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AL aqueous reaction types, 112 array detector, 158 ascorbic acid, 135 aspiration, 342 atmospheric pressure chemical ionization (APCI), 392, 394 atomic absorption spectrometry (AAS), 341, 346 atomic emission spectrometry (AES), 354 atomic fluorescence spectrometry, 357 atomic mass unit, see unified atomic mass unit atomic emission spectrometry (AES or OES), 341 atomic energy levels, 151 atomization, 342 autotitrator, 128 auxiliary electrode, 329 CO PY R IG HT ED absolute temperature, T, 311 absorbance, A, 160, 162, 347 absorbance maximum, λmax , 164 absorption coefficient, a(λ), 162 absorption of light, 148, 160 accuracy, 15, 28 acid–base equilibria, 114 acidic and basic salts, 189–190 acidity, 180, 189, 192, 196–199, 257 activation energy, Ea , 310 activity, 199, 205 activity coefficient, γ , 205, 209 adduct, 247 adjusted retention time, tR , 372 affinity chromatography, 84 alkalinity, see also basicity, 157 agarose gel, 398 alpha fraction, α, 76, 226, 263, 286 alpha fraction plot, 227–228, 234, 266 alumina, Al2 O3 , stationary phase, 84 amine functional group, 187 amphiprotic species, 192, 194–195, 235 analyte, defined, 5 analyte loss, 57 analytical balance, 45 anode, definition, 315 anodic stripping voltammetry (ASV), 335 antibody/antigen inteaction, 96 MA TE RI INDEX back titration, 130–131, 255 background, 35 background correction, in atomic absorption spectrometry, 353 bandpass, spectral, 356 baseline, 35 basicity (alkalinity), 192, 194, 196 Beer-Lambert law, 159–165 Benedict’s solution, 166 Basics of Analytical Chemistry and Chemical Equilibria, First Edition. Brian M. Tissue. © 2013 John Wiley & Sons, Inc. Published 2013 by John Wiley & Sons, Inc. 407 408 INDEX bias, 15 blank, 56 breakthrough volume, VB , 89 bridging ligand, 248 Brønsted-Lowry definition of acids and bases, 113, 179 buffer, 221 buffer capacity, 229 burette (or buret), 46, 127 C18 stationary phase, 93 calibration, 28 calibration curve, 35, 37, 165, 167 calibration function, 37, 327 calmagite indicator, 129, 259 capacitive current, 330 capillary electrophoresis (CE), 401 capillary GC column, 389 carboxylic acid group, -COOH, 186 carryover, see memory effect cathode, definition, 315 cation-exchange, 86 cation-exchange chromatography, 94 certified reference material (CRM), 43 channeltron, 360 charge balance, 107, 185 chelate, definition, 115, 248 chemical ionization (CI), 392 chemical potential, 310 chemically modified field effect transistor (CHEMFET), 327 chemical reaction, 105 chiral chromatography, 383 CHNO analysis, 108, 340 chopper, optical, 348 chromatogram, 372 classical methods, 103 colorimeter, 157 column chromatography, 82, 91 combustion analysis, 108, 340 common-ion effect, 280–282 comparator, 157 competing equilibria, 260–263, 282–286 complex, definition, 115 complexation equilibria, 116, 250 complexation reaction, 112, 115 common concentration units (table), 8 competing equilibria, 256, 260 concentration, light absorption dependence, 162 concentration cell, 316 concentration polarization, 135 conditional or effective formation constant, , 262 βeff conductivity, electrolytic, 190 conjugate weak acid–base pair, 188 constant current source for coulometry, 134 constant weight, 121 contamination, 56, 59, 344 control chart, 57 control standard, 56 coordinate covalent bond, 129 coordination complex, 247 coordination number, definition, 115, 247 co-precipitate interference, 124 Coulomb’s law, 94 coulometry, 104, 134 coulometric titration, 135 critical pair, in a chromatogram, 379 crown ether, 81 cumulative formation constant, βn , 116 current, electrical, 319, 