Manual of qualitative chemical analysis

Front matter

Green «o zo so

Tl

Sr

SECTION I Operations, § 1

2. Crystallization, §3 6

3. Precipitation, §4 7

4. Filtration, §5 8

5. Decantation, §6 9

6. Evaporation, §7 11

7. Distillation, § 8 12

8. Ignition, §9 13

9. Sublimation, § 10 13

10. Fusion and Fluxing, § 11 ... . 14

11. Deflagration, § 12 15

12. The use .of the blov?pipe, § 13 16

13. Spirit and gas lamps, § 14. . . . 20

14. Colored flames and spectral

analysis, § 15 25

Appendix to the First Section

Apparatus and utensils, § 16 29

Section II

A. Reagents in the humid way.

PAOI

I. Simple Solvents.

3. Ether, 1

4. Chloroform, and [-§20... 36

5. Sulphide of Carbon, )

II. Acids and halogens, § 21. . . . 36

c Oxygen acids.

1. Sulphuric acid, § 22 37

2. Nitric acid, § 23 38

3. Acetic acid, § 24 39

4. Tartaric acid, § 25 40

6. Hydrogen acids and halogens.

2. Chlorine, § 27 42

3. Nitrohydrochloric acid, § 28. . 43

4. Hydrofluosilicic acid, § 29 .. . . 43

c. Sulphur acids.

III. Bases and metals, § 31 50

a. Oxygen bases.

a. Alkalies.

1. Potassa and soda, § 32 51 ft. Alkaline eartlis.

1. Baryta, § 34 5C vi

CONTENTS.

y. Heavy metals and their oxides.

4. Hydrate of teroxide of bis-

5. Binoxide of lead, § 40 58

h. Sulphur bases.

1. Sulphide of ammonium, § 41. 58

2. Sulphide of sodium, § 42 60

IV. Salts.

a. Salts of the alkalies.

1. Sulphate of potassa, § 43 61

2. Phosphate of soda, § 44 61

3. Oxalate of ammonia, § 45 ... . 61 4 Acetate of soda, § 46 62

5. Carbonate of soda, § 47 62

6. Carbonate of ammonia, § 48.. 63

7. Bisulphite of soda, § 49 64

8. Nitrite of potassa, § 50 64

9. Bichromate of potassa, § 51 . . 65

10. Antimonate of potassa, § 52. . 65

11. Molybdate of ammonia, § 53. 66

12. Chloride of ammonium, § 54.. 66

13. Cyanide of potassium, § 55. .. 67

14. Ferrocyanide of potassium,

§56 68

1 5. Ferricyanide of potassium, § 57 69 16 Sulphocyanide of potassium,

§ 58 69

Z>. Salts of the alkaline earths.

1. Chloride of barium, § 59 70

2. Nitrate of baryta, § 60 71

3. Carbonate of baryta, § 61. . . . 71

4. Sulphate of lime, § 62 72

5. Chloride of calcium, § 63 72

6. Sulphate of magnesia, § 64. . . 72

c. Salts of the oxides of the heavy metab.

1. Sulphate of protoxide of iron,

§65 73

2. Sesquichloride of iron, § 66. . 73

3. Nitrate of silver, § 67 74

4. Acetate of lead, § 68 75

6. Nitrate of suboxide of mercury,

§69 75

6. Chloride of mercury, § 70 76

7. Sulphate of copper, ?) 71 76

8. Frotochloride of tm, § 72 77

9. Bichloride of platinum, § 73. . 77 10. Sodio-protochloride of palladium, § 74 78

PAOI

11. Terchloride ofgold, § 75 78

V. Coloring matters and indifferent VEGETABLE SUBSTAN- CES, § 76.

1. Test papers.

a. Blue litmus paper 79

0. Reddened litmus paper. ... 79

y. Georgina paper 79

6. Turmeric paper 80

2. Indigo solution, § 77 80

B. Reagents in the dry way.

I. Fluxes and decomposing agents.

1. Mixture of carbonate of soda

and carbonate of potassa,

§78 81

2. Hydrate of baryta. § 79 82

3. Fluoride of calcium, § 80 . . . 83

4. Carbonate of lime, § 81 83

5. Chloride of ammonium, § 82.. 83

6. Nitrate of soda, § 83 84

II. Blowpipe reagents.

1. Carbonate of soda, § 84 84

2. Cyanide of potassium, § 85. . . 85

3. Biborate of soda, § 86 86

4. Phosphate of soda and ammo-

5. Nitrate of protoxide of cobalt,

§88 88

SECTION III. Reactions, or the dfportment of

BODIES WITH reagents, § 89 . . 89

A. Deportment and properties op

THE metallic oxides AND THEIR

RADICALS, § 90 90

FIRST GUOUP, § 91.

