ANALYTICAL CHEMISTRY Volume I. Qualitative Analysis. Ninth English Edi

640 Pages·2012·18.5 MB·English

ANALYTICAL CHEMISTRY
BASED ON THE TEXT OF F. P. TBEADWELL
REVISED AND ENLARGED BY WiLLIAM T. HALL
Volume I. Qualitative Analysis. Ninth English Edi
tion. 630 pages. 6X9. 18 figures. Cloth.
Volume II. Qitantitative Analysis. Ninth English
Edition. 806 pages. 6 X 9. 121 figures.
Cloth.
LABORATORY METHODS OF INORGANIC
CHEMISTRY
BY
H. AND W. BlLTZ
TRANSLATED BY
W. T. HALL AND A. A. BLANCHARD
Second Edition. 261 pages. 6 X 9. 27 figures.
Qoth.
TEXTBOOK OF QUANTITATIVE ANALYSIS
BT
WILLIAM T. HALL
Third Edition. 364 pages. 6 X 9. 51 figures.
Qoth.
OUTLINES OP ORGANIC CHEMISTRY
" BY
THE LATE F. J. MOORE
REVISED BY
WILLIAM T. HALL
Fourth Edition. 338 pages. 5H X 8J^. Cloth.
Analytical Chemistiy
BASED ON THE GEBMAN TEXT
OP
F. P. TREADWELL,
Late Professor of Analytical Chemistry at the
Polytechnic Institute of Zurich
TEANSLATED AND BEVISED
BT
WILLIAM T. HALL, S.B.,
Professor Emeritus of Analytical Chemistry at the
Massachusetts Institute of Technology
VOLUME I
QUALITATIVE ANALYSIS
NINTH ENGLISH EDITION
5©^
h^
NEW YORK
JOHN WILEY & SONS, INC.
LONDON: CHAPMAN & HALL, LIMITED
\h^^
IN THE REPRINTING OF THIS BOOK, THE RECOM
MENDATIONS OF THE WAR PRODUCTION. BOARD HAVE
BEEN OBSERVED FOR THE CONSERVATION OF PAPER
AND OTHER IMPORTANT WAR MATERIALS. THE CON
TENT REMAINS COMPLETE AND UNABRIDGED.
Copyright, 1903, 1906, 1913, 1916, 1921, 1930, 1932, 1937
BT
WILLLiM T. HALL
1903 Copyright renewed 1931
Copyrighted Canada, 1932, 1937. International Copyright, 1932, 1937
WILLIAM T. HALL, Proprietor
PRINTED IN THE UNITED STATES OP AMERICA 9/43
PREFACE TO THE NINTH EDITION
Many changes have been made in this revision. Part I, which
deals with the principles upon which analytical chemistry is based,
has been largely rewritten to make it correspond more closely to modem
chemical theory. Part II, which treats of the reactions of cations, has
been rearranged so that the order of treatment may correspond to the
sequence in which the laboratory tests are made. In previous editions,
the reactions of the alkali cations were discussed first and the cations
of the silver group, which constitute Group I of the analytical pro
cedure, were considered last. Since this has caused some confusion
in the minds of beginners, it is believed that the new arrangement will
be found more convenient.
Considerable new material has been introduced throughout the book.
The description of properties of the elements has been amplified and
many new tests describe with special attention to drop reactions.
A procedure for semi-microchemical analysis has been introduced.
Since it was th* earnest desire of the publishers not to increase the price
of the book, tbe liitroduction of the new material made it necessary to
discard considerably portions of the former text. Thus, for the analysis
of each ^ up o^^afQons, a single scheme of analysis is now recom
mended which will, it is hoped, make it easier for the beginner. The
excellent scheme of Noyes and Bray for the analysis of the rare
and common metals has been omitted with regret. The procedure is
so long that few students find time to follow it throughout and it has
been found better to refer them to the original text of Noyes and Bray
where greater attention is paid to the necessary details of manipulation
and considerable information is given about tests that were made in de
veloping the scheme. In some cases, as in the analysis of the platinum
metals and in the tests for the earths and earth acids, the scheme of Noyes
and Bray no longer corresponds to the best modem practice.