329 cuvette, 157 cyclic voltammetry (CV), 334 Daly detector, 360 Davies equation, 207 Debye–Hückel equation, 205 degrees of freedom, 18 -dentate, 248 derivatization, 168 desolvation, 342 detector, defined, 5 detector, optical, 158 detectors, HPLC, 383 deviation, 17 diatomic molecule, 152 differential pulse polarography (DPP), 333 differential pumping, 392 diffraction grating, 158, 356 diffusion coefficient, D, 332, 335 diffusion current, at dropping mercury electrode, 332 diluent, 73 direct analysis, 61 discontinuous electrophoresis, 400 distance of closest approach, see ion size parameter distribution constant, 75 distribution diagram, see alpha fraction plot Dixon’s Q Test (to discard an outlier), 26 Donnan potential, 322 drift, 35 dropping mercury electrode (DME), 331 dynamic range, 33 INDEX eddy diffusion (van Deemter A term), 377, 380 EDTA titration, 129 efficiency, in chromatography, 375 electrochemical cell, 314 electrochemical cell, shorthand line notation, 315 electrochemical cell voltage, Ecell , 315–316 electrolysis, 315 electrolyte, 70 electrolytic cell, 315 electromagnetic (EM) radiation, 142 electromagnetic (EM) spectrum, 146 electron ionization (EI), 392 electroosmotic flow, 401 elemental analysis, 340, 363 electrothermal vaporization, 350 electron charge, 311 electron multiplier tube (EMT), 360 electron-pair acceptor, 115 electron-pair donor, 115 electron transfer, 119 electronegative atom (see also Pauling electronegativity), 296 electronic excited state, 153 electrophoresis, 398 electrospray ionization (ESI), 394 electrostatic interaction, 94 eluent, 82 eluent suppressor, in ion chromatography, 385 elution, 82 emission of light, 148, 167 end point, 125 Environmental Protection Agency (EPA), 8, 16, 35, 224 enzyme-linked immunoassay (ELISA), 96 equilibrium, calculation, 212–213 equilibrium, definition, 309 equilibrium, versus reaction, 112, 309 equilibrium concentration, 183 equilibrium constant, K, 112 equilibrium constant expression, rules, 75 equilibrium constants, types of, 112 equipment blank, 56 equivalence point, 125 equivalence point, pH calculation, 231 error sources, 59 ethylenediamminetetraacetic acid (EDTA), 129 evaporative light scattering detector (ELSD), 383 extractant, 73 409 extraction, 71–73 extraction calculations, 77–80 false negative, 57 false positive, 56 faradaic current, 330 Faraday constant, F = 96485.3 C/mol, 135, 311 Faraday cup, 360 Fehling’s solution, 166 field blank, 56 filtering, 120 flame atomic absorption spectrophotometer, 349 flame temperature, 344 flash chromatography, 85, 380 flow rate, in chromatography, 376 fluorescence, molecular, 167–170 fluorescence spectrum, 169 fluorometer, 169 fluorometry, 170 Food and Drug Administration (U.S. FDA), 4 formal concentration, 183 formal equilibrium constant, K , 113, 199, 205 formation constant, Kn or βn , 116 formation constants, metal-EDTA, 129 fractions, collecting from a column, 83, 92 fragment ions, 391, 393 fragmentation pattern, 391 frequency (of EM radiation), 142 fronting, chromatographic peak, 378 full-width at half maximum (FWHM), 358 functional group, 66 galvanic cell, 315 galvanostat, 329 gamma-ray spectral region, 146 gas chromatography (GC), 388–390 gas constant, R = 8.3145 J/mol · K, 311 GC detectors, 389 gel-filtration, see size-exclusion chromatography, 84 gel-permeation, see size-exclusion chromatography, 84 generator electrode, 135 Gibbs energy, G, 310–312 glucose, 166 good laboratory practice (GLP), 10 good manufacturing practice (GMP), 13 gradient elution, 381 Gran plot, 133 graphite furnace, 350 410 INDEX grating spectrophotometer, 158 gravimetric factors, 122 gravimetric procedure, 