A system of instruction in qualitative chemical analysis

Front matter

22102071734

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Preface

a laboratory, omit many things which it is absolutely necessary for him to know from some sources. Indeed this is the only work in the English language adapted for self-instruction. With a previous general acquaintance with chemistry, derived from attendance on a course of lectures, or from the perusal of some introduction to the science of which many excellent ones exist, any person may take up this work, and make himself an expert analyst. And after all the assistance given by a teacher, the chemist, when left to his own resources, still requires a guide to whom he may safely have recourse for facts which have escaped his memory. Both as a systematic course of study, and as a book of reference, Dr. Fresemus* work is unrivalled. It has been duly appreciated, since it is now translated into most European languages, and reprinted in America.

J. LLOYD BULLOCK.

22, Conduit Street , May, 1846.

TO THE

THIRD EDITION.

Every successive addition of this work must necessarily be in advance of all former editions. The science itself is in a state of continual progress. The author, occupying a distinguished position in the foremost rank of chemists, whose original labours perpetually extend its boundaries, of course includes the latest discoveries in his scientific instructions. He supervises every sheet of my translation, incorporating as we proceed, every fact ascertained, and every improvement devised in the processes. The work, therefore, represents the state of the science at the moment we go to press ; and in this respect, as well as in its other transcendent merits, it stands unrivalled.

If anything were needed in the former editions, it was a simple method of arranging the numerous references in the systematic course ; this defect is now supplied. A marginal number is printed to each paragraph, which will greatly facilitate the student in turning from one point to another, and tracing his path through the various processes.

J. LLOYD BULLOCK.

<1

PREFACE

BY PROFESSOR LIEBIG.

Dr. Fresenius conducts the course of elementary instruction, in mineral analysis, in the laboratory of the University of Giessen. During the two last sessions he has followed the method described in his work, “ Elementary Instruction in Qualitative Chemical Analysis.” This method I can confidently recommend from my own personal experience to all who are desirous of obtaining instructions in inorganic analysis, for its simplicity, usefulness, and the facility with which it may be apprehended .

I consider Dr. Fresenius’ work extremely useful as an introduction to Professor H. Rose’s excellent manual, and for adoption in institutions where practical chemistry is taught, but it is especially adapted to the use of Pharmaceutical Chemists.

Further, a number of experiments and discoveries have been recently made in our laboratory, which have enabled Dr. Fresenius to give many new and simplified methods of separating substances, which will render his work equally welcome to those who already are familiar with the larger works on inorganic analysis.

JUSTUS LIEBIG.

Part I. Introductory Part

PAGE

PRELIMINARY REMARKS.

Definition, design, object, and importance of qualitative chemical analysis, and conditions whereon a successful study of the science depends . . .1

SECTION I. Operation, § 1 . .3

2. Crystallization, § 3 . .5

3. Precipitation, § 4 . .6

4. Filtration, § 5 . . .7

5. Decantation, § 6 . .8

6. Evaporation, § 7 • .9

7. Distillation, § 8 . .10

9. Sublimation, § 10 . .11

10. Fusion and Fluxing, § 11 . 12

11. Deflagration, § 12 . .13

12. The use of the blow-pipe, § 13 . 13

Appendix to the First Section

Apparatus and utensils, § 14 . .16

Section II

A. Reagents in the humid way.

I. General Reagents.

a. Reagents principally used as simple solvents.

l>. Reagents principally used as chemical solvents.

c. Reagents which serve principally to separate or otherwise to characterize groups of substances.

II. Special reagents.

a. Reagents which serve principally for

the detection of the bases.

b. Reagents which serve principally for

the detection of the acids.

page

B. Reagents in the dry way.

I. Fluxes.

II. Blowpipe reagents.

A. Reagents in the humid way.

I. General reagents.

a. Reagents principally ttsed as simple solvents.

b. Reagents which are principally used as chemical solvents.

1. Hydrochloric acid, § 19

. 21

2. Nitric acid, § 20

. 22

3. Nitrohydrochloric acid, § 21

. 23

4. Acetic acid, § 22 .

. 23

5. Chloride of ammonium, § 23

. 24

c. Reagents which serve principally to separate or othrvnse characterize groups of substances.

