Index

A concentration, 31
Absolute acidity, 54 molal, 34
Acetic acid, 37, 50 molar ratio, 31
glacial, 52 Activity coefficient, 31
Acetonitrile, 54 Adsorption, 133
Acid, 26, 36 Adsorption indicator, 219
anionic, 29 Affinity, 4
corresponding, 29 A-iron(III) hydroxide-oxide, 117
medium strong, 36 Alanine hydrochloride, 188
monobasic, pH-logcidiagram, 62 Alcohole, 50
polybasic, pH-logcidiagram, 64 Alkene, 50
polyprotic, polybasic, 38 Alkenol, 50
strong, 36 Alkine, 50
very strong, 36 Alkyl group, 50
very weak, 36 Alkynol, 50
weak, 36 Alumina, 26
Acid-base buffer, 86 Aluminum hydroxide, 120
Acid-base indicator, 209 Aluminum hydroxo complex, 124
Acid-base pair Aluminum(III)-hexaquoion, 37
corresponding, 28, 37 American convention, 140
Acid-base theories, 17 Amino acid, 77, 103
Acid-base titration, 182 Amino group, 77
Acidic solution, 35 Aminopolycarboxcylic acid, 103
Acidic surface group, 82 Ammonia, 29, 37, 103, 193
Acidity, 53 liquid, 52
Acidity constant, 31 Ammonium, 29, 37
apparent, 41, 42 Ammonium cerium(IV) sulfate, 208
apparent, of perchloric acid, 56 Ammonium chloride, 68, 69
macroscopic, 79 Ammonium formiate, 69
microscopic, 78, 79 Ammonium ion, 208
Acid strength, 35 Amperometry, 173
carbonic acid, 41 Analyte, 173
hydrofluoric acid, 40 Antimonate, 208
inorganic acid, 38 Antimony(III) oxide, 117
metal aqua ion, 42 Antimony trisulfide, 131
of a dissolved compound, 53 Approximate equations
of the solvent, 53 validity areas, 70
organic acid, 50 Argentometry, 196
Activity, 9 Arrhenius, Svante August, 20

© Springer Nature Switzerland AG 2019 243

F. Scholz and H. Kahlert, Chemical Equilibria in Analytical Chemistry,
https://doi.org/10.1007/978-3-030-17180-3
244 Index

Arsenic trisulfide, 130 Buffer solution, 86, 186, 203

Arsenite, 166, 208 Buffer system, 90
Association constant, 40 Burette, 170, 171
Asymmetry potential, 232
Autoprotolysis, 52 C
Autoprotolysis constant Cadmium ion, 103
of water, 32, 182 Cadmium sulfide, 130
pressure dependency, 33 Cady, Hamilton Perkins, 24
temperature dependency, 33 Calcium hydroxide, 116, 117
Autosolvolysis, 24 Calcium ion, 216, 225
Auxiliary complexing agent, 193 Calconcarboxylic acid, 216
Auxiliary ligand, 98 Calomel electrode, 237
Azo dye, 211 Carboanhydrase, 42
Carbonate melt, 26
B Carbon dioxide, 41
Barium hydroxide, 116, 117 Carbonic acid, 37, 41, 86
Base, 26 kinetic aspects, 42
corresponding, 29 Carbonyl moiety, 51
polyacidic, 38 Carboxylate anion, 51
Base strength Carboxylic acid, 51
organic base, 50 Carboxylic group, 77
Basicity, 55 Catalymetry, 7, 166
Basicity constant, 32 Catalysis, 13
Basic solution, 35 Central ion, 93
Baucke, Friedrich G. K., 233 Cerimetric determination, 201
Behrend, Anton, 230 Cerimetry, 208
Benzene, 54 Cerium(III) hydroxide, 116, 117
Berthelot, Marcelin Pierre Eugène, 5, 12 Cerium(IV), 166
Berthollet, Claude Louis, 5 Cerium(IV)/cerium(III), 201
b-cadmium hydroxide, 117 Chelate, 189
b-zinc hydroxide, 117 Chelate effect, 11, 102, 103
Berzelius, Jöns Jacob, 18 Chelate forming ligand, 103
Bicarbonate, 29 Chelation therapy, 104
Biilmann, Christian Saxtrop, 155 Chemical potential
Bis(biphenyl)chromium(I)/bis(biphenyl) absolute, of electrons, 162
chromium(0), 162 Chemical potential of solvated protons, 54
Bis(η5-cyclopentadienyl)iron(III)/bis Chloric acid, 38
(η5-cyclopentadienyl)iron(II), 162 Chloride, 198
Bismuth(III) sulfide, 130, 131 Chlorous acid, 38
Boiler scale, 104 Chromate, 48
Böttger, Wilhelm, 230 Chromate ion, 218
Boyle, Robert, 17, 169 Chromium(III) hexaaqua ion, 49
Brønsted, Johannes Nicolaus, 20 Chromium(III) hydroxide, 116
Brønsted-Lowry Theory, 20, 52 Clausius, Rudolf, 10
Bromatometry, 208, 219 Clay mineral, 82
Bromocresol green, 213 Cobalt(II) hydroxide, 116, 117
Bromothymol blue, 213 Cobalt(III) ion, 208
Bromtrifluoride, 24 Colloid, 50, 219
Buffer, 175 Colloidal particle, 208
Buffer acid, 87 Color indicator, 171, 209
Buffer base, 87 Color map, 225
Buffer capacity, 87, 186 Colour indicator, 171
Buffer curve, 87 Common ion addition, 110
Buffer equation, 86, 210 Concentration
Index 245

