CHEMISTRY OF SPECIFIC, SELECTIVE AND SENSITIVE REACTIONS BY

FRITZ FEIGL, Eng., Dr.Sc. Laboratory of Mineral Products, Ministry of Agriculture, Rio de Janeiro, Brazil Member of the Brazilian Academy of Sciences Formerly Professor of Analytical and Inorganic Chemistry at the University of Vienna TRANSLATED BY RALPH E. OESPER Professor of Chemistry, University of Cincinnati, Ohio

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d. FachbereTfRTT^er Technischen Hochschule Darmstadt

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r 1949 ACADEMIC PRESS INC., PUBLISHERS NEW YORK, N. Y.

CONTENTS Page I. GENERAL COMMENTS ON THE ANALYTICAL USEFULNESS OF CHEMICAL REACTIONS

1

II. THE CHARACTERIZATION OF CHEMICAL TESTS BY SENSITIVITY, SELECTIVITY, SPECIFICITY, AND LIMITING PROPORTION. THE ROLE OF REACTION CONDITIONS

7

III.

TYPES OF COMPLEX AND COORDINATION COMPOUNDS WHICH PLAY A ROLE AS REACTANTS AND PRODUCTS OF REACTION IN ANALYTICAL PROCESSES

23

Ammonia and Its Derivatives as Constituents of Complex Compounds Water and Its Derivatives as Constituents of Complex Compounds Aoido Compounds Coordination of Elements Polyaeids ' Inner Complex Compounds Organic Molecular Compounds Complex Compounds of Undefined Stoichiometric Composition

28 30 34 36 39 41 51 60

IV. THE MASKING AND DEMASKING OF REACTIONS

Masking Demasking

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V. ENHANCEMENT OF REACTIVITY OF COMPOUNDS AND REACTION SYSTEMS

Raising the Reactivity by Complex Formation Catalyzed Reactions and Induced Reactions Induced Precipitation and Induced Solution VI. THE EFFECT OF CERTAIN ATOMIC GROUPINGS ON THE SPECIFIC AND SELECTIVE ACTIVITY OF COMPOUNDS IN INORGANIC ANALYSIS .

Acidic OH Groups Bound to Carbon Atoms The Specific and Selective Action of Rhodizonic Acid The Selective Activity of Pyrogallol and o-Situated Phenolic OH Groups The Germanium—Specific Action of 9-Pheriyl-2,3,7-Trihydroxy-6Fluorone Analytical Behavior of 8-Hydroxyquinoline (Oxine) and Its Derivatives The Selective Action of 4-Hydroxybenzothiazole The Behavior of o-Hydroxyaldoximes The Behavior of Hydroxyanthraquinones The Selective Action of Dicyandiamidine (Guanyl Urea) The Thallium-Specific Group —CO—CH2—CO— (in the Presence of Carbon Disulfide)

67 104 109

109 122 147

167

173 174 177 179 181 192 196 201 205 208

Xii

CONTENTS

The Behavior of the Group —CO—C (: NOH)— in Aliphatic Chains The Zirconium-Specific Action of Mandelic Acid Behavior of a- and o-Aminocarboxylic Acids a-Amino-ra-Caproic Acid Anthranilic Acid (o-Aminobenzoic Acid) Quinaldic Acid (Quinoline-2-Carboxylic Acid) Quinoline-8-Carboxylic Acid Other o-Aminocarboxylic Acids Acidic SH Groups, Bound to Carbon Atoms Selective Actions of 1,2-Mercaptobenzenes Selective and Specific Actions of Thioglycolic Acid £-Aminonaphthalide (Thionalid) The Cobalt and Nickel Salts of Thioglycolic Acid Anilide Selective Precipitations with Mercaptobenzothiazol The Analytical Behavior of Diphenylthiocarbazone (Dithizone) The Selective Activity of Rubeanic Acid Acidic NOH Groups Selective Actions of Nitrosonaphthols Selective Actions of Nitrosoarylhydroxylamines (Cupferron and Neocupferron) The Copper-Specific Group

G—Q

209 213 215 217 219 221 224 225 225 226 230 233 236 241 248 251 252 262 266

OH NOH —C—C— 270 || || HON NOH Selective Actions of Organic Nitro Compounds toward Alkali Metals 280 The Palladium-Specific Action of 6-Nitroquinoline 284 Acidic Inorganic Groups in Organic Compounds 288 The Selective Activity of the SO2H and SeO2H Groups 289 OH The Nickel and Palladium Precipitating Group