1. Reagent papers, § 24

. 24

a. Blue litmus paper

. 24

/3. Reddened litmus paper

. 25

y. Georgina paper

. 25

8. Turmeric paper

. 25

. 26

. 27

4. Sulphide of ammonium, § 27

. 29

5. Sulphide of sodium, § 28 .

. 30

6. Potassa and soda, § 29

. 31

7. Carbonate of soda, § 30

. 33

8. Ammonia, § 31

. 33

9. Carbonate of ammonia, § 32

. 35

10. Chloride of barium, § 33

. 35

11. Chloride of calcium, § 34 .

. 36

12. Nitrate of silver, § 35

. 37

13. Sesquichloride of iron, § 36

. 37

b

XVJ11

Contents

PAGE

II. Special reagents in the humid way.

a. Reagents which serve principally for the detection or separation cf individual bases. -

Appendix to the first group

SECOND GROUP.

Baryta, strontia, lime, magnesia, § 91.

Special reactions.

cl. Magnesia, § 95 . . .71

THIRD GROUP.

Alumina, sesquioxide of chromium, § 97.

Special reactions.

b. Sesquioxide of chromium, § 99 .75

FOURTH GROUP.

Oxide of zinc, protoxide of manganese, protoxide of nickel, protoxide of cobalt, protoxide of iron, sesquioxide of iron, § 101.

Special reactions.

a Oxide of zinc, § 102 - - 77

b. Protoxide of manganese, § 103 . 79

c. Protoxide of nickel, § 104 . .80

d. Protoxide of cobalt, § 105 . S2

e. Protoxide of iron, § 106 . .83

/. Sesquioxide of iron, § 107 . .84

Appendix to the fourth group

Sesquioxide of uranium, § 109 . . 88

FIFTH GROUP.

Oxide of silver, suboxide of mercury, oxide of mercury , oxide of lead, teroxide of bism uth, oxide of copper, oxide of cadmium , § 110.

CONTENTS.

XIX

PAGE

First section of the fifth group : oxides which are precipitated by hydrochloric acid.

Special reactions.

a. Oxide of silver, § 111 . . 89

b. Suboxide of mercury, § 112 . 90

c. Oxide of lead, § 113 . .91

Second section of the fifth group : oxides which are not precipitated by hydrochloric acid.

Special reactions.

a. Oxide of mercury, § 115 .93

b. Oxide of copper, § 116 . .95

c. Teroxide'of bismuth, § 117 .97

d. Oxide of cadmium, § 118 . . 98

SIXTH GROUP.

Teroxide of gold, binoxide of platinum, teroxide of antimony, binoxide of tin, protoxide of tin , arsenious acid, and arsenic acid, § 120.

FIRST SECTION.

Special reactions.

a. Teroxide of gold, § 121 . . 101

b. Binoxide of platinum, § 122 . 102

SECOND SECTION OF THE SIXTH GROUP.

Special reactions.

a. Teroxide of antimony, § 124 . 103

b. Protoxide of tin, § 125 . . 106

c. Binoxide of tin, § 126 . . 108

d. Arsenious acid, § 127 . .109

e. Arsenic acid, § 128 ~ . .118

B. DEPORTMENT OF THE ACIDS AND THEIR RADICALS WITH REAGENTS, § 130 121

I. Inorganic acids.

FIRST GROUP.

Acids vihich are precipitated from neutral solutions by chloride of barium : arsenious acid, arsenic acid, chromic acid, sulpjhuric acid, phosphoric acid, boracic acid, oxalic acid, hydrofluoric acid, carbonic acid, silicic acid,

§ 131.

First section of the first group of the inorganic acids . . .122

a. Arsenious acid and arsenic acid,

§ 132 . . . 122

b . Chromic acid . . .123

Appendix to the first section of the first page

Second section of the first group of the inorganic acids.

Third section of the first group of the inorganic acids.

a. Phosphoric acid, § 135 . . 126

b. Boracic acid, § 136 . . . 130

c. Oxalic acid, § 137 . .131

d. Hydrofluoric acid, § 138 . . 132

Fourth section of the first group of the inorganic acids.

a. Carbonic acid, § 140 . . 136

b. Silicic acid, § 141 . . .137

SECOND GROUP OF INORGANIC ACIDS.

