fft

*

(AC 52.5^. 2

ELEMENTS OF CHEMISTRY:
THEORETICAL AND PEACTICAL.

BY

WILLIAM ALLEN CILLER,
BKVISED BY

M.D.,

LL.D.

LATB PBOFBSSOB OF CHBMISTBY IN KING'S COLLEGE, LONDON.

HERBERT McLEOD,

F.C.S.

PKOFESSOS OF EXPERIilHXIAL SCIENCE, INDIAN CIVIL ENGINEERING COLLEGE, COOPER'S HILL.

PART

H.

INORGANIC CHEMISTRY,

FIFTH EDITION, WITH ADDITIONS.

LONDON

:

LONGMANS, GREEN, READER, AND
1874.

DYER.

LOVDOff .
,.

I

MIBt

OOTSJTT

PREFACE
TO

THE FIFTH EDITION.
IN this Edition of Part' II. a considerable alteration has been

made

in the order in which the non-metallic elements

and

their

with the object of facilitating compounds the progress of the student in the theoretical part of the science,
is

are described.

This

by commencing with the elements which form the least complex compounds, and gradually passing to those which form more numerous and complicated seven typical elements, and
are
first

substances
their

;

for

the

same reason
be

compounds with one another,

studied before dealing with those of which they

may

regarded as representatives.

Hydrogen,

as

the

standard

of reference

for

the

atomic

besides being employed as

weights of the elements and for the specific gravities of gases, the measure of the atomicity of the
first

other elements, occupies the
positive substances.

place, as the type of electro-

by chlorine as a specimen of an electro-negative element, one remarkable for its chemical activity, and which forms a large and important series of comIt is followed

binations.

The compound of

this

element with hydrogen forms

the subject of the next section.

Oxygen

is

now brought

before

the notice of the student as one of the most important elements, and on that account is frequently placed first in order, as was the case in previous editions of this work ; being a dyad, how-

does not produce such simple combinations as those of Its compounds with chlorine. hydrogen and with chlorine and
ever,
it

hydrogen are next
carbon,

described.

Then

'

follow boron, a triad

;

a tetrad; nitrogen, a pentad; and

sulphur,

a

hexad,

lv

PREFACE.

and the compounds they produce with the elements previouslystudied.

Many

of those compounds of carbon which

are

essentially

organic have

been placed in the Appendix in order that they be removed to Part III., to which they properly belong. may The remaining non-metals are described in an order consistent
with that employed in the case of the typical ones. The chapters on the metals remain as before, except that the

chlorides, bromides, and

iodides

are placed before the

oxides,

sulphides,

and

oxysalts.

The

section

on gas analysis has

also

Appendix, as being mineral chemistry.

more nearly

allied

been placed in the to organic than to

last chapters have undergone considerable alterasome account being given of the recent researches in thermo-chemistry, a subject which promises to be of great

The three

tion,

service in the

advancement of theoretical chemistry. The formulae remain almost as in the last Edition, unless a

For the convenience of some, conchange has been necessary. stitutional formulae have been occasionally introduced, and the kind
adopted are those suggested by Dr. Frankland. These have always been placed in square brackets, so as to indicate clearly that they
are an interpolation into the original work, although they are
consistent with the ideas developed in previous editions.

The Editor takes this opportunity of expressing his sincere thanks to his friend, Mr. C. E. Groves, F.C.S., for his invaluable
assistance in selecting
careful

new matter
proofs,
at

for this

edition,

and for

his

revision of

the
to

a time
to

when

indisposition

almost

threatened

put a

stop

the

completion of the

work.
COOPEE'S HILL, December, 1873.

TABLE OF CONTENTS.
CHAPTER
HO. OF PARAGRAPH.
I.

Nomenclature

Classification of

Elements

.

i

331 Principles of Chemical Nomenclature 332 Empirical, Eational, and Constitutional Formulae

333 General Arrangement of the Elements

........ ..... ........
......
16
17

15
I

9 12

CHAPTER
A. FIRST DIVISION

II.

NON-METALS

289

Hydrogen ............. 334 Hydrogen ..................

21
17

CHAPTER
Chlorine
335 Chlorine
Chlorides

III.

Hydrochloric Acid

336 Hydrochloric Acid 337 Solution of Hydrochloric Acid 338 Action of Hydrochloric Acid on Metallic Oxides

.............. .............. ..........
....
CHAPTER
IV.

......

.

22

33
22

26

29
31

Oxygen

339 Oxygen 340 Nature of Combustion
341 Varieties of Oxides

342 Ozone

............ ...... ............. ... ........... ..................
CHAPTER
V.

Combustion

Ozone

......

33

50
33 40

44
45

Water
343 344 345 346 347 348

Water
Distilled

Various kinds of Natural Waters

....... ...... ............... Oxyhydrogen Peroxide Hydrogen ........ .*....
Water Composition of Water Synthesis of Water Eudiometers
.
.

Hydrogen .................. ..........
4

Peroxide of

.....

50

69
50

54
59 61 65 67

Jet

of

II.

b

VI

TABLE OF CONTENTS.

CHAPTER
NO. OP PARAGRAPH.

VI.

Oxides and Oxacids of Chlorine
349 Oxides and Oxacids of Chlorine 350 Hypochlorous Anhydride
351 Bleaching Compounds

70

84
70
ib.

Hypochlorous Acid

352 Estimation of Bleaching Power of Chloride of Lime 353 Chloric Acid Chlorates 354 Perchloric Acid 355 Chlorous Anhydride 356 Peroxide of Chlorine

...

73

76
77

79 81 82

CHAPTER
Boron
357 Boron 358 Boracic Anhydride and Acid 359 Boric Trichloride

VII.

84
Borates

89 84
86

89
VIII.

CHAPTER

Carbon Carbonic Anhydride 1. Carbon 360
361 Diamond 362 Graphite

Carbonic Oxide 90

131

90
91

93

363 364 365 366 367 368 369 370

Consumption of Smoke Coke
Charcoal

96
97

Amorphous Carbon

98
101

General Properties of Carbon
Principle of the Safety Nature of Flame

Lamp

104
107 112

Theory of the Blowpipe Use of the Mouth Blowpipe
II.

113

371

Carbonic Anhydride

U5
118
123 125
.

372 Natural Sources of Carbonic Anhydride 373 Synthesis of Carbonic Anhydride 374 Carbonates 375 Carbonic Oxide
.

127

CHAPTER

IX.

376

Nitrogen The Atmosphere I. Nitrogen

131

138

131
.

II. Composition of the 377 378 Estimation of Aqueous Vapour

Atmosphere

.

.

133
135 136

379 Estimation of Carbonic Anhydride

TABLE OF CONTENTS.

Vll

CHAPTER
NO. OP
PAKAUK.il'lf.

X.

Compounds
I.

of Nitrogen of Nitrogen with and Chlorine.

138

173

Compounds

Hydrogen
138 144 146
147
.
.

380 Ammonia,
381 Solution of

Ammonia

382 Amidogen Ammonium 383 Chloride of Nitrogen

384
385 386 387 388 389 390 391 392
Nitric

II. Oxides

and Acids of Nitrogen

*

148
149 150 154

Anhydride Nitric Acid Action of Nitric Acid on Metals Hydrates of Nitric Acid Common Impurities of the Acid Nitrates Nitrous Oxide Nitric Oxide
Difference

Tests

....
and

156
157

160
163 166

Nitrous Anhydride 393 Peroxide of Nitrogen

between

Mixture

Combination

168

394 Oxy chlorides of Nitrogen
3 94 a Boric Nitride

Aqua Regia

171

173

CHAPTER
Sulphur and
. .

XI.

its

Compounds

173

215
173 176
177

395 Sulphur 396 Various forms of Sulphur 397 Electro-positive and Electro-negative Sulphur 398 Hydrosulphuric Acid or Sulphuretted Hydrogen

....

399 Hydrosulphates and Sulphides 400 Hydric Persulphide 401 Sulphur Chloride 402 Compounds of Sulphur with Oxygen 403 Sulphurous Anhydride 404 Sulphites 405 Sulphuric Acid Theory of its Formation 406 Sulphuric Acid Process of Manufacture 407 Sulphuric Acid and its Hydrates 408 Nordhausen Sulphuric acid 409 Sulphuric Anhydride 410 Impurities in the Commercial Acid 411 Sulphates. Tests for Sulphates
.

179 182

184
185 186
187

190
192
195 197

199
ib.

.'

201

202

Vlll

TABLE OF CONTENTS.
'

N0

P

PAEAQKAPH.

PAGB
. .

412 Hyposulphurous Acid or Hydrosulphurous Acid 413 Thiosulphuric or Sulpho-sulphuric Acid, hitherto called Hyposulphurous Acid
. .

205
ib.

414 Hyposulphuric (Dithionic) Acid
415 Trithionic Acid 416 Tetrathionic Acid 417 Pentathionic Acid

'.

208
209
ib.

^

.

.

ib.

418 Thionylic Chloride or Sulphurous Chloride 419 Sulphuryl Chloride or Chlorosulphuric Acid 420 Boric Sulphide
421 Nitrogen Sulphide 422 Carbonic Bisulphide 423 Carbonic Sesquisulphide 424 Hydrogen Car bosesquisulphide

210
ib. ib.

211
ib.

213 214
.

425 Carbonic Oxysulphide 426 Nitrosulphuric Acid 427 Sulphazotized Acids

.

ib.

ib.
ib.

CHAPTER
Bromiue
428
429 430 431 432
I.

XII.

Iodine

Fluorine

......

215

238

Bromine

215
217

Hydrobromic Acid Bromides Bromic Acid
Other Compounds of Bromine
II.

219 220
ib.

433
434 435 436 437 438 439 440
Iodides

Iodine

221
224
225 226
lodic

Hydriodie Acid
Chlorides and Bromides of Iodine

Oxides of Iodine
Periodic Acid

lodic

Anhydride

Acid

.

.

.

.

227

229
ib.

Iodide of Nitrogen Iodide of Sulphur Sulphuryl Iodide 441 Natural Relation of the Halogens

230
ib.

442

III. Fluorine

.....
.

232
ib.

443 Hydrofluoric Acid -Fluorides 444 Boric Trifluoride Fluoboric Acid

Hydrofluoboric Acid 445 Determination of Combining Number of Fluorine

....
238

236
237

CHAPTER
Silicon
446 Silicon

XIII.

and

its

Compounds
Forms

254
238

Its Different

TABLE OF CONTENTS.
iro. o PARAGRAPH.

IX

447

Silicic Silicic Silicic Silicic

Hydride
Chloride

.

241

448 449 450 451 452 453 454 455 456 457 458

242

Bromide
Iodides
.

244
ib.
ib.

Chloroform Fluoride of Silicon
Silicon
Silicofluoric
Silicic

245
ib.

Acid
Silica

Anhydride

Hydrates of
Silicates

246 248

Compounds Leukon
Silicic

of Silicon with

Oxygen and Hydrogen

....

251

252 253

459 460

Silicic Nitride
*

254
.

Sulphide

ib.

CHAPTER
Pentad Elements

XIV.
its

Phosphorus and

Com254
281

pounds
461 Relations of the Pentad Elements

462 Phosphorus 463 Different Modifications of Phosphorus 464 Phosphides of Hydrogen Phosphuretted Hydrogen Gas 465 Liquid Phosphide of Hydrogen 466 Solid Phosphide of Hydrogen 467 Chlorides of Phosphorus 468 Phosphorous Chloride (Trichloride) 469 Phosphoric Chloride (Pentachloride) 470 Oxychloride of Phosphorus (POC1 3) or Phosphoryl Chloride 471 Sulphochloride of Phosphorus (PSC1 3 ) 472 Bromides of Phosphorus 473 Iodides of Phosphorus 474 Phospham 475 Oxides and Acids of Phosphorus
.

254 256 260
.

263
265 266
ib.

ib.

267
.

ib.

268
ib.

ib.

269 270
ib.

476 Phosphoric Anhydride 477 Phosphoric Acid 478 Orthophosphoric or Tribasic Phosphoric Acid 479 Pyrophosphoric Acid 480 Metaphosphoric Acid 481 Phosphorous Anhydride Phosphorous Acid Phosphites 482 Hypophosphorous Acid Hypophosphites 483 Oxide of Phosphorus 484 Sulphides of Phosphorus

271

272

274
275
.

.

278 279
281
ib.

X

TABLE OF CONTENTS.

CHAPTER XV.
NO. OP PAUAQKAFH.

PAOB

Hexad Elements
485 Natural Relations of the

Selenium

Tellurium

.

.281
.

289
.

Hexad Non -metallic Elements

.

281

486

I.

Selenium

283
285
ib.

487 Seleniuretted Hydrogen 488 Chlorides of Selenium 489 Oxides of Selenium, Selenioua Anhydride and Acid

Solenites

ib.

490 Selenic Acids

Seleniates

286
l b-

491 Carbonic Selenide

492

$ II.

Tellurium

287
288
ib.

493 Telluretted Hydrogen 494 Chlorides, Bromides, and Iodides of Tellurium 495 Oxides of Tellurium Tellurous Acid 496 Telluric Acid

*b.

289

CHAPTER
B. SECOND DIVISION

XVI.
290
823

THE METALS

General Remarks on the Metals and on their

Compounds
I.

Theory of

Salts

....

290

361

General Properties of the Metals.
2gc

497 Characteristics of a Metal 498 Lustre, Opacity, and Colour,

Odour and Taste

ib

499 Hardness, Brittleness, and Tenacity 500 Malleability and Ductility
501 Specific Gravity

291
29.
291

502 Fusibility 503 Volatility 504 Conducting Power for Heat and Electricity

29
29;
291*

505 506 507 508

Alloys Condition of the Metals in Nature
Distribution of the Metals

.30)
.

Mining Operations 509 Mechanical Treatment of the Ores 510 Roasting, or Oxidation 511 Reduction, or Smelting 512 Classification of the Metals

30 30 30
31 31 31

_

;

'

>

j

j.

315

TABLE OF CONTENTS.

XI

II.

General Properties of the Compounds of the Metals with the Non-metallic
Elements.
PAOB

PARAGRAPH.

513 Compounds

of

Hydrogen with the Metals

321
ib.

514 515 516 517 518 519 520

Chlorides

Estimation qf Chlorine

327
ib.

Bromides
Iodides

Fluorides

328 329
ib.

Oxides
Estimation of Oxygen in Metallic Oxides

521 Sulphides 522 Estimation of Sulphur in the Metallic Sulphides 523 Selenides and Tellurides

330 340 344 345
ib.

524 Nitrides
525 Phosphides

ib.

526 Compounds of Carbon, of
III.
527 Acids and Bases

Silicon,

and of Boron with Metals

.

ib.

Theory of

Salts.

346
ib.

528 Oxyacids and Hydracids 529 Binary Theory of Salts 530 Objections to the Binary Theory
531 Sulpho-Salts 532 Varieties of Salts

.

348 350
351

352
ib.

533 Neutral or Normal Salts 534 Polybasic Acids Acid Salts
535 Double Salts

536 Subsalts

.

.'

537 Oxychlorides and Oxyiodides

353 358 360 361

CHAPTER
Group
I.
I.

XVII.
361

Metals of the Alkalies
Potassium.
.

450

538 Notation for Mixtures of Isomorphous Compounds 539 Potassium 540 Preparation of Potassium 541 Properties of Potassium 542 Potassic Chloride, or Chloride of Potassium 543 Potassic Bromide, or Bromide of Potassium

.

.

.

362 363 364 366 367 368
ib.

544 Potassic Iodide, or Iodide of Potassium 545 Potassic Fluoride, or Fluoride of Potassium
.

369

Xll

TABLE OF CONTENTS.
'

W0

*

PABAGBAFH.

FABB
.
.

546 Potassic Silicofluoride, or Silicofluoride of Potassium 547 Oxides of Potassium Tetroxide (K 2 OJ and Dioxide (K 2 O 2 ) of
.

369
ib.

Potassium

548 Potash

Potassic Hydrate, or Hydrate of Potash

.

.

.

.

549 Sulphides of Potassium 550 Sulphate and Bisulphate of Potassium
551 Nitre Plantations
Potassic Nitrate, or Nitrate of Potassium
' . .
. . .

552 Refining of Saltpetre
553 Gunpowder
Nitrite, or Nitrite of Potassium 555 Potassic Chlorate, or Chlorate of Potassium 556 Potassic Perchlorate, or Perchlorate of Potassium

554 Potassic

370 374 375 376 379 380 384
ib.

....

385
ib.

557 Potassic Carbonate, or Carbonate of Potassium

558 Alkalimetry 559 Alkalimetry 560 Hydric Potassic Carbonate, or Bicarbonate of Potassium 561 Characters of the Salts of Potassium

Method of Neutralization Method of Will and Fresenius

387
391
.

.

392
ib.

562

II.

Sodium
Sodium Sodium Iodide of Sodium

563 Sodic Chloride, or Chloride of 564 Sodic Bromide, or Bromide of

393 394
397
ib.

565 Sodic Iodide, or 566 Soda Sodic Hydrate, or Hydrate of Soda Sulphides of Sodium 567 Sodic Sulphate, or Sulphate of Sodium Hydricsodic Sulphate,
or Bisulphate of

398

Sodium

568 Sulphite and Bisulphite of Sodium

399 403
ib.

569 Sodic Nitrate, or Nitrate of Sodium 570 Sodic Carbonate, or Carbonate of Sodium Manufacture 571 Bicarbonate and Sesquicarbonate of Sodium
572 Phosphates of Sodium

Process of

its

......

404 409
412 414 4 [6 418

.411

573 Borates of Sodium

574 575 576 577 578 579 580
.

Silicates of

Sodium

Glass

Table- of Chief Varieties

Bohemian Glass
Plate Glass and
Bottle Glass

Crown Glass

Window

Glass

.

ib.

420
Devitrification

Reaumur's Porcelain
Flint Glass

421
ib.

Optical Glass 581 Coloured Glasses 582 General Properties of Glass

423
.
..

425
425
ib
.

583 Characters of the Salts of Sodium

584

III.

Lithium
.
.
..

585 Lithic Chloride 586 Lithic Oxide Salts of Lithium

........

42^
ib

TABLE OF CONTENTS.
VO. OP PARAGRAPH.

587

IV. Rubidium
431
.

588 Compounds of Rubidium

589

V. Caesium

....

.

432
433

590 Compounds of Caesium

591

592
593

594

VI. Salts of Ammonium. Compounds of Ammonia with Oxyacid Anhydrides Sulphatammon Sulphuric Ammonide Sulphurous Ammonides Compounds of Ammonia with Hydracids

....

434 435
ib.

436
ib.
.

Ammonium 596 Chloride of Ammonium (Sal Ammoniac) Ainmonic Iodide 597 Solution of Ammonia 598 Sulphides of Ammonium Ammonic Hydric sulphide 599 Ammonic Sulphate, or Sulphate of Ammonium 600 Ammonic Nitrate, or Nitrate of Ammonium 60 1 Carbonates of Ammonium 602 Phosphates of Ammonium
595 Theory of
. .

437 439

.

440
441

442
ib.

603 Ammoniated Salts 604 Action of Ammonia on Metallic

443 444
445 447 440
ib,

Salts in Solution

605 Characters of the Compounds of Ammonium 606 Estimation of Ammonia by Precipitation
607 Estimation of Ammonia by Acids

CHAPTER
Group
608
609 610 611 612
II.

XVIII.
.

-Metals of the Alkaline Earths

450

476

I.

Barium

450
451
ib.

Baric Chloride, or Chloride of Barium Baric Silicofluoride

Baryta

Baric Dioxide, or Peroxide of Barium

ib.

Sulphides of Barium
.

613 Baric Sulphate, or Sulphate of Barium 614 Baric Nitrate, or Nitrate of Barium

.

....

.

.

453 454
ib.

615 Baric Carbonate, or Carbonate of Barium 616 Characters of the Salts of Barium

455
ib.

617

II.

Strontium
Strontic Silico-.'

456
ib.

618 Strontic Chloride, or Chloride of Strontium
fluoride

619 Strontia 620 Strontic Sulphate, or Sulphate of Strontium 621 Strontic Nitrate, or Nitrate of Strontium
622 Strontic Carbonate, or Carbonate of Strontium 623 Characters of the Salts of Strontium
II.

457
ib.
ib.

458
ib.

C

XIV
wo<

TABLE OF CONTENTS.
*
PJLOK

PABAGEAPH.

624
625

III. Calcium
Calcic Chloride, or Chloride of Calcium Calcic Iodide

458
Calcic

Bromide

626 Calcic Fluoride, Fluor-spar, or Fluoride of Calcium 627 Lime Quicklime Slaked Lime 628 Mortars and Cements 629 Hydraulic Limes and Mortars 630 Other Uses of Lime 631 Sulphides of Calcium 632 Phosphide of Calcium 633 Calcic Disilicide, or Silicide of Calcium 634 Calcic Sulphate, or Sulphate of Calcium Plaster of Paris 635 Calcic Nitrate, or Nitrate of Calcium 636 Calcic Carbonate, or Carbonate of Calcium Chalk, Marble 637 Calcareous Waters Clark's Soap Test
.
.

.

.

459 460
ib.

.

.

.

462 464 466 467
ib.

468
.

.

ib.

470
.

ib.

471

638 Building Materials 639 Phosphates of Calcium 640 Boro-natro-calcite
641 Characters of the Salts of Calcium
.

473 475 476
ib.

CHAPTEE
Group
642

XIX.
477
504

III. Metals of the Earths

I.

Aluminium

477
478 480
481
ib.

643 Properties of Aluminium 644 Aluminic Chloride, or Chloride of Aluminium
645 Fluorides of Aluminium 646 Alumina 647 Trisodic Aluminate, or Aluminate of Sodium

484
ib.

648 Aluminic Sulphate, or Sulphate of Aluminium 649 Different varieties of Alum 650 Phosphates of Aluminium
651
Silicates of

485 489
ib.

Aluminium

Clays

652 Aluminous Rocks and Minerals 653 Porcelain and Pottery Ware

654 General Remarks on Pottery 655 Ultramarine 656 Characters of the Salts of Aluminium 657 Separation of Alumina from the Alkaline Earths

492 494 497
499
501
ib.

658

II.

Grlucinum

ib

659 Salts of Glucinum 660 Characters of the Compounds of Glucinum

502
ib

TABLE OF CONTENTS.
NO. OP PABAGEAPH.

XV

III. 66 1 Yttria 662 Erbia

Yttrium and Erbium.
503
ib.

IV. Cerium, Lanthanum, and Didymium.
663 Cerium 664 Lanthanum

504
ib. ib.

665 Didymium

CHAPTER XX.
Group IV.
666
I.

Magnesian Metals

505

527

Magnesium

505
507 508
ib.
ib.

667 Magnesic Chloride, or Chloride of Magnesium 668 Magnesia

669 Magnesic Sulphide, or Sulphide of Magnesium 670 Magnesic Sulphate, or Sulphate of Magnesium 671 Magnesic Nitrate, or Nitrate of Magnesium 672 Carbonates of Magnesium Magnesic Borate 673 Silicates of Magnesium 674 Phosphates of Magnesium
. .

509
ib.

511
ib.

675 676 677 678

Characters of the Salts of Magnesium Characters of the Metals of the First Group

512
ib.

Estimation of Potassium and Sodium Conversion of the Alkali-Metals into Chlorides
.

...
.

513
ib.

679 General Characters of the Metals of the Second Group 680 Separation of the Alkaline Earths from the Alkalies 68 1 Separation of the Alkaline Earths from each other 682,683 Mode of Collecting and Washing Precipitates
.

.

.

....
.

...
.

514
ib.
ib.

.

516

684

II.

Zinc

.

517
518 519 520
ib.

685 Extraction of the Metal English Method 686 Extraction of the Metal Silesian Method 687 Extraction of the Metal Belgian Method 688 Preparation of Pure Zinc

689 Properties of Zinc 690 Its Alloys, and Industrial Applications 691 Zincic Chloride, or Chloride of Zinc 692 Zincic Oxide, or Oxide of Zinc
.

521
ib.

522
ib.

693 694 695 696

Zincic Sulphide, Sulphide of Zinc, or Blende Zincic Sulphate, or Sulphate of Zinc Zincic Carbonate, Carbonate of Zinc, or Calamine Characters of the Salts of Zinc

....

523 524
ib.

ib.

XVI

TABLE OF CONTENTS.

PARAGKAPH.

697 Estimation of Zinc in Analysis 698 Separation of Zinc from the Alkalies and Earths

.....
.

525
ib.

699

111.

Cadmium

..."/....'..

.

ib.

Cadmium 700 Compounds 701 Characters of the Salts of Cadmium
of

526
527

......
Group V.
702
I.

CHAPTER

XXI.
less allied to

Metals more or

Iron 528

623
5 28

Cobalt

77.-!-"T/ro

703 Cobaltous Chloride, or Chloride of Cobalt 704 Oxides of Cobalt Zaffre Smalt Thenard's Blue 705 Ammoniacal Compounds of Cobalt 706 Sulphides of Cobalt .'...'.' 707 Cbba'ltous Sulphate

....

530
531 533

535
ib.

708 Cbba'ltous Nitrate 709 Carbonates of Cobalt 710 Characters of the Salts of Cobalt
.

.

.

.

.

..*..*.

....

.

.

.

ib.

536
ib.

711 Estimation of Cobalt in Analysis 712 Separation of Cobalt from the preceding Metals

537

538

713

,

11.

Nickel.

.

.

.

..'

539
540
541
ib.

714 Nickelous Chloride, or Chloride of Nickel 715 Oxides of Nickel
716 Sulphides of Nickel 717 Nickelous Sulphate, or Sulphate of Nickel 718 Nickelous Nitrate, or Nitrate of Nickel 719 Carbonates of Nickel 720 Characters of the Salts of Nickel
721 Estimation of Nickel in Analysis 722 Separation of Nickel from Cobalt

542
ib
ib

ib

-54,'
ib

723

III.

Uranium

.

*

.

.

.

.54^
.

724 Chlorides of Uranium 725 Oxides of Uranium
726 Characters of the Salts of Uranium 727 Estimation of Uranium
*
.

.