amount, 31 DMSO, 54
analytical, 57 Döbereiner, Wolfgang, 138
apparent, 41 Dodeka molybdato phosphate, 49
molar, 31 Donor atom, 93
Condensation reaction, 44
Conductometry, 173 E
Copper(I) ion, 208 Electrical conductivity, 239
Copper(II) ion, 208 Electrical work, 202
copper(II) hydroxide, 117 Electric potential, 137
Copper(II) sulfide, 130 Electrode
Co-precipitation, 116, 131 of the first kind, 230
Corrosion, 165 of the second kind, 237
Cremer, Max, 233 Electrode potential
Crotogino, Friedrich, 230 conventional, 139
Cr(III)-EDTA complex, 178 Electromotoric force, 137
Crystallization germs, 108 Electron, 136
Cubic equation, 58 Electron conductor, 137
Cumulative stability constant, 96 Electron gas, 162
Cyanidbestimmung nach Liebig, 208 Electron-withdrawing group, 50
Electroosmotic flow, 82
D Electrophoreses, 81
Davy, Humphry, 20 Electrode
Decamethylferrocene, DMFC, 162 of the second kind, 230
De Donder, Théophile Ernest, 4 Elementary charge, 136
Degeree of protolysis, 75 E-logcidiagrams, 163
Degree of dissociation, 73 Elsey, Howard McKee, 24
Degree of protolysis, 72 End point of a titration, 222
dependence on pH, 73 Enol, 50
dependence on the overall acid Enthalpy, 8
concentration, 74 Entropy, 10, 103
Degree of protonation decrease, 11
of an indicator base, 53 increase, 10
Degree of titration, 181, 191, 196, 205 Entropy production, 4
De Saint-Gilles, Léon Péan, 5 Enzymatic analysis, 7
Descroizilles, François Antoine Henri, 170 Eosin, 219
Dicarboxylic acid, 51 Equilibrium, 3
Dichloromethane, 54 dynamic, 3
Dichromate, 208 heterogeneous, 230
Dichromate/chromium(III), 150 protolysis, 28
Dichromate ion, 48 static, 3
Dichromatometry, 208 Equilibrium constant, 9
Dielectric constant, 55 conditional, 145
Diethylene triamine, 94 of zwitterion formation, 78
Diethylenetriaminepentaacetate, 94 redox equilibrium, 142
Diethylenetriaminepentaacetic acid (DTPA), Equivalence point, 174, 180, 181, 222
180 Eriochrome Black T, 215
Differenciating effect, 56 Erio T, 180, 215, 225
Dihydrogen phosphate, 37 Erlenmeyer flask, 175
Dilution factor, 184 Error
Diphenylamine sulfonic acid, 221 absolute, 198
Disorder, 103 negative systematic, 222
Dissociation, 107 positive systematic, 222
of an indicator acid, 53 random, 181, 221, 142
DLVO theory, 208 relative, 198
246 Index