The section on spectroscopy has also been shortened with regret.
The technique of spectroscopic analysis has developed so remarkably
during recent years that it is now beyond the scope of this book to give
adequate treatment to this important method of analysis. The syllabus
of the course in qualitative analysis given at the Massachusetts In
stitute of Technology has also been omitted, partly to save space and
iv PKEFACB TO THE NINTH EDITION
partly because of changes made from year to year in the actual method
of instruction.
Tke labor of proofreading has been lightened very considerably by
• conscientious work on the part of my associates Professor Stephen G.
Simpson and Mr. Robert M. Sherman, Jr., who have offered many
valuable suggestions.
"WILLIAM T. HALL
MASSACHUSETTS INSTETDTB or TECHNOLoar
April, 1937 '
CONTENTS
PART I
GENERAL PRINCIPLES
PAQB
International Atomic Weights, 1937 Back Caver
Qualitative and Quantitative Analysis 1
Reactions in the Wet Way 1
Law of Mass Action 2
Theory of Electrolytic Dissociation or Ionization 4
Ionization Values of Common Electrolytes 11
Nomenclature of the Ions , 12
Mass-Action Law in Terms qf Activities 12
Activity Coefficients .* 13
Equilibrium between a Solid and Two Liquids 14
Ionization Constants of Weak Acids 16
Ionization Constants of Weak Bases j 17
Ionization of Water. The Hydrogen Exponent 17
Solubility Product 19
Complex Ions 27
Reactions of the Ions 29
Oxidation and Reduction 30
Electromotive Series and Electrode Potentials 39
Normal Potentials 43
Oxidation Potentials 46
The Effect of a Common Ion 49
Hydrolysis 52
Amphoteric Electrolytes 58
Detection of Acids and Bases. Theory of Indicators 61
Colloidal Solutions 64
Evaporation of Acids 68
Filtration and Washing of Precipitates 70
Reactions in the Dry Way 71
Spectrum Analysis 79
Division of the Metals into Groups , 85
Periodic Table 87
Concentrations of Reagents 88
Reactions of the Elements 93
Abbreviations of Chemical Abstracts 93
v
VI CONTENTS
PART II
REACTIONS OF THE METALS (CATIONS)
GROUP I PAQB
SilTOr ? 99
Mercury (Mercuious Salts) ; 104
Lea,d 110
Analysis of Group 1 115
•
GROUP II
Mercury (Mercuric Salts) 118
Lead \: ! '. 123
Bismutk ; 123
Copper - 128
Ca-dmium •; 138
Arsenic 141
Antimony '. / .' 159
Tin / 166
Aaa.l3-sis of Group II.... .• 178
GROUP III
Aluminum 188
Ckromiom ; ; 195
Iron ; 205
Manganese 218
Nickel 230
Cobalt .• 238
Zinc ' 245
Separation of Group HE from Groups IV and V. , 250
Analysis of Group III 251
. GEOU"P IV (ALKALINE EABTHS)
General Characteristic Reactions i. _ 259
Calcium 259
StroatiuEi .,,....,... 264
Barium ., 266
Magnesium ,; -. 270
Separation of the Metals of Group IV.... ' 275
GROUP V (ALKALIES)
Potassium ^.-r. 280
Sodium :...." 284
Ammonium 289
Separa-tion ot the Metals ot Group V 295
CONTENTS vii
PART III
REACTIONS OF THE ACID CONSTITUENTS (ANIONS) ^^^^
Division of the Acids into Groups 297
GROUP I
Hydrochloric Acid .'. 299