a. Potassa, § 92 91 c. Ammonia, § 94 95

Rpcapitula.tion and remarks, § 95 . . 96

Caesia, rubidia, lithia, § 96 ... . 98

SECOXD GROUP, §97. 100

a. Baryta, § 98 lOO

h. Strontia, § 99 ]02 d. Magnesia, § 101 105

RecapttuMion and remarks, ^ 102. 107 a. Alumina, § 104 HO

CONTENTS. Vll

Z>. Sesquioxide of chromium, §

105 112

Kecapitnlation and remarks, § 106. 113 Glucina, thoria, zirconia, yttria, terbia, erbia, oxides of cerium, lanthanum, and didymium, titanic, tantalic, and hypocolumbic acids, § 107 114-120

FOURTH GROUP, § 108 120

a. Oxide of zinc, § 109 120

6. Protoxide of manganese, § 110 122

c. Protoxide of nicl^el, § HI. . 124

d. Protoxide of cobalt, § 112. . . 126

e. Protoxide of iron, § 11.3 128

/. Sesquioxide of iron, § 114. . 130

Eecap it Illation and remarks, § 115. 131 Oxides of uranium, vanadium, and thallium, § 116 134-136

FIFTH GROUP, § 117 136

First division of the fifth ijrowp : oxides which are precipiiaied by hydrochloric acid.

a. Oxide of silver, § 118 137

b. Suboxide of mercury, § 119. 138 c Oxide of lead, § 120 139

Second division of the fifth group : oxides vjhich are not precipitated by hydrochloric acid.

a. Oxide of mercury, § 122.... 142

b. Oxide of copper, § 123 143

c. Teroxide of bismutii, § 124.. 146

d. Oxide of cadmium, § 125 . . . 147 Recapitulation and remarJcs, § 1 26. 148

Protoxide of palladium, oxide of rhodium, oxides of osmium and ruthenium, § 127... 149-151

SIXTH GUOUP, § 128 152

First division :

a. Teroxide of gold, § 129 152

b Binoxide of platinum, § 130. 154 Recapitulation and remarks, § 131 . 155

Second division :

a. Protoxide of tin, § 132 155

b. Binoxide of tin, § 133 157

c. Teroxide of antimony, § 134. 159

e. Arsenic acid, § 136 173

Eecopitulation and remarks, § 137. 175

Oxide of iridium, oxides of molybdenum, tungsten, tellurium, and selenium, § 138 . 179-182

PA OB

B. Deportment of the acids and

THEIR RADICALS WITH REAGENTS.

§ 139 182

I. Inorganic acids.

First division :

Chromic acid, § 141 184

Sulphurous, hyposulphurous, and iodic acid8,"§ 142 186-188

Second division :

Sulphuric acid, § 143 188

Hydrofluosilicic acid, § 144 189

Third division :

a. Phosphoric acid, § 145 190

Bi- and tnbasic phosphoric b. Boracic acid, § 147 195

c. Oxalic acid, § 148 196

d. Hydrofluoric acid, § 149 198

Phosphorous acid, § 151 202

Fourth division :

a. Carbonic acid, § 152 203

b. Silicic acid, § 153 204

SECOND GROUP 207

a. Hydrochloric acid. § 155. . . . 207

b. Hydrobromic acid, § 156.. . . 209

c. Hydriodic acid, § 157 211

d. Hydrocyanic acid, § 158. . . . 214 Hydroferrocyanic and hy-

droferricyanic acids 216

e. Hydrosulpiiuric acid, § 159.. 217 Recapitulation and remarks, § 160. 218

Nitrous, hypochlorous, chlorous, and hypochlorous acids, § 161 220-221

THIRD GROUP.

a. Nitric acid, § 162 222

b. Chloric acid, § 163 223

Perchloric acid, § 165 225

II. Organic acids.

a. Oxalic acid 226

b. Tartaric acid, § 166 226 viii

CONTENTS.