systematic, 181, 221 Guldberg, Cato Maximilian, 5, 12

Ethanol, 30, 50
Ethylenediamine, 94, 103 H
Ethylenediaminetetraacetate, 94, 99 Haber, Fritz, 233
Ethylenediaminete-traacetic acid (EDTA), 97, Hammett acidity function, 53
148, 190, 224 Hammett, Louis P., 53
Eu-doped LaF3single crystal, 233 Henderson-Hasselbalch equation, 86, 210
Eutrophication, 104 HEPES, 90
Extent of reaction, 8 Heteropoly anion, 49
Extinction, 209 Heteropoly metal ion, 46
Extinction coeffizient Hexacyanoferrate(III)/hexacyanoferrate(II),
molar, of permangantate ion, 209 237
Home, Francis, 169
F Homeostasis, 4, 42
Fällungstitration, 196 Homogeneous precipitation, 133
Ferrocenium/ferrocene, 162 Horstmann, August Friedrich, 5
Ferroin, 221 Hume-Rothery, William, 131
Ferrometry, 208 Hydoquinone/quinone, 237
Flood, Håkon, 26 Hydriodic acid, 37
Fluorescein, 219 Hydrobromic acid, 37
Foreign ion addition, 113 Hydrocarbonate, 86
Formal potential Hydrochloric acid, 29, 37, 66
redox indicator, 220 Hydrocyanic acid, 37
Formiate, 29 Hydrofluoric acid, 37, 40
Formic acid, 37, 50 Hydrogen bond, 55
Franklin, Edward Curtis, 24 Hydrogen carbonate, bicarbonate, 37
Fredenhagen, Karl, 142 Hydrogen fluoride, 54
Fugacity, 7 Hydrogen oxalate, 29, 37
Hydrogen peroxide, 159, 208
G Hydrogen phosphate, 37
Gallium(III) hydroxide, 117 Hydrogen sulfate, 29, 37
Galvanic cell, 137 Hydrogen sulfide, 37, 40, 125
Galvanic concentration cell, 6 Hydrogen sulfide separation procedure, 129
Galvanic half-cell, 137 Hydronium ion, 28, 29
Galvanic plating, 104 Hydrophobic effect, 11
Galvanic potential difference, 137 Hydrosulfide, 37
Galvanic series, 140 Hydroxide, 82
c-aluminum(III) hydroxide-oxide, 117 Hydroxide ion, 29
Gay-Lussac, Joseph Louis, 171 Hydroxo complex, 44, 98
Generalized Brønsted acidity scale, 54 Hydroxyl radical, 159
Geoffroy, Claude Joseph, 169 Hyperbola, 62
Geoffroy, Étienne François, 5 Hypochlorous acid, 38
Gibbs energy, 107
Gibbs free energy, 8 I
molar, 4 Iceberg water, 11
relative changes, 8 Indication
Gibbs-Helmholtz equation, 6, 103 conductometric, 239
Gibbs, Josiah Willard, 5 instrumental, 229
Glass, 82, 83 potentiometric, 230
Glass electrode, 82, 230 spectrophotometric, 237
Glauber, Johann Rudolph, 17 Indicator, 175
Glycine, 78, 81 bichromic, 210
Glycine hydrochloride, 82 monochromic, 210
Goethite, 46, 117 Indicator acid, 209
Index 247