Acids which are precipitated by nitrate of silver, but not by chloride of barium : hydrochloric acid, hydrobromic acid, hydriodic acid, hydrocyanic acid , hydrosulphuric acid.

a. Hydrochloric acid, § 143 . .139

b. Hydrobromic acid, § 144 . . 140

c. Hydriodic acid, § 145 . . 142

d. Hydrocyanic acid, § 146 . . 144

e. Hydrosulphuric acid, § 147 . 146

THIRD GROUP OF THE INORGANIC ACIDS.

Acids which are not precipitated by salts of baryta nor by salts of silver : nitric acid, chloric acid.

a. Nitric acid, § 149 . . 148

b. Chloric acid, § 150 . .149

II. ORGANIC ACIDS.

FIRST GROUP.

Acids which are invariably precipitated by chloride of calcium : oxalic acid , tartanc acid , citric acid, malic acid, parataric or racemic acid.

a. Oxalic acid . . .151

b. Tartaric acid, § 152 . . 151

Appendix. Racemic or parataric acid,

§ 156 . . . 155

SECOND GROUP OF THE ORGANIC ACIDS.

Acids which chloride of calcium fails to

XX

CONTENTS.

PAGE

'precipitate under any circumstances, but which are precipitated from neutral solutions by sesquicldoride of iron : succinic acid, benzoic acid.

a. Succinic acid, § 157 . .156

b. Benzoic acid, § 158 . . 156

Recapitxdation and remarks, % 159 . 157

PAGE

THIRD GROUP OP THE ORGANIC ACIDS.

Acids which ore not precipitoded by chloride of calcium nor by sesquichloride of iron ; acetic acid, formic acid.

a. Acetic acid, § 160 . .158

b. Formic acid, § 161 . . 159

Part II. Systematic Course Of Qualitative Chemical Analysis

PAGE

Preliminary remarks on the course of qualitative analysis in general, and the plan of this part of the present work in particular . .163

Section I. Practical Process

A. The body under examination is solid.

I. It is neither a pure metal nor an

II. The substance is a metal or an

B. The substance under examination is a

II. Solution of bodies or classification of substances according to their deportment with certain solvents, §167 . . . _ .. 172

A. The substance under examination is

neither a metal nor an alloy, § 168 172

B. The substance under examination is a

metal or an alloy, § 169 . .174

III. Actual examination.

SIMPLE COMPOUNDS.

A. Substances soluble in water.

Detection of the base, § 170 . 176

A. Substances soluble in water.

Detection of the acid.

I. Detection of inorganic acids, § 171 182

A. Substances soluble in water.

Detection of the acid.

II. Detection of organic acids, § 172 . 184

B. Substances insoluble or sparingly

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

Detection of the base, § 173 . 185

B. Substances msoluble or sparingly soluble in water, but soluble in hydrochloric acid, nitric acid, or nitrohydrochloric acid.

Detection of the acid.

I. Detection of inorganic acids, § 174 187

B. Substances insohdde or sparingly soluble in water, but soluble in hydro-

PAGE

chloric acid , nitric acid, or nitrohydrochloric acid.

Detection of the acid.

II. Detection of organic acids, § 175 . 189

C. Substances insoluble or sparingly soluble in water, hydrochloric acid, nitric acid, or nitrohydrochloric acid.

Detection of the base and the acid,

§176 . . . 189

COMPLEX COMPOUNDS.

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

Detection of the bases, § 177 . . 191

Treatment with hydrosulphuric acid, precipitation of the metallic oxides of Group V., 2nd section, and of Group VI., § 178 . . . 194

Treatment of the precipitate produced by hydrosulphuric acid Math sulphide of ammonium ; separation of the 2nd section of Group V. from Group VI.,

§ 179 . . . 196

Detection of the metals of Group VI.

Arsenic, antimony, tin, gold, platinum, § 180 . . .197

Detection of the metallic oxides of Group V., 2nd section. Oxide of lead, teroxide of bismuth, oxide of copper, oxide of cadmium, oxide of mercury, § 181 . . . 200

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 nickel, protoxide of cobalt, proto and sesquioxide of iron, and also of the phosphates of the alkaline earths, § 182 . . . 202 .