PA OB

c. Citric acid, § 167 228

d. Malic acid, § 168 229

Racemic or paratartaric acid, § 170 231

SECOND GROUP 232

a. Succinic acid, § 171 232

b. Benzoic acid, § 172 233

PAOB a. Acetic acid, § 174 234

6. Formic acid, § 175 236

Recapitulation and remarks, § 176. 237 Lactic, propionic, and butyric

Part II. Systematic Course Of Qualitative Chemical Aitaltsis

PAGE

Preliminary remarks on the course of qualitative analysis in general, and the plan of this part of the present work in particular 243

Section 1. Practical Process

I. Preliminary examination, § 178 246

A. The body under examination

is solid 246

I. It is neither a pure metal nor

II. The substance is a metal or

B. The substance under examina-

tion is a fluid, § 181 254

II. Solution of bodies, or classification of substances according to their deportment with certain solvents, § 182 255 A. The substance under examination is neither a metal nor an

B The substance under examination is a metal or an alloy, § 184 258

III. Actual analysis. .... 259

SIMPLE COMPOUNDS.

A. Substances soluble in water.

Detection of the base, § 185.. 259 Detection of the acid. 1. Detection of inorganic acids,

§ 186 266

PAGB

II. Detection of organic acids,

§ 187 269

B. Substances insoluble or sparingly

soluble in water, but soluble in hydrochloric acid, nitric acid, or nitrohydrochloric acid.

Detection of the base, § 188. 271 Detection of the acid.

I. Detection of inorganic acids,

§ 189 273

II. Detection of organic acids,

§ 190 275

C. Substances insoluble or sparingly

soluble in water, hydrochloric acid, nitric acid, or nitrohydrochloric acid.

Detection of the base and the acid, § 191 275

COMPLEX COMPOUNDS.

A. Substances soluble in water, and also such as are insoluble in water, but dissolve in hydrochloric acid, nitric acid, or nitrohydrochloric acid.

Detection of the bases, § 192 I. Substances soluble in water.

Detection of silver and suboxide of mercury 273

II. Substances soluble in hydro-

chloric or nitrohydrochloric acid 281

III. Substances soluble in nitric acid.

Detection of silver and suboxide of mercury 281

Treatment with hydrosulphuric acid, precipitation of the me-

CONTENTS. ix tallic oxides of Group V., 2d division, aud of Group VI., § 193 282

Treatment of the precipitate produced by Iiydrosulpiiuric acid witii sulpliide of ammonium ; separation of the 2d division of Group V. from Group VI., § 194 283

Detection of the metals of Group VI. Arsenic, antimony, tin, gold, platinum, § 195 285

Detection of the metallic oxides of Group V , 2d division.

Oxide of lead, teroxide of bismuth, oxide of copper, oxide of cadmium, oxide of mercury, § 196 288

Precipitation with sulphide of ammonium, detection and separation of the oxides of Groups III. and IV. Alumina, sesquioxide of chromium, oxide of zinc, protoxide of manganese, protoxide of nicicel, protoxide of cobalt, proto- and sesquioxide of iron, and also of those salts of the alkaline earths which are precipitated by ammonia from their solution in hydrochloric acid : phosphates, borates, oxalates, silicates, and fluorides, § 197 290

Separation and detection of the oxides of Group II., which are precipitated by carbonate of ammonia iu presence of chloride of ammonium, viz., baryta, strontia, hme, § 198.. 299

Examination for magnesia, § 199 300

Examination for potassa and soda, § 200 301

Examination for ammonia, § 201 302

DETECTION OF TQE ACIDS.

1. Substances soluble in water.

I. In the absence of organic acids, § 202 302

II. In presence of organic acids,

§ 203 305

2. Substances insoluble in water, but

soluble in hydrochloric acid, nitric acid, or nilrohydrochloric acid.

I. In the absence of organic acids, § 204 308

II. In presence of organic acids,

§ 205 309

B. Substances insoluble, or sparingly soluble both in water and in hydrochloric acid, nitric acid, or nitrohydrochhric acid.

Detection of the bases, acids, and non-metallic elements, § 206 309

Section II

practical course in particular Cases.

I. Special method of efiecting the

analysis of cyanides, ferrocj'anides, &c., insoluble in water, § 207 314

II. Analysis of silicates, § 208... 316

A. Silicates decomposable by

B. Silicates which are not de-

composed by acids, § 210.. 319

0. Silicates which are partially

decomposed by acids, § 211 322

III. Analysis of natural waters,

§212.