Indicator base, 209 Lambda sensor, 133

Indicator error Lambert-Beer‘s Law, 237
systematic, 222 Latimer diagram, 160
indium(III) hydroxide, 117 Latimer, Wendell Mitchell, 160
Inductive effect, 50 Lattice energy, 107
Inert complex, 98 Laundry detergent powder, 104
Inner energy, 8 Lavoisier, Antoine-Laurent, 17
Inner salt, 77 Law of mass action, 5, 9, 31
Instability constant, 95 Lead(II) oxide, 117
Interface, 139 Lead(II) sulfide, 127, 130, 131
Iodide, 198 Lead(IV) oxide, 117, 208
Iodine, 208 Levelling effect of the solvent, 53
Iodine-starch complex, 219 Levelling effect of water, 36
Iodometric titration, 219 Lewis, Gilbert Newton, 7, 21
Iodometry, 208, 209 Lewis, William, 170
Ion conductor, 137 Ligand, 93
Ion pair, 40, 98 bidentate, 93, 94
Ion pair formation constant, 56 hexadentate, 93, 94
Ion potential, 43 monodentate, 93
Ion product octadentate, 94
of water, 32 pentadentate, 93, 94
Ion sensitive electrode, 132, 230, 233 tetradentate, 93, 94
Iron(II) hexaqua ion, 37 tridentate, 93, 94
Iron(II) hydroxide, 116 Liquid ammonia, 30
Iron(II) ion, 208 Liquid hydrogen sulfide, 30
Iron(III) ion, 208 Liquid junction, 139
Iron(III)/iron(II), 163, 201 Liquid junction potential, 139
Iron(II, III) oxide, 117, 118 Lowry, Thomas Martin, 20
Iron(II) sulfide, 130 Luther, Robert Thomas Dietrich, 159
Iron(III) aqua ion, 46 Luther’s rule, 158
Iron(III) hexaqua ion, 29, 37 Lux, Hermann, 26
Iron(III) hydroxide, 117 Lyate ion, 30, 37, 52
Iron(III) oxide hydrate, 46 Lyonium ion, 30, 37, 52
Irreversibility, 13
Isoelectric focusing, 81 M
Isoelectric point, 81, 83 Manganese(II) hydroxide, 117
Isopoly cation, 48 Manganese(II) ion, 208
Isopropyl alcohol, 50 Manganese(II) sulfide, 130
IUPAC, 174, 222 Manganese(IV) oxide, 208
Manganese sulfide, 131
J Magnesium hydroxide, 116, 117, 216
Jander, Gerhart, 24 Magnesium ion, 225
Manganometry, 208
K Masking, 104
Keto-enol tautomery, 50 Mathematical approximation, 56
Ketone, 50 Maximum effective work, 202
Klarpunkttitration, 208 Membrane electrode, 230
Klemensiewisz, Zygmunt, 233 Mercury-mercury oxide electrode, 237
Mercury(I) ion, 208
L Mercury(II) oxide, 117
Lable complex, 49, 98 Mercury(II) sulfide, 130
Lability, 49 Metal aqua complex, 45, 98
248 Index