Chlorine 305
Hypochlorous Acid 306
Hydrobromic Acid 310
Bromine 313
Hydriodic Acid 315
Iodine 319
Detection of HCl, HBr, and HI in the Presence of One Another 320
Detection of Halogen in the Presence of Cyanide 323
Hydrocyanic Acid 324
Cyanogen 331
Detection of Nitrogen in Organic Substances 331
Detection of HCN in Presence of HCl, HBr, HI,H4Fe(CN)6], H3[Fe(CN)6] and
HCNS. 332
Ferrocyanic Acid 333
Ferricyanic Acid 336
Thiocyanic Acid ,, 339
Detection of HCNS in Presence of Halogen and Cyanide , 341
Detection of HCNS, H4[Fe(CN)6] and HsIFeCCN)^ 343
Cobalticyanic Acid 344
GEOUP II
Nitrous Acid 345
Hydrogen Sulfide (Hydrosulfuric Acid) 350
Sulfur 355
Acetic Acid 357
Cyanic Acid 360
Hypophosphorous Acid 362
Hydrazoic Acid 364
GROUP III
Sulfurous Acid 365
Carbonic Acid. . . .- .' 370
Percarbonic Acid 374
Boric Acid 375
Perboric Acid.' 378
Oxalic Acid 379
Tartaric Acid 382
Citric Acid 387
Phosphorous Acid 390
viil CONTENTS
-e PAQE]
Metaphosptorio Acid » • 393
PjTDphosphoric Acid • 395
Iodic Acid 396
GRODE IV
Phosphoric Acid 399
Hypopliosphoric Acid 405
Phosphorus 406
Arsenious Add 142
Arsenic Acid 147
Chromic Acid ; 199
Thiosulfuric Acid '••• 411 '
Detection of Sulfurous aad Tfi'iosulfuric Acids in the Presence of Hydrogen
Sulfide. " 414
GBO:TP V
Nitrie Add 416
Detection of Nitric Acid in tie Presence of Nitrous Acid 420
Chloric Acid 422
Detection of HydrocUoric, Nitric, and Chlorie^Aeids in the Presence of One
Another 424
Perchloric Acid 426
Persulfuric Acid 428
Monopepsulfuric Acid (Care's Acid) 431
GEOTTP VE
Sulfuric Aeid 432
Hydrofluoric Acid 435
Fluosilicie Aeid : 441
GaoOT VII
Silicic Add 443
Treatmenl; of Jnsoluble Silicates .".... 446
Silicon 450
PART rv
SYSTEMATIC ANALYSIS ,
Analysis of Solid and Non-melallie Substances.,. • •. • 453
Preliniinsiiy Examination ^ 453
Dissol-ving thft Substance 460
Solubility Ta.We , '• 462
Methods of Getting Insoluble Substances into Solution._ .^.-^. 467
Examination for the Mstals (Ca,tions) 471
Examination for the Acid Constituents (Anions), Method of Treadwell 474
Examination for Acid Constitueats, Method of A. A. Noyes 479
CONTENTS IX
PAGE
Analysis of Alloys 489
Analysis of a Liqiiid 489
Analysis of a Gas 490
SUPPLEMENT
Semi-micro Analysis ~ 493
Cation Analysis 494
Anion Analysis • • • 501
PART V
REACTIONS OF SOME OF THE RARER METALS
GBOUP II
Molybdenum 506
SftVKCiVQHi 508.
Tellurium 511
Germanium 514
Gold 615
Platinum 621
Palladium 524
Rhodium 527
Osmium , 630
Ruthenium •.' 532
Iridium , •. • 533
Separation and Detection of the Six Platinum Metals 636
GROUP III
Beryllium or Glucinum 540
Uranium 542
Titanium 546
Zirconium 552
Thorium 556
Hafnium. 559
The Rare Earth Metals 560
Scandium 562
Yttrium 563
Europium 566
Gadolinium • 566
Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, Lutecium 566
Cerium 566
Lanthanum 571
Neodymium and Praseodymium 572
Samarium 573
Thallium 573
Indium 576
Gallium 578
Vanadium 579