

GC syringes, 31–32

Sample mass spectrum, 228, 234–235,

solving, 31

260, 283
Side-hole point syringe tip, 32f, 32
1-ethoxybutane, 298–300 Silyl derivatizing reagents,
aliphatic halogenated compounds, commonly used, 186f
325
reaction of, 186f
aromatic halogenated compound, 328
SIM. See Selected ion monitoring

branched alkanes, 333

SIM analysis, 208

of chlorofluorcarbons, 314
SIM chromatographic peak, 208

hexanal, 241f, 241

SIM technique, 137–138

hexanamide, 247
PTH-amino acids, 270t

alkanes, 332
Simple mixtures, GC separations, 221

nitroaromatics, 357f, 360

Single-stage separator, 87–88

unknown glycols and, 321f, 320

SIS. See Selected ion storage

Sample spectra searches, 160f, 155

SLOT column. See Support-coated

Sampling rate tab, 175–176

open-tubular column
Sandwich technique, 30f, 29–30
Soft ionization techniques, 90, 104–105,
Saturated aliphatic hydrocarbon
182

compounds, GC separation of, 331

Solid samples, direct sample interface, 43

Saturated halogenated compounds,

Solid-phase extraction, sample

323. See also Capillary column

preparation, 279

SBSE. See Stir-bar sorptive extraction

Solid-phase microextraction (SPME), 40

Scroll pumps, 101

fiber assembly, 41f, 40

Secobarbital, 277
sampling procedure, 42f

Secondary alcohols, 232–233

Solids, volitile compounds in, solvent-

Secondary amides, 245–246

free determination, 36

Secondary amines, 253

Solvents, 15, 19

Sedatives, 278
column phase and, 22f

methylation of, 279

consideration, amines, 263

Selected ion monitoring (SIM), 7,

extraction, sample preparation, 278

140–141, 207
focusing, 21

Selected ion storage (SIS), 140–141

and impurities, 401–402

Selected ion-monitoring
mass spectra of, 402

chromatogram, 141–142
Wiley Registry, 9th ed., 402

Selected reaction monitoring (SRM),

NIST08 Mass Spectral Database, and

145, 207
impurities of, 402

Selected reaction monitoring (SRM)

purified, 16–17

analysis, 208
selection, 9

Index 609

Space-charge effect, 118

underivatized, 405

Spatial domain MS/MS, 143

Steroids (derivatized), GC separation

Spectral acquisition, 9
of, 403

high speeds, 140

MO-TMS derivatives, 403–404

Spectral dark matter, 165

TMS derivatives, 403

Spectral skewing, 139f, 138–139, 152

Steroids (underivatized),

Spectrum number, 91–92

GC separation of, 403

Speed-enhancement factor, 64
mass spectra of, 404

Spiked samples, 217–218

characteristic fragment ions, 405

Split injection mode, 18

molecular ion, 404

carrier gas in, 18f Stir-bar sorptive extraction (SBSE),

Split ratio, 18–19 43

Split vent, of gas chromatograph, Stock solution, 212

mechanical pump exhaust and, 101

diluting, 213

Split-flow turbo pump, 102–103

Substance, unknown, identification of,

Splitless injection, 21f

150–151

Splitless injection mode, 20f, 18–19

Substituted phenols, ortho effect,

carrier gas, 20f

386–387

Splitless injection parameters, 23

Sugars, 407–410

Split/splitless injector, 9, 18f, 17

derivatized, GC separation of, 407

Split/splitless injector liners, 24f

mass spectral interpretation, 408

Splitters, 73
TMS derivatives of,

glass Y-shaped connectors, 74f, 75f,

mass spectra of, 408–409

73
sample mass spectrum, 409

SPME. See Solid-phase

Sugar alcohols (as acetates),

microextraction
GC separation of, 407

SRM. See Selected reaction

mass spectra of, 409–410

monitoring
fragmentation, 409–410

Stable isotopes, naturally occurring, 169

molecular ion, 409

Stafford, G., 110–111

Sulfur compounds, 71, 411–414.

Standard additions method, 216

See also Capillary column

calibration curve for, 217f, 217–218

GC separations, 411

Standard solutions, making, 212

mass spectra of, 411

Standard Spectrum Tune, 136f, 136–137

Sulfur emission profiles, 72f
Static headspace, 39
Support-coated open-tubular column
Static tune procedure, 137
(SLOT column), 49–50
Stationary phases, 50
Symmetrical ether, 299f
thickness of, 54
Syringe, 25, 31–32