kinetic features, 49 P
Metal aqua ion, 42 Paratungstate ion, 48
Metal-EDTA complex, 215 Perchlorate, 208
Metal hydroxo complexes, 11 Perchloric acid, 37, 38
Metall-indicator complex, 214 Permanganate, 48, 156, 167
Metallochromic indicator, 214 Permanganate/Mn2+, 237
Metal oxide, 46 Permanganometry, 209
Metal oxide hydrate, 46, 49 Peters, Rudolf, 7
Metal-protein complex, 103 Pfaundler von Hadermur, Leopold, 12
Metal sulfide, 125 pH
Methanol, 30, 50 approximation equations, 64
Methylene blue, 210, 221 Phenolphthalein, 213
Methyl orange, 211, 220 Phenosafranin, 221
Methyl red, 210, 211, 219 pH-logcidiagram, 182, 223
Mixed crystal, 131, 198 pH-logcidiagram, 59
Mohr, Friedrich, 171 pH meter, 230
Molality, 34 Phosphate Buffered Salt Solution (PBS), 90
Molar ratio, 31 Phosphate ion, 39
Molybdate, 48 Phosphoric acid, 37, 38, 40, 181
Monobasic acids, 57 Photometry, 173
Münz, Ferdinand, 190 Photosynthesis, 46, 118
Murexide, 215 Phthaleins, 211, 212
Pinchcock burette, 171
N Pipette, 171
Nernst equation, 6, 7, 137 PKa
Nernst, Walther, 6, 142 organic compounds, 50
Neutral solution, 35 PKavalue, 36, 37
Newton, Isaac, 5 Plating potential, 104
Nickel(II) hydroxide, 116, 117 Platinum black, 138
Nitrate, 208 Plutonium(IV) hydroxide, 117
Nitric acid, 37 Point of zero charge, 84
Nitrilotriacetate, 94 Polybasic acid, 58
Nitrilotriacetic acid, 191 Polyiodide chain, 219
Nitrite, 208 Polyphosphate, 104
Nitrite ion, 176 Potassium chromate, 218
Non-specific Indikator, 219 Potassium dichromate, 208
n-th ionization potentials, 43 Potassium iodide, 208
Potassium perchlorate-potassium
O permanganate, 132
Occlusion, 133 Potassium permanganate, acidic, 208
Ostwald’s law of dilution, 72, 75 Potential
Ostwald, Wilhelm, 142, 173, 230 absolute chemical of protons, 54
Oxalate, 94, 166 biochemical standard, 160, 161
Oxalic acid, 37 chemical, 4, 5, 9
Oxalic acid/oxalate, 208 formal, 145, 150
Oxidation, 135 formal, including activity coefficients, 146
Oxidation number, 135 formal, including activity coefficients and
Oxidation state, 135 side reactions, 147
Oxide, 82 mixed, 167
Oxide hydrates, 82 real, 145
Oxygen, 46, 159 redox, pH-dependent, 150
Index 249

standard, 139 S
Potentiometry, 173, 182, 201, 230 Salt bridge, 139
Pourbaix diagram, 164 Salting in effect, 113
Pourbaix, Marcel, 164 Salting out effect, 111
Precipitate, 108 Sample, 173
Precipitation equilibrium, 108 metal oxide-hydroxides, 114
Precipitation titration, 171 Saturation activity, 109
Precipitation zone, 116 Saturation concentration, 109, 110, 113
Predominance diagram, 164 metal oxides, 113
Priestley, Joseph, 18 metal hydroxides, 113
Process pH dependency, 113
enforced, 10 Scheele, Carl Wilhelm, 18
spontaneous, 10 Schwarzenbach, Gerold, 190
Propionic acid, 50 Sędziwój, Michał (Michael Sendivogius), 18
Protein, 77 Side reaction
Proton, 136 ligand, 96
Pure phase, 108 metal ion, 98
PVC membrane, 233 Side reaction coefficient, 96, 147
Pyrite, 46 Ethylenediaminete-traacetic acid (EDTA),
Pyrolusite, 156 192
ligand, 97
Q metal ion, 98, 193
Quartz, 83 pH-dependence, 99
Quinhydrone, 151 Silberchlorid, 196
Quinone, 150 Silica gel, 83
Silicate, 83
R Silver chloride, 110
Radical scavenger, 159 Silver chromate, 218
Rate constant, 12, 42 Silver dichromate, 218
Reaction enthalpy, 103 Silver electrode, 233
Reaction rate, 86 Silver halid, 218
Redox equilibrium Silver hydroxide, 218
heterogeneous, 166 Silver-silver chloride electrode, 237
homogeneous, 166 Simultaneous titration, 198
kinetic aspects, 166 Sodium acetate, 69
Redox indicator, 219 Sodium chloride, 69
metal complex, 219 Sodium sulfate, 108
organic, 220 Sodium thiosulfate, 208
Redox potential Solid phase, 107
nonaqueous solvent, 161 Solid solution, 131
absolute, 162 Solubility equilibrium, 107
Redox reaction, 135 Solubility product, 108
Redox titration methods, 206 Solvation, 107
Redox titratios, 201 Solvation enthalpie, 107
Reduction, 135 Solvation entropie, 107
Reference electrode, 155, 235, 237 Solvent
Reference half-cell, 138 amphiprotic, 52
Resonance effect, 50 non-aqueous, 52
Reversibility, 13 protic, 28, 29
Riesenfeld, Hermann, 6 Solvoacid, 24
Rouelle, Guillaume-François, 17 Solvo acid-solvobase theory, 24
Solvobase, 24
250 Index