121 gravimetry, 104, 120–124 guard columns, 381 half reaction, 299 Henderson-Hasselbalch equation, 226, 228 high performance liquid chromatography (HPLC), 380–387 hold-up time, tM , 372 hollow-cathode lamp, 348 homeostasis, 268 HPLC detectors (table), 384 hydrophobic interaction chromatography, 383 hydrogen energy levels, 151 hydrogen half reaction, see standard hydrogen electrode (SHE) hydrolysis reactions, 114, 186, 256–258 hydronium ion, H3 O+ , 182 hypothesis testing, 23 “ice” table for weak acid calculation, 217 ignition (of precipitate), 107, 120 immiscible, definition, 66 imunoassay, 96 indicators, titration, 126 inductively coupled plasma mass spectrometry (ICP-MS), 341, 361 infrared light, 146, 153 injection, in chromatography, 372 inner filter effect, in fluorescence, 171 insoluble, definition, 66 insoluble salt (also see precipitate), 69–70 interferences, 40 interferences, spectral, 356, 363 intermediate reagent, in coulometric titration, 135 internal standard, 40, 375 International Union of Pure and Applied Chemistry (IUPAC), xi, 13 iodine, as titrant, 135 ion detector, for mass spectrometry, 360 ion-selective electrode, 322–325 ion-sensitive field effect transistors (ISFET), 327 ionic solids, 65 ionic strength, 203–204, 235, 239, 252, 278–282 ionic strength adjustment buffer (ISAB), 322 ion-exchange stationary phases, 85, 94 ion optics, 391 ion pairs, 81 ion size parameter (table), 206 ion source, 391 ionization methods, 391, 392 isocratic elution, 381 isoelectric focusing, 400 isoelectric point, 400 isomer separation, 84 judgmental sampling, 54 Ka , 114 Kb , 114, 188, 193 Kn or βn , 116 Ksp , 117, 268 Kw , 190–194 Karl Fischer titration, 136 kinetics, 105, 309 label, 96 labile, 248, 249 laser ablation sampling, 346 laser-induced breakdown spectrometry (LIBS), 346 least squares, 37 Lewis acid and Lewis base, 180 ligand, definition, 115, 247 light power measurements, 160 limit of detection (LOD), 33, 35 limit of quantitation (LOQ), 35 limiting current, in voltammetry, 332 limiting reagent, 110, 114, 184, 188, 216 line notation, for electrochemical cell, 315 linear range, 34 linear regression, 37 linear-sweep voltammetry, 330 liquid chromatography (LC), 91 liquid–liquid Extraction, 73 lock-and-key interaction, 96 log alpha plot, 266 longitudinal diffusion (van Deemter B term), 377 luminescence, 167 L’vov platform, 350 magnetic-sector mass spectrometer, 396 masking, 61, 251 mass analyzer designs (table), 395 mass balance, 107 mass filter or mass analyzer, 359, 391 mass spectrometry, 357–361 mass spectrometric detector (MSD), 390 mass-to-charge ratio (m/z), 391 mass transport, in voltammetry, 331 material safety data sheet (MSDS), 13 INDEX matrix-assisted laser desorption ionization (MALDI), 392, 396 matrix effect, 40 mean, 17 measurement range, 33 measurement terms (table), 5 memory effect, 344 mercury emission spectrum, 152 mesh size, 84 metal hydrolysis reaction, 256 metal ion pKa (table), 257 metastable system, 112 method detection limit (MDL), 35 method development, 28 method validation, 29 micellar electrokinetic capillary chromatography (MEKC), 402 microchannel plate (MCP), 360 microtiter plate, see well plate microwave spectral region, 146 mixed-mode stationary phase, 95 mobile phase, 82 molar absorption coefficient, ε(λ), 163 molar solubility, s, 275–280 molecular energy levels, 152 molecular ion, 391 molecular transitions, 154 monochromator, 158 miscible, definition, 66 mixture, definition, 66 multiphase, definition, 66 multiple path term, see eddy diffusion National Institute of Standards and Technology (NIST), 41, 43, 60, 104 NIST atomic spectra database, 151 near infrared light, 146 nebulization, 342 nebulizer, designs, 343 Nernst equation, 302, 312–313 net reaction, 113, 185 neutral density filter, 163 neutralization reaction, 113, 185, 188, 216 neutralization titration, 126 Nikolsky–Eisenman equation, 327 nitrogen/protein analysis, 109 NOx , 107 noise, 33, 34, 35 normal distribution, 22 normal-phase partition chromatography, 87 normal pulse polarography (NPP), 332 numerical prefixes (table), 7 411 octanol–water partition coefficients (table), 77 Ohm’s law, 319 optical density (OD), 163 optical emission spectrometry (OES), see atomic emission spectrometry organic functional groups (table), 67 ORP electrode, 128, 320 outlier, 25 oxidation, definition, 298 oxidation state, 119, 296–298 oxidizing agent, 300 parabens, 385 partition ratio, 75 partition stationary phases, 87 partitioning, 73–76 path length, b, light absorption dependence, 162 Pauling electronegativity, 180–181 peak area versus peak height, 383 peak broadening, in chromatography, 377 Peirce’s criterion (to discard an outlier), 27 percentage dissociation, 197 percentage relative standard deviation (%-RSD), 20 percentage-transmittance, %-T , 163 peristaltic pump, 342 pH, 192 pH buffer, 221–222, 229 pH electrode, 326 pH meter, 128 phosphorescence, 167 photon, 143 pOH, 192 pipette (or pipet), 46 Planck’s constant, k = 6.626 × 10−34 J·s, 143 plate height, H , 376 plate number, N, 376 polarity, solvent, 66–67 polarity index, 67–68 polarization (of EM radiation), 142 polarography, 330 polyacrylamide gel, 398 polyprotic weak acids, 233–242 polychromator, 356 population standard deviation, 18 potentiometry, 319–324 potentiostat, 329 precipitation reaction, 112, 117 precipitate, 117 precipitate equilibria, 118, 267–271 412 INDEX precipitating agent, 120 precipitating agents (table), 122 precision, defined, 15 primary standard, 43 proportionality factor, 30 protecting reagent, 251 proton, H+ , 182 proton exchange, 81 pulse counting, 361 purification methods, 72 pyrite, FeS2 , 270, 297 quadratic equation, 197 quadrupole mass filter, 359, 394 qualitative analysis, defined, 5 quality assurance (QA), 11 quality control (QC), 11 quantum yield, in fluorescence, 170 radio wave spectral region, 146 radioactive cesium, 81 Randles–Sevcik equation, 335 random sampling, 54 random errors, 15 reaction coordinate model, 309–310 reaction quotient, Q, 112, 269, 311 reaction types, aqueous solution, 112 reactions, that go to completion, 111 reducing agent, 300 redox equilibria, 119 redox reactions, 112, 119, 298 redox reactions, balancing, 304–308 redox processes (table), 296 reduction, definition, 298 reduction potential, E, 300 reference electrode, 320, 325 reflectron, 396 refractive index, n, 144 refractive index (RI) detector, 383 relative abundance, 391 relative acid strength, see acidity relative standard deviation (RSD), 19 repeatability, 15 replicate measurements, 15 reporter, 96 reproducibility, 15 residual, see deviation resistance, electrical, 319 resistance to mass transfer (van Deemter C term), 378 resolution, Rs , in chromatography, 373, 379 resolution, in mass spectrometry, 358 resolution, in optical spectrometry, 356 resonance, 148 retardation factor, RF , 371 retention, in chromatography, 82, 372 retention factor, k, 374 reversed-phase partition chromatography, 87 reversed-phase stationary phase, 93, 95, 385 Rowland circle polychromator, 356 running gel, 400 sample, defined, 5 sample preparation, 58, 62 sample preparation example, 60 sample preparation methods (table), 63 sample standard deviation, see standard deviation sample storage, 55 sampling plans, 53 sandwich immunoassay, 96 saturated, definition, 66 saturated solution, 69 scan rate, in voltammetry, 335 scattering of light, 148 scrubbing, 72 secondary standard, 43, 45 selected ion monitoring (SIM), 395 selectivity, defined, 5 self reversal, see background correction sensitivity, defined, 5 sensitivity, 30 separations, analytical, 367 separations, for purification, 88–95 separatory funnel, 73 sequential extractions, 77 signal averaging, 15 SI base units (table), 6 SI derived units (table), 7 signal, defined, 5 signal-to-noise ratio (S/N or SNR), 35 silica, SiO2 , stationary phase, 84 simultaneous equilibria, see competing equilibria size-exclusion stationary phase, 84 size-exclusion chromatography, 95 slightly soluble, definition, 66 skimmer, 359, 392 sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), 399 soft ionization, 393 soil pH, 210 solar spectrum, 150 solid-phase extraction (SPE), 82, 88 INDEX solubility of organic compounds in water (table), 68 solubility product, Ksp (table), 272 soluble salts, 69–71 solute, definition, 66 solution, definition, 66 solution conductivity, see conductivity, electrolytic solution resistivity, 191 solubility, definition, 66 solubility product, 118, 268 soluble, definition, 66 solvent, definition, 66 SPE cartridge, 89 SPE column conditioning, 90 specific ion interaction theory, 207 spectator ion, 71, 114 spectrometer, 157 spectrometry, 142 spectrophotometer, 157 spectroscopy, definition, 142 spectrum, 150 speed of light, c = 2.998×108 m/s, 144 spike, 56 spiked field blank, 56 spontaneous reaction, 308–312 stability constant, 115, 251 stacking gel, 400 stains, for TLC, plates, 370 standard addition, 41 standard hydrogen electrode (SHE), 300, 302, 315 standard operating procedure (SOP), 11 standard deviation, 17 standard error, 22 standard deviation of the mean (SDOM), see standard error standard reduction potential, E o , 300, 311 standard reduction potentials (table), 301 standard reference materials, NIST, 60 standards, 43 stationary phase, 82 stationary phases, SPE types (table), 83 stationary phases, HPLC types (table), 382 steady state system, 112 stepwise complexation, 263–267 stepwise formation constant, Kn , 116 Stokes shift, 169 stripping, 72 strong acid, 181 strong acids and strong bases (table), 182 strong base, 181 strong electrolyte, 70, 180 413 strong ion exchanger, 86 systematic error, 15 systematic sampling, 54 tailing, chromatographic peak, 378 temperature programming, in GC, 388 test portion, defined, 5 thermodynamic equilibrium constant, K, 113, 199 thermodynamics, 105, 309 thin-layer chromatography (TLC), 368–372 time-of-flight mass spectrometer (TOF-MS), 395 titrant, 124 titration, 104, 124–132 titration, concentration dependence of equivalence point, 232 titration curve, 132 titration error, 125, 133 titrimetric factor, 125 total retention time, tR , 372 transmittance, T , 160 ultraviolet (UV) spectral region, 146, 164 unified atomic mass unit, 6 unit conversion, 8 United States Department of Agriculture (USDA), 4, 261 UV/Vis absorption, 141 UV/Vis absorption spectrum, 156 van Deemter equation, 377 variance, 21 vibrational energy levels, 153 visible light, 147 voltammetry, 328–335 volumetric flask, 46 volumetric glassware, 46 washing, loss of precipitate during, 123 water, self-dissociation, 190, 193 water hardness, 129 wavelength, of EM radiation, 142 weak acid equilibrium calculation, 212–215 weak acids and weak bases, 186 weak acid and weak base equilibrium, 187–189 weak acid titration, 230 weak base equilibrium calculation, 216 weak ion exchanger, 86 well plate, 88, 96 wet-chemical methods, 103 X-ray spectral region, 146 Zeeman method, see background correction