Separation and detection of the oxides of Group II., which are precipitated by carbonate of ammonia in presence of chloride of ammonium, viz., baryta, strontia, lime, § 183 . . 208

CONTENTS.

XXI

PAGE

Examination for magnesia, § 184 . 210

Examination for potassa and soda, § 185 210 Examination for ammonia, § 186 . 211

Detection of the acids.

I. In the absence of organic acids,

^ 187 . • • .212 A. 1. Siibstances soluble in water.

Detection of the acids.

II. In presence of organic acids, § 188 215

A. 2. Substances insoluble in water, but

soluble in hydrochloric acid, or in nitric acid.

Detection of the acids.

I. In the absence of organic acids,

§ 189 . . . . 218

A. 2. Substances insoluble in water,

but soluble in hydrochloric acid, or nitric acid.

Detection of the acids.

II. In presence of organic acids, § 190 220

B. Substances insoluble, or sparingly

soluble both in water and in hydrochloric acid.

Detection of the bases, acids, and

metalloids, § 191 . . 220

Section II. Practical Course, In Particular Cases

I. Special method of effecting the decom-

position of cyanides, ferrocyanides,

&c., insoluble in water, § 192 . 225

II. Analysis of silicates, § 193 . . 226

A. Silicates decomposable by acids,

B. Silicates which are not decompos-

able by acids, § 195 . . 229

C. Silicates which are partially decom-

posed by acids, § 196 . “ . 230

III. Analysis of waters, § 197 . . 231

A. Analysis of the fresh waters (spring

water, well-water, brook-water, river- vater, &c.), § 198 . . 231

B. Analysis of mineral waters, §

199 . . . 234

1. Examination of the water.

a. Operations at the spring, § 200 . 235

b. Operations in the laboratory,

§ 201 . . . . 236

2 . Examination of the sinter deposits,

§ 202 . . . . 239

IV. Analysis of soils, § 203 . .241

1. Preparation and examination of the

aqueous extract, § 204 . . 242

2. Preparation and examination of the

acid extract, § 205 . . 244

3. Examination of the inorganic con-

stituents insoluble in water and acids, § 206 . . .245

4. Examination of the organic consti-

tuents of the soil, § 207 . . 245

PAGE

a. Estimation of the organic substances soluble in water . .245

b. Treatment with an alkaline carbonate .... 246

c. Treatment with caustic alkali . 246

V. Detection of inorganic substances in

presence of organic substances,

§ 208 . . 246

1 . General rules for the detection of

inorganic substances in presence of organic matters, which by thencolor, consistence, &c., impede the application of the reagents, or obscure the reactions produced, §

209 . . . 247

2. Detection of inorganic poisons in

articles of food, in dead bodies,

&c., in chemico-legal cases, § 210 24S

A. Method for the detection of a. Method for the detection of undissolved arsenious acid, § 212 . 250

b. Method for the detection of arse-

nic in whatever form of combination it may exist, which allows also a quantitative determination of that poison, and permits at the same time the detection of other metallic poisons which may be present, § 213 . . .251

aa. Decolorization and solution . 251 bb. Separation of the arsenic as

tersulphide . . . 252

cc. Purification of the crude tersulphide of arsenic . . 252

dd. Determination of the weight of the tersulphide of arsenic . 252

ee. Reduction of the tersulphide of arsenic . . . 253

B. Method for the detection of hydrocyanic acid, § 214 . . 253

3. Examination of the inorganic constituents of plants, animals, or parts of the same, of manures, See. (analysis of ashes)

A. Preparation of the ash, § 215 . 255

B. Examination of the ash . . 255

a. Examination of the parts soluble

in water . . . 256

b. Examination of the part soluble

in hydrochloric acid . . 257

c. Examination of the residue insoluble in hydrochloric acid . 257

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

I. Additional remarks to the preliminary

II. Additional remarks to the solution of

III. Additional remarks to the actual

CONTENTS.

PAGE

A. General review and explanation of the analytical course . . 261

a. Detection of the bases . .261

b. Detection of the acids . . 264

33. Special remarks and additions to

the systematic course of analysis.

§ 178 . . . . 269

§ 181 . . . . 269

§ 182 . . . . 270

§ 192 . . . . 272