.

.

541
il

54
il

IV. Iron
728 Iron Ores
Meteoric Stones
.

54,
.

il.

729 Smelting of Clay Ironstone 730 Theory of the. Blast Furnace
731 Hot Blast

55

55
55

;

>

732 Composition and Properties of Cast Iron

55)

TABLE OP CONTENTS.
PARAGRAPH.
. 733 Conversion of Cast Iron into Wrought Iron Refining Danks's Process Siemens's 735 Production of Wrought Iron direct from the Ore
.

XVII

.

563

734 Puddling

564
568 569 575 576 578 579
ib.

process

736 Manufacture of Steel
737 Preparation of pure Iron 738 Properties of Bar-Iron Rusting ,of Iron 739 Passive Condition of Iron in Nitric Acid 740 Alloys of Iron -Hydride of Irqn ... 741 Ferrous Chloride
.

.

.

.

.

.

.

.

742 Ferric Chloride

'.'.'.'.'

.

.

.

580
581
ib.

743 Bromides, Iodide, and Fluorides of Iron 744 Ferrous Oxide, or Protoxide of Iron .
745 Ferric Oxide, or Sesquioxide of Iron 746 Magnetic Oxide of Iron
747 Ferric Acid
.'

.

.

582

584 585
ib.

748 Nitrides of Iron 749 Silicide of Iron
750 Ferrous Sulphide, or Protosulphide of Iron 751 Ferrio Bisulphide, Iron Pyrites, or Bisulphide of Iron
752 Magnetic Sulphides .-.-.. 753 Potassic Ferric Sulphide
.
. .

ib.

...........

586 587 588
ib.

Phosphide of Iron 755 Ferrous Sulphate, or Protosulphate of Iron 756 Ferric Sulphate

754 Mispickel

ib.
ib.

590
. .
. .

757 Nitrates of Iron 758 Ferrous Carbonate, or Protocarbonate of Iron
;

ib,

591

759 Oxalates of Iron 760 Phosphates of Iron
76 1 Characters of the Salts of Iron 762 Estimation of Iron, and Separation from the Alkalies 763 Separation of Iron from Aluminium and Glucinum
.
.

592
ib. ib.
.

....
.
. .

594
ib.

764 Separation from Zinc, Cobalt, Nickel, and Manganese 765 Separation of Iron from Uranium 766 Estimation of Mixed Ferrous and Ferric Salts 767 Analysis of Cast Iron, Steel, and Bar-Iron

595
ib.

ib-

597
.
.

768

V. Chromium
Chromium

...

.

.

.

.

.

P;*-;

599
600
ib.

769 Chlorides of

770 Chromic Hexafluoride, or Fluoride of Chronmun 771 Chromous Oxide, or Protoxide of Chromium 772 Chromic Oxide, pr Sesquioxide of Chromiurn
773 Chrome Iron-stone

.....

60 1
ib.

604
ib. ib.

774 Ammoniacal Compounds of Chromium 775 Chromic Anhydride j Chromic Acid

PIGB H0 * PAEAGRAPH.......... .. .... ......................... or Protoxide of Tin 804 Stannic Oxide....... Certain Metals which form Acids with 624 688 Oxygen Tin I. 624 796 797 Processes for Extracting the Metal 798 Properties of Tin /99 Preparation of Tin-Plate 800 Alloys of Tin ........ ........... Titanium ...... ..... ...... .......... ..... ' 605 608 ib.. or Binoxide of Tin Metastannic Acid 805 Stannic Acid Stannates 806 Sulphides of Tin 807 Characters of the Salts of 808 Estimation of ...... 634 ib.... 809 II............... .... 610 611 786 Chlorides of 787 Oxides of 788 ssay of Black Oxide of 789 790 791 792 793 794 Acid Manganates Permanganic Acid 613 615 617 618 Manganous Sulphide. 638 639 640 641 ... VI.. Manganic . or Sulphide of Chromium 779 Nitride of Chromium 780 Sulphates of Chromium 781 Chromic Nitrate. .. 810 Chlorides and Fluoride of 811 Oxides of Titanium Titanic Acid (Anhydride) 812 Characters of the Compounds of Titanium ...... ...... Titanium ........ ...........XV111 TABLE OF CONTENTS.. ...... or Carbonate of Manganese Characters of the Salts of Manganese .... XXII....... . Compounds Chromium .. ' 625 627 628 629 631 632 633 ib.... Chromium .............. ...... Manganese 785 Manganese .............. . Tin ......... or Bichloride of Tin 803 Stannous Oxide........... ...... So i Stannous Chloride. or Sulphide of Manganese Manganous Sulphate. 622 ib- CHAPTER Group VI..... - 776 Chromates 777 Chlorochromic Acid 778 Chromic Sulphide... .......... or Nitrate of Chromium 782 Oxalates of 783 Characters of the 784 Estimation of of . 609 ib.................. 619 621 ib................... ...... or Sulphate of Manganese Manganous Carbonate...... ...... ........ Chromium .. or Protochloride of Tin 802 Stannic Chloride...... ib.... 637 ib. .. A Manganese ... . .............. 795 Estimation of Manganese.... ib....... .... Tin ..... .... ib. .... 813 Estimation of Titanium ............. Manganese .. ...... ... 642 .......... .....

642 ib. 842 Estimation of Arsenic 843 Separation of Arsenic from other Metals ib... Tungsten 823 824 Chlorides of Tungsten 825 Oxides of Tungsten Tungstic Acid 826 Sulphides of Tungsten 827 Phosphides of Tungsten 828 Characters of the Salts of Tungsten Tungstates 648 ib. Bromide..TABLE OP CONTENTS... SIX PAOB III.. 844 845 846 847 848 IX. Zirconium Thorinum ' . Niobium Tantalum Bromides of Vanadium 653 830 1 VII. or Oxide Properties of 673 674 677 ib.. - ib. and other Compounds of Vanadium 833 Characters of the Compounds of Vanadium Vanadium 656 834 VIII. or *AfcAGBi. 838 Arsenic Acid Arseniates 839 Sulphides of Arsenic Realgar Orpiment 840 Characters of the Compounds of Arsenic 841 Search for 663 664 666 Reinsch's Test Arsenic in Organic Mixtures Marsh's Test 668 673 . 818 Chlorides of Molybdenum 819 Oxides of Molybdenum 820 Molybdic Anhydride Molybdates 821 Sulphides of Molybdenum 822 Characters of the Salts of 645 ib. and Fluoride 837 Arsenious Acid Arsenites . Molybdenum V. ib. 647 ib. of Antimony 849 Antimonic Acid Antimoniates 850 Metantimonic Acid Metantimoniates 851 Sulphides of Antimony 852 Characters of the Compounds of Antimony 678 679 680 681 682 .. 829 VI. 658 660 ib.PH. 83 832 Oxides. Arsenicum 656 835 Arseniuretted Hydrogen 836 Arsenious Chloride. 817 IV. VanadiumChlorides of 654 ib.. Iodide.. Antimony Antimony Antimoniuretted Hydrogen Chlorides of Antimony Antimonious Oxide.. 814 Zirconium 815 Compounds 816 Thorinum and of Zirconium its Salts 643 ib. wo. Molybdenum 644 ib. . 652 653 ib.

or Refining 867 Kernel-Roasting 868 Properties of Copper 869 Brass 870 Cuprous Hydride.' . 710 . or Sulphide of Bismuth Nitrates of Bismuth . of _ . 711 ib. or Subiodide of Copper 874 Cuprous Oxide.. . 700 701 ib. Copper . 684 686 ib. 884 II.' . or Hydride of Copper 871 Cuprous Chloride. ..BAGRAFH.. TABLE OF CONTENTS. 706 & 707 708 ib. 703 Tricupric Nitride.. . ^. 853 Estimation of Antimony 854 Separation of Antimony from other Metals 683 684 855 856 857 858 859 860 86 1 X. 885 Extraction of Lead 886 Pattinson's Process for Extracting Silver from Lead 887 Separation of Silver from.. CHAPTER Group VII.^ ..8 1 692 694 695 696 698 699 ib. 689 738 Copper . 863 Welsh Process of Copper Smelting Calcination of the Ore 864 865 866 Melting for Coarse and for Fine Metal Blister Copper . .. or Suboxide of Copper 875 Cupric Oxide. Lead .. 689 690 ib. . or Black Oxide of Copper 876 877 878 879 880 8..' 687 ib.. Lead * Thallium . . Phosphide Copper Sulphates of Copper . 704 ib . .. Poling. . Nitrates of Copper Carbonata^of Copper 882 Characters of the Salts of Copper 883 Estimation of Copper. Indium 862 I. or Nitride of Copper Sulphides of Copper Grey Copper Ore Selenide of Copper.^ ..] . or Chloride of Copper 873 Bromides of Copper Cuprous Iodide. 713 714 716 ib ^89 Properties of Lead 890 Combined Action of Air and Water on Lead 717 . . or Subchloride of Copper 872 Cupric Chloride. ib.. or PA.XX wo.' r . . Bismuth Bismuthous Chloride Bismuthous Iodide Oxides of Bismuth Bismuth Sesqui sulphide. Lead by Cupellati on 888 Other Processes for Extracting Lead .. ..'-. Characters of the Salts of Bismuth Estimation of Bismuth 688 XXIII.

738823 738 Group 912 I. 728 730 7 ... 742 744 746 747 ib. or Black Oxide of Mercury 920 Mercuric Oxide. Phosphates.. and Borates of Lead Carbonates of Lead White Lead Characters of the Salts of Lead Estimation of Lead . and Fluoride of Lead 719 720 ib.'"... TO. 894 Plumbic Oxide Protoxide (Litharge) 895 Eed Oxide of Lead (Minium) .'.... or Peroxide of Lead Plumbates 897 Plumbic Sulphide. 923 Mercuric Sulphide. . Cinnabar.. and Alloys of Lead 892 Chloride. .'. or Vermilion 924 Oxychlorides of Mercury 925 Nitride of Mercury ..' 896 Plumbic Dioxide. . .. . '*-'.. Indium # 737 ib. 909 Compounds of Indium 910 Characters of the Indium Compounds CHAPTER XXIV..' 916 Action of Ammonia on Corrosive Sublimate 917 Bromides of Mercury .'..". . Mercury . ... . or Mercurous Chloride 915 Corrosive Sublimate. Oxychlorides. .. 73i 905 III. 748 749 750 ib. . - . .". 913 Properties and Uses of Mercury 914 Calomel. . ib. " . . 922 Sulphides of Mercury - . and Sulphide of Nitrates of Lead Nitrites of .'.. Group VIII.'... 898 899 900 901 902 903 904 Sulphate. 752 753 ib. Thallium of Thallium . Lead ' . 723 Plumbic 724 726 727 ib. .'..*./.. or Sulphide of Lead (Galena) Selenide 721 722 .'. .. OF PARAGRAPH. .'. .' 918 Iodides of Mercury 919 Mercurous Oxide.. .'. 911 General Eemarks upon The Noble Metals this . v ib. . . . 738 741 . .' ^".! . . . . . and Bromide of Lead 893 Iodide.TABLE OF CONTENTS. .'.. ' Lead . XXI 891 Uses. 734 735 908 IV. 732 906 Compounds 907 Characters of the Salts of Thallium '. . . . or Mercuric Chloride .' f J .".'"'. .. 926 Sulphates of Mercury . . or Red Oxide of Mercury 921 Mercuramine . .

781 949 Characters of the Salts of Silver 950 Estimation of Silver 951 Separation of Silver from other Metals 782 783 ib. . . . 948 Phosphates of Silver ..' 788 789 792 793 958 959 960 961 962 963 964 Chlorides of Gold Bromides.. .. or Peroxide of Silver .. Silver 756 758 7^ T 931 Extraction of Silver by Amalgamation 932 American Method of Amalgamation 933 Separation of Silver from Copper by Liquation 934 935 936 937 938 939 940 Plating and Silvering Silvering of Mirrors . < 7^4 765 766 768 773 774 Alloys of Silver Assay of Silver by Cupellation Assay of Silver by the Humid Process Preparation of Fine Silver Chlorides of Silver 941 Argentic Bromide.. or Sulphate of Silver 947 Argentic Nitrate... . 966 Properties of Platinum 967 Platinum Black 968 Applications and Alloys of Platinum 969 Chlorides of Platinum 801 . or Protoxide of Silver 944 Fulminating Silver Diargentic Dioxide. .. or Nitrate of Silver ^i^'. . . . Platinum 796 799 800 ib. and Fluoride of Silver 943 Suboxide of Silver Argentic Oxide..... . 7^3 ib. 776 ib. 945 Argentic Sulphide. 952 111. 794 795 ib... 927 Nitrates of Mercury 928 Characters of the Salts of Mercury 929 Estimation of Mercury 753 754 755 930 II. Gold- ... . or Bromide of Silver 942 Iodide.. .. and Iodides of Gold Oxides of Gold Aurates Sulphides of Gold Purple of Cassius . .. 955 Processes of Gilding 956 Alloys of Gold 957 Assay of Gold Amalgams of Gold .. 777 778 ib.XX11 TABLE OF CONTENTS. or Sulphide of Silver 946 Argentic Sulphate... .... 783 785 786 787 . ib. 780 ib.. 796 965 IV.. Characters of the Salts of Gold Estimation of Gold Separation from other Metals . 953 Properties of Gold 954 Preparation of Fine Gold . ...

and Attraction. Bromides. 807 ib. . .. of Chemical Attraction 992 General Eemarks I. 808 977 978 Chloride. .. .. . Palladium 808 810 . On some Circumstances which modify the Action 823 . 811 812 VI.. Osmium 817 818 819 987 Chlorides of Osmium 988 Oxides and Sulphides of Osmium 989 IX. o* P1BAGBAPH. Rhodium . 982 Chlorides. 850 823 Influence Adhesion.. and Cyanide of Palladium 979 Oxides. . Sulphate. Iridium 820 990 Chlorides. XX111 970 971 972 973 974 Ammoniacal Derivatives from the Chlorides of Platinum Bromide and Iodide of Platinum Oxides of Platinum Sulphides of Platinum Other Compounds of Platinum . Sulphides. and Iodides of Iridium 991 Oxides and Sulphides of Iridium . Oxides. and Nitrate of Palladium 980 Characters of the Salts of Palladium 981 V. 812 -. 975 Characters of the Salts of Platinum 976 Estimation of Platinum ib. 803 806 ib. 829 830 833 . 984 Treatment of the Ore of Platinum 985 Euthenium its Chlorides and Oxides 815 816 986 VIII.. Ruthenium. . Chemical Volatility on of Cohesion..821 822 CHAPTER XXV. Iodide. wo..TABLE OF CONTENTS. 993 Influence of Cohesion 994 Influence of Adhesion and Solution 995 Influence of Volatility on Chemical Attraction 996 Aid afforded to Chemical Attraction by Mechanical Action 824 ib. 825 826 997 998 999 1000 1001 Influence of Pressure in preventing Decomposition Action of Acids on Salts in Solution . ." and Sulphides of Ehodium 983 Characters of the Salts of Ehodium 813 814 VII. 827 ib- Action of Bases on Salts in Solution Mutual Action of Salts in Solution Influence of Mass on the Formation of Compounds . .

1019 Aid derived from Isomorphism Specific Heat. 851 1013 Suspension of Chemical Action by Depression of Temperature 1014 Attraction between Hydrogen and the Non-metals . 863 CHAPTER XXVH. . 1 020 Numerical Data upon which the Calculation of the Atomic Weight of each Element is founded102 1 Table of Atomic Weights 1022 Numerical Relations of Atomic Weights 1023 Dumas' Experiments on Atomic Weights 1024 Stas's Experiments on Atomic Weights . .. ion Influence of Temperature on Chemical Attraction 1012 Dissociation . On the Determination of the Combining Numbers and Atomic Weights of the Elementary Bodies 864885 1018 Aid derived from Analysis in fixing the Atomic Weight of a Body ... ... TABLE OF CONTENTS. . . . . &c. . 862 . . 1002 Gladstone's Experiments on the Influence of Mass 1003 Experiments of Bunsen and of Debus on the Effects of Mass i"bo4 Experiments of Harcourt and Esson on Chemical Change . Thermo-Chemistry 1010 General Remarks 850 . . . . . ... 883 884 . 853 855 856 86 1 . 1007 Catalysis Liebig's Theory 1008 Effects of Motion on Chemical Attraction 843 844 . 864 865 . 839 841 1005 Surface Actions of Platinum 1006 Qther Surface Actions . 868 881 882 . 1009 Concurring Attractions Mercer's Theory of Catalysis 845 846 CHAPTER XXVI. 1016 Phenomena of Neutralization 1017 Double Decomposition . 834 837 .XXIV NO. 864 850 . . . .. ... OP PARAGRAPH. 1015 Attraction between Oxygen and the Non-metals .. .

912 ib. but Inflammable 1024 aa (3) Gases not Absorbable by Potash. and Mellitic Acids Compounds 1024 m of Carbon with Nitrogen. Compounds iro. . ib. not Inflammable 1024 bb (4) Gases not Absorbable by Potash.. . Cyanogen 1024/1 Hydrocyanic or Prussic Acid 904 . .- 10240 Cyanides 1024 p Chlorides of Cyanogen 1024^ Bromides and Iodides of Cyanogen 1024 r Cyanic Acid 1024 s Fulminic Acid 1024 1 Isomerism 10241* Paracyanogen 10241. ib. ib. 914 General Remarks on Gras Analysis. o* PARAGRAPH. 886 888 890 893 ib. Compounds of Cyanogen with Sulphuretted Hydrogen .. or Ethylene Diiodide 1024 f Oi] Gas (Tetryleneor Butylene) 1024$ Chlorides of Carbon 1024 h Carbonic Bromide (CBr4) 10241 Carbonic Oxydichloride or Phosgene Gas I 895 ib. . 1024 w Modes of discriminating different Gases 10240. but Inflammable 1024 cc Example of the Analysis of Coal Gas . of Carbon and Hydrogen. 1024 y (i) Gases Absorbable by Potash. Compounds of Carbon with Oxygen and Hydrogen. 1024 a Light Carburetted Hydrogen or Marsh Gas 1024 b Olefiant Gas. 10246 Glycol Diiodide. or Ethylene 10240 Dutch Liquid Action of Chlorine upon it 1024 d Gly col Dibromide. . 915 ib. or Ethylene Dibromide (C 2 H 4 Br2 ) . . 907 909 910 ib. Croconic. not Inflammable 1024 z (2) Gases Absorbable by Potash. 913 . ib. XXV APPENDIX. . . .TABLE OF CONTENTS. 896 901 1024 k Oxalic acid 1024 I Ehodizonic. Analytical Classification of the Gases. 916 917 ib. 918 923 INDEX .

.

Names of Elements. .Symbols and Atomic Weights of the Elements as used in this Volume.

.

and the properties of the bodies and their origin often make it extremely difficult to decide to which diviIt is.. II. especially if it be derived from the animal or the vegetable kingdom. B . CLASSIFICATION OF THE ELEMENTS. The same laws which regulate the formation and decomposition of inorganic bodies prevail also in the case of organic compounds. Chem. and In even of the proportions in which those components occur. venient in many cases to retain the distinction.PART II. description of the chemical properties of the different elementary substances. complex nature. THE division of chemistry into inorganic and organic purely artificial. becomes an indispensable supplement to its name. this object is very completely attained. x. the less complicated substances with which the chemist has to In those of a more deal. The object of the inventors of this language was. but also to convey a knowledge of their components. it will be needful to explain the principles upon which the nomenclature in use amongst chemists has been founded. not merely to give a distinguishing name to the substances spoken of. Before proceeding to a Principles of Chemical Nomenclature. and the formula of a substance. and perhaps the most accurate definition of organic chemistry is that given by Schorlemmer (Jour. the employment of symbols (13) becomes necessary. consion they should be considered to belong. in order that the composition of the body may be fully indicated. " the The chemistry of the Hydrocarbons and their derivatives. 428) viz. and of the compounds which are the result of their union with each other."" student Avill definition when he be able fully to appreciate the signification of this studies the compounds which carbon produces with other elements. [2]. CHAPTER NOMENCLATURE (331) is I. INORGANIC CHEMISTRY. Soc. however.

the usually that by which it is distinguished as is the case with many in chemical language. if the substance of the metals. other to form a binary compound that is to say. inasmuch as one of them neutralizes three time In order. a necessary component of water The attempt to introduce a strictly systematic nomenclature for the elementary substances has failed. sodium. copper. molecule. as is required by another acid such as the nitric (HN0 3 ). iodine. therefore. the name is some marked peculiarity by which the element generally indicative of is characterized. owing to the strong hold stance that it is . iron. for example. from v$wp. will require three times as much potassium to form with it a neutral salt. 14) to the loose way in which the terms atom. chlorine. osmium. For example. it will be convenient to speak of the relative quar tities of each acid above cited as a molecule of their respective acids . &c. but covered a in the case of the metals more recently dis- has been assigned to them. such as lead. Phosphorus. light bearing) because when exposed to the air it emits a feeble light which is visible in a darkened room iodine derives its name from to* i&jc . as are not equivalent to each other. BINARY COMPOUNDS. ytiraw) and so on. CHEMICAL NOMENCLATURE Elements. and in which also one atomic proportion* only of each substance is concerned the and silicon is indicated 2. have similar and the existence of a certain analogy between boron by the common termination of both. an acid like the citric (H s C 6 O r ). When elements combine with each Binary Compounds. and fluorine. which the popular names of those in familiar use have retained upon the language. properties . bromine. much potassium as the other. and at the same time to secur brevity in our descriptions. a term wai ranted by the fact that the formula of each represents the simplest expression i symbols which can be adopted to indicate the smallest particle of the compoun - i 1 which can exist either in combination or in separate form. is so named (from ^wr fopog. potassium. Among the non-metallic elements analogies are also pointed out by a similarity in the termination of the name common termination in um : for instance. and havf pointed out the essential difference between the signification of the two terms. hydrogen is so called from the circum(water producer. . a compound in which two elements only are present. in reference to the violet colour of its vapour . aluminium. or zinc be one which is familiarly known if it be a body which the researches of the of each : common name chemist have brought to light. * We have already called attention (iza. iridium. (violet). In the is case of the elementary bodies. to avoid this solecism. palladium. The proportion of citric acid represented by th( formula (H gC 6 6 ? ) is nevertheless sometimes inaccurately termed its equivalent and the same term is also applied to the proportion of nitric acid represented b the formula (HNO 3 ) yet it is manifest that these quantities of the two acid H fi H 1 .2 1. and equivalent are often employed by chemists. as. for example.