A. Analysis of the fresh waters-

(spring- water, well- water, brook water, river-water, &C.), § 213 323

B. Analysis of mineral waters,

§214 327

1. Examination of the water.

a. Operations at the spring, §•215 328

b. Operations in the laboratory, § 216 329

2. Examination of the sinter

deposits, § 217 334

IV. Analysis of soils, § 218 337

1. Preparation and examination

of the aqueous extract, § 2 1 9 338

2. Preparation and examination

of the acid extract, § 220.. 340

3. Examination of the inorganic

constituents insoluble in water and acids, § 221. . . 341

4. Examination of the organic

constituents of the soil, § 222 '. 341

V. Detection of inorganic sub-

stances in presence of organic substances, § 223 . . . 343

1. General rules for the detec-

tion of inorganic substances in presence of organic matters, which by their color, consistence, &c., impide the application of the reagents, or obscure the reactions produced, § 224 343 in articles of food, in dead bodies, &c., in chemico-legal cases, § 225 34&

X

CONTENTS.

PAQB

L Method for the detection of arsenic and all other metallic poisons.

A. Method for the detection of

undissolved arsenious acid,

§ 226 346

B. Method of detecting arsenic

and other metallic compounds which are soluble in water, by means of dialysis, § 227 347

C. Method for the detection of

arsenic in whatever form of combination it may exist, which allows also a qtiantitative determination of that poison, and permits at the same time the detection of other metallic poisons which may be present, § 22 ■< 349

II. Method for the detection of

III. Method for the detection of

phosphorus, § 230 360

3. Examination of the inorganic constituents of plants, animals, or parts of the same, of manures, &c. (analysis of ashes), § 231 366

A. Preparation of the ash . . . 366

B. Examination of the ash . . 366 a. Examination of the part

soluble in water 367

h. Examination of the part soluble in hydrochloric

acid 368

c. Examination of the residue insoluble iu hydrochloric acid 369

Section III. Explanatory Notes And Additions To The Systematic Course Of Analysis

I. Additional remarks to the preliminary examination, To

§§ 178-181 370

II Additional remarks to the solution of substances, &c.,

III. Additional remarks to the actual analysis, To §§ 185-

207 372

A. General review and explanation of the analytical course 372 a. Detection of the bases. ... 372 b Detection of the acids. ... 376 B. Special remarks and additions to the systematic course of

analysis 379

PA on

^''195 383

§ 196 383

8 198 386

§ 206 386

§ 207 387

Appendix

I. Deportment of the most important medicinal alkaloids with reagents, and systematic method of effecting the detection of these substances, § 232 389

I. Volatile alkaloids.

II. Non-volatile alkaloids.

FIRST GROUP.

SECOND GROUP.

a. Nareotina, § 236 395 c. Cinchonia, § 238 398

THIRD GROUP.

a. Strychnia, § 240 400 c. Veratria, § 242 404

Salicine, § 244 406

Systematic course for the detection of the non-volatile alkaloids treated of in the preceding paragraphs, and of salicine. 406

I. Detection of the alkaloids, and

of salicine, in solutious supposed to contain only one of these substances, § 245 406

II. Detection of the alkaloids, and

of salicine, iu solutions supposed to contain several or all of these substances, § 246 . . . 409

III. Detection of the alkaloids, in presence of coloring and extractive vegetable or animal matter, § 247 411

1. Stas's method of detecting

poisonous alkaloids 411

2. Otto's modification of Stas's

method 4]j

3. Method of L. von Uslar and

J. Erdinann 414

4. Detection of strychnia by

means of chloroform 416

CONTENTS. xi

PAQB

5. Graham and Hoffmann's

method of detecting strychnia in beer 417

6. Dialysis of the alkaloids 417

II. General plan of the order and

succession in which substances should be analyzed for practice, § 248 418

III. Arrangement of the results of the analyses performed for practice, § 249 420

IV. Table of the more frequently occurring forms and combinations of the substances treated of in the present work ; ar-

PlOB

ranged with special regard to the class to which they respectively belong, according to their solubility in water, in hydrochloric acid, nitric acid, or nitrohydrochloric acid, §

250 422

Table 424

Notes 424

V. Table of weights and measures 427

Index 429

P^KT I.

INTRODUCTORY.

PKELIMINARY EEMARKS.

DEFINITION, GENERAL PRINCIPLES, OBJECTS, UTILITY, AND IMPORT- ANCE OF QUALVIATIVE CHEMICAL ANALYSIS, THE CONDITIONS AN'^ REQUIREMENTS FOR A SUCCESSFUL STUDY OF THAT SCIENCE.