Steroids, 403–406
filling, 29

derivatization of, 403

gas-tight, 35

MO-TMS derivatives of, mass

tips, 32f, 32

spectra of, 405

beveled point, 32f

TMS derivatives of, mass spectra

conical point, 32f, 32

of, 405
System background, 275–276
610 Index

Tandem mass spectrometry (GC/MS/

Thermal modulators, 73, 78

MS), 11, 142

Thermionic-specific detector (TSD),

Tandem quadrupole mass

cross section, 69f

spectrometer, 143–144
Thermoconductivity, compounds and,

Tandem-in-space mass spectrometry,

21f

143f, 143, 145

ThermoScientific DES GC/MS

Tandem-in-time mass spectrometry,

system, 4f

144f, 143, 146

Thimet. See Porate

Target analyte, 209–210

Thioesters, 414

TBCMS adduct (Tertbutyldimethylsilyl

Thioethers (sulfides), 412–413

adduct), 185
fragmentation, 412–413

TBDMS derivatives, 270t

general formula, 412

fragment ions of, 271

molecular ion, 412

TBDMS-derivatized amino acids,

Threshold rate tab, 175–176
characteristic ions of, 269t
TIC chromatogram. See Total ion
GC separation of, 267f, 265
current chromatogram
mass spectral interpretation, 268
Time-of-flight (TOF) analyzer, 10–11,
retention times and accurate masses,
113

266t
Time-of-flight (TOF) GC-MS, 123

TBDMS-derivatized glutamic acid,

Time-of-flight (TOF) mass

271f
spectrometer, 5, 65–66, 99, 208

TBDMS-derivatized PTH amino

accurate mass assignment and, 175

acids, GC conditions for, 265

calibration of, 134

TCD. See Thermal conductivity

resolution, 98

detector
TMS. See Trimethylsilyl
Temperature program, compounds
TMSDEA reagent, low-molecular­
and, 78–79
weight aliphatic acids, 221

Temperature program rates, 60

TOF. See Time-of-flight

increasing, 65
Toluene, 174f, 173

Temperature-programmed injection,
impurities, 402

26f, 26
side-chain oxidation and

Tenax, 39–40
hydroxylation, 280

Terephthalates, 394
Total ion current (TIC)

Tertbutyldimethylsilyl adduct. See

chromatogram, 91–92

TBCMS adduct
Trace analysis samples, 28

Tertiary alcohols, 232–233

Trace Quantitative Analysis by Mass

Tertiary amides, 246

Spectrometry, 218

Tertiary amines, 253

Transmission quadrupole GC-MS,

alpha cleavage, 253f

113

Tertiary carbenium ions, 333

Trapping material, 34–35

n-tetradecane, 333f
Traps, 61

Thermal conductivity detector (TCD),

Trichloroethane, 159

15, 66, 317–318

Trichlorofon, structure of, 377

cross section, 67f

Trichloronitrotoluenes, 360

Index 611

Trimethylsilyl (TMS), 185

Unspiked samples, 217–218

ether, 187f
Uric acid-TMS, 367

nucleosides, 369
Urine

of precursor, 281
acids found in, 224

Trimethylsilyl (TMS) derivatives. See OPD and, 278

specific chemical/steroids
Trimethylsilyl (TMS)-derivatized
Vacuum system, 99

glycols, 320
Valve applications, web sites for, 77–78

Trimethylsilyl (TMS) reagents, 187–188

Valves, 75f, 73, 75

contaminates after, 273

Van Deemter equation, 62–63

derivatization with, contaminates

Van Deemter plot, 63f, 63

after, 273
Venting, mechanical pump exhaust

Trimethylsilyl-α-glucose, 409f
and, 101

Trimethylsilyl-major metabolite, 281

Viscous-flow pressure region, 87–88

Triple quadrupole mass spectrometer,

Volatile analyte, 213

143
Volatile compounds, 137

TRI-SIL Z reagent, 261

into gas phase, 36–37

TruTOF HT, 125

solvent-free determination, 36

TSD. See Thermionic-specific detector

Turbo pump. See Turbomolecular

Wall-coated open tubular column
pump
(WCOT column), 49

Turbomolecular pump (Turbo pump),

Waters GCT Premier, 126

102f, 101–102
WCOT column. See Wall-coated

TwisterTM device, 43
open tubular column

Wide-boiling hydrocarbon mix, 27f,

Unbranched aliphatic ethers, mass 26

spectra of,
Wiley Registry, 9th ed., 106–107, 153

fragmentation, 294
pesticides, 379–380

general formula, 293

solvents, and impurities of, 402

molecular ion, 294

Wiley Registry of Mass Spectral Data, 151

Unknown glycols,

molecular weight and, 320

X + 1 elements, 169

sample mass spectrum, 321f

X + 2 elements, 169

Unknown mass spectrum, 203f X + 2 isotope peak patterns, 171f

of postulated structures, predicted X elements, 169

mass spectra, 201

Xylene, 164f, 335

Unknown sample, 215–216

molecular ion fragmentation of,

Unsaturated aliphatic hydrocarbon

335

compounds, GC separation of, 331

Xylenol-TMS, 387

Unsaturated halogenated compounds,

323
Y-shaped connectors, 74f, 75f, 73