It is to be observed that in employing symbols is the symbol of the basylous or electro-positive element (261) usually placed first : The compounds of . a combination of ployed oxygen with zinc is : The following table designated oxide of zinc or zincic oxide. the symbols of the different compounds are given in the fifth column. nature of both the components is specified by the name emfor instance. will illustrate the manner in which such modifications are applied .NOME X CLATURE MULTIPLE COMPOUNDS.

a different plan is At the time that adopted to mark this important peculiarity. the compound SbCL is chloride. for example. termed either antimony pentachloride or perchloride of antimony. or super. as. NOMENCLATURE ACIDS. the compound (SnS 2 ) should. is frequently termed the peroxide. and chromium sesyuionide (Cr 2 O 3 ). we speak of sesym'sulphide of iron one and a half/ S The highest oxide. as indeed its name (signifying generator of acids) implies. If the oxides. contains still more oxygen than the one to which the terminatioi ic had been already appropriated. sulphurous (H 2 SO 3 ) indicate acids in which { smaller proportion of oxygen is present than in nitric and sul name which ends with In a few cases an acid has been discovered whicl phuric acids. in this case the prefi: per (which is an abbreviation for virep. oxygen was considered to be the element upon which the existence of the acid character mainly depended. The system of nomenclature was therefore specially adapted to this idea. which has the composition HC1O 4 . chloride. calcic persulphide or pentasulphide This practice of using indifferently a Greek or a Latin prefix in the names of compounds belonging to the same series is etymologically reprehensible. for instance. or i \ to i is expressed by the Latin prefix sesqtri. If. pound of of water. It frequently happens that an element forms more than one acid with oxygen the compound which contains the largest propor: tion of oxygen is in this case indicated by making the name terNitric acid (HNO 3 ).4 of antimony trichloride. the comis and CaS 5 termed indifferently of calcium. the acid of nitrogen in which the largest quantity of oxygen if found in like manner sulphuric acid (H'2 SO 4) is the most hignh : A second acid which contains acid of sulphur. which means For example. is minate in the syllable ic. i represented as HC1O 3 . or sulphide. but an acid was subsequently found t< exist. possess acid characters. be termed the deutosulphide or disulphide. above) is em . for example. tin (SnS) be termed the protosulphide. perFor example. (Fe 2 3 ). or j^ersulphide. Chloric acid. though in this case the use of the name bisulphide is generally sanctioned by custom. in order to preserve consistency. Acids. (SbCl 3 ) is used as synonymous with antimony The more complicated relation of 3 atoms to 2. when combined with the elements 4. is the case with some of the higher oxides of nitrogen. the nomenclature was devised by Lavoisier and his coadjutors. same elements united with a smaller proportion of oxygen oxidized ceives a the re- the syllable ous : thus nitrous acic acid and (HNO 2 ). for instance.

to designate indifferently either the anhydrous bodies formed by the union of oxygen with the non-metallic elements. . These acids are usually distinguished by prefixing the word hydro. : sulphuric acid. however. technically called sulphur and hydrogen form H 2 S /iyrfrosulphuric acid cyanogen and hydrogen form HCy. This is nowhere more conspicuous than in the differences which prevail in the mode of designating the different varieties of salts. cyanhydric acid. or the hydrated compounds S0 4. or bodies destitute of hydrogen). a great deal of confusion unfortunately exists at the present moment in the nomenclature adopted by different authors. has revealed other acids in . a . with a still smaller amount of oxygen is known as Aj^ochlorous acid. these terms they speak of chlorhydric acid. Thenard. nitric acid.NOMENCLATURE ployed. hydrochloric acid. indicated the salt formed by the combination of sulphuric acid with the alkaline base potash . as occurs with most of the insoluble oxides. is then dihydric sulphate. the prefix hypo (from VTTO below) is usually employed for instance. oil of produced by the action of water upon the anhydrides. hydrocyanic or prussic and so on. the salt obtained by neutralizing nitric acid with soda. a longer The term acid has been employed by chemical writers up to a late period. but which are compounds of hydrogen. we shall limit the term * H acid to those hydrated bodies which are H really salts of acetic acid. as an abbreviation for hydrogen for instance. chlorine and : hydrogen form an muriatic acid : : HC1. produced by the application of the same term to two substances essentially distinct. The progress of research. If the base has no single distinguishing name. Owing to the change which has recently taken 5. O is new compound has been termed perchloric acid. Some writers. : place in the views prevalent respecting the atomic constitution of chemical compounds. such as 2 vitriol or sulphuric acid. such as CO2 and S03 (now commonly termed anhydrides. or sulphate of hydrogen . is hydric nitrate. At was the time that our nomenclature was originally devised it supposed that a salt consisted of a combination of an acid with a basic oxide. or nitrate of hydrogen or acetate of hydrogen. nitrate of soda. and the name given to each salt was framed upon this idea . HN0 3. acid. which oxygen is wanting. hydrogen . for example.* known in which the proportion of oxygen is smaller than that which exists in the compound to which the termination ous has been appropriated. and so on. a S04 . To avoid this contusion. transpose and sulphydric acid. HC H O 2 2 hydric acetate. and the When an acid SALTS. following the example of acid. sulphate of potash. Salts. chlorous acid consists of HC1O 2 whilst the compound HC1O.

however. salts. |Dipotassic sulphate. Nitrate of sodium.. sodic nitrate. (Acetate 3 { Cupric diacetate. r wn 3 a v c i sodium nitrate. into acetate Many chemists have sought to remedy this inconsistency by introducing in every instance the name of the basyl or the metal into the salt.C NOMENCLATURE requisite. in naming sucl compounds the termination of the acid is changed into ate : thu: the salt formed by the action of nitric acid upon lime is termec calcic nitrate. and formiale of lead . and plumbic formiate. lowing table . omitting the word of altogether so that they speak of potassium sulphate. When acids ending in ic form salts. copper acetate. Lastly. and lead formiate. Formiate of Iqad. the When the acids by their action upon bases form degree of oxidation in the acid is still indicated by the name o the salt. as well as of acetate of copper and formiate of lead. sodium nitrate. name was oxide When. although cases will occasionally occur in which the other forms of nomenclature will be employed. for instance. From what has been just stated. r p. : _ 4 j Sulphate of potash. ^Plumbic diformiate. which will generally be adopted in work. cupric acetate.. in accordance with the principle just explained. Sulphate of potassium. acetic acid acts upon of copper. SALTS. but these long names became almost immediately shortened of copper. of oxide of copper. for reasons to be explained immediately. to place . so that he speaks of potassic sulphate. 2 Copper acetate. (Formiate of oxide of lead. not only employs the name of the metal but modifies its termination . terms which are obviously inconsistent with the names given to the salts of the alkalies and of the earths. or more strictly. and nitrate of sodium. acetate of oxide of copper. instead of that of the base or metallic oxide. Acetate of copper. Potassium sulphate. Lead formiate. [bodic nitrate. . whilst it still employing the first in naming the salt. Some writers. name of the metal or basyl. it will be seen that four different usages are more or less prevalent in naming salts these may be contrasted and compared together as in the folIt is this last modification this . They speak therefore of sulphate of potassium. prefer. calcic dinitrate (Ca2NO 3 ) . (Nitrate of soda. and formiate of oxide of lead . or produced were formic acid upon oxide of lead. the salts named. Berzelius.

for example. or sulphate of potassium (K 2 SO 4 . or the sulphide* and the sulphites. the protoxide (FeO). represents the composition of the Iron. is a compound. twice).O. but there is another compound of potassium with acid) ) sulphite. If the name of the acid end ia changed to ite in naming the salt. or sulphate of potassium and hydrogen. contains one proportional more of oxygen than disodic one equivalent of the oxion (or radicle of an be united with one equivalent of a metal. of the necessity of distinguishing clearly between compounds such as the sulphites and the sulphates. a metal forms only one basic oxide that is to say. which is made to precede the name of the acid contained in the neutral salt. again. sulphurows acid and baryta by their mutual action form a salt called baric sulphite (BaSO3 hypochlorows acid and soda potassic perchlorate (KC1OJ. It may here be well to caution those who are just commencing the study of chemistry. 7 sulphuric acid acts upon protoxide of iron. often described as of iron but there is another series of salts of iron .. protosalts : salts corresponding to were formerly distinguished as FeSO 4 . or more correctly. for example. whereas disodic sulphite (Na 3 SO 3 ) is a more complex compound formed by the action of two compound bodies upon each other. this compound present 4) is known as the bisulphate of potash. for example. as (KHSO hydric potassic sulphate. may form Such salts of protoxide of iron. Disodic sulphide (Na3 S). the salt procalled sulphte of iron. or ferrous sulphate (FeSOJ perchloric acid by its action upon potash furnishes the salt called When duced is : oils. : .NOMENCLATURE SALTS. Generally speaking. the circumstance of the additional equivalent of acid in this and in other analogous cases being still often conveniently indicated by the prefix bi (from the Latin bis.H 3 O.6H. If more than sulphuric acid. there is no A compound difficulty in pointing out this fact in the name. or sesquisults of iron crystallized sulphate . containing a product of the direct combination of two elementary substances. in which two equivalents of the dyad oxion are to one equivalent of the metal .2 O. but there are several exceptions to this rule. is the termination ) : by their mutual action form sodic hypochlorite (NaCIO). of two equivalents of sulphion (SOJ" and two of potassium (K 2 ) would be spoken of as dipotassic sulphate. or di (from the Greek St'c). only one oxide which has the power of forming salts by interaction with acids . Disodic sulphate (Na2 SO 4 ).j) of the metal thes3 were distiuguished as the persalts. protosulphate derived from the peroxide or sesquioxide (^e.

so that they are frequently the compound spoken of is one of constant For example. ferrous oxide. a strict adherence to system is often not only useful. and Na 2 SO 4 sodic sul2 phate. although still used.. represents the sulphate of the peroxide or sesquioxide of iron. calcic dinitrate. Again. . KHSO 4 hydric potassic sulphate. baric dinitrate. nitrion (NO 3 )' . following : K SO dipotassic sulphate. Again. Yet we commonly speak of them as calcic nitrate and baric nitrate. there are abbreviated to calcic phosphate. calcic sulphate. but necessary to avoid confusion. Berzelius preferred to eall the pro- toxide of iron. SALTS. only one of nitriou is present. so that.3SO 3 or Fe 2 3SO 4 . in the ordinary or tribasic phosphates. ferrous sulphate. Na 3 SO4 CaSO 4 It is. and do not in the name indicate the presence of two prowhilst in the sodic salt NaNO3 which is portions of nitrion of as sodic nitrate. customary to speak of the normal or neutral salt of any acid without the numerical prefix . are not free from ambiguity. These terms. For example. while the sesquioxide he termed ferric oxide. in the case of the nitrates of the dyad metals.8 NOMENCLATURE . and the This sesquisulphate was upon his plan called ferric sulphate. for example. many salts of varying composition formed from the same acid. correctly spoken . . though in reality these names do not indicate their atomic K difference from the normal is salt of a dyad like calcium. or sesquisulphate of iron. the sul- phate of which (CaSOJ both commonly and correctly spoken of as calcic sulphate. Ca2NO 3 Ba2NO o a . the salts are strictly dinitrates. however. Many of these systematic names have an uncouth aspect. the common lime phosphate (Ca3 2PO 4 ) should be designated as tricalcic diphosphate. and are often long and inharmonious.. Fe. though usually this is When. . and will usually be employed in this work. . . disodic sulphate. for instance. however. 2 4. and it is frequently termed the persulphate. being a monad. the sulphates of the alkaline and earthy metals would receive systematic names such as the abbreviated when recurrence. and the protosulphate. SO 4 is simply called potassic sulphate. form of nomenclature unites brevity with precision.O 3 .

has the following empirical formula : (i) MgH SO nJ 14 that is to say. its constituents are present in the ratio of i i atom of magnesium. the proportions of the different basyls require indication : H 3 PO 4 trihydric phosphate. A body can but it have but one empirical may be represented by a variety of constitutional formulae. Other forms of nomenclature are applied in particular cases. as diphosphate and of HNaH NPO cosmic ammonic hydric the oxion. the sodium. the of a use of composition body by symbols. AND CONSTITUTIONAL FORMULAE. In expressing the (332) Empirical and Rational Formulae. thus substances. for example. lastly. and n of oxygen. . 14 of hydrogen. . By prefixing the numeral in the name to the particular constituent in the salt. be useful to speak of Ca3 2PO 4 as (superphosphate of lime) as tricalcic di phosphate of CaH 4 2PO 4 . in the three phosphates of soda formed from the ordinary tribasic acid. but these will be best explained as the examples to which they refer arise. 4 4 (microsodic phosphate. Again. and one rational formula. he may attempt an explanation of the mode in which he conceives those elements to be associated together. in which case he gives what is termed the empirical formula of the body . the chemist may either content himself with simply stating the restilt of analysis by a mere enumeration of the elements and the relative number of proportionals of each. according to the different views which may be taken as to the mode in which its components are arranged. H 3 NaPO4 sodic dihydric phosphate. . we indicate the number of proportions of the par- ticular component which it precedes. HNa PO4 hydric disodic phosphate. . or he may give the numbers and relative proportions of the atoms present in one molecule of the rational formula. Crystallized magnesic sulphate. and thus assign to it a theory constitutional formula. or tetrahydric salt). which in frequently the same as the empirical formula or. calcic it may sometimes . whether it be the hydrogen. of sulphur. Na 3 PO 4 trisodic phosphate. . the compound.EMPIRICAL. RATIONAL. . showing mineral is and by the arrangement of his symbols may give expression to a of constitution of the the body.

6H 2 0. 6 molecules of the be expelled. thus molecules in the may justify combined with the salt. But it is water may found that at a heat of 100 C. guided by the results of the electrolysis of the salt. and : the salt often represented as consisting of magnesia. Each of the last five a constitutional far formula for magnesic sulphate. . as Mg.S0 3 . may The water which it contains however. and each conveys more information Each represents a theory founded upon I modes of particular decomposition which the salt may be made to than the formula No. 7 OH 2 . suppose that when once an acid and a base have reacted on each other. never so written. that the oxygen atoms in the salt are diftwo being combined with the sulphur.6 may be indicated by slightly altering the second formula.S0 3 . . sulphuric anhydride.10 It is. and they prefer to represent the (4) salt accordingly. partly Many chemists. so that it appears to occupy a posithis fact different from that of the other . as these are the materials out of which it may be formed thus is : (2) MgO.H 3 0..H 2 0. and water. AND CONSTITUTIONAL FORMULAE. 7 H 3 0. RATIONAL.6H 2 0. compound (6) SO(OH) 2 (0 2 Mg). EMPIRICAL. be entirely driven off by a heat a little above 200 C. an combination the seven molecules of water atomic forming present being merely united to the salt by a looser kind of attraction. producing what is sometimes called a molecular com- or we may suppose . is the different condition in which one of these water placed the conclusion that it is intimately the two atoms of hydrogen being present in the form of hydroxyl. their elements are arranged in an order different from that in which they existed when separate. bination : (5) S0 2 (0 2 Mg).S0 4 . and two ferently placed.60H 2 formulae is . whilst the seventh molecule requires a : much tion in the salt higher temperature. experience. finally. however.. in being occupied linking together the sulphur and magnesium. or. as : follows (3) MgO.

occur have devised to represent been quently special symbols In these formulae the MgO them. thus the radical in question may be written Mgo" and may be dignified by the special name maynesoxyl being an The thick initial letter. of our knowledge of the comthe conditions faithfully represent which are The last two pounds they employed to indicate. and is kind of formula adopted. The value of is not so apparent in mineral chemistry as in organic. formulae above given are the symbolic representations of what expedients. though each may represent the grouping of its component elements under particular circum- Constitutional formulae are indeed indispensable as the of the theories which guide the chemist in his researches.EMPIRICAL. that indicates all atoms and compound already explained (16 a). radicals following are directly combined with it. RATIONAL.. by a large number of chemists. in fact. AND CONSTITUTIONAL FORMUL. Anhydrous magnesic sulphate graphically represented would be Mg / \ O \ / O and the hydrate with one molecule of water Mg / \ O \ O / S II H O O H O as a compound dyad radical 2 appears united to the and as radicals of this kind fredirectly sulphur. in principle at least. must consequently always be regarded as and must modified or discarded when they no longer be such. in this latter it is almost indispensable. exponents or which aid him in arranging and interpreting phenomena . 2 . they are only temporary stances. so that the two foregoing graphic formulae may be written symbolically or or S0 and 2 (0. and they may this be called the graphic or pictorial formula.Mg)" SOJVIgo" SO(OH) 2 (O 3 Mg)" SOHo Mgo". like the theories that they embody.E. but. 11 It is impossible that all these formulae should truly indicate the molecular constitution of the salt. as analogue of hydroxyl HO or Ho.

the constitutional formula will therefore be . or \CO(OH) In all fOH (COHo union it. the other being linked by oxygen to the second carbon atom while the carbon atoms are directly united. when polished. powerful acids. and are most of them insulators of the voltaic current. non-metals with oxygen generally show but little tendency to unite with acids on the contrary. are characterized by a combination of opacity and compactness. a peculiar brilliancy. to determine whether a bod} should be regarded as a metal or not. Three of the atoms of hydrogen appear to be differently placed from the fourth. readily soluble in water acid-forming oxides. Arsenicum has a high metallic lustre. under certain circum- may be obtained in solution. in certain The compounds of the forms. as shown by the brace. . however. acts as conductors of electricity. and constitutional The by those of acetic acid. furnish Work. if acted on by water. Carbon and silicon. but it possesses high lustre. are endowed with well-marked acid properties Tellurium also exhibits the closest analogy with selenium an< with sulphur. differences The formulae between empirical. form powerful bases. these formulae the brace indicates direct between the elements the symbols of which are placed next to (333) General Arrangement of the Elements adopted in this The general division of the elementary bodies into nonThere is metallic and metallic has been already pointed out. the higher oxides of most of them form compounds which. and both its oxides. certain is sometimes difficult. however. no strict line of demarcation between the non-metallic and the metallic elements.12 GENERAL ARRANGEMENT OF THE ELEMENTS. (OH. rational. wher The metals. are and even silica. three being directly combined to one of the carbon atoms. but it is more closely allied to phosphorus thai to any other elementary substance. and most of them. The molecule contains C 3 H 4 O 2 the rational formula. and some conducting power for electricity. . It dissolved in water. except silica. The bodies which are considered as non-metallic constitute the electro-negative ingredient in the binary combinations which they form with the metals. they are good conductors of heat and electricity. which gives them. however. the empirical simplest formula obtained by analysis is CH 2 O may be well illustrated formula. These . on the other hand. termed the metallic lustre . stances. by combination with oxygen.

-> 5 in number. 2. in the following order. Metals more or T. 4. in number. as already stated. II. 2. Erbium. 3 in number. since a complete study of these elements and of the compounds they form with one another will much facilitate the further consideration of the groups which they represent. V. Cerium. Yttrium. . 2. 4. Barium. III. excepting in those instances in which it seemed more advantageous to the student to follow a different In most cases we shall first examine the chemical course. nitrogen. Magnesian Metals . Iron. it will be found a convenient arrangement to consider in the first place hydrogen. Uranium. Manganese. and sulphur as typical of all the rest. though. the classification does not in all cases bring together those which. 3. Glucinum. the metals will be arranged in eight groups. 13 of the simple substances into non-metallic is. IV. Terbium. Earth. 3 in number. Nickel. however. Sodium. actions upon other elements. The elements which compose each group generally present some natural resemblance.Metals 1. Potassium. | Zinc. carbon. Strontium. Alkali-Metals 3. Lithium. 3. convenient to the student. Cadmium. and it will The order in which the therefore be retained in this work. 3. 2. Z. Lanthanum. Caesium. Cobalt. though analogy has guided us. 6. subdivision The and metallic which a different elementary bodies will be treated is not in all cases that rigid adherence to analogy would indicate.GENERAL ARRANGEMENT OF THE ELEMENTS. For the convenience of description and of reference. Chromium. I. I. less analogous to Iron 6 5. Calcium. and shall afterwards examine the more important compounds into the formation of which it enters. Alkaline Earth-Metals 2. 4. | Magnesium. boron. In describing the properties of the elementary bodies. properties which uncombined form its are exhibited by each of the elements in its we shall then study the general nature of . 7. oxygen. o- Aluminium. 5. Rubidium. chlorine. 8 in number. 6. Didymium. in chemical habitudes. \j 1. are really the most closely allied. 8.

Bismuth. the elements. 4. Noble Metals 1. . 2. 7. Mercury. 3. Tungsten. Thallium. Gold. 5. in others they are more obscurely marked. 9. 1 Vanadium. Rhodium. I. Silver. Arsenicum. 4. IO. 9. 5. Lead. 3. If a strictly natural order were to be followed in grouping it would. Osmium. Copper. Indium. Niobium. as well as of the noble metals. 8. VI. 6. and in the case of the metals of the earths proper.GENERAL ARRANGEMENT OF THE ELEMENTS. 4 Metals. out the most important nattiral groups into which the ing elementary bodies indication admit of being subdivided. Palladium. the natural chemical relations of these elements with the others are as yet but incompletely known. 12. VIII. 9 in number. Zirconium. Iridium. 7. Ruthenium. 2. 12 in number. Metals which yield Acids 1. 4. The detailed of the points of resemblance between the members composing each group must be deferred until the properties of In many instances these natural the group are considered. . Tin. VII. 8. Titanium. Molybdenum. Thorinum. Platinum. Tantalum. 6. l 3. Antimony. 2. relations between the individual elements thus grouped together are very striking. In the table which follows. the principal elementary bodies are represented in two converging series. however. be necessary to modify the This will be rendered evident by pointforegoing arrangement.

Oxygen. Iodine. MONADS. Boron._ Indium. TETRADS. Rhodium. DVADS. Tellurium. Carbon. Fluorine. TRIADS. Bromine. Selenium. 15 Chlorine.GENERAL ARRANGEMENT OF THE ELEMENTS. Gold. Sulphur. .

. THE following table gives a general view of some of the most The squares emimportant of the constants of the non-metals. corresponding to " Atomic the numbers given in the column of Weight/' assuming that the space occupied by one gramme of hydrogen under similar circumstances of temperature and pressure would fill a space of one square or one volume. THE NON-METALS. One gramme of hydrogen at o C.16 CHAPTER A. II. NAME. and 76o mm< pressure. " Atomic Volume/' indicate the ployed in the column headed relative volumes occupied by a quantity in grammes of each of the different elements in the gaseous condition. occupies a space of 11-19 litres. FIRST DIVISION. TABLE OF NON-METALS.

. .) long. though a supTo the porter of combustion. Hydrogen may also be obtained from water by the action size of a If a piece of this wrapped up in blotting paper. Tree oxygen Free chlorine . . 30 cm.. the volumes of which amount to double the combining volume of hydrogen..PREPARATION OF HYDROGEN. 10 or 12 inches (25 and inverted in the pneumatic trough. H 2 Se = = = = = = = = weight. bubbles of gas will be quickly disengaged. the mouth of a strong wide of sodium... T"l 28 36^5 18 fT"] [^ 34 81*3 C . voltaic battery is evolved from the platinode or negative former gas the name of hydrogen (from {/oy> water. at the other pole another gas is developed which is not inflammable. Preparation. . . metal of the pea be or and rapidly introduced beneath tube. . . . as for example: Equal vols. By passing a current of electricity from a HH Q through water acidulated with sulphuric acid.. . t Molecular formulae will always be employed where it is practicable. Free nitrogen . i. the great diffusibility of the gas rendering it extremely difficult to prevent admixture of atmospheric air. Sp. 2. . * Probably this number is a little too high in consequence of the presence of a small quantity of air in the hydrogen. sodic hydrate having been formed by the displacement of half of the hydrogen in the molecule of water by the equivalent of sodium 2 H 2 O + Na 2 = 2 NaHO + H 2 A convenient method of preparing hydrogen by this process. wt. 32 71 I . and will colOn inverting the tube and lect in the upper part of the tube... Molecular Free hydrogen .. yewaw to generate) has been given. 2 f"^] I. Molecular volume.. HH 00 C1C1 . .. 17 HYDROGEN : H= i. I . 0*0692 . and is termed oxygen (339).f . which is found on examination to be inflammable . and' this liquid is reproduced by their union in the proportion of two measures of hydrogen to one measure of oxygen. many compounds. Steam Sulphuretted hydrogen Seleniuretted hydrogen II. This is one of the element (334) principal constituents of in and exists other water.. . NN HCl Hydrochloric acid . . r . H HS 2 2 . Monad. Oxygen and hydrogen are the sole ingredients of water. a gas plate.fte/. the applying a light. . the gas will take fire and burn with flame liquid in the tube will be found to be alkaline.* Atomic volume ["J. filled with water .. if the atom of hydrogen H= i . i . .. : .. . and will change the yellow colour of turmeric to brown. . Molecule in free state ~J . Such molecular formulae will indicate quantities of each compound.. gr.

by transmitting steam over charcoal. and a regular stream of bubbles of hydrogen rises into the inverted vessel. let a FIG.] Deville and Debray prepare hydrogen on a large scale 4. D. B . attached to one extremity of the pipe . the oxygen will enter in vapour into combination with the heated iron. magnetic oxide of iron boiler. and an inverted jar filled with water placed it . into a basin of water. The decomposition may be represented 2 in symbols as follows : = FeO.) wide. whilst the liberated hydrogen will pass on. fig. products if the temperature be kept sufficiently low : . 275. being formed. placed over the mouth of a bent tube attached to the other extremity of the iron pipe. upon iron at a high temperature.) long and -fV of an inch (5 mm. or coke. shown at A A. in this way the water comes slowly in contact with the metal. piece of iron piping. nearly pure.18 is PREPARATION OF HYDROGEN. heated Carbonic anhydride and hydrogen are the sole to dull redness. The tube thus charged is thrown and sealed at one end. and may be collected over water in a jar. In order to effect this.Fe 23 O [Fe 3 + 4 H 2 . to force the sodium into a small piece of glass tube about | of an inch (20 mm. be filled with iron turnings or nails. 275. and heated to redness in a furnace. and let a current of steam be driven through the tube from a small c. the aqueous its passage will be decomposed. over Hydrogen may be also obtained by the action of water 3.

and similar to that known as the dry lime puriIf the temperature be allowed to rise too high. is dissolved by the alkaline liquid 2KHO + Zn but this becoming from K ZnO 2 2 2' method is interesting its theoretical bearings rather than from any practical utility. the metal displacing the hydrogen contained in the hydrate. or zincic in the gaseous form. while the hydrogen passes off The change may be illustrated by the following equation [S0 2 (OH) 2 + Zn= S0 8 (0 8 Zn)" + H 9 . is Hydrogen gas is soon evolved in great poured upon the zinc. which becomes called sulphate of zinc. The most convenient way. and carbon. 19 is purified by causing it to traverse an apparatus filled with slated lime. cess the zinc may be regarded as displacing the hydrogen of the salt acid. will furnish about 10 litres. or 30 grms. is by the action of diluted sulphuric acid on zinc.) of the granuinto grains or flakes lated zinc is introduced into a retort. The gas furnished by the action of diluted sulphuric acid on zinc also possesses a peculiar odour. : dissolved. and poured from the height of a metre into a pail of cold water. due to the presence of a peculiar compound of hydrogen and carbon. The zinc may be melted in an iron ladle. fier for coal gas. . prepared by cautiously mixing one part of oil of vitriol with 6 parts of cold water. by which means it is granulated. but this may be removed by allowing the gas to stream through a tube filled with : fragments of wood-charcoal (Stenhouse). In this pro- abundance : . arsenicum. or reduced about half an ounce (15 grms. The gas part of the carbonic anhydride (375)j an<^ this gas is converted into carbonic oxide cannot then be removed from the mixture. and is frequently contaminated with small quantities of compounds of hydrogen with sulphur. of procuring hydrogen 6.] An 2. however. must be allowed to escape afterwards the gas maybe collected in the usual way. and about 7 ounces (200 c.PREPARATION OF HYDROGEN. c. Scraps of iron may be substituted for zinc. but in this case the it has a gas is less pure disagreeable odour. solution of potassic hydrate. and forming the sulphate.\ ounce of zinc is sufficient to liberate from the acid about gallons of the gas. Hydrogen may also be obtained by heating zinc with a 5. stirring all the while.) : of a diluted acid. whilst the compound of zinc as it is formed. the first portions of gas which are contaminated with the air contained in the retort.

and carry with to the lightness of the Owing : ajar may be easily filled with it by displacement without using the pneumatic trough A tube. tioned. in the manner shown at A. 8 or 10 inches (20 or 25 centimetre*) long. and 760' Bar. though it cannot support life not poisonous. which was discovered by Cavendish in 1766. being more than six times as great as that of atmospheric air at the same temperature. Owing to its levity. power upon light is higher than that of any other gas. notwithstanding its much greater density. provided that it be still held ii the inverted position while if the mouth be turned up wards. 100 volumes of water. 276. has caused this latter. all temperatures between 32 and 75' 2 (o and 24 C. after the atmospheric air in the bottle has been allow ec to escape. and was called by him inflamWhen prepared with the precautions just menmable air. may be Properties.. it obtained.). transparent. 276. i litre at o C. dissolving 1^93 vols. or nitrate of silver. and inodorous gas. and a little less than a fourteenth of that of air. fig. or 100 cubic of hydrogen at : and 30 in. but owinj renders the voice temporarily much sharper an< more shrill than usual. and when mixed with a certaii proportion of oxygen may be breathed fo is to its rarity. according to Bunseu.20 It PROPERTIES OF HYDROGEX. when the hydrogen is compressed till its weight is the same as that of an equal bulk of air. rapidly. and will ascend a weight of several grains. tasteless. has been extensively used for aerostatic purposes. although the facility with which coal-gas can now be inches of it at 60 F. to be universally substituted for hydrogen in filling balloons. Pure hydrogen. is fixed by a cork. may be collected by holding a jar over the tube as at B. FIG. light may easily be inflated with it tag made of the craw of a turkey. and then through a solution through of corrosive sublimate. (it has never been liquefied. Hydrogen is an elementary substance. . weighs o'o896 grm. and tht gas. the gas will have escaped after the lapse of a fev . gas. The hydrogen will be retained for some minutei even if the jar be removed. . it some time without inconvenience.. seconds. A dion.) and is very slightly soluble in water. Bar. Hydrogen is the lightest form of matter which is known its weight is only one-sixteenth of that of an equal bulk of oxygen. it is Its refractive a colourless. freed from these impurities by causing it to pass first a strong solution of potash. or of collohydrogen. into a threenecked bottle containing some granulated zinc dilutee sulphuric acid is introduced through the funnel. weigh but 2' 1496 grains.

some of the most important gaseous compounds of the different elements with hydrogen are enumerated in each case. though slowly sulphur. FTP. Hydrogen has a smaller combining number than any other elementary body. and The proportion in which the different elements combine with hydrogen to form gaseous compounds affords a well-marked character which serves as a foundation for grouping the different elements into natural families. it also combines. . in the table which follows. when extinguished. bromine. and it has hence been taken as the unit or standard of comparison. For example. its Its combining volume proportional i or { number |. 21 Hydrogen unites directly with several elements if heated with If heated with them. Hydrogen plunged into is extremely inflammable . or i. yellowish. particularly with oxygen and with chlorine. and (H = i vol. and with difficulty. is therefore unity. both for atomic weights and combining volume. : Q HH Compounds with Monads. the gas jet of hydrogen takes fire A burns a lighted taper is but the taper is in air with a pale. a jar of it.GASEOUS COMPOUNDS OF HYDROGEN. or phosphorus. the quantity represented by the formula given indicates 2 volumes of the gaseous compound = 2 vols. feebly luminous flame of a very high temperature.