Chemistry is the science which treats of the various materials entering into the structure of the earth, their composition and decomposition, their mutual relations and deportment in general. A special branch of this science is designated Analytical Chemistry^ inasmuch as it pursues a distinct and definite object — viz., the analysis of compound bodies, and the examination of their component elements. Analytical chemistry, again, is subdivided into two branches — viz., qualitative analysis, which simply studies the nature and properties of the component parts of bodies ; and quantitative analysis, which ascertains the quantity of every individual element present. The office of qualitative analysis, therefore, is to exhibit the constituent parts of a substance of unknown composition in forms of known composition, from which the constitution of the body examined, and the presence of its several component elements may be positively inferred. The efficiency of its method depends upon two conditions— viz., it must attain the object in view with unerring certainty, and in the most expeditious manner. The object of quantitative analysis, on the other hand, is to exhibit the elements revealed by the qualitative investigation in forms which will permit the most accurate estimate of their Aveight, or to effect by other means the determination of their quantity.

These different ends are, of course, attained respectively by very different ways and means. The study of qualitative analysis must, therefore, be pursued separately from that of quantitative analysis, and must naturally precede it.

Having thus generally defined the meaning and scope of qualita-

PRELIMINARY REMARKS.

tive analysis, we have now still to consider, in the first place, the preliminary information required to qualify students for a successful cultivation of this bi-anch of science, the rank which it holds in the domain of chemistry, the bodies that fall within the sphere of Its operations, and its utility and importance ; and, in the second place, the principal parts into which its study is divided.

It is, above all, absolutely indispensable for a successful pursuit of qualitative investigations, that the student should possess some knowledge of the chemical elements, and of their most important combinations, as well as of the principles of chemistry in general ; and that he should combine with this knowledge some readiness in the apprehension of chemical processes. The practical part of this science demands, moreover, strict order, great neatness, and a certain skill in manipulation. If the student joins to these qualifications the habit of invariably ascribing the failures with which he may happen to meet, to some error or defect in his operations, or, in other words, to the absence of some condition or other indisrpensable to the success of the experiment — and a firm reliance on the immutability of the laws of nature cannot fail to create this habit — ^he possesses every requisite to render his study of analytical chemistry successful.

Now, although chemical analysis is based on general chemistry, and cannot be cultivated without some previous knowledge of the latter, yet, on the other hand, we have to look upon it as one of the main pillars upon which the entire structure of the science rests ; since it is of almost equal importance for all branches of theoretical as well as of practical chemistry ; and I need not expatiate here on the advantages which the physician, the pharmaceutist, the mineralogist, the rational farmer, the manufacturer, the artisan, and many others derive from it.

This consideration would surely in itself be sufficient reason to recommend a thorough and diligent study of this branch of science, even if its cultivation lacked those attractions which yet it unquestionably possesses for every one who devotes himself zealously and ardently to it. The human mind is constantly striving for the attainment of truth ; it delights in the solution of problems ; and where do we meet with a greater variety of them, more or less difficult of solution, than in the province of chemistry ? but as a problem to which, after long pondering, we fail to discover the key, wearies and discourages the mind : so, in like manner, do chemical investigations, if the object in view is not attained — if the results do not bear the stamp of truth, of unerring certainty. A halfknowledge is therefore, as indeed in every department of science, bat more especially here, to be considered w^orse than no knowledge at all; and a mere superficial cultivation of chemical analysis is consequently to be particularly guarded against.

§ 1, 2.]

SOLUTION.

A qualitative investigation may be made with a twofold view — viz., either, 1st, to prove that a certain body is or is not contained in a substance, e.g. lead in wine ; or, 2nd, to ascertain all the constituents of a chemical compound or mixture. Any substance whatever may of course become the object of a chemical analysis.

In this work, those bodies which, are most important in practical chemistry, from their wide distribution and their uses in medicine and the arts, are treated of in full detail ; while, to facilitate the beginner's progress, the rarer elements are noticed more briefly, and in such a manner that they may be separately studied.

The study of qualitative analysis is most properly divided into four principal parts — viz.,

1. Chemical operations.

2. Reagents and their uses.

3. Deportment of the various bodies with reagents.

4. Systematic course of qualitative analysis.

It will now be readily understood that the pursuit of chemical analysis requires practical skill and ability, as well as theoretical knowledge ; and that, consequently, a mere speculative study of that science can be as little expected to lead to success as purely empirical experiments. To attain the desired end, theory and practice must be combined.