Sørensen, Søren Peter Lauritz, 33 acid-base titration, 182

Specific indicator, 219 chloride and iodide with silver nitrate, 198
Stability constant complexometric, 191
conditional, 96, 99 hydrochloric acid with sodium hydroxide,
conditional (effective) pH-dependence, 99 184
effective, of the metal-indicator complex, iron(II) ions with permanganate in acidic
192, 215 solution, 207
stepwise, 95 magnesium ions with EDTA, 192
Standard Hydrogen Electrode, 138 moderately strong or weak acid, 186
Standard molality, 34 polybasic acid, 187
Standard solution, 173 precipitation titration, 196
Standard solvation Gibbs energy, 54 redox titration, 201
State of equilibrium, 86 slope, 228
Steric effect, 55 Titration error
Stockholm convention, 139 absolute, 222
Succinic acid, 55 random, 192, 228
Sulfate ion, 38 Titration methods, 175
Sulfonephthaleins, 211, 213 Titrationsgrad, 201
Sulfur dioxide, 54 Titration of halides
Sulfuric acid, 29, 37, 38, 54 according to Mohr, 218
Supersaturated solution, 108 Titration vessel, 175
Surface charge, 84 Titrator, 173
Surface OH group, 83 Titrimetry, 173
Total water hardness, 216
T Transition interval, 228
Tashiro, 210 redox indicator, 220
TBS, 90 width, 228
TBS-T, 90 Transition interval of an indicator, 210
Terpyridine, 94 Trichloroacetic acid, 50
Thiosulfate ion, 208 Triethylene tetramine, 94
Thorium(IV) hydroxide, 117 Trifluorethanol, 50
Tin(II) ion, 208 Trifluoroacetic acid, 50
Tin(II) oxide, 117 TRIS, 90
Tin(IV) oxide, 117 TRIS-glycine, 90
Titanium(III) chloride, 208 Tris(1,10-phenanthroline)iron, 221
Titanium(IV) hydroxide, 117 Tris(2,2´-bipyridyl)ruthenium, 221
Titanometry, 208 Tungstate, 48
Titrand, 173 Two EMBED Equation.DSMT4 model, 83
Titrant, 173 2,3,22,23-dibenzo-1,4,7,10,13-pentathia-
Titrate, 171 tridecanoate, 94
Titration, 169, 173
according to Fajans, 219 U
according to Volhard, 218 Uranium(IV) oxide, 117
back, 176 Uranylium(IV) ion, 208
complexometric, 189 Uranyl/uranium(IV), 237
direct, 175 Urotropin, 133
displacement, 179 Usanovich, Mikhail Il’ich, 26
end point, 181
indirect, 180 V
inverse, 175 Vanadyl ion, 208
permanganometric, 205 Van’t Hoff, Jacobus Henricus, 6, 12
self-indicating, 208 Volhard, Jacob, 218
substitution, 179 Volumetric analysis, 171, 173
Titration curve, 181 Volumetric pipette, 175
Index 251

Von Grotthuss, Theodor, 239 Z

Von Helmholtz, Hermann, 6 Zeolith A, 104
Von Liebig, Justus, 20 Zeolithe, 82
Zinc-ammine complex, 194
W zinc hydroxide, amorphous, 117
Waage, Peter, 5, 12 Zinc ion, 193, 194
Water, 54 Zinc(II) oxide, 117
Water hardness, 224, 225 Zirconium dioxide, 133
Wenzel, Carl Friedrich, 5 Zirconium(IV) oxide, 117
Zundel complex, 35
X Zwitterion, 77
Xylenol orange, 217