6o 68 per - cent. and a few other rarer elements discharge the functions of four atoms of hydrogen. and from this circumstance the name halogens o iodine. . of specific gravity from i'i6o to 1*170 canized caoutchouc. Monad (335) Chlorine. constituting This necessary of life occurs plentifully in ordinary table salt. platinum. The preparation of chlorine is an enormous chloride sufficiently of lime. Hydrochloric acid in solution. of chlorine.* was discovered by Scheele in 1774. sea-salt) has been applied to them. 2*4566 . is run through a curved funnel into the stills. chlorine. and is thus equivalent in function to three atoms of hydrogen. hold 200 gallons or about 900 litres of made of Yorkshire together with ironwork. 2*47 . Observed \_ sp. The hydrogen previously charged with oxide of manganese in small lumps of the acid is wholly converted into water bj the oxygen of the oxide of manganese. beds in various parts of the world. each atom of the metal forming a stable compound with 4 hydrogen in atoms of chlorine. ] . wt. Rel. tin.22 CHLORINE. for the triads embrace gold and rhodium. CHAPTER CHLORINE Theoretic sp. their representatives among the metals. Preparation. gr. []j. It liquid . Among the metals. is practised on of scale in the manufacture bleaching powder. dantly met with in combination with sodium. an atom of each of which unites with three atoms of chlorine. (which is obtained as a waste product in the manufacture of sodic carbonate from sea salt). bromine an< which are closely allied to one another. Cl = 35*5. one-half of the chlorine combining with the manganese whilst the other half escapes ir * The group of halogens consist of the elements fluorine. and is the most abundant of It contains the saline bodies existing in the waters of the ocean. : III. They form with metals com pounds analogous to sea salt. Molecule in free state C1C1 as in HC1. salt-producers (from aXy. vol. large to these are usually generally prepared in capacious stills. gr. the most important member of the group It is abunof halogens. In the fourth column the compounds enumerated contain four atoms of combination with another (tetrad) element. and the joints flags clamped rendered tight by vul- The lower part of these stills is enclosed ir a case through which a current of steam is transmitted. or i . Atomic 35-5 .

'Mn^ + ^HCT = in the conversion of the MnCJl. by elevation of temperature. and 4 parts of pounded sodic chloride mixed intimately with 3 parts of finely pulverized black oxide of manganese. and the manganese in that of manganous sulphate. was probably formed in these cases. explosions have in some Hypooperating on the large scale.. usually resorted to for the preparation of the gas Three ounces or 100 grms. 2. previously diluted with 7 parts of water and allowed to cool.PREPARATION OF CHLORINE.) owing to a neglect of instances this occurred in precaution. little hydrochloric acid is always formed A . The decomposition may be represented as follows MnO 3 + sNaCl + 3 SO 2 (OH) ~ = SO (O 2 Mn)" + SO 2 (OH) 2 2 (ONa) The gas comes off slowly in the cold. Care must be taken not to use an acid 15 litres) more dilute than 1-15 in the preparation of the gas. oxide of manganese with half a pint (350 cub. illustrated Manganic dioxide. In this case the whole of the chlorine io is expelled in the gaseous state. or one of the explosive oxides of chlorine. + aH^O + "cl7 This transformation takes place in two stages. Manganous chloride. on the small of powdered centim. (100 c. chlorous acid. acid. Water. since. the ultimate result of the reaction by the following symbols : 23 may he Chlorine. Hydrochlor. whilst the oxygen of the oxide is separated in the form of water derived from the produced oil : by combination with hydrogen of vitriol. Chlorine may also be easily obtained from a mixture of parts by weight of oil of vitriol. c. but freely on the application of a gentle heat. of the commercial muriatic acid diluted with 3 ounces of water.) scale in the laboratory. the first consisting manganic oxide into manganic chloride C14 : Mn MnO + 4 HC1 = aH O + MnCl4 2 2 . the gaseous form . which. the sodium remaining in the form of hydric sodic sulphate. will yield between 3 and 4 gallons (about of the gas. decomposes into manganous chloride and free chlorine MnCl 4 This process is = MnCl + 2 C1 3 .

(371 and 482 C. attended with coughing. Under a pressure of 4 atmospheres at 60. Chlorine is soluble in about half its bulk of cold ( 140 C. cannot be advantageously collected over cold water. and astringent ' taste of the gas. The temperature at which the transformation takes is between place 700 and 900 F. or i op cubic inches at 60 F. According to Schonfeld. large in passing a mixture of hydrochloric acid and air (as it comes from the salt cake furnacesj through a brickwork chamber containing fragments of firebrick which have been saturated with a solution of cupric sulphate or cupric chloride. Another process for the manufacture of chlorine on a 3. which liquefies under a mixture of crushed ice and water. water at 50 (10 C. a litre at o C.. if it be enclosed in hermetically sealed tubes. hydrate (Cl 3 .) (Journ. distressing irritation of the air passages. and 76o weighs 3-1808 grms. weigh 76*3 grains. reaction : but it is easily removed from the chlorine by allowing the gas to bubble up through a vessel containing water. The salt to but deterno chemical copper undergo change. green).) dissolves 2*585 times its bulk of the gas . or to collect the gas by the process of disWith water. which is readily formed by agitating the gas and water together. [a].ioH 2 O). Chlorine. . odour. gr. appears mines by its presence the decomposition of the hydrochloric acid by the oxygen of the air. Chem. in the manner shown in fig. from ^Awjooe. has the colour. even if largely diluted with air. Soc. about 1*33 and at the cold of 220 remains unfrozen even electricity. x. Properties. in consequence of this solubility.). 307.) 1*365 times its bulk. it is condensed to a it does not conduct yellow limpid liquid. water being produced and chlorine liberated. at 59 (15 C. 725). Chlorine is a transparent gas of a greenish colour (whence the name is derived. It produces. water. It is much heavier mm than air. It consists scale has been recently introduced by Deacon. of sp.24 in tliis PROPERTIES OF CHLORINE. and at 104 (40 C. chlorine forms a definite placement in dry bottles. yellow and of a powerful suffocating odour. since it is easily decomposed by a gentle heat into water and free chlorine. furnishes a ready method of obtaining liquefied chlorine. It is necessary. when breathed. and the solution.) 2*368. which may be readily obtained in" the crystalline state by passing a current of chlorine through This hydrate. therefore. and 30 inches Bar. either to use warm water in the pneumatic trough. and mercury is acted upon by the gas with great rapidity. where a similar apparatus is employed for carbonic oxide.

however. table colouring matters contain hydrogen. Uses. which at the moment that it is set free enters readily : into combination. the hydrogen of the combustible vapour of the wax combining with the chlorine. Another valuable property of chlorine is its disinfecting power. in bleaching and for disinfecting purposes. finely times with such energy as to inflame them j a bit of paper dipped into oil of turpentine and plunged into the gas bursts into flame. take this is spontaneously the case with phosphorus fire when introduced : into chlorine same . whilst part of the carbon. Chlorine is not combustible. Besides the application of chlorine on the large scale. and deposits an abundance of a black carbonaceous compound. A taper burns in it with a reddish. for each atom of hydrogen so withdrawn from the original coman atom of chlorine is substituted. . that is its power of destroying noxious vapours and miasmata . and forming a hydrogen uniting the powerful acid. and are decomposed whilst colourless. somedivided state do the many of the metals in a finely among them are copper leaf. and it cannot be subsequently restored. it is principally to this action that its bleachThe preparation of potassic chlorate ing properties are due. and it does not combine directly with oxygen. . is deposited. it is frequently employed for this purpose in fumigating buildings after the occurrence of contagious diseases. hydrochloric (HC1) . Most of the vegepound. for which its Many bodies. or w ith tincture r of litmus. by chlorine. and liberates oxygen. smoky flame. with some of the blue liquid formed by dissolving indigo in sulphuric acid. The action of chlorine upon bodies containing hydrogen It is combines with part of the and it withdraws from the combination . compounds chlorine are formed in the place of the coloured comcontaining with If a solution of chlorine be mixed pounds hydrogen. and A great number of organic arsenicum. whilst at the same time often of a very peculiar kind. or nearly colourless.CHLORINE ' BLEACHING ACTION. chemical attraction is but small. forming a layer amounting about one-fourth of the volume of the liquid in the tube. powdered antimony. it is in continual requisition in the laboratory as an oxidizing agent owing to its attraction for hydrogen it readily decomposes water. substances rich in hydrogen are decomposed by chlorine. each atom of hydrogen with an of atom chlorine. the colour will in each case be immediately and almost completely discharged. or with ordinary writing ink. 25 to the pressure In the tubes.

i8'25- The most im- portant of the compounds of chlorine with the non-metals is that which it forms with hydrogen. but it is insoluble in nitric argentic chloride which The white free chlorine acts upon argentic nitrate in the of water. and formerly distinguished for each basic oxide of the metal. a small quantity of chlorate is formed at the presence same time as the chloride. constitution. . Sp. often. Hydric chloride. metal in more that combines with the same chlorine happens than one proportion (FeCl 2 ) : for and ferric chloride (Fe 2 Cl 6 ) example. the addition of a solution of argentic nitrate produces a white curdy flocculent precipitate of changes to violet on exposure to the light. but the moment that they are brought into direct sunlight they unite with a powerful explosion. = 36'5). precipitate is easily re-dissolved by adding a small quantity of solution of ammonia. chlorides of gold and platinum. 1-2629. a corresponding generally. many it attacks energetically at comusual temperatures. 1^2474. several of which with all the non-metals. Rel. : When (336) HYDROCHLORIC ACID Theoretic Vol. and of the sesquioxides of cobalt and nickel. recognised by free or combined with a metal. as the bichloride) may be obtained. in researches it upon the nature of many products furnished by organic chemistry. ferrous chloride may be formed with plati. as in the series of compounds obtained from Dutch liquid. (PtCl 2 ). Gr. With the all pounds of great importance it the metals. if kept in the dark. they are all more or less soluble in water. platinous chloride chloride exists. they other. Atomic and MoL J. wt. exhibiting the phenomena of combustion . and p'latinic chloride (PtCl 4 . Chlorine when its in solution in the uncombined form is easily Whether odour and its bleaching properties. num. and. especially the former two. of them. the compounds which it forms are termed chlorides. and a This sudden comcolourless. The two gases may be mixed in without action upon each remain and will equal volumes. with iron.x? HYDROCHLORIC ACID. (353) i f ferric acid. intensely acid gas is the product. [ : Muriatic Acid. is used as a means of throwing light upon their molecular Chlorides. Observed. and mercurous and cuprous The lower chlorides. and forming comalso enters into combination with mon argentic chloride. Chlorine combines uniting spontaneously with . afford illustrations of this mode of employing it . and chloride of lead are but exception of It frequently sparingly soluble. nitric acid being liberated acid.

. The presence both of hydrogen and of chlorine in the acid is The gas easily shown by the following experiment (Graham). 277. Hydrogen = H = Cl By weight. In diffused daylight the combination takes place gradually .jO-f-2Cl 2 =4HCl + O 3 is . that of chlorine in. but the application of a lighted match. unites with i volume of hydrogen. One volume of chlorine thus instantly determines its explosion. d. i fol- Chlorine . aII. or the passage of the electric spark through the mixture. producing 3 volumes of hydrochloric acid. is dried by being passed through a tube. bination is 27 also effected by the action of the electric light and of that produced by the combustion of a mixture of nitric oxide and carbonic disulphide vapour. ferrous or salt stannous chloride is formed.. be exposed to the sun's rays. The metal burns vividly. fig. and the oxygen of the water is liberated is So powerful if either a solution : however. and oxygen is set free . at the same time.. some . with a tube upon first of these.COMPOSITION OF HYDROCHLORIC ACID. . although. or the gas itself in a moist state. no condensation occurring in the act of union. filled with calcic chloride this tube is con: nected by a vulcanized caoutchouc joint. a. is hydrochloric acid gas mixed with an ignited porcelain tube. As Hofmann has shown. formed. the decomposition may also be effected without the aid of heat by agitating a given measure of dry hydrochloric acid gas with an amalgam of sodium. hydrochloric acid is in the dark. and liberates a quantify of hydrogen. The composition of hydrochloric acid lowing : is consequently the By vol. chlorine on the other hand. acid in the retort. b.. If moist chlorine be transmitted through a red-hot porcelain tube. formed being Analogous results are obtained if iron or tin be substituted for sodium . which two bulbs have been blown in the : c. 35*5 or 97-26 ro 36-5 2-74 i Hydrochloric acid HCl = loo'oo 2 the attraction of chlorine for hydrogen. water. The composition of hydrochloric the volume of which common is one half of that of the hydrochloric acid . and pure hydrogen is left. chlorine has no power to decompose water. when and transmitted through liberated and water produced. air acid may be analytically determined by heating sodium in a measured volume of the gas. hydrochloric acid is formed. whilst hydrogen is set at liberty. by the hydrochloric generated action of sulphuric acid on sodic chloride. is reduced to one half. introduced into In a few minutes the volume the gas as it stands over mercury.

Hydrochloric acid gas is easily procured by introducing fragments of common salt (which has been fused in a crucible at a red heat and then poured out on to an iron plate and allowed to cool) into a glass retort. and may be collected either over mercury. to employ slightly diluted by Gregory. contained in a retort. taining the oxide. furnished with a bent glass tube this mixture evolves scarcely any hydrochloric acid at the ordinary temperature. is quickly reddened. it remains in the bulb. 2 2 8 . congas. d. the gas escapes in abundance. sulphion as is shown in the following equation : common NaCl + [NaCl 2 H SO4 = HC1 + NaHSO4 + SO (OH) = HC1 + SO (OH)(ONa)]. or by displacement of : the air from dry bottles. but when gently heated. or flask./. A far more convenient method. 277. showing itself by its peculiar The colour and its bleaching effect upon the litmus-paper.28 PREPARATION OF HYDROCHLORIC ACID. reaction is represented by the following symbols : 4. /.HCl + MnO 2 = Preparation. .. which receives the escaping On applying heat to the bulb. or 1 1 parts by measure of sulphuric acid and 8 of water. whilst water is formed and becomes condensed in the second bulb. is produced. In this case half the hydrogen of the oil of 'vitriol is transferred to the chlorine of the salt. An ounce. or 30 grms. how- ever. : pounded anhydrous black oxide of manganese is placed a piece of litmus-paper inserted in the bottle. of salt yields about 700 cubic inches (13 litres) of the gas. and as it is not volatile. manganous chloride FIG. whilst the remaining hydrogen and the combine with the sodium and form hydric sodic sulphate. Six parts sulphuric acid as suggested of common salt are added to a cold mixture of 10 parts by weight of oil of vitriol and 4 of water. and adding to it twice its weight of is oil of vitriol. e in the meantime free chlorine passes on into the bottle.

and an intensely acid taste . and should be immersed in a vessel of cold water. atmospheric moisture. Hydrochloric acid is enormous quantities in the manufacture of salt cake : extensively employed in the arts. the refracting power of this liquid is less than that of Hydrochloric acid gas is incombustible. 29 Hydrochloric acid is a colourless gas. it produces white fumes by condensing the into the air escape water. it irritates the eyes. the second bottle may contain 4 parts of water for 3 of sodic chloride employed. and it extinguishes It reddens dry litmus-paper. The retort is connected with a couple of Woulfe's bottles . It is also very injurious to vegetation. causing the leaves to shrivel * It is heavier than air . and 76o weigh 1*6352 grm. but only one-half the quantity of sulphuric acid prescribed above is used. in the first a small quantity of water is placed to detain any impurities which might be carried over mechanically with the gas . or 100 cubic inches at 60 Under a pressure of 40 and 30 inches Bar. whilst the hydrochloric acid is absorbed in a series of salt-glazed stone. of a pecu- liar. weigh 39*23 grains. and forming with it a body less volatile It is instantly absorbed by water a lump of than pure water. frozen . 1*27. mm C. The Solution of hydro(337) Solution of Hydrochloric Acid. Properties. chloric acid in water is an indispensable requisite in the laboIt is easily prepared for use by passing the gas obtained ratory. like those employed in the preparation of nitric acid (386)..PROPERTIES OF HYDROCHLORIC ACID.ware jars. and if breathed even when largely diluted produces coughing. when allowed to burning bodies. it becomes condensed to a colourless at atmospheres 50 (TO C. particularly in the preparation of chlorine as a preliminary to the manufacture of chloride . the easily soluble hydric sodic sulphate remaining in the retort. as the condensation of the gas is attended with a great disengagement of heat. and a higher temperature is + H 3 SO 4 = 2HC1 + Na 2 SO 4 2HC1 + SO (ONa) 2]. For manufacturing purposes the decomposition is effected in iron cylinders. The sulphuric 2NaCl 2 applied than when glass : vessels are employed. On applying a gentle heat to the retort the acid comes over and is absorbed by the water . : ice liquefies in a jar of the gas and absorbs it with great rapidity. arranged as Woulfe's bottles produced it is in and containing water. liquid sp. gr.) it dissolves bitumen has of which never been . i litre of the gas at o and turn brown. as before mentioned into water. pungent odour. 2 [aXaCl + SO (OH) 2 is = acid in this case in the proportion of one equivalent to each equivalent of -salt. normal sodic sulphate remaining in the cylinder. as explained above.

of hydrochloric acid.* Common hydrochloric acid may therefore easily be purified by dilution till it has a Bineau. by a slight elevation of with the temperature. gr. the the of acid. the amount of acid fell to ip'O.). gr. when distilled under that pressure. probably they exist in a state of mere admixture. Soc. at a temSuch an acid contains about 20 per perature of 233 (112 C. as well as arsenious chloride and sulphurous with the distillate. and distilled. whilst under a pressure of 76o per- centage of acid.or 2 of ijJ2o atmospheres.6H O) of sp. t Chlorine. It is also largely used as a solvent of lime and potassic chlorate.centage of acid was 2 1 '3. as well as in the manuby the dyer facture of sal ammoniac. and that there ia no definite hydrate of this acid . corresponding mm the to the formula 2HC1. the composition of the liquid in the last case corresponding nearly to HC1. and then passes over unchanged. as low as i8'2 of HC1 per cent. it dissolves ' 0*745 of its weight. at this point it distils unchanged. by varying the pressure under which the distillation is effected. has a density of 0*69. fuming portion indicated by the formula. . which. According to this observer (Ann. was reduced to 20-24 (HC1.). Water at o C. gr. . 259). parts gas abundantly. until the liquid which remains has a denweaker sity of I'loo. * Roscoe and Dittmar (Q.8H 20) . obtained a hydrate (HC1. containing 25 per cent. it loses hydrochloric acid. of ri at 60 (i5*5 C. at this strength it contains more than 44 per cent. i volume vapour of the acid and 8 volumes of aqueous vapour being united without condensation . xii. shown that this apparent constancy of composition is really an accidental circumstance. sp. of hydrochloric acid. the distillate contained 23-2 per cent. at 39'2 (4 C. which is about the prois a colourless. f cent. but that for every pressure an aqueous solution exists. of acid. and under or 3 atmospheres. under a pressure of 76o mercury. or about its times bulk of hydrochloric acid gas. Chem.8H 2 O. 128). increasing in volume 492 The solution about one. and at I5*5 C. Water liquid. passes over if present. the per.30 SOLUTION OF HYDROCHLORIC ACID.third. until it acquires A the density of noo. however. dissolves 0-825 mm of acid gas. tin and for calico printer.. and corresponds approximately in com-? HC1.I5H 2 O.9H 2 O. of the anhydrous acid. de Chimie [3]. which. and then distilling. concentration of the acid at the ordinary temperature of the air in vacua over ^sulphuric acid. dismm tilled under 38 o pressure. if distilled under a pressure mm. acid when distilled parts with its water freely. have. HC1. 1*128. vii. possesses a fixed composition and fixed boiling-point.) absorbs '804 of its own weight. acid. For example. position with the formula. no. by sp. however. 2280^ f 'ts weight of hydrochloric according to these observers. J. when distilled under a pressure of $o mm - of mercury.3H 2 O. If the strong acid be placed in a retort. and acquiring a density of 1*2265.

) (E. and on saturating it with ammonia it should give no precipitate of ferric oxide .STRENGTH OF SOLUTIONS OF HYDROCHLORIC ACID. sulphuretted hydrogen should likewise produce no turbidity in it. which consists in the addition of a mixture of ferric chloride and potassic liable ferricyanide is : if- sulphurous acid be present. free chlorine. 31 Commercial hydrochloric acid has a yellow colour and is to be contaminated with iron. Davy. or sulphurous acid were present. which would be the case if arsenic. Strength of Hydrochloric Acid. Prussian blue formed by the reducing action of the acid on the mixture. acid should leave no residue when evaporated. Sulphuric and sulphurous If pure. 77 (25 C.} Specific gravity. no white cloud of baric sulphate should be produced by the addition of baric chloride. the acids and free chlorine are also often present in it. the latter derived from the sulphuric acid employed in its preparation. and with the chlorides of sodium and arsenic. and after dilution with three or four times its bulk of water. . Traces of sulphurous acid are also easily detected by Lowenthal's test.

oxide of a present.] . if to a solution of cupric chloride water. sometimes happens that no chloride corresponding to the There is. the reaction is similar. exist in solution But although the metal may in the form of chloride. for example. when a strong base. 3 molecules of water are is formed.32 in ACTION OF HYDROCHLORIC ACID ON METALLIC OXIDES. an ordinary CuCl 2 + aKHO give [CuCl 2 + 2K(OH) give sKCl + CuH 2 O 2 3 KCl + Cu(OH) 2 . + HCl yield NaCl + 0. and one of ferric chloride obtained in solution : 6HCl + Fe 3 O 3 It give 3 H 2O + Fe 2 Cl 6 . the hydrogen of the acid changes places with the metal. in fact. else evaporates monad of the hydrate to form water which remains in the solution or on the application of heat. 2 BaCl 2 + H 2 O. instance of double decomposition : It is. in this case i molecule of plumbic dioxide (PbO 2 of lead decomposes 4 molecules of hydrochloric acidj 2 molecules oxide : ) . A reaction not less instructive occurs when oxides containing a larger proportion of oxygen than the protoxides are treated with hydrochloric acid. and the metal exchanges places with two atoms of hydrogen : T1 2 O + 3 HC1 BaO + aHCl yield 2T1C1 + yield H O. as shown by the following symbols. no stable tetrachloride exists. When. HO. this circumstance does not prevent its precipitation as oxide. provided that the metal be capable of forming an oxide insoluble in. potassic chloride whilst cupric hydrate is precipitated. and which hydrated When the metal. most cases a saline compound is obtained in which neither is hydrochloric acid nor the metallic oxide contains neither hydrogen nor oxygen. but two atoms of hydrochloric acid are concerned. For example. for instance. formed and dissolved. a solution of potassic hydrate be added. 6 molecules of are decomposed. and is exactly sufficient with the hydroxyl. 2 NaHO H When the anhydrous oxide of either a monad or a dyad is employed. such as potassic hydrate is added to a solution which contains the chloride of the metal in question. is acted upon by hydrochloric acid. such as sodic hydrate. the potassium and is copper change places. whilst the metal and is the chlorine unite directly with each otKer forming a chloride. I molecule of ferric oxide (Fe 2 O 3 ) is hydrochloric acid subjected to its influence.

