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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