The Zirconium-Binding Group —AS=^O

291

OH The Selective Action of Bis-p-Chlorophenylphosphoric Acid The Specific Action of the Acidic —O—OH Group Selective Actions Exercised by Organic Derivatives of Ammonia Organic Bases that Form Water-Insoluble Nitrates Selective Behavior of p-Fuchsine Selective Precipitations through Coordinative Binding of Benzidine The Selective Action of a,a'-Dipyridyl and c*,a-Phenanthroline and Their Ferrous Compounds Selective Activity of the p—ON—C6H4—N

Group

294 297 302 305 310 312 319 326

The Silver-Binding NH—Group 328 Redox Reactions with Benzidine and Benzidine Homologues 332 Specific and Selective Effects Based on Condensation Reactions between Organic and Inorganic Compounds 337 The Methylene Blue Reaction of Hydrogen Sulfide 338

CONTENTS

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Condensation of Formaldehyde with Ammonia or Alkali Bisulfite 339 Condensation of Aromatic Aldehydes with Hydrazine 342 .Condensation Reactions of Diacetylmonoxime and Salicylaldehyde with Hydroxylamine 343 Selective Condensation Reactions of Salicylaldehyde by Formation of Inner Complex Salts 345 Condensation Reactions of 2,4-Diamino-6-Hydroxypyrimidine and Chrysean with Nitrous Acid 350 Condensation of 1,8-Diaminonaphthalene with Nitrous Acid or Selenious Acid 351 Oxidative Condensation of 8-Hydroxyquinoline with Hydroxylamine 353 Condensation Reactions of Organic Hydroxy Compounds with Boric Acid 354 Condensation Reactions of Pyrocatechol with Hydroxides of Metals and Nonmetals 361 The Formation of Thioketone with Free Sulfur 366 VII. EFFECT OF CERTAIN ATOMIC GROUPINGS ON THE SPECIFIC AND SELECTIVE ACTIVITY OF COMPOUNDS IN ORGANIC ANALYSIS 369

Preliminary Tests Based on Group Actions 371 Direct Examination for Certain Atomic Groups by Reactions with 373 Inorganic and Organic Reagents 1,2-anti-Dioximes R—C—C—R 374 HON NOH Acyloinoximes R—CH—C—R

375

1 IINOH OH Aromatic o-Hydroxyaldoximes /

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\—C=NOH

1,2-Isonitrosoketones R—CO—(:N0H)—R a,a'-Dipyridyls \

/ ~ \

375

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/

Sulfinic Acids R—SO2H Arsonic Acids R—AsO(OH)2 Mercaptans and Thioketones R—SH and \ c = = S Phenols and Polyphenols Nitroso Compounds, Primary Aromatic Amines, and Aliphatic or Aromatic Hydrazines Organic Compounds with Reactive CH 2 and NH 2 Groups Conversion of Organic Compounds into Products with Characteristic Atomic Groups Conversion of Nitro to Nitroso Compounds Conversion of 1,2-Diketones into anti-Dioximes Conversion of Ketomethylene Compounds into anti-Dioximes Conversion of Aromatic Sulfonic Acids into Phenolates Conversion of Primary and Secondary Alcohols into Alkali Xanthates Conversion of Carboxylic Acids (and Their Derivatives) into Hy-

375 375 376 376 376 376 377 377 378 379 379 379 380 380

XIV

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CONTENTS

droxamic Acids Conversion of Amines into Rhodanine Dyes

380 381

VIII. REGULARITIES AND ANOMALIES IN THE SOLUTION OF MATERIALS IN INDIFFERENT SOLVENTS 383 IX. THE INFLUENCE OF SIZE—AND WEIGHTING—EFFECTS ON SOLUBILITY AND SALT-FORMING ABILITY 411 X. SURFACE EFFECTS IN ANALYTICAL CHEMISTRY

Color, Solubility, and Suspendibility of Solids as a Function of Particle Size . Colloidal Range, Colloidality, Changes of State in Colloid Systems Mutual Actions of Inorganic Materials in the Colloidal Range . Protective Colloid and Peptization Action, Colloid Masking and Sensitization by Organic Compounds Adsorption as a General Phenomenon of the Accumulation of Materials on Surfaces Modification of the Reactivity of Materials by Adsorption The Adsorption of Dyes Adsorption Compounds • Isolation and Separation of Materials by Adsorption (Adsorption Analysis) .Capillary Analysis and Capillary Effects in Spot Test Analysis Chromatography Foaming Analysis XI. XII.

GENETIC FORMATION OF MATERIALS AND TOPOCHEMICAL REACTIONS

433

433 444 464 477 492 521 530 547 567 569 589 610 613

THE ANALYTICAL USE OF FLUORESCENCE EFFECTS AND PHOTOCHEMICAL REACTIONS

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671

AUTHOR INDEX

695

SUBJECT INDEX

710