Consequently an extensive change becomes necessary both in notation. 1*1072. CHAPTER OXYGEN : IV.~ 2 i.NaNO 3 . 33 of plumbic chloride are formed. Theoretic Sp. occupying the same volume as a molecule of oxygen. = I.Gr. instead of equations by which chemical reactions are represented in this work the molecular. insoluble in dilute nitric and is immediately blackened The dry potassic dichromate and sulphuric acid yield a red liquid (CrO 2 Cl 2 ). Mcrcurous nitrate also gives a white precipitate of mercurous chloride (calomel) in solutions of metallic chlorides: 2 (NO 3 ) 2 + 2NaCl==2NaNO 3 Hg + Hg2 Cl 2 acid. if that of hydro- gen remains unaltered. [N 2 is 4 (0 2 Hg 2 )" -f 2NaCl= 2ko 2 (ONa) + Hg 3 Cl 2 ] by ammonia. as in H O. ReL Dyad. the = 16. free hydrogen = 9. and also in the interpretation of chemical phenomena generally. but insoluble in nitric acid. '. . the atomic weight of hydrogen being HH. which forms a yellow solution with ammonia this reaction distinguishes the chlorides from the chlorides when heated with : bromides. Atomic Vol. '~ Molecule in free state (339) Preparation. ^~ wt. 1*1056. Observed Gr. or potassic cyanide. and the volume occupied by 8 parts by weight of oxygen was employed as the unit of gaseous volume . unless specifically stated to be otherwise. Sjy.TESTS FOR CHLORIDES of \vater and i -OXYGEN. The chemical researches of the philosoof last the phers century are especially remarkable ou account of the important information which they afforded about the nature * Formerly the symbol for oxygen was taken as O 3. when a solution of argentic nitrate is added to the liquid . H HO D . the molecule of If the atomic weight of oxygen be represented as will with a molecular and molecular volume be OO. This precipitate is soluble am- monia. NaCl + 3 AgNO in becoming AgCl -i. In the variousi molecular weight of water will be H 2 = 18. be repreII. OOP J . oxygen weight 32. curdy precipitate of argentic chloride. but the arguments of Gerhardt and the progress of research require that the number for the atomic weight of oxygen should be doubled. The precipitate soluble in chlorine water. insoluble. although soluble in solution of sodic thiosulphate. O=i6. and the molecule of free ^]. 16. whilst 2 atoms of : chlorine are liberated Pb0 2 + 4 HCl chlorides in solution is give acid The presence of hydrochloric and of the soluble indicated by the formation of a white. volume of compounds will. .

SS or 82 = 64. others compound . as is well known. as was once supposed. fig. the receiver still contains a large quantity of a gaseous body in which a candle will not burn. and which does not burn in the ordinary sense of the term. soon begins to burn dimly. Indeed. as formerly practised. provided with a neck of con- sented uniformly by 2 volumes. the edge of which floating is plunged beneath the water. A limited quantity of air will the flame becomes extinguished. rather complicated. contrary. the molecule of sulphur Se 2 = 159. and Each of these bodies tellurium. however. Combustible bodies. and at But the extinct. for but a limited combustion period a lighted taper support inverted under an on water bell-glass.g. The molecule of these elements contains two atoms: e. the knowledge thus obtained may atmosphere. instead of by the anomalous method of representing some compounds by 2-. some of which are elementary. the molecule of selenium. On placing a lighted taper under the receiver of the air-pump and exhausting the air. : Oxygen belongs to a class of elements including sulphur. The experiment may be performed flasjf as follows : Into the bulb of a or retort (A. which may be termed electro-negative dyads. Lavoisier contrived to obviate this inconvenience by acting upon the air with a substance which produced a solid body as the result of the chemical action. group may be equivalent in combination to two atoms of hydrogen or of one of the halogens. These researches have abundantly proved that the air is far from It has been being. found. direct proofs of the compound character of the are afforded by examining the effects produced upon atmosphere it bodies. the most remarkable and abundant of which are the elements oxygen and nitrogen. 278). selenium.34 of the COMPOUND NATURE OF THE ATMOSPHERE. because the products which are formed by the burning body rise in the form of gas. be regarded as the starting-point of the brilliant chemical discoveries which have since succeeded each other with such rapidity. and become mixed with the remaining portion of air. others by 4-volume formulae. forming a gaseous compound in which the three volumes are condensed into the be said to space of two one atom of the elements belonging to this . ceases to burn becomes taper length long before : the air is all spent . an elementary body. so that it left the air unmixed with any gas which rose air into its constituents from the burning body. is characterized by the power of uniting with twice its volume of hydrogen. . The material he employed to separate the was metallic mercury. The results obtained by burning a candle in a limited portion of air are. a substance which acts very slowly. a mixture of the to be several on substances. by burning The most cannot burn without the free access of air.

To this gas the name of Oxygen (generator of from ov sour. and the remaining air. when cold. When this point is reached. an ounce or jecting above the level of the mercury.PREPARATION OF OXYGEN. If this tempe- rature be continued for three or four consecutive days. bath. so as to leave the open end of the neck prothe flask is siderable length. which may be collected over water. with at- mospheric The bulk is of this portion of air then accurately observed. into a jar partially filled air. Heat now applied to the flask. and the flame of a candle is instantly extinguished. be performed with accuracy. acids. and the temperature and barometric the time is pressure at of the obser- vation are recorded. If a portion of this residual air be decanted into another jar. termed nitrogen (376). and the necessary part which it performs in the maintenance of life. and yivvcutt to produce) has been given. ani the air. and a gas will be disIf the experiment engaged. 7 35 : two of metallic mercury is introduced the neck of then bent in the manner shown in the figure. and from the abundance in which it occurs. and the bent portion plunged into a mercurial FIG. will slowly decrease in bulk. the number and the variety of its compounds. it must be regarded as the most remarkable and important of the simple bodies. The above experiment shows that the red scales consist of a p 2 . covered with red scales. 278. the air inclosed both in the flask and in the jar will The mercury in the flask will gradually become participate in the action. It is an elementary body. If the red scales which are formed upon the mercury be introduced into a small glass retort and exposed to a strong heat. and depressed the level of the mercury in the jar. drops of mercury will become condensed in the cool part of the retort. steadily at and maintained a point just below that required to make the mer- cury boil. until fresh scales no longer continue to be formed. the source of heat may be removed. which at first expanded from the action of the heat. the quantity of the gas obtained will be exactly equal in volume to the bulk absorbed from the air by the mercury. will be found to measure about one-fifth less than it did at the commencement. the heated mercury having effected the removal of the oxygen from the air. in an almost pure state. it will be found to be unfit for the support of animal life . they will gradually disappear. a mouse or other small animal introduced into it speedily dies. The gas thus obtained is an elementary body.

at a red heat. mixed with some carbonic anhydride and nitrogen . of mercury and oxygen which : compound is decomposed by heat according to the equation There are several other methods of procuring oxygen gas. furnished with a cork to which is adapted a Wide bent tube for may . there are.. whilst a reddish-brown oxide of manganese remains behind. more or less completely. furnishes about one-ninth of its weight of oxygen . 279.36 PREPARATION OF OXYGEN. to the neck of which an iron pipe by grinding. The mineral must be reduced and introduced into an iron fig. FIG. 20 grammes of this be heated over a gas flame or a charcoal fire. other modes of procuring oxygen economical. usually comes off at a later conveyed to the gasholder by means of a the oxide of manganese period. in 1774. About half an ounce. often to the cent. the oxygen with which the metals were combined. 279. or in a Florence flask. by which he first isolated pure oxygen. 280). is of great interest from a historical point of view . however. but as met with in com- merce it seldom yields more than half that quantity. F (fig. supply of very pure may also be obtained action of readily by the heat upon the salt known as chlorate of potash. the simplest of which consist in the exposure of certain native metallic oxides to a high temperature. The original method of Priestley above described. by heating the red oxide of mercury to about 752 (400 0. to small fragments of about the size of a pea. and contaminates the oxygen FIG. a pound giving off inches. Pure black oxide of manganese. parts with onethird of the oxygen it contains. or a about 1400 cubic kilogramme about ^o litres 3. amount of $ or 6 per the gas rekindles it may be col- When a glowing match. 3Mn0 2 giving JVln 3 O -I- 4 O 2 .i-:- As piece of flexible metallic piping of suitable length. and the gas the bottle is fitted =. by which they are made to give up. or potassio chlorate. black oxide of manganese (Mn02 ). usually contains water as well as a portion of nitrate and some calcic carbonate. or from 15 to salt. bottle. For the supply of large quantities of oxygen it is usual to employ the 2. is heated in a furnace. the first effect of heat is to drive off a quantity of steam. in a green glass retort.). howwhich are more convenient and ever. A oxygen of the gas. the latter.280. a mineral which. lected for use.

201. or if not wanted for immediate use. those already mentioned are the best. and at a temperature a little melting point emits a large quantity of gas. whilst the chlorine and potassium unite. hence the necessity of of chlorine. and the heat must be carefully point the oxygen is disengaged with very great employing a wide delivery tube. and barium.8'J grins. delivering the gas its : 37 the salt fuses below a red heat. may be stored up in a gas-holder (39).). (232 and 260 0. or by passing chlorine into a solution of perature . sodium. the metals. furnish the gas when strongly heated . it may also be obtained by heating chloride of lime or the action of heat on a mixture of bleaching powder. (C10 3 ) with potassium when heated sufficiently. fig. JIG.PREPARATION OF OXYGEN. been found that many metallic oxides. and are the materials most Bed lead. which remains in the retort when the operation is over. as shown at B. has. as at a particular rapidity. or chlorine potassic or sodic hydrate containing a small quantity of cobaltic hydrate in suspension . ]- the quantities of chlorate employed are rather large. or nearly i| gallons of the gas. convenient in practice to mix potassic chlorate with about a fourth of its weight of black oxide of copper (CuO) or of oxide of manganese. that has been pre- viously heated this to redness and allowed to cool. may be a compound of . .and constitute the white salt. potassic chloride. powdered oxide of manganese or ) potassic bichromate (K 2 CrO 4 CrO 3 when heated with twice its weight of concentrated sulphuric acid in a glass retort also evolves oxygen. The above - oxygen furnished by the chlorate amounts to more than one. cause the expulsion of the gas at a much lower temperature. ranging between 450 and 500 F. Potassic chlorate considered chlorion as (KC103 ). which may be collected in jars over water in the pneumatic trough. and the peroxides of most of frequently employed.third of the weight of the salt used . The change may be thus represented in symbols : 2KC10. and gives up all its oxygen in the gaseous form. If a jar of the gas be closed with a glass plate it may be inverted. and its power of supporting combustion tested by a taper. and baric dioxide likewise yield oxygen when submitted to a high tem- by and steam. sulphates. 281. = 2KC1 + 3 2 [ 2 I gg K) = 3 KC1+ 3 S . as well as the nitrates of potassium. if mixed in a fine powder When the with the pulverized chlorate in a proportion of not less than one part to ten of salt. but . contains traces The gas which is obtained in way always watched. Oxygen may be obtained from various other substances. although such oxides do not It is therefore appear to experience any chemical change during the operation. as at A. however. sulphuric acid. of the crystals should yield about 775 litres. I ounce or 2. the salt is decomposed. such as those of silver and lead. the heat 4It required is apt to soften the glass of the flask in which it is decomposed.

with elimination of water. an iron tube sufficiently long to reach to the bottom of the acid luted into the tubulure. 2 2 2 Ba02 was also proposed by Boussingault as a source of hoped to convert baryta alternately into the dioxide. converting the precipitated cobaltous hydrate into cobaltic hydrate. while zincic oxide remains in the retort : [2 2ZnS0 = 2ZnO + 2S0 + S0 (0 Zn) = 2 ZnO + 2S0 + OJ 4 2 2. Oxygen. as represented by the following equation is : Sulphuric acid. evolving pure oxygen. 2 K Cr 2 2 7 + 'ioH 2 S04 = ^JKH~OT + 2 2(Cr^SOj 3 6 + 8H^O +^b / 2 r 2 Cr0 2 (OK) L +ioS0 Cr02 (OK) 2 (OH) 2 = 4 S0 (OH)(OK) + 2S (0 6 Cr2 r+80H + 3 2 -| 2 . whilst the liberated chromic acid. 8. operation the sulphuric acid is decomposed into sulphurous anhydride. Part of the sulphuric acid 6. and may be used indefinitely. 2OH . whilst the sodic hydrate is converted . and then to decompose this dioxide by a still more elevated temperature. through a bent funnel. In this allowed to pass in. the chlorine is at the first moments absorbed. If a stream of chlorine be passed through boiling water and the resulting mixture of steam and chlorine transmitted through a porcelain tube filled with fragments of pumice stone and heated to bright redness. and chromic sulphate being produced. on the application of a full red heat. acid.HC1 + Oz The oxygen is produced and oxygen liberated. as in metallurgic operations. by heating it to a dull redness in a current of air. The cobaltic hydrate undergoes no change. gives up half its oxygen. Hydric potars. and water. and becomes converted into chromic sulphate. drop by drop. : Sulph. sulph. Dried zincic sulphate also readily yields oxygen and sulphurous anhydride 9. hydrochloric acid is + 2C1 2 = 4. He . hydric potassic sulphate. Sulphurous anhydride.38 PREPARATION OF OXYGEN. Co 2 (HO) 6 and subsequently the liquid effervesces. in presence of the excess of sulphuric acid. This change may be represented in the following manner Potass. Baric dioxide. and when the retort is at a full red heat. When a current of chlorine is passed into a hot solution of sodic or potassic 7hydrate to which a few drops of a solution of cobaltous chloride or nitrate have been added. . The volatilized products are transmitted through a small spiral condenser to condense the water and undecomposed acid. and thus to be able to employ the same quantity of baryta for an indefinite number of times to extract oxygen from the atmosphere. / Water. sulph.(OH) a = = 2H 2 2 OH 2 + + 2SO^ aSOa + + OJ 2. When potassic dichromate (bichromate of potash) and sulphuric acid are 5. 2 freed from hydrochloric acid and any excess of chlorine that may be present by washing it with a solution of sodic hydrate. and the oxygen is collected in the usual manner. into chloride. When oxygen is required in large quantities. dichrom. heated together they undergo decomposition oxygen. forming hydric potassic sulphate. oxygen. oxygen. tubulated earthenware retort is charged with A fragments of -the retort is fire-briclc. 2H 2 S04 [>SO. Deville and Debray recommend the decomposition of sulphuric acid by heat as the cheapest source of the gas. Chrom. 10. 'whilst the sulphurous anhydride is removed by subsequent washing with water. "s employed in displacing the chromic acid from the dichromate.

282. A piece of watch spring or thin steel wire will burn in oxygen with brilliant scintillations. only one element (fluorine) being known with which it does not combine.PROPERTIES OP OXYGEN. small animal will by live in a confined space filled with oxygen for a longer period A than in an equal bulk of air. Richardson has found that . as do also many metals . burns in oxygen with an intense bluish white light. fig. In these cases the oxygen combines with the burning body. but nevertheless becomes so emaciated from inability to eat sufficient to supply was necessary to discontinue the experiment. even after washing with potassic hydrate and sul- . the waste that it At the temperature gas which has . sulphur and charcoal burn vigorously in the gas. Oxygen possesses extremely powerful chemical other elementary substances. bursts when plunged into the gas. and burn with extraordinary brilliancy. Zinc foil. and heated strongly by a spirit lamp. Oxygen is essential to the support of animal life. during which time it eats voraciously. of 45 F. Phosphorus burns in it with a brilliancy which is painful to the eye . in like manner. Hitherto the difficulties 39 its attending the use of this method hare prevented application in the arts. the wood will instantly burst into flame. B. but the gas cannot be breathed undilutedxwith impunity for any considerable time .been once breathed rapidly produces narcotism and death. Many bodies which burn tranquilly in air often deflagrate with violence in oxygen.) the rabbit was speedily When the oxygen was narcotized and died unless removed. producing in each instance a new substance. 282. Properties. cooled by a freezing mixture the narcotism was so perfect and The rapid that operations could be performed on the animal. the use of the tinder being to start the combustion.) for three weeks. attractions for oxygen gas possesses the power of supporting combustion in an eminent degree. (23'9 C. Owing to the energy with which many of these combinations take place. and hence the older chemists was termed vital air.a rabbit may be kept alive in a stream of pure oxygen at the temperature of 75 F. c. FIG. also. if placed in a small copper spoon. Dr. quite different in properties both from the oxygen and from the body burned. W. a piece of potassium of the size of a pea. (y-2 C. if some German tinder be fastened to the wire and ignited preinto flame viously to introducing it into the gas . If a splinter of wood with a glowing spark on any part of it be plunged into the gas. tipped with sulphur and kindled.

100 volumes of water. ^ oxygen is its remarkable power of supporting combustion. and.. and when the combustion is over. All attempts hitherto made to reduce it to the liquid form by the combined application of pressure and cold have proved fruitless. biilk. but the smallest spark upon the surface of the charcoal will suffice to determine its immediate A and vivid combustion. .. or 100 cubic inches at 60 F. taste.. and 30 inches Bar. weighing 34*303 grains it is only in soluble which about of its takes up water. afterwards the heat which is liberated during the process is more than sufficient to carry it on . in the gas. combustion is said to occur. gravity. : J litre at O C. It is. easy its to show that there is no actual components operation. but that the constituents of the candle in burning have combined with a in this certain proportion of oxygen. according to Eegnault. and the act of combination proceeds with increasing rapidity. oxygen restored it to its original healthy condition. and at 15 . at o C. and 2*99 at 15. Whenever any rapid chemical action attended with production of light and heat takes place. like this substance its susceptibility to magnetization is diminished. dissolving 4*11 vols. The distinguishing feature of (340) Nature of Combustion. although the combustible or body which is burned may undergo such a complete change of form as even to disappear from our A candle in burning seems to sight. its specific (325). Of Oxygen. yet phuric acid. is destitute of colour. being I '10563 and 76o mm. and although no carbonic anhydride could be detected it produced the same effects on the rabbits at all The passage of a fe\v electric sparks through the temperatures. like air. by a sufficient elevation of temIt is heavier than the atmosphere. an insignificant trace of ash from the wick is all that remains to the eye. It must be borne in mind that there is no destruction of matter or loss of weight either during combustion or in any other case of chemical action. carbonic anhydride and aqueous vapour. stick of charcoal may be kept in oxygen at ordinary temperatures. perature or even temporarily suspended. be completely destroyed . It has been ascertained that oxygen possesses feeble magnetic properties. In order to commence this action it is generally necessary to apply heat. . however. and that the aeriform compounds. according to Bunseu. and smell. for years without entering into combination with the gas.pressure. at ^'r slightly o C. weighing i'4298 grin. which are the result of destruction of .10 NATURE OF COMBUSTION. similar to those of iron. all known substances it exerts the smallest refracting power upon the rays of light..

the flnsk c half filled with limee are filled with fragments of soda. at the with the lime and The apparatus having been forming anhydride combining same time the arm of the balance to which the apparatus is attached gradually more descends. by which they may be suspended from FIG. The water air-pump mentioned same above. or potassic the The U-tube b is two U-tubes d and cylinder is in connexion bent glass tube /* passing through a empty. carefully counterpoised. water. to retain any aqueous vapour or carbonic anhydride which may have escaped through b and c . showing that the products of combustion of the caudle weigh than the body burned. is an instrument constructed on the water being used instead of mercury. 283. is connected with an The exit of the last tube of flexible caoutchouc aspirator or water air-pump by means of two lengths thus preventing tubing joined by a piece of glass tube# rigidly fixed in a clamp. and the other lime. principle as Sprengel's air-pump (70). condenses in b. Water at the same time. the gain in weight representing the quantity of oxygen which has produced the chemical change by its combination with the materials of the candle. attached to the balance. action in set and the replaced. a. aspirator being lighted.MATTER NOT DESTROYED BY COMBUSTION. The following apparatus affords a convenient method of showing this. By its means a rapid current of air may be drawn through an apparatus. 41 the combustion. these different parts of the apparatus being firmly fixed to a piece oi' wood i. cork perforated with three or four holes to admit air is inserted into the lower end of a glass tube. The upper end of the 113' with the rest of the apparatus tightly fitting cork. and the lime-water in c becomes turbid from the carbonic insoluble calcic carbonate. which may be an ordinary Argand lamp glass on this rests a cup to catch any drops of wax which may fall from the small A : piece of candle fixed into it. although invisible. the arm of the balance. and . hydrate. the communication of motion to the / any apparatus the candle is taken out. 283. i. really weigh more than the original candle . fig.

this was covered with a serving of tar and hemp. the oxidation continues to spread through the entire mass of the metal .). coiled into a mass about 30 feet or 9 metres in diameter. about 163 nautical miles in length.42 SPONTANEOUS COMBUSTION. laid aside in heaps. a distinct elevation of temperature is often perceived. and the water was in consequence drawn off. the case of iron. powder as a preliminary to the manufacture of gunpowder. but if moisture be present it quickly becomes rusty. where the process is more rapid. and the temperature goes on rising until the mass bursts into flame. of the Mediterranean electric cable. leaving a quantity of cable. and the whole enclosed in a strong casing of iron wire. the external surface of the iron wires. with an eye or central space of 6 feet (rather less than 2 metres) . nearly 3 feet (0-9 metre) from the bottom. during the period. and to give rise to apprehensions that the insulating power of the cable would be destroyed by the softening of the gutta-percha. when spread over so large a surface. The instrument is known as Bunsen's pump. but in other instances. The copper conducting wire of this cable was coated with gutta-percha. fine .) part of the time. absorbs oxygen rapidly. and which offers a large surface to the air.5 metres). At the ordinary temperature of the atmosphere oxygen quently enters fre- so slowly into combination that the heat disenis not gaged perceptible. and sometimes rises high enough to cause the materials to burst into flame. These tanks leaked. The cable as it was air * manufactured was coiled in tanks filled with water. A bar of polished iron will remain unchanged for any length of time in In dry air. a near approach to a vacuum can be obtained. The oxidation of the metals has been observed to take place much more rapidly in a moist than in a dry atmosphere. although the as low as temperature of the air did not exceed 66 (19 C. the height of the coil was about 8 feet (2. rose in 4 days from 66 to 79 (19 to 26 C. and was 59 (15 C. (5 to 10 kilog. in the air. The oxidation occurred only on . In other parts of the mass the heat rose so high as to cause the water to evaporate sufficiently rapidly to produce a visible cloud of vapour. that portion in contact with the tarred hemp remaining perfectly bright. occasionally exhibits and it is still more often manifested when tow this phenomenon that has been used for wiping machinery lubricated with oil is The oil. This is seen when a heap of iron turnings of from 1 1 to 22 Ib.) is moistened with water and exposed to the and a curious illustration of the fact was afforded during the manufacture .). as occurs with When considerable masses of iron are allowed to rust. with a fall tube of about 36 feet. and the temperature at the centre of the coil. as when a bar of iron is gradually rusting In other instances.* the heat accumulates. . producing what are called cases Charcoal that has been reduced to of spontaneous combustion. Rapid oxidation took place. No doubt the rise of temperature would have been still greater had it not been checked by the affusion of cold water but the oxidation and the heating were renewed when the affusion was discontinued.

in this way the machine of the blast furnace action of the smith's bellows and the blowing may be explained. important to remark that the quantity of heat emitted during the combination of a given quantity of oxygen is definite. be arranged under one of three classes. as well as by carrying away the gaseous products of combustion which are incapable of combining with the fuel. however. and is by development of heat . the is temperature which produced by combustion is lower. zinc. and at the same time the colour of the blood is changed a dusky purple to bright crimson. and which. with reference to combustion. be set on The second fire . carbonic anhydride is eliminated and passes off with the expired from air. being quite independent of the rate at which the combustion is effected (199 et seq. be re- . if suffered to accumulate. class consists of bodies which. however. When chemically upon the oxygen is mixed with a gas which does not act it. like oxygen. a superficial coating of oxide formed. these are termed supporters of combustion. The activity of the combustion is greatly augmented by increasing the number of particles of oxygen which are brought in a given time into contact with the combustible. It is. an of the air accompanied oxidation of a portion of the constituents of the blood occurs. as with the nitrogen of the atmosphere. analogous to combustion. and part of the heat developed is employed in raising the temperature of the inert gas. is attended with a slow change. allow other substances to burn in them freely. is 43 and some other metals. The influence of a long chimney in producing a powerful heat in the furnace at its base is similar . or shutting the door of the ash-pit. and protects the metal beneath from further change. lead.RAPID AND SLOW OXIDATION. like charcoal. in ordinary language. and varies only with the chemical nature of the burning body. and the operation proceeds more slowly because fewer particles of oxygen come in contact with the burning body in a given time. The first class consists of bodies which. would cut off the supply of fresh oxygen .). during is which the oxygen brought into contact with the blood through the of the agency lungs. whilst the effect of diminishing the supply of air by closing the damper. The act of respiration in animals. but which cannot themselves. All bodies may. It must. actually burn when sufficiently heated in a gas belonging to the first class : these substances are termed combustibles. which adheres firmly to the surface. is seen in the diminished temperature and reduced consumption of fuel which occur under such circumstances.

two remarkable that amongst the various compounds formec classes exist which are in chemical properties directly opposed to each other. only body support existence in the atmosphere. that the terms combustible and supporter of combustion membered are merely relative. that is. : part compounds that may have at some time or other beer. as burning taste.44 VARIETIES OF OXIDES. The third class embraces such bodies as will neither burn themselves nor support the combustion of others they may be made red hot. produced by been already burned. for although under ordinary circumstances hydrogen is a combustible and oxygen and chlorine supporters of combustion. atmosphere and is not less extensively met with amongst the solid constituents of the earth its varieties chalk. and turns many vegetable blue colours. (34 1 ) Varieties of Oxides. rock-crystal. and marble of sand. Many substances. to a bright red All the nonwhich. the element which maintains combustion on the surface of our planet. such an infusion of litmus or purple cabbage. vital functions in both . by their union of an oppo- . and earthy bodies in general. metallic elements. in all as well as the its It is also oxygen. give Many rise to bodies possessing properties of the metals. various kinds of clay. quartz. which. &e. and in many cases intensely : powerful acids. by their combination with oxygen. and a body which has combined with oxygen is said to have become oxidized. yet these two last-mentioned gases are quite capable of burning when surrounded by an atmosphere of hydrogen. it the most widely diffused and abundant of constitutes about a fifth in bulk of the forms eight-ninths of all the water on the globe. flint. form one or more compounds with oxygen. however. when united with the elements of water. they are for the most. like phosphorus. they are bodies that have combustion . possesses the characters of an acid. by oxygen. but do not burn . from its which is fitted to combustion. in short. with other elements are in chemical language termed oxides. yield acids. change. producing a liquid which has a It is sour. for The number and oxygen It . generally diffused in the forms of life j vegetable being indeed absolutely essential to weight ol animal and the main- tenance of the and although not the it is. with the exception of hydrogen and fluorine. limestone. The compounds which oxygen forms. iron-rust. sand. yield a compound which is freely soluble in water. variety of these compounds are very is the elements. great. and are no longer fitted to undergo this. with oxygen. each contains about half : silica. afford examples of this kind .

long that of diluted chlorine. is a third which are indisposed to enter into combination with either acids or bases. may be mentioned as instancefL such oxides are often produced by the union of this kind These indifferent oxides of two other oxides with each other. Independently of its power of supporting animal life and It is combustion. sulphuric acid. Intermediate between the acid and the basic oxides class of oxides. and neutralize the acids Ferrous oxide. a peculiar odour is perceived. owing to the formation of red fumes of peroxide of nitrogen solution of cuprous oxide in 'ammonia (391) is : A and a colourless instantly rendered blue by the action of uncombined oxygen. the but observations of divided were cause of this odour . it unites with a larger number of atoms of oxygen than when a base is the result of the combination. The black oxide of manganese or the (MnO 2 ).OZOXE. which is dissolved rapidly by water.Fe2 O 3 ). and red lead (2PbO. of a soapy. disagreeable taste. oxide with any gas containing uncombined oxygen immediately N becomes of a reddish-brown colour. are sometimes termed saline oxides. and produces a colourless liquid. and a peculiar odour it has a caustic action on the skin. preserve their basic character.MnO. to emit an odour) and its in allusion to Opinions upon the strong peculiar odour. furnishes a white alkaline sub- stance. Other metals form oxides which. / \ When a succession of electric sparks O O transmitted through atmospheric air or dry oxygen. It is found in almost all cases that when an element combines with oxygen to form an oxide which by addition of water produces an acid. whilst water is set free. but if a little pyrogallic acid be added. site 45 kind. insoluble in a solution of potash. when burned in oxygen. (342) is OZONE : O3 . which has by some been compared to To the body which produces it ozone of Schonbein gave the (from ow. to the alkaline liquid the gas is rapidly absorbed. magnetic oxide of iron (FeO. name . Potassium. restores the blue : colour to litmus which has been reddened by an acid. and the mixture of nitric solution becomes of a deep brown colour. and completely neutralizes the strongest acids. is in soluble and forms with it a crystalinstance.PbO 3 ).^). from their analogy to salts in : * L^ ^** composition. oxygen may be distinguished by direct tests. for example. for perfectly. although not soluble in water. (MnO. lizable salt. and which have been termed bases.

wires of an induction coil. and a comparatively large proportion converted into ozone. One of the most convenient forms of apparatus for the preparation of ozone is that devised by Siemens. maximum the discharge By Ozone is much denser than rable portion of the gas into ozone. and having a current of ice cold water passing through it in order to prevent the heating of the apparatus. Trans. 1860) have shown that in order to produce the oxygen. and passing a current of pure dry oxygen through the annular space between the two tubes. whilst the oxygen resumed its original volume. but notwithstanding the powerful odour thus produced. oxygen itself. One of the easiest methods of exhibiting the production of ozone consists in transmitting a current of oxygen through a tube into which a pair of platinum wires is sealed. and kindles the less inflammable variety of phosphuretted hydrogen . consisting of a long glass tube coated on the interior with tin foil. amounting to one-twelfth of the entire volume operated on and on heating the gas to 550 (288 C. is several accurate experimentalists indicate that it modification produced in oxygen itself. in converting a consideeffect in electrifying jsilently. Later researches have. they succeeded. a minute porAndrews and tion only of the oxygen undergoes this change.) the ozone disappeared. it contains ozone oxidizes : it has a powerful odour. with the points at a little distance apart on con: necting one of the wires with the prime conductor of an electrical machine in good action.46 OZONE. whilst the other wire is in conducting communication with the earth. they effected a contraction in bulk of the gas . rendered it probable that these properties are due to the formation of peroxide of hydrogen in . Ozone may also be obtained without the aid of electricity. The passage of the electric spark immediately destroys a large proportion of the ozone which had been previously produced. Tait (Phil. when great care was taken to prevent the transmission of sparks. Houzeau states that the oxygen evolved from baric dioxide (BaO 2 ) by the addition of oil of vitriol. has recently proposed to replace the inner tube by a brass box tinned on the outside. it is necessary to transmit operating in sealed tubes upon pure and dry oxygen. over which passes a slightly larger tube covered with tin foil on its On connecting the inner and outer coatings with the terminal outer surface. however. after it has been heated it no longer possesses these properties. by which owing to a it is made to assume a more active condition. and he found that ammonia. the characteristic: odour of ozone is immediately developed in the issuing gas . this gas is acted upon by the silent Wills discharge. by a continuous electrical discharge maintained for many hours.

phosphates. Mag. and if : potassic little of potassic chromate acidulated with a agitated with a few drops of a solution of perchrouiic acid in the ether is obtained. with that produced by voltaic action.). Von Babo's experiments tend to show that SchonbeinV so-called antozone is it is peroxide of hydrogen. is decomposed electrolytically by the voltaic battery. the oxygen is evolved has a powerful odour of ozone. as well as with that obtained by the oxidation of phosphorus. 1850 and 1862) oxygen which escapes.* to its PREPARATION. of peroxide of hydrogen evolves oxygen. the residual ether contains peroxide of hydrogen. that ozone should be the isolated form of A mixture of a solution of potassic permanganate with one one of these bodies. They are ingenious. It is also probable that ozone is formed in other slow oxidations. at a temperature of from 60 to 70 (15 to 21 C. neither is dry phosphorus. suspension in 47 the oxygen as it If a stick of phosphorus. When dilute sulphuric acid. a fact which is true also of electrolytic ozone. sulphate green oxygen in the permanganic or chromic acid is in an opposite polar condition to the second atom of oxygen in the peroxide of hydrogen . The experiments of Andrews (Phil. solution a blue acid. If the phosphorus be not then : removed. Trans. and several other salts of the alkalimetals. or a solution of thq sulphates. for 1858. but although the existence of two oppositely polarized forms had previously been rendered probable by the experiments of Brodie and others. benzol. sulphuric .). and these conclusions have * The reader is referred for Schonbein's speculations upon the existence of two opposite forms of oxygen. whilst hydrated peroxide of manganese is precipitated. to the Phil. such as that of ether.OZONE small quantity. the slow oxidation of the phosphorus is attended with the production of ozone in an hour or two this attains its maximum. moistened with a few drops of water. the tendency to union between these two supposed oppositely polar forms of oxygen is conceived to be the cause of the decomposition. is only present in very minute quantity. be placed in a bottle of atmospheric air. 1855 and 1860) have shown the identity of the ozone obtained by the electricity of the machine. whilst sulphuric acid gives off oxygen on the addition Hence it has been supposed that the chromic is produced. be plunged into a jar slow oxidation. as obtained by any of these processes. the vapour undergoes seems to be formed the vapours turn starch paper. Trans. chromates. t If a clean glass rod heated to about 500 (260 C. and in like manner a solution of chromic acid acidulated with of peroxide of hydrogen. not in accordance with analogy. being diluted with from 50 to 200 times its is volume of oxygen. and oil of turpentine. owing to its combination with the No ozone is formed if the air be perfectly dry. ozone and antozone. the ozone disappears by degrees. Phil. oxygen ozonized by phosphorus. Schonbein appears to have proved that in all such cases the formation of ozone accompanied by that of peroxide of hydrogen (H8 2 ). and escapes. and the result of their union is the gaseous (See also Brodie.f Ozone. that employing plates of platinum or gold as electrodes. moistened with a solution of iodide. blue . and ozone containing a few drops of ether.

48 OZONE PllOPEKTIE*. Chem. indeed. The experiments of Sore by oil of turpentine. Annal. been confirmed by Soret and by Von Babo (Ann. little silver Dry mercury. paraffin. as well as dry ozone. whilst decomposition of ozone by on the absorption of ozone three become condensed into two. or no absorption occurs. When the ozone and the metals are perfectly dry. also freely absorbed by a solution of potassic iodide.) and under the ordinary pressure absorb about 0*5 volumes of the gas. equal in bulk to itself. Ozone dis the recent investigations of Sir Benjamin Brodie. which has been confirmed b. absorb it ozone. tha it furnishes the readiest and most delicate method of detecting the presence of traces of ozone in the air . is liberated at the moment that the . setting th iodine at liberty. ' Ozone is very slightly soluble in cold water. places iodine from its combinations with the metals. as Schoubem himself at one time supposed. } ii. on converted their and become surface into oxides rapidly. becomes blu from the action of the liberated iodine on the starch. and on its ratr of diffusion. which . though this metal does not ente:* into direct combination with ordinary oxygen either when mois. forming th characteristic blue iodide of starch. is not acted on. who maintained (Pogg. it acts rapidly as a and converts blue indigo into isatin : powerful oxidizing agent. 38) that electrolytic ozone contains a peculiar peroxide of hydrogen. pure oxygen con . it is Air charged with ozone exerts an irritating action upon the respiraOzone possesses considerable bleaching powers. or dry. SuppL-bd. Properties. Pharm. iron. favour this supposition. . however. moistened. on two volumes are liberated on the a metal. immediately contraction follows the absorption of ozone by these agents this point was carefully and minutely observed by Andrews am Hence it seems to be probable that the ozone is resolve< Tait. 266). It is remarkable that no removes iodine. copper. combination with the iodine in this other portion enters into way it would appear tha volumes of oxygen volume being fixed. an excellent means for connecting the forms and used in experimenting with of the different parts apparatus and when silver. Carius states that 100 volumes of water at 32 (o C. however. tory organs. and corrodes most organic matters. such as cork or caoutchouc therefore : even becomes a peroxide. Ixxxix. into a quantity of ordinary oxygen. in opposition to Baumert. Indeed. a slip of papc moistened with starch paste and potassic iodide when exposed t<a gas containing the smallest admixture of ozone. this reaction takes place so easily.

especially when the wind blows off the sea. cold manganic dioxide. argentic dioxide. (MnSO 4 ) prolonged. : = 4KHO + 2l iodate. If the paper be stained black with plumbic sulphide (PbS). sometimes. is by no means characteristic of its presence is . from potassie iodide by nitrous acid. although a very senozone. potassie hydrate being formed by the absorption of oxygen. the compound absorbing the ozone and becoming oxidized to the whilst sulphuric acid white plumbic sulphate (PbSOJ.ATMOSPHERIC OZONE. all signs of ozone Ozonized air is also deozonized by transmission over disappear. tained in a tube is 49 entirely to the inverted over a solution of potassie iodide absorbed by the liquid. cumstances connected with ozone One is of the most singular cirthe effect produced by eleva- tion of temperature. however. by chlorine.) it is slowly converted into ordinary oxygen. soaked in a mixture of starch and potassie iodide be exposed in the open air for five or ten minutes. 2 . for when heated a little above 212 (100 C. agents sitive one for ozone. it often acquires a blue tint. and becoming converted into the insoluble hydrated peroxide. the existence in its % in more powerful certain. are seldom seen in towns. and the change is instantaneous at the temperature of 572 (300 C. oxidizing but that this is atmosphere of some agent than ordinary oxygen ozone cannot be said to have been the action unequivocally proved. and by various this besides so that reaction. peroxide formed. if the gas be subjected passage of a discharge of electricity through it for a sufficient length of time. K . particularly in damp or foggy These effects weather. of the proportion of II. the intensity of which varies on different days . be liberated during lengthened periods.KI + sHoO + O. but generally in the open country. potassie of hydrogen and peroxide of potassium are Paper soaked in a solution of manganous sulphate likewise shows the presence of ozone by turning brown. or on the seav coast.). while iodine is set free (^. no change is produced by such exposure. By placing the flame of a spirit-lamp so as to heat a part of the tube through which the electrified oxygen escapes. or plumbic dioxide. and theorists are not wanting who believe they have traced the prevalence of cholera and other epidemics to the unusual absence of ozone in the air Iodine may.) If the experiment be owing to the manganese in the sulphate absorbing oxygen. is set free. in order to obtain some idea the agent which produces this effect. They are plausibly supposed to be owing to the presence of traces of ozone in the atmosphere. this stain will gradually disappear. Schonbein. If a piece of paper.

the change in the iodized test paper being due to the combined effects of moisture. WATER: Rel. white starch : which are preserved in a stoppered bottle kept in the dark. 2 [ . V. for they are In each of its universally felt and appreciated. 9 Vol. but Cloez conclusively proved that this is not the case. Although the be cloudless and if the may atmosphere be perfectly clear. and to ameliorate the social condition of man. it supplies one of the most convenient channels of communication between places widely separated. Vapour. it furnishes to man a continual source of power in the flow of streams : . and light upon it. Sp. As ice. Theoretic. three physical conditions. a solid bridge of communication between distant places in the liquid condition. we must perceive the entire adaptation of this . Gr. PEROXIDE OF HYDROGEN. charged with aqueous vapour it will entirely intercept the obscure heat radiated from the earth. 0*622. of Vapour ^J. Nor must we pass over the important effects produced by the opacity to heat of the contained in the aqueous vapour air. as Liquid I'ooo. H O=i8. and further. too. i part prepares the test-paper of a definite strength. if night rightly considered. It was at one time believed that the green parts of plants evolved ozone under the influence of the solar rays. Atomic and Mol. as Ice 0*91 8. (343) ON the uses of water it is almost needless to enlarg^. wt. and rivers . it is absolutely necessary to the existence of vegetable and animal life in this shape. oxygen. as applied in the steam-engine. by dissolving of pure potassic iodide free from iodate in 200 parts of distilled water which is thickened by heating it with TO parts of this is then spread upon slips of unsized paper. it is food the storehouse of countless myriads of creatures fitted for use as in the state of vapour. and also Bellucci have CHAPTER WATER. and which acts as a sort of screen in preventing radiation from the earth. it furnishes in northern lands for months together. the blessings which it confers upon man are inestimable. it has : furnished a power which has in later years done more than any other physical agent to advance civilization. to economize time. as 0*6228 Observed. In each and all of these points.50 WATER.

or heaving with the gently undulating tide. To such causes we must refer the formation of sedimentary rocks. or the lake. as with a fleecy mantle. it bathes the soil all will testify to and the personal experience of the charm which the waterfall. In its solid state we are familiar with it in the form of blocks of ice. we cannot to be impressed with the important effects produced by the movements of water at periods anterior to the existence of man. fail it 51 was designed by the Glancing at the physical condition of our planet. freezes and assumes a variety of crystalline forms derived from 2 . when free from admixture. whilst few can behold unmoved the unbounded expanse of ocean. is a clear. It may further be observed that there is no form of matter which contributes so largely as water to the beauty and variety of the globe that we inhabit. transparent liquid. seems to remind lashed into foam by the storm that sweeps over its surman of his own insignificance.PROPERTIES OF WATER. aa rain or dew. the rivulet. are due to the refractive power of floating spiculse of ice upon the sun's rays. adds to the beauty of the landscape . destitute of taste or smell. which. water. . wonderful compound to the ends which Creator to fulfil. of sleet and hail. colourless when seen in a volume of small traverses thickness. whilst the gorgeous hues of the clouds around the setting sun.) depth of the water increases. from the The rare but splendid spectacle of piercing frpsts of winter. but exhibiting a pale blue tint when the light a column of six feet. whilst the accu- mulation of drift and a variety of other extensive geological changes must be traced to the same ever-acting and widely operating agency. or of snow protender plant. elevation and filling-up of hollows at others . which by their ever-changing shadows diversify. At the ordinary temperature of the air. the landscape over which they are flitting. the colour passing to a deep bluish green as the it At temperatures below 32 (o C. as well as in more recent times. are due to the refractive action of water and watery vapour upon the solar rays. obser: vation shows that denunciation is proceeding at some points. the stream. and of the power of Him who alone can lift up or quell its roaring waves. of hoar- frost fringing tecting the every shrub and blade of grass. mock suns. at every moment. and the glowing tints of the rainbow. Properties. In vapour how much variety -is added to the view by the mist or the cloud. and their arrangement in successive strata upon the surface of the earth even now. or parhelia. In its liquid condition. or when face. whether motionless.

A litre of water. because when the temperature rises to about 640 (338 C. and the important purposes thereby attained as the great dilatation which it undergoes on freezas well (151). sphere (143). which regards these bodies as formed by the union of an anl^dride with a base. its refractive power on light Its continues to increase regularly. or I kilogramme. some presented to the acid the water is again elimibe expelled by the application of heat. has once been allowed to combine with water. that sulphuric anhydride has been added to a on heating the mixture the water large quantity of water powerful base is nated. and it hence has been termed basic water. for example. shown Experience 997) ounces avoirdupois. water is eliminated. as though it contracted. and .). and finally no further separation can be effected. at 4 density which the specific gravities of all solids and liquids are compared. or cube of 10 centimetres in the side. Its anomalous expanat about 212 it boils (106 C.l 4 . . 3 2 2 Upon the older view of the constitution of salts. if. weighs in air 252-456 grains.).SOt sulphate of lead. : S= 16 and . Supmay pose. oxide of lead be added. and a cubic foot very nearly 1000 (more exactly is invaluable as a solvent. It is found on . and anhydrous plumbic sulphate is 2 obtained : PbO+ H SO 4 2 [PbO-rS0 2 (OH) 2 =H O + PbSO =OH -fS0 (0 Pb)". passes off readily at first.g.analysing the acid when . is taken as rooo. that the composition of the liquid may be But if to this represented very nearly by the formula H 2 SO 4 concentrated acid. e. that notwithstanding the gradual dilatation of water at temperatures below 39*2 (4 C. it has reached this point.SOV of vitriol PbO. Pb 103) : EO. the water would in the foregoing instances supply the place of a base. O= 8. been already pointed out. Water evaporates at all the rhombohedron and six-sided prism. It is perand to test enters into combination neutral with papers fectly has various oxides forming acids and bases. sion by heat have shown. the under and ordinary pressure of the atmotemperatures. or so-called anhydrous acid. at 4 C. and it forms the standard with C. a cubic inch of water at 62 F. the separation of the water from the compound is generally impracticable . weighs 1000 grammes. but by degrees it becomes necessary to increase the temperature in order to expel the water.) the entire liquid distils over. or in English weights and measures. however. : (if H-oil i. At last the acid begins to evaporate also. To the chemist water that when an anhydride. have Arago and Fresnel ing (76). leaving the less volatile acid behind.52 WATER IN COMBINATION.

unite with a definite quantity of salts in The compounds of water a body is Many crystallizing of which. the on the number of molecules crystalline form of the salt depending On the application of a gentle of water with which it is united. Potash in the form in which it is residue to dull redness. moreover. be by the addition of an acid. Anhydrous potash. the amount heat. water. Sulphuric acid.HO) : this equivalent of water cannot .HYDRATES WATER OF CRYSTALLIZATION. This older explanation is inadmissible if water be represented as consisting of . anhydrous potash (which may be formed from the hydrate of the alkali by heating it with two potassium. HHO . whilst potassic sulphate and water are simultaneously formed.so 4 . such as sulphuric acid then. . if it be supposed that. such as potash or soda. caustic potash is a compound formed upon HO the same plan or type as water. frequently varies. by the application of heat.HO + JfO. this be again expelled without altering the chemical In this case the water is spoken properties of the saline body. For instance. borax always crystalof as water of crystallization. but that it contains an atom of potassium in place of one of the atoms of hydrogen present in the molecule of water.HO + HO. it commonly said to be anhydrous (from o not. contains obtained by evaporating down its aqueous solution and heating the the elements of one equivalent of oxide of potassium and one of water expelled except (KO. and the two of hydrogen in the acid. changing places with each other. SO 2 (OK) J the two atoms of potassium of the base. KHO acid KKO/ : upon potassic hydrate is then a true case of double decomposition.SQ. v$wp water). [ TKHO + 57so = 2 OKH + S0 (OH) = 4 2 2 2HHO 20HH + + K. When is are frequently termed hydrates. Potassic hydrate. and may be thus represented The reaction of sulphuric Potassic hydrate.A -2. anhydrous sulphate of potassa is obtained (KO. 53 Still adopting the older view. described as being entirely free from water. Water.SO3 ). In such a case the water in combination with the base appears to perform the part of an acid. These relations of the three different com: pounds may be thus represented Water. hydrogen being liberated) is viewed as containing atoms of potassium in place of the two atoms of hydrogen in the molecule of water. it then cannot be expelled from them until some acid has been added. may . it has been supposed in a similar manner that water combines with the powerful bases. Further. yet in the latter case the presence of in hydrogen potassic hydrate may be equally well accounted for. Potassic sulphate.

c. which is firmly secured at both ends bj A small wooden vice. with 10 molecules of water (Na 2 B 4 O 7 . which is supported in a small mercuria The bulb.. d.ioH 2 O). and the other gases present in the air. approaches nearest to it. or from 14 to 16 ounces. Sodic carbonate (Na 3 CO 3 . the water speedily begins to gm . Potassic carbonate and calcic chloride offer CO instances of this kind. capable oJ containing 400 or 4^0 cub. anc A connected by a vulcanized caoutchouc tube. bath. 2 inches (5 cm. having been about half filled with the water. in oblique rectai) gular prisms. Other salts. centim. d 30 mm- with an expanded funnel-shaped mouth. no more air escapes from the tube. globular flask. if a solution saturated at 91 (33 C. the same thing occurs in the case of sodic sulphate (Na2 SO 4 ioH 2 O). is filled with mercury and placed over the end of the long tube. and heat applied to the flask . . collected after a long continuance of wet weather. the mouth o which is kept just below the surface of the mercury. is made use of to compres: ligatures. th< Th< jar. When. on the contrary. tensive solvent powers. to the extent of about i\ volumes of air in 100 of water. until all the air is expelled from the tube. absorb moisture from the mere exposure . be very slowly heated. sodic sulphate crystallizes. but from a more concentrated solution. under ordinary circum- but stances. atmosphere. but even that always contains atmospheric air. in oblique four-sided prisms with 10 molecules of water. if the solution of the salt be not sufficiently concentrated to begin to crystallize till the temperature falls to T 33 (56 C. This tube ii bent in the manner represented in the figure .ioH 2 O) for crumbles down or effloresces to a white powder and example. Rain water. c. the sulphate is deposited in rhombic octohedra which contain no water : crystals containing salts part obtained. So. is connectec with the flask by the caoutchouc tube. and often of common and some organic impurities. the longer limb being upwards o inches ('j6o in length. they are then said to deliquesce. upoi which is blown a bulb. the vulcanized tube and to cut off communication between the flask and th< The water in c is now made to boil briskly for ten minutes or bulb. : vice is removed. borax is deposited in regular octohedra with only 5 molecules of water. 284. such as is usec for taking the density of vapours. is filled with the water to be examined.54 lizes SEPARATION OF AIR FROM SOLUTION IN WATER. c. again. air The quantity of which is contained in spring or other water can be readily ascertained in the following manner. after the boiling has been continued for a few minutes. fig. water is never met with naturally in a state of purity. and ) terminating below in a recurved extremitj designed to deliver the gas disengaged from the water. a. and become damp or even liquefy in the water so absorbed .) . to a piece of barometer tube. into a graduated jar. The first fall of rain after an interval of dry weather contains always traces of nitrates salt and of salts of ammonium. 3) (K 2 Owing to its ex(344) Various kinds of Natural Waters. such as is seen at/".). quarter of an hour. Many 7 molecules of water may also be with their water of crystallization by to air. b.) or more in diameter.

c. c. FIG. When the operation has terminated. is to prevent the water from boiling over into the jar. Nitrates are often abundant in these and other well-waters of towns. and nitrogen being in each case almost exactly in the proportion of i measure of oxygen to 2 measures of nitrogen. or of mercury. but the most usual saline impurities are calcic carbonate and sulphate. 2 One object of the globe. aud the operation terminated by a few minutes' brisk boiling. but this is a matter of small consequence. were : submitted to experiment tiin. Sandstone are impregnated to a greater or less extent with calcic sulphate . contains air. the gas is allowed to cool. but the deep springs are very uniform when examined even at considerable intervals. contained in '85 c. and The waters of the New Red magnesic sulphate and carbonate. c. cen- of the I specimen of air . It will be found that all water. the same bulk of the 5 second and the third specimen 2-38 c.SPRING WATER. owing to contamination with sewerage products. and the quantity increases till the water boils. The nature of the salts will of course vary with the character of the soil through which the water percolates. d a little steam : always condenses in the jar above the mercury. 100 first cub. The nature and amount of the salts found in waters of shallow wells vary considerably at different times. by which the delivery tube will be filled with steam. and the shallow wells ill the gravel of the London district contain a considerable quantity of the same salt. common salt. three samples water twice distilled in glass vessels. Gentle ebullition must be continued steadily for a full hour. always contains more or less of saline matter dissolved in it. and is transferred to a tall jar of water. including even that which has been recently distilled. where its bulk can be measured. For ex- of ample. Most spring waters are charged with a notable pro- . te which they owe their hardness. and all the air will be driven over into the jar. which have in many cases undergone the partial oxidation. Spring Water. 55 off gas . of air were present the oxygen 2'ijJ. although it may be perfectly transparent.

and at Cheltenham. giving the brisk effervescent character noticed in Seltzer water. At Carlsbad and Aixla-Chapelle this temperature varies from 160 to 190 (71 to 88 C. those at Cheltenham are of this kind. vary with the nature of the salt in solution. and the Vichy waters abound still more in this salt. per litre. which dissolves a considerable amount of calcic carbonate . so that a running stream will seldom contain more than 12 or 14 grains litre). Heat as a Mode of Motion. as in some of the Harrogate and Moff'at waters. or from of chalk per gallon. where common salt and . the Tunbridge Wells springs. as the case with the deep-well waters of London.) Iceland are heated even beyond the temperature of 100 C. of chalk per gallon in solution (170 or 200 mgrms. The Geysers of (Berzelius. in which case they generally abound in carbonic acid. and at intervals the boiling water is ejected with ex- plosive violence. In other instances. and contain chlorides of calcium and magnesium. (See Tyndall. and some of . which also contains a notable proportion of hydric sodic carbonate (NaHCO . giving the nauseous taste and smell to such sulphureous waters. like the springs at Epsom. which abound in maguesic sulphate. Mineral Waters are waters impregnated with a large proportion of any one of the above-named salts. nearly one-third of which 1 8 to 20 grains becomes separated by exposure of the water to the atmosphere. Many mineral waters contain salts of iron in solution. the springs are merely saline. the calcareous springs in the chalk districts around London contain from 255 to 285 mgrms. Such hot springs either occur in the vicinity of volcanoes. 4th ed. In other instances carbonic acid is very abundant. 126.). in the tube.56 MINERAL WATERS. and contain purgative salts. portion of carbonic acid.) The Geysers of the Yellowstone river no doubt owe their activity to the same cause. which impart to them an inky taste they are then frequently termed chalybeate waters. of these springs are of a temMany : perature considerably higher than that of the surface of the earth where they make their appearance. or with some substance not so commonly met with such waters are usually to medicinal which reputed possess qualities. and almost always traces of sulphuretted hydrogen. Less frequently. the so-called bicar3 bonate of soda). sulphuretted hydrogen is the predominating ingredient. as well as in common salt and other salts of sodium : or they spring from great depths in the rocks of the earliest geological periods. per Waters which have filtered through a bed of chalk also is frequently contain sodic carbonate in considerable quantity.

dissolved in the water cannot. The Geysers are silica. solution. Filtration through beds of iron turnings has likewise been practised in some cases with similar advantages. Spencer has particularly called attention. although salts. and if the stream be unpolluted by the influx of the sewerage of a large town. (Report of Commission on the Pollution of Rivers. River water almost always requires filtration p. indeed. be arrested provision is made for this filtration. and if waterthrough works designed to supply such water be properly constructed. but it has recently been shown that the self-purifying power of running water is not so great as was formerly supposed. Suspended matters. many even of these soluble impurities are removed. but the oxygen is in this case in great measure Animal charcoal also absorbed from the water the iron. Runnin" * *3 1 however. and it appears probable that this action. In the gradual percolation of water through the porous strata of the earth. derived from the extensive surface of If the sewerage country which has been drained by the stream. particularly those of organic origin. may furnish a valuable auxiliary to the methods of filtration at present in use. often contains a smaller amount of drinking than ordinary spring water. by . of course. i. of large towns situated on the banks be allowed to pass into the stream. in but matter removed. The magnetic oxide of iron. 18. this process is generally fully adequate to preserve it in a wholesome state. 57 sodic sulphate are the predominant constituents. partly by adhesion to the surface of the filtering material. Vol. salts. fish-spawn. the continual exposure of fresh surfaces to the action of the atmosphere promotes the oxidation of the organic water is.RIVER WATER PURIFICATION OF WATER. On the Mersey and Ribble Basins. such as silt or mud. leaves. 1870. and vegetable colouring other bodies. rich in which add greatly to their therapeutic activity. 1868. it is of course still less fit for domestic use. Many of these saline springs also contain small quantities of iodides and bromides. but chiefly by a slow oxidation in the pores of the soil. are thus weeds. to which Mr. matter. which in some cases forms nearly one-half of their River Water. endowed with a self-purifying power of the highest importance . is less fitted for it soluble constituents.) sand before it is fit for domestic use . seems to exert a peculiar influence in promoting the oxidation of organic matter contained in water which is allowed to percolate through it. and finely divided by such a filter. as it holds in solution a much larger proportion of organic usually matter of vegetable origin.

which is discharged into the ocean I y pure water alone evaporating from the surface of tl e former . which are perpetual y . colourless. the carbonic acid being expelled by this means and the calcic carbonate and part of the calcic sulphate whic . Such waters adm t of being softened considerably by the addition of a certain prc When the hardness is owing to calcic o portion of lime water. will cause the decolorization 0:" : a solution of the permanganate. a return to the surface of the sc 1 provided for in the marine plants. acidulated solution of potassic permanganate is rendered nearly This test. soluble in water. the addition of sodic carbonate precipitate s the carbonates of these metals and softens the water. and constitutes an excellent filtering material. and auric chloride imparts a brown tint to the water under such circumstances. i were held in solution are then deposited. owing to the precipitation of metallic Even at ordinary temperatures a very dilute gold. when boiled with them. as the sea is the receptacle for all tl Sea Water t s e fixed contents of the water rivers. Water is familiarly spoken of as hard or soft. Those waters which contain compounds of cal cium or magnesium occasion a curdling of the soap. as is pract cally known to laundresses. Soft waters do not contain these salts. ani I dissolve the soap without difficulty. might be entirely overlooked. exerts a remarkable effect in promoting the oxidation of organic matters in solution. to which it owes its saline bitter taste. however. and fish. as thesr ^ bodies produce with the fatty acid of the soap a substance no. is not a certain indication of the presence of organic matter thus the presence of mineral reducing agents. 1 " is largely impregnated with common salt an magnesic chloride. as ferrous salts and nitrites. and on the other hand there are many organic bodies which reduce potassic permanganate so slowly that their presence is the case with urea. This The only organic body which reduces the permanganate completely in the cold during 10 minutes appears to be oxalic acid. although easily applied. .58 HARD AND SOFT WATER SEA WATER. according to it action on soap. The argentic chloride becomes purplish. Many hard waters becom softer by boiling. creatin. and hippuric acid. might be supposed that the quantity of salts which it contains continually on the increase. and cause a ' fur ' c r incrustation upon the inside of the boiler. magnesic sulphates. there is. by reduction to a lower state of oxidation. sugar. The presence of organic matter in water is easily ascertained the reducing influence which it exerts upon chloride of silver by or of gold.

. 0*02929 2*29578 1-40662 0*03301 traces traces .. and phosphates... according to the part of the it is collected.. Magnesic bromide Magnesic sulphate Calcic sulphate Calcic carbonate .. while those of the Mediterranean are more so. which may be effected on a small scale in glass retorts. . .. The mean specific gravity of sea water is i '027.. Mag. Trans... 0-003 lOOO'OOOOO Specific gravity . Iron pipes may also be safely used for the purpose of condensation.. An elaborate paper on the composition of sea water in various parts of the world. and barium.. by G. Ammonia . .. . dis(345) For chemical purposes water is always purified by tillation.. is addition of lime to the water before submitting it to distillation useful. have been found in the waters of the ocean.. its depths by the force of storms.... boiacic acid. which are apt to pass over if magnesic The chloride be present. owing to the decomposition of this salt. ... The waters of the Baltic and of the Black Sea are less salt than the average.. but nitrates have as yet eluded the most careful observation. . 1865. as well as of silica. and also traces of hydrochloric acid.... Forchhammer. Mediterranean. the British Channel is composed as follows : ranges from 3*5 to 4 per cent. but lead must be avoided. . 1027-4 at 16 1025*8 at 21 C... and the quantity of salts According to Schweitzer (Phil. ... . ... p... and The the still should not be employed for any other purpose. . as it retains the excess of carbonic acid. will be found in the Phil. xv. . 1839.. . Feme oxide ... xxvii. The waters of the Mediterranean in the Levant are more salt than those of the same sea near the Straits of Gibraltar. . Water Sod ic chloride Potassic chloride . 203. . the water of that of the Mediter- ranean.. . 58)... ..... . de C/iimie [3]... 9 '55^ 2 '477 J '357 0-114 Iodine ..... .. .SEA WATER DISTILLED WATER. and more conveniently on a large scale in a copper still provided with a tin or copper worm... analysed by Usiglio (Ann. aluminium. 963-74372 28-05948 0-76552 3 962-345 29-424 '55 3' 21 Alagnesic chloride 66658 . .. strontium. The specific gravity of sea is water globe where subject to trifling variations. for Minute quantities of manganese.. .. will be seen to agree very closely with it in composition : British Channel... ... 104). lOOO'OOO C.. by predatory and by the industry of mail. .... 59 being raised from birds.

which now largely prepared on long sea voyages. no stain or otherwise some saline impurity is present. con- A taining two platinum plates. as we have seen. 285. I : Symb. contain traces of ammonia : when a few drops of because they usually distilled water left. When converted into vapour 18 grammes of steam occupy twice the bulk of i gramme of hydrogen at is the same temperature . portions of water should be rejected. and if two similar jars be filled witl water. formula is HO 2 [or OH ]. Water was long supposed to be an elementary substance .60 first ANALYSIS OF WATER. a and b t is filled with water. anc is arranged so as to transmit the currenl of a battery consisting of three or four o: Grove's cells (266). the molecular volume of aqueous vapour therefore if the atomic volume of hydrogen be taken [_ J. Fig. glass vessel. r~j. and one inverted over each plate the wires the volume of the gas which rises from th< platinode or negative plate b. gas rises fron each. th will show itself to be oxygen by rekindling to . as Its composition Hydrogen Oxygea is shown in the following table Dumas.M. however. 2 and its molecular weight 18. are evaporated upon a slip of glass. Its it oxygen the in the proportion of being a compound of hydrogen with two atoms of the former to one of therefore latter. is not the case. navy being fitted with suitable distillatory apAs organic matter is present both in ordinary water renders the water agreeable and wholesome as a beverage. H = 2 By weight. Immediately that tin two platinum plates are connected witl of the battery. 2 O =16 18 88 80 88-88 I HO An is lOO'OO elegant mode of showing the composition of water analytically afforded by the voltaic battery. after due aeration. is entirely got decomposition during distillation. H. Distilled water is mark should be the ships of paratus. slightly acidulated with sulphuru acid to improve its conducting power. a . this. the distillate is liable to acquire a disagreeable taste in consequence of a portion of the impurities undergoing This.J or By vol. will be fount gas in the tube O be exactly double of that which rise from the zincode or positive plate. and in sea water. 2 or ii. rid of by filtration through charcoal.

inch of each other.3 -. especially if the metal be in a finely divided their immediate combina(65). is a strong glass purpose a modification of which FIG. but the passige of an electric spark. represented at A. is sufficient. in some instances. D. fails to cause their union. state tion. and. by discharging a small Leyden jar. . water by the union of the hydrogen with the oxygen of the atmosphere. if it be gradually applied. The air is exhausted. Through the upper part two platinum wires are inserted to within mm . the interior of the glass quickly becomes bedewed with moisture owing to the formation of (346) Synthesis of Water Eudiometers. whilst that in flame. when mixed. 286. a. this vessel. extinguishing it. or the eighth of an The vessel can be closed at the bottom by a glass stopcock. con- taining a mixture of two measures of hydrogen and one mea- sure of oxygen on opening the stopcocks a portion of the mix: ture enters the vessel are then closed . through the platinum wires. the cocks electric and an spark passed through the mixture. produces the same effect from the heat evolved. . 286. the application of a lighted or even of a glowing match. even when raised till it is equal to that of 150 atmospheres. Oxygen and hydrogen may be kept in a state of mixture at the ordinary temperature of the air for an unlimited period without entering into combination.to determine Sudden compression of the gases. B. fig. whilst a still greater amount of compression. and the vessel screwed upon the top of a jar. the mere contact of a cold metallic substance. forming steam. when a light approaches If a cold bell jar be held over a burning jet of dry hydrogen. in his inquiries respecting the formation of water. Cavendish. effected the He employed for combination of the two gases by means of the electric spark. but taking fire 61 H is hydrogen. b* A bright flash is seen at the moment of the the gase3 combine. a glowing match. which becomes condensed on the sides of the glass the whole of the discharge. c. if mixed in the above all * The discharge from the secondary current of an induction coil may in such cases be advantageously substituted for the spark of the Leyden jar.SYNTHESIS OF WATER. : and two gases. such as platinum.

287. convenient is wires. for the purpose of trans mitting an electric spark across the tube. the spark again transmitted. near the sealed end. the sealec limb being accurately graduated to tenths of a cubi< centimetre. and hydrogen If the will in what proportion the gases were originally mingled. It consists of a stout syphon tube. to supply the place of those just combined. and the bulk of this air is thei accurately measured. which is easily effected b i . called the Eudiometer. that devised by Hofmann. A principle. - adding more mercury. open at one exInto the side^ tremity and closed at the other. one of the most this instrument which are in use. fig. this portion of a : i : ' - t $ i a spring when the mixture in the closed limb of the eudiometer The remaining gas now occupii exploded by the passage of the electric spark. leaving column of atmospheric air between it and the mercury . and if hydrogen be in excess. The uniformity in the composition of chemical compounds. stopcocks a fresh quantity of the gases may be admitted. 287. is constructed upon this by means of which various gaseous mixtures may be analysed with Of the many different forms of great exactness. Suppose i be desired to ascertain the proportion of oxygen ii atmospheric air a small quantity of air is intro . or other suitable divisions. no matter electric spark. and the process repealed until the whole of the gases are consumed. of the tube. or by drawing it off throug the caoutchouc tube fixed upon the small outh tube just above the bend. a. into the sides of which two trary proportion platinum wires are fused for the purpose of transmitting the mixture be capable of exploding at all. enter into combination with each other. be found combination to have occurred in the proportion of two measures of hydrogen to one measure of oxygen. two platinuir. taking care that the level the same in both tubes. is strikingly illustrated by means of a mixture of oxygen The two gases may be mixed in any arbigases. the excess of hydrogen will be left unaltered after the transmission of the spark. On again opening the proportions. t . FIG. and which is closed b means of a screw tap. the superfluous oxygen will be found remaining uncombined. are fused. so that mercury must be poured into the open limb until it stands .62 SYNTHESIS OF WATER EUDIOMETERS. valuable instrument. If oxygen be used in excess. c. and an appreciable quantity of water formed. in a suitable vessel. A quantity of pure h) drogen about equal in bulk to the air is nei Tli introduced. and the constant proportion in which the elements combine with one another. owing to the condensation of the steam which lias been form* by the union of the oxygen contained in the atmospheric air with a portion of tl acts as s s i ) hydrogen. duced into the instrument which has been previously filled with mercury. open extremity of the tube is now closed with a tightly-fitting cork. b. and the volume of the mixture again accurately measured. a smaller volume.

or that 2 volumes of hydrogen and I volume of oxygen furnish by their union 2 volumes of steam. If will If a mixture of oxygen and hydrogen be fired in the air in is considerable quantity. The eudiometer is now closed with a cork. the gases combine with a flash. two limbs is made level. be seen that the aqueous vapour occupies a volume exactly two-thirds of that of the gases originally employed. what is still when a quantity of soapsuds blown up . For accurate experiments. 288. containing fousel it now the mercury in the two limbs of the eudiometer is again levelled. 333. provided with an exit tube and FIG. xxvi. better.). whilst the current of vapour is still maintained . as when a bladder-full ignited. A mixture of two volumes of hydrogen and such as is furnished by the electrolytic decomposition of water into the sealed limb. before the volume of the gas is measured for the third time. gases. (Ann. de Chimie. A which boils at 269 (132 C. [3].SYNTHESIS OF WATER EUDIOMETERS. fig. One-third of the reduction in bulk experienced by the gas will represent the entire volume of oxygen which the mixture contained. condenser below. a very complete though expensive form of eudiometer upon this principle has been contrived by Regnault. 63 the same level in both tubes. of i is of oxygen introduced which it should occupy 5 or 6 inches (12 rr oil 15). is or. A volume of aqueous vapour which For this purpose the closed limb of the syphon eudiometer is surrounded by a second wider tube. is then passed for some minutes through the wide tube. occupies a space exactly equal to two-thirds of that of its constituent gases. 288. and the height at which the expanded gas stands is then marked by means of an elastic band which slides on the outer tube. so as to bring the mixed gases to the The mercury in the temperature of 132 C. and the electric spark transmitted.) modification of the foregoing experiment enables us to show that the is formed by the union of oxygen with hydrogen. as shown at d. and the volume of the vapour produced is seen to be less than that of its constituent 1 gentle current of vapour from a small flask.

and immediately afterwards becomes condensed great dilatation first occurs. the liquid steam which is formed expands suddenly from the high temperature attendant on the combustion. a similar but feebler explosion occurs when a light is applied . A. of hydrogen. the propi tion of hydrogen which has combined with the oxygen can be calculati oxide of its >f it i - 1. quant y oxide if placed in the globe. the heat evolved is less intense. is it where the heat applied. If a tube about two feet long and open at both ends.64 SYNTHESIS OF WATER EXPLOSIVE MIXTURES. if still further diluted. 289. is The apparatus of cupric A A * For a to an article detailed account of these singing flames we must refer the rea< er by Prof. the flame will suddenl 7 elongate itself and at the same time a clear musical note will be heard . this is caused by a series of small explosions that succee 1 each other so rapidly and at such regular intervals as to give rise a musical sound. the explosion becomes more feeble. Tyndall published in the Philosophical Magazine or July. required for this purpose is represented in fig. be placed over a jet of burning hydrogen. F. the mixture merely burning slowly . the pitch and quality of which vari( s with the size of the flame and with the length and diameter f to < the tube. thus producing an assemblage of If sound waves that cause the sensation of a loud report. and determining the weig of the water thus produced. and the loss sustained by the oxide. until at a certain degree of dilution no explosion occurs. followed by the formation of a partial vacuum.* Pure water may be formed in considerable quantities \>y a method differii g from those hitherto described. : the hydrogen be mixed with air. and the combustion less sudden. which is constructed of relracti y curn it glass.c oxygen. but the combustion takes fire only just at the spot does not spread through the mass. hence it is especially necessary in all experiments with hydrogen to allow time for -the expulsion of the atmospheric air from the apparatus before setting fire to the issuing gas. prepared from zinc and sulphuric acid in the bottle. At a red heat hydrogen deprives cupi . so that by passing a current hydrogen over a weighed quantity of the oxide. and the globe and its contents are then accurately weighed. into bubbles by forcing some of the gaseous mixture out of a bladder through the extremity of a tube dipping into the a loud and sharp report attends the combination . 1857. . sures of hydrogen are The explosion is most mixed with 5 of violent air: if when 2 mea- the mixture be diluted with a large excess either of hydrogen or of air. and forms water. the operation at the same time furnishes a mea is of ascertaining accurately the relative weights of oxygen and hydrogen whi h enter into the composition of water.

heat is applied to the globe. shows the quantity of Two grammes of hydrogen are in this hydrogen that has combined with it.COMPOSITION OF WATER BY WEIGHT. H. and carburetted compounds. so that the hydrogen when it arrives at F is When the air is completely displaced. and by its motion shows the : When the globe. first when with then when oxide. part with their oxygen. the small amount of vapour which and pure. manner proved to require exactly 1 6 grms. whilst the difference between the amount of oxygen. and the third. This is mostly condensed in the receiver G. Ann. air. de Chimie.) progress of the gas. E. sulphur. is filled with fragments of pumicestone moistened with a solution of corrosive sublimate the second. F . D. way to contain 63*4 of copper and (347) Hydrogen in the act of combining with oxygen emits a very intense II. the cupric oxide gives up its oxygen. 189. The mercuric salt and the potash remove the traces of arsenicum. the first. and the oil of vitriol absorbs the last traces of moisture. and tube of acid. and to traverse three bent tubes in succession . by a current of Many other metallic oxides besides oxide of copper. of oxygen for their conversion into water. FIG. when heated in a current of hydrogen. which prevents the entrance of extraneous moisture. 65 allowed to bubble up through a solution of potassic hydrate B. and are If the bulb be weighed brought back to the metallic condition. (Hg01 2 ). viii. and water is formed. (Dumas. and till the tube has become cool. [3]. the hydrogen is displaced and on weighing it at the termination of the experiment the loss gives the quantity of oxygen which has combined with the hydrogen. is charged with pumice moistened with oil of vitriol. perfectly dry passes off being completely absorbed in the bent tube H. will thus have been effected of oxide the 79*4 parts of analysis A : cupric oxide are found in this 1 6 of oxygen. contains fragments of fused caustic potash. the loss of weight sustained by the oxide furnishes the proportion of true and very accurate oxygen combined with the metal. is cold. which the gas might otherwise carry over. and that of the water condensed iu the receiver. F. and a third charged empty. filled with fragments of pumice moistened with oil of vitriol the whole of the water is by this means arrested. c. I is a bulb tube containing a little oil of vitriol. time after the stream of gas has been continued till all formation of water ceases. 289. G.

b. this earth does not fuse. a heat may be obtained which can scarcely be surpassed Sometimes the two by chemical means. filled with pieces of very fine brass wire. 290. ^ was seen across the Irish Channel. oil. Without this precaution a cavity would be formed opposite to the from volatilization or mechanical abrasion of a small quantity of the lime. and Eock partially volatilized: iron and steel burn with vivid scintillations. and when the rays are concentrated the lime. connected at H with a gas-holder supplying hydrogen. and most of our ordinary combustibles which burn with flame. and drawn out into threads like glass. fig. hydrogen to I volume of and burned through a tube of of construction. This may be maintained for hours. 1845. This tube has a blowpipe jet at one extremity. The temperature produced by their combustion is so intense that thick platinum wire is melted with ease. about 6 inches or 15 centimetres mm in -) long. at On December. although less perfectly. is directed upon a small cylinder of lime. by introducing a or hydrogen. Drummond. emitting a very pure white light of great steadiness and intensity. if care be taken to expose to the flame fresh surfaces of the lime by causing the cylinder to revolve slowly. which is but very feebly luminous. to be used in the trigonometrical survey of Great Britain. tallow. Wood.M. better OXHYDROGEN BLOWPIPE By DRUMMOND S LIGHT. by occasionally turning the pin. so that the two gases may become mixed just before they issue from the com- mon orifice of the tube a. This light was originally proposed by Lieut. parabolic reflector it by a may Be seen at very great distances. which are packed closely toand then wedged in very tightly by driving a stout conical piece of wire into the axis of the tube. through a cork which . When the oxy-hydrogen flame. coal-gas. by an observer stationed at the top of Snowdon. alcohol. and at the other a screw which can be connected with a stopcock adjusted to the neck of a bladder containing the mixed gases. crystal also may be liquefied. and it has more than once been seen at a distance of 1 1 2 miles. gases are mixed in the proportion of 2 volumes oxygen. furnish considerable quantities of water in this manner. (during daylight) from the top of Slieve Donard. gfcther. particular known as Hem- It consists of a brass ming's safety jet. Water is formed abundantly whenever combustible bodies which contain hydrogen are burned with free access of air. or still passing a jet of oxygen into a flame of coal-gas into the centre of a jet jet of oxygen. an interval of 108 miles in a direct line. c. but becomes white hot.66 heat. and two-thirds of an inch (i6 diameter. or. half-past the 3 1st 3 P. as at o. in Ireland. and the stem of a tobacco pipe may be fused into an enamel-like bead. A striking experiment may be performed with hydrogen. wax. which supports jet. by means of clockwork. tube. which shows how purely conventional are the terms ' combus' Let a tall bottle with a tibles/ and supporters of combustion/ narrow neck be filled with hydrogen gas .

6H 2 O).. an insoluble baric sulphate is thus precipitated." ' When the hydrochloric acid is nearly saturated with the dioxide. and the jet of oxygen will be burning in an atmosphere of hydrogen. combines with an additional atom of oxygen. 1818. it is merely chloride F2 . then insert the cork and issuing. Ba02 6H 2 +2HC1= H \ 2 2 + 6H 2 + BaCl. Hydric dioxide. whilst the liberated hydrochloric acid is able to decompose a fresh quantity of baric dioxide. which. Combustion. oxygen would have appeared to us in the light of a combustible gas. Water is not the _ Thenard in the year only compound of oxygen with hydrogen. Sp. Hydric peroxide is obtained from this hydrated compound by decomposing it by means of hydrochloric The hydrated is acid. discovered a remarkable substance. in fact. which must be added The addition of sulphuric acid produces with the same precautions as at first. for a moment. (348) PEROXIDE OF HYDROGEN ] ( . Suppose. no change on the hydric peroxide which is present in the solution . the dioxide is gradually dissolved without effervescence. and hydrogen in that of a supporter of combustion. is termed peroxide of hydrogen. that the earth's atmosphere had contained hydrogen instead of oxygen. 67 passes easily into the neck of the bottle fit a jet connected with a gas-holder containing oxygen . In consequence of the unstable character of Preparation.PEROXIDE OF HYDROGEN. through which a immediately stream of oxygen is gently The flame will appear to attach itself to the tube coi- veying the oxygen. principle. and becomes baric dioxide (BaO 2 ). jet. '453. or Hydroxyl i (H 2 O 2 =34) I L nu Utl .Gr. it is hydric pure cated state.6OH2 + 2HC1 = JJ + 6OH 1 + Bad. is somewhat tedious and compli- Caustic baryta (BaO). hold the bottle mouth downwards and set fire to the hydrogen. Ba". which unites readily with water forming a hydrate (BaO 2 . when heated to dull redness in a current of oxygen gas. reduced to a paste by grinding it in a mortar with added in small quantities at a time to hydrochloric acid diluted with water. To procure in though simple enough : somewhat difficult to obtain it in a it an indirect process is adopted. which as it contains 2 atoms of oxygen in combination with 2 atoms of hydrogen. 2 . of Liquid. and kept cool by immersing the vessel in ice and water . the baric is decomposed by the cautious addition of dilute sulphuric acid. occurs at the place where the two gases come into contact. baric chloride and peroxide of hydrogen being formed : water. baric dioxide. peroxide.

alternately adding baric dioxide. until a trace only of hydrochloric acid the liquid. so as to avoid introducing any excess of baryta the liquid is cnce more filtered. decomposed by suspending it in water. as it would imm< diately cause the decomposition of the hydric peroxide. which added drop by drop. t Oxide of silver cannot be substituted for the sulphate. [3] Iviii. until a liquid is obtained which consists of dilute hydric peroxide containing 30 or 40 times its bulk of oxygen. the proportion of gaseous oxygen collected in th voltameter being then always a little below the theoretical quantity. and removing the barium in the form of baric sulphate. de Chimie. which is precipitated the hydric peroxide remains unchanged in the liquid. In its most concentrated state hydric peroxide i: Properties. In order to obtain the hydric peroxide. Baric dioxide may also I . with an odour somewhai resembling tjhat of chlorine very much diluted . A * Pelouze substitutes the baric dioxide in the . circumstance furnishes an easy method of analysing the hydri peroxide. while acid. a temperature of about 68 (20 C. but the solution so obtained is dilute. of syrupy consistence. The sulphuric acid is m as baric sulphate by the careful addition of baryta water. The same series of operations is repeated upon the liquid three or four times in succession. given 'weight of the liquid is placed in a small .heated easily destroyed by elevation of temperature. water alone remaining. This acid is again able to decompose a fresh portion of the baric dioxide. unstable compound . effected left in by adding argentic sulphate. 479) that in various prowhere ozone is formed.* After the removal of the haric sulphate by filtration. and when diluted i is and when . small quantities of hydric peroxide are also produced and in the electrolysis of acidulated and saline solutions when ozone is formed traces of the peroxide are likewise produced if the operation is conducted at a low temperature.). . an expedient for getting rid of the barium and setting free the hydrochloric acid.of the air-pump the water then evaporates much more rapidly than the peroxide^ leaving the lattei is at last : now removed in a concentrated form. a colourless liquid. through which a current of carbon anhydride ie transmitted.68 PEROXIDE OF HYDROGEN. and a large quantity of The hydrochloric acid has now to be removed. cesses Schonbein has shown (Ann. and is now a solution of hydric peroxide in water. . and this is hydrochloric acid. the liquid is transferred to a basin and placed over sulphuric acid in the exhausted receiver . it remains liquic at a temperature of This peroxide is a ven 22 ( 30 C. the liquid obtained is simply a very dilute solution of hydrio peroxide with an excess of hydrochloric acid. althougl ebullition for a few minutes is sufficient to the whol less expel of the additional atom of Thi oxygen. 3 - .) is suffi cient to cause the oxygen to begin to escape in small bubbles to the boiling-point of water the gas is evolvec with a rapidity almost amounting to an The liquii explosion.f is Sulphuric acid is thus substituted for the hydrochloric the form of the insoluble argentic chloride. it form of an silicofluoric acid for hydrochloric acid in decomposin shortens the operation by removing the barium at one insoluble baric silicofluoride. is misjcible with water in all proportions.

and are hastened by the addition of a little free alkali. but they are themselves reduced to the metallic state. of hydrogen combined with 16 of oxygen. if placed upon the tongue. of oxygen expelled. or upon finely divided metallic silver. the taste of the liquid being astringent and somewhat metallic. or with peroxide of manganese or lead. it is decomposed with explosion and great elevation of temperature. retort. hydric peroxide will contain 2 mgrms. which is the more rapid the finer the subdivision of A similar the body by which the decomposition is occasioned. but the mere contact of many finely divided metals and metallic oxides which do not themselves silver. it will be found that for each 16 mgrms. and deducting the weight thus obtained from that of the peroxide operated upon. These decompositions are all rendered less rapid by the addition of a few drops of sulphuric or hydrochloric acid.OR HYDRIC PEROXIDE. and platinum produce an instantaneous evolution of oxygen gas. undergo any change. consequently allowing for the presence of a minute : /-quantity of water contained in the peroxide. 69 and diluted with 10 or 13 times its bulk of water. as water contains 2 mgrms. Hydric dioxide bleaches a solution of litmus. . oxygen is given off freely. the temperature is raised to ebullition. however. effect is produced by contact with the oxides of these metals. By means of hydric peroxide the black plumbic sulphide (PbS) is converted into the white sulphate of the metal (PbSOJ. is that not only is it decomposed by substances which possess an attraction for oxygen. platinum. It is especially to be remarked that the oxides of silver. gold. and platinum not only decompose peroxide of hydrogen. black oxide of or ma-nganese. and destroys sensation for a time. If hydric peroxide in its concentrated form be allowed to fall drop by drop upon argentic oxide. and many metallic protoxides become oxidized to the maximum. gold. of hydrogen united with 32 of oxygen. One of the most remarkable properties of hydric peroxide. and many other vegetable colours . blanches it. a little more than 18 of water remain. and the gas is collected over mercury and measured when cold the weight of the oxygen can be calculated from its bulk. osmium. occasions its decomposition. a drop of it.

place with production of a gas which may 391. Rel. Mol. HC10 HC102 HC103 HC10 4 = = = = 52^5 68*5 84*5 100*5 Millon's experiments have rendered it probable that other oxidized compounds also exist. . OXIDES AND OXACIDS OF CHLORINE. three of which isolated . be liquefied by surrounding the tube receiver. Several compounds of oxygen and chlorine may. however. D. wt. obtained a solution of corrosive sublimate with caustic by precipitating an takes action potash.. the result of the combination of some of those already mentioned with the anhydrides. 43 '5 . (20 If dry chlorine be passed slowly Boiling-pi. . HgO + 2Cl =HgCl + CI 3 3 2 O. Mol. The mer- . . and dried by allowing it to traverse the bent tube. : acids of chlorine may also be ob- Hypochlorous acid Chlorous acid Chloric acid Perchloric acid . Cl. (350) Vol.. be obtained by indirect methods. they are the following : have been In ioo parts. or dioxide C102 C1 2 4 or = = = = 87 119 67-5 |~["~j 8r6o 59*66 52*59 [^j ' { t ~~| + + + 18*40 40-34 47*41 135 Four monobasic oxidized tained.. CI 2 C1 2 S Chloric peroxide. washed with water in the bottle. viz. and this oxygen at the moment of its liberation unites with two other atoms of chlorine to form : . 3*01 about 68 tube. through a filled with well-dried mercuric oxide. with a mixture of ice and salt.hypochlorous anhydride. c. A. filled with pumice-stone moistened with oil oi vitriol. Hypochlorous anhydride Chlorous anhydride . * s O. (349) THE attraction of chlorine for oxygen is so feeble that the two elements do not enter directly into combination with each other. B.. The chlorine is prepared in the flask. The reaction between the chlorine and mercuric oxide appears to be of a simple nature 2 atoms of chlorine displace I atom of oxygen in the mercuric oxide. vol. E. L chloric and perchloric HYPOCHLOROUS ANHYDRIDE (C1 2 O = 87) [OC1J . Gr. Theoretic Sp. jj fig.70 CHAPTER VI..).. C.

2 When chlorine acts upon the oxides of metals which have but a feeble attraction for oxygen.. however.. Hypochlorous anhy- dride as thus prepared is a deep red liquid. of chlorine and i volume of oxygen.. C1 2 O + 2 O = 2HC1O [OC1 2 + or Cl(OH)] . the warmth of the hand being sufficient to cause it to explode . 291.. Hydric hypochlorite. 7ior8r6 16 87 18-4 2 loo'o . 2 Hypochlorous acid.HYPOCHLOROUS ACID. By volume. forming a pale yellow solution. H OH = 2 OC1H]. consequently it necessary to avoid any rise of temperature in the tube con- taining the mercuric oxide during the preparation . : The composition of the gas is therefore as follows Chlorine Oxygen Hypochlorous anhydride . .. FIG. which is it is This vapour is remarkable for the ease with decomposed into chlorine and oxygen. O C1 2 = = = By weight.. with a peculiar suffocating chlorous smell. curie chloride. and a weak i part of be obtained acid agitating by may easily hypochlorous . which emits a vapour of a deeper colour than. solution of paration of hypochlorous anhydride. has an acrid. these bases are often completely Advantage was taken of this reaction in the predecomposed. unites 71 with the undecomposed oxide producing a browu crystalline oxychloride. that of chlorine. but not sour taste. HC1O=52'5 [OC1H Water dissolves about 200 times its bulk of gaseous which hypochlorous anhydride. 2 volumes of the anhydride in this way produce a mixture of 2 volumes.

Oxychloride of mercury. selenic. OH + 3HgO 2 HgCl O Hg O +2 Cl(HO) very interesting method of forming hypochlorous acid is to pass air saturated with hydrochloric acid through a hot saturated solution of potassic permanganate acidulated with sulphuric acid. and chloric acid is formed . evolution of chlorine silver : also is immediately converted into whilst oxygen is liberated. the metallic chloride appearing to undergo no alteration. Charcoal. water is formed. The contact of argentic chloride with the ' solution o the acid decomposes the latter. care being taken that the mercuric oxide is in The chlorine is rapidly absorbed . the solution on being decanted is found to contain hypochlorous acid. according t< the experiments of Gay-Lussac. Hypochlor. phosphoric.72 HYPOCHLOROUS ACID. When hypochlorous acid or any o its salts is ' ' each acid is heated with hydrochloric acid in excess. acid. slight excess. iodic sulphuric. arsenic. Chlorine. is twice as great as that of th< chlorine which it contains. it acts as a powerful oxidizing agent. and are converted by it into carbonic. forming a brown insoluble oxychloride of that metal . causing the separation of botl oxygen and chlorine in the gaseous form. The reaction Water. which. and antimonic acids re spectively : if the solution be concentrated the action is sometimes attended with oxidized with chloride Iron filings are explosion. The most important property of hypochlorous acid is its bleaching power. selenium. 2~HClb. phosphorus. sulphur. and finely powdered antimony. and copper and mercury combine with both the oxygen and the chlorine. being rapidly decomposed by exposure to the light bubbles of chlorine escape. The distillate is a dilute solution ol' A hypochlorous acid formed by the direct oxidation of hydrochloric acid In a concentrated form the solution of hypochlorous acid is very unstable. attacking the skin and turning i brown. rapidly decompose a solutioi of hypochlorous acid. part of the oxide of mercury is decomposed by the chlorine. iodine. the red oxide of mercury with 12 parts of water in a large bottle of chlorine gas. furnishing oxy chlorides. is as follows : Mercuric oxide. arseni cum. and the mercuric chloride thus produced unites with the unchanged mercuric oxide. a molecule o decomposed. and 2 atoms of chlorim .

the hypochlorous acid thus liberated exerts its usual bleaching action on vegetable colours. The chlorine must be important. introduced a method of preparing chlorine for the manufacture of bleaching powder. is made to act. acid. whilst sodic operation chlorine and nitrous anhydride produced . a quantity of calcic chloride and chlorate to that is formed. Kollox Works. Hypochlorous acid by action upon the alkalies and earths. such as the carbonic. chloride of potash. The solutions of these salts are also decomposed on gently heating them. Mr. Sodic sulph. by with sulphuric acid. and exposing it to the action of chlorine gas in layers of 5 or 8 centim. take up about half its weight of chlorine .+ JO + 3 OH. which are readily decomposed even by feeble acids. and a peculiar compound possessed of bleaching It is in this way that the bleaching comproperties is produced. Chlorine. and chloride of soda. oilyof the explosive compound known as chloride of its nitrogen (383) are formed.BLEACHING COMPOUNDS. 73 of sal HC1 + HC1O = H. being converted into a mixture of chloride and chlorate.). If the base upon which chlorine (351) Bleaching Compounds. : the A few years ago.NO (NO j . Glasgow. 4NaCl + 'aXaNOj 2 + '3!^ = 'sNa^SC^ + 3 S0 (OH) = 2 2 +1sCT2 + N 2 3 + 3H 2 0. Water. upon perforated shelves in chambers made of lead. the reaction may be traced by the equations following : Sodic chloride. Dunlop. (2 or 3 inches) in thickness. decomposing a mixture of common salt and sodic nitrate In this sulphate is are evolved. heat be allowed to rise much beyond 100 (38 C. | r I 4 NaCl + 2 N0 (ONa) 3S02 (ONa) 2 + aCl. Of these bleaching compounds the chloride of lime is the most It is prepared by slaking well-burnt lime. Sulph. If a fragment ammoniac be suspended looking drops in a solution of hypochlorous acid. furnishes salts termed hypochlorites. absorbed. of the St. but it is not possible to combine calcic hydrate in the form of powder with an entire equivalent of chlorine so as to form a compound CaOCl 2 product always contains a considerable excess of lime. or of Yorkshire flagstones. the gas is pounds so extensively used in the arts under the names of chloride of lime. are prepared. be a powerful one. ^{^ride. such as an alkali or alkaline earth. t. 3KC1O becoming sKCl + KC1O 3 This change is . retarded by the addition of an excess of caustic alkali. admitted gradually. the reaction being similar which occurs during the preparation of potassic chlorate Slacked lime (CaH 2 O 2 ) may in this operation be made to (353). in order to prevent too rapid a rise of temIf the perature consequent upon a quick absorption of the gas. Sodic nitrate.jO + Cl 3 . are liberated.

calcic not deliquescent. : give rise to a similar succession of decompositions Sulph. dry carboni scarcely any anhydride completely decomposes dry chloride of lime witl evolution of chlorine. Calcic chloride. Ch. moreover. by is rapidly absorbed. Sodic chloride. but bleach is ing powder. Nitric acid. whilst the chlorine passes on to A current of air is made to act on the nitrous sulphuric acid. is are probably direct combinations of chlorine with the oxides. yielding a solution containing calcic chloridi and hypochlorite. Calcic hypochlorite. from the aqueous solution. Chlorine. : Calcic hydrate. in which case they would be double salts more than questionable. [4] xii. . Chlorine. If the compound be supposed to be a pure chloride of lirne or calcic oxydichloride. by which the nitrous acid becomes converted into nitric acid. be supposed that a hypochlorite the following decomposition must occur is . chloride. I- 2 S0 2 (OH) 2 l_ + 2N0 2 (OH) + 4NaCl = 2S0 NO O + 3 OH NO _j 2 | 2 (ONa) 2 + 2 C1 + 2 ( The nitrous sulphuric acid may also be at once used in the leaden chambers i\ the manufacture of oil of vitriol (406). when properly made. It is stated by Kolb (Ann.UO of the properties and reactions of chloride of lime indicati is calcic chloride hypochlorite CaCl(OCl). This body is decomposed by water with separatioi of calcic hydrate. Phys. the reaction i* simply an absorption of chlorine. Chloride of lime. Water. however. Many chemists consider both chloride of lime and the cor- responding compounds with potash and soda to contain hypochlorites of the metals. 366 that dry bleaching powder. Sodic sulph. formed but if it is produced Water. by which the compound CaOCl . they of the hypochlorite and chloride of the metal. Calcic hydrate. owing to the absorption of oxygen and the mixed acids being made to act upon fresh sodic . is a definite compound.acid. and yield alcohol. which the nitrous anhydride are caused to pass through a vessel containing oil of vitriol. This. CHLORIDE OF LIME - ITS COMPOSITION. having the compositioi Ca3 H 6 O 6 Cl 4 . a body inter . only one-half of the calcium is precipitated as carbonate by a curren chloride to of the gas.74 The mixed gases the lime. + Some that it Cad + &2C1O + 2. Calcic chloride. without the addition of nitre. ^^e. deliquescent and soluble in alcohol. whereas. prepared by saturating calcic hydrati with dry chlorine. Calcic hypochlorite. f Water. + Calcic chloride is ici = CacT + CaaCIO + 2H).

aqueous hung up in the room to be for emit chlorine fumigated.\ per cent. dilute hypochlorous acid may be distilled off and condensed in a suitable receiver. however. if the The reaction which occurs Calcic hypochlorite. this solution is not. rendered apparent till the goods are : immersed in very dilute sulphuric acid. be extensively used as a disinfecting agent. and greasy and resinous matters it is then well washed. gradually absorbs carbonic anhydride. ing boiled successively with lime water. [Cl 2 (0 2 Ca}" + S0 2 (OH) 2 = S0 (0 Ca)" + 2 2 2C1(OH)]. Chloride of lime is consumed in vast quantities in the bleachThe calico is well washed. The calcic chloride taking no part in the reaction under these conditions. and decomposing one another. Calcic sulphate. hydrochloric and hypochlorous acids being simultaneously produced. but in quantities too small to be injurious to the inmates. not hypoa circumstance which causes it to chlorous acid. Hypochlorous acid. The effect of containing 2 or <2. evolution of acid a free when the causes any poured upon powder chlorine. assuming that the chloride and hypochlorite : bleaching powder is a mixture of + 2H 2 SO 4 = 2CaSO4 + 2HC1 + 2HC1O [CaCl 3 + Ca(OCl) 2 + 2 SO 2 (OH) 2 = aSO 2 (O 2 Ca)" + aHCl + 20C1HJ CaCl 2 + CazCIO then but aqueous solution be mixed with half the quantity of sulphuric acid reqtiired to neutralize the lime. in order the weaver's dressing.CHLORIDE OF LIME - ITS APPLICATIONS. which decomposes the . slowly many hours. and exhales. and of calico and other fabrics. with very dilute sulphuric to remove acid. 75 mediate between calcic chloride and calcic hypochlorite. is as follows : Sulphuric acid. and always contains a excess of slight excess of water as well as of calcic hydrate. and with a weak Solution of caustic soda. and not a mixture of the two salts. under these circumstances. the reactions being the An following. Commercial chloride of lime is only partially soluble in water. and digested in a solution of chloride of lime. Chloride acid it when exposed of lime emits the peculiar odour of hypochlorous to the air . Cloths dipped in an when solution of the chloride. but chlorine. of bleaching powder. however.

unt the whole of the ferrous salt is converted into ferric sal' The progress of the oxidation is ascertained by means of solution of chloride of lime is . + Ca(OCl)Cl . 292). + 2HC1 + CaS0 + H O. Vi 2 S0 2 (OH). the cloth and by liberating chlorine within the fibres of Still. . it is rapidly removes the colour. 1 . of water. It depends upon the determination of the quantity of a ferrous salt which a given weigh of bleaching powder in the presence of an excess of acid can convert into i: ferric salt if ferrous sulphate be used. however. capable of holding 100 cut cub. 7*8 grms. it is colouring matter rendered soluble by the action of the chlorine again passed through a weaker solution of chloride of lime. by the addition of an acid is . of warm i . the A still more convenient plan has been described by Graham. in order to remove the last traces of sulphuric acid which would otherwise destroy the fibre. and a second not perfectly white. i >> then added gradually to th ferrous sulphate (constantly stirring the mixture). and acidulated wit sulphuric or hydrochloric acid . The calico is therefore washed. and subsequently he determined portion of its chlorine only which available for amount of available chlorine by the quantity of a standard solution o' arsenious acid which could be converted by a known weight of the bleaching power into arsenic acid. which strikes a deep blue with the liquid if Several drops of the fenicyanide ai contain any unchanged ferrous sulphate. finally it is thoroughly washed in a copious stream of water. or potassic ferricyanid (K s FeCy 6 ). The commercial value of bleaching powder depends upon the quantity chlorine which can be liberated from this it of u. centim. . . to remove the chloride of lime. : and then through dilute acid . . of the bleaching powder are rubbed u ^ > in a mortar with 60 FIG. of clean dry crystals of the greei sulphate are dissolved in about 60 cub. : spotted plate. . and the washings added to the liquid in th burette. 292. the chlorine becoming converted : into hydrochloric acid. which is filled . Gay-Lussac proposed to estimate the bleaching power by measurement of tht bulk of a solution of indigo of known strength which a given weight of the chloride is able to deprive of its blue colour . as shown in the following equation 2FeS0 4 + |>S02 (02 Fe)" 7 '8 its + 2H S04 + CaOCl = Fe^SO. i solution of the red prussiate of potash. .76 ESTIMATION OF THE BLEACHING POWER OF CHLORIDE OF LIME. centim. grms. after each addition of the chloride of lime to th i . and graduated into too equal parts fror i above downwards. over a white and. 2 atoms of chlorine are required for the conversion of two molecules of that salt into I molecule of ferric sulphate . for it bleaching purposes. The openings a top are closed with the finger and thumb. . centim.S 3 + 2HC1 + (0 Fe 2 2 4 a 6 6 2) S0 grammes 2 (02 Ca)" of crystallized ferrous sulphate require I gramme of chlorine fo conversion into the ferric sulphate. and the content Th of the vessel are mixed thoroughly by agitation. The mortar is washed with a littl more water. . (352) Estimation of the Bleaching Power of Chloride of Lime. of water. time subjected to the action of dilute caustic alkali. and transferred to a burett or tall narrow tube (fig. In making an experiment upon th> value of a bleaching powder. up exactly to o. water. itself.

3 ' The is potassic chlorate being comparatively little soluble in water In freed from the chloride by two or three crystallizations. or over the water-bath at a heat not exceeding 100 (38 C. obtained by the following proportion. of cobalt. If a current of chlo- rine gas be passed into a solution of caustic potash potash and 3 parts of water). and the chloric acid is liberated 2KC1O 3 + H 2 SiF6 = 2HC1O 3 + K 2 SiF6 Or. chloride being continued until the blue colour no longer The stronger the bleaching powder. The cipitate is concentrated better. : furnishes a powerful oxidizing agent. becoming converted into a mixture of potassic chloride and chlorate . 77 the addition of the solution of sulphate. a drop of the iron solution is mixed with one of these. until it forms a syrupy liquid of a faint chlorous odour. may be readily obtained by adding a neutral solution of chloride of lime to neutral solutions of the salts . in which represents the number of measures poured from the burette m : in : I : : 2O lo : x (the number of grms. still . Peroxide of bismuth. the fewer will be the number of appears. Hydric chlorate (353) (HC1O 3 = O [OK orCl O O O K . of chlorine in 10 grms. 6 atoms of chlorine and 6 molecules of potassic hydrate furnishing 5 molecules of potassic chloride and i of the chlorate. of these metals. This number of divisions divisions required to be poured from the burette. but the corresponding acid it is known.CHLORIC ACID. and of lead. a solution of baric chlorate is exactly decomposed acid solution poured off from the pre- by evaporation in vacuo. and heating the liquid. of the powder) . when mixed with hydrochloric acid. CHLORIC ACIT>. a solution of chloride of lime. by sulphuric acid. and a powerfully acid . order to obtain chloric acid. which forms an insoluble compound with the potassium. whilst water is liberated 3 C1 2 + 6KHO = 5KC1 + KC1O + 3H2O. of bleaching powder which contain The strength of the powder is therefore I gramme of available chlorine. of nickel.). 200 Chloride of lime is frequently employed for converting a lower oxide of a metal into one of its higher oxides indeed. divided by 20 will indicate the number of grms. ing liquid is formed. Chloric anhydride has not been is isolated. rapidly loses its bleaching properties on the application of heat. the potassic chlorate is decom- posed by the addition of hydrofluosilicic acid. This (i part of caustic and a bleachabsorbed.

rine and of potassium in potassic chloride being known.) of sulphur be triturated in a mori with 3 grains (2 decigrammes) of potassic chlorate. and in its concentrated form it chars and even sets fire to paper. When a fragment of a chlorate is placed in a drop of oil of vitriol. In diffused day4 . On one gradually undergoes spontaneous decomposition. cons 3- quently have the general formula M'C1O 3 They are all decor iposed by heat . for example. for if a given weight of the chlora:e be calcined with suitable precaution. although left untouched. heat upon potassic chlorate has already been mentioned as affordThis salt ing a very convenient source of pure oxygen (339). and then mixing them cautiously on a card with a feather. Chloric acid is monobasic. occasion a small specimen which I had sealed up in a glass tube was placed aside upon a shelf . but in a few weeks. oxygen is expelled. the chlorates . CHLORIC ACID CHLORATES. perchloric acid. the friction attended with a series of small explosions. the loss indicates the enti:-e The proportions of chloquantity of oxygen which it contained. 2KC1O 3 becoming 2KC1 + 3O 2 This decomposition also furnishes data for ascertaining the composition of chloric acid. The chlorates produce scintillation when throv n j- upon ignited charcoal. while free chlorine and oxygen escaj a . a yellow colour is produced. they explode violent y. if half a grain (30 or 40 mgrms. By a temperature a little above 100 (38 C. and the pec uliar odour of chloric peroxide (C1 2 O 4) becomes apparent. such as phosphorus or sulphur. fuses when heated is perature to about 698 (370 C. and generally a chloride of the metal is left behind. and when heated with combustible su stances. . the cor iposition of chloric acid is readily calculated. and water . The metallic salts of chloric acid require a higher temperaThe action of ture for their decomposition than the acid itself. the chlorine in which can be detected >y 1 argentic nitrate. Nit ic ' detonates powerfully when struck or rubbed acid decomposes the chlorates with formation of a nitrate and perchlorate of the metal.) the acid is decomposed into oxygen 8HC1O 3 light. the tube exploded in consequence of the expansive force of the liberated gases. gas. It is instantly decomposed by contact with organic matter. A mixture whi ir is . Chlorates.). chlorine. and at a higher temultimately converted into potassic chloride and oxyge n .h may be obtained >y powdering separately equal parts of antimonious sulphide (Sb 2 3 ) and potassic chlorate. it yielding 4HC1O + 2H 2 O + 3O 2 + 2C1 2 gas.78 reaction. It frequently happens that mere friction with these bodies is sufficient to cause a powerful detonation .

Paper soaked in a solution of a chlorate and allowed to dry. is immediately converted into oxygen gas and potassic chloride. many of them also are soluble in alcohol. Potassic chlorate. the temperature be moderated and the process stopped when one-third of the total quantity of oxygen has been expelled. when in solution. and exerts its oxidizing Iron. they increase the rapidity . but mercurous chlorate is least so their solutions are not precipitated by argentic nitrate . when it exists in a solution of power. often affords a con- protoxides into converting the addition of by hydrochloric acid to the peroxides solution. even in small quantity. by adding first a few drops of a solution of the blue colour indigo. as follows * :* During the decomposition of the chlorate a considerable development of this may be rendered manifest by projecting into the melted salt which is evolving oxygen. and then a solution of sulphurous acid even without the of heat. venient method of since the metallic ferrous liquid salt. the pasty mass will be found to contain the potassium salt of an acid with a still higher proportion of oxygen. molecules of water. and they are all soluble in water.). 79 2 2 8KC10 3 + 4 HNO 3 = ) 4KC1O. (354) PERCHLORIC ACID Sp. The chlorates when in solution. burns in the same manner as touch-paper. instead of heating potassic Hydric per chlorate .PERCHLORIC ACID. gr. If. chlorate to complete decomposition. Although heat occurs . Perchloric anhydride is . that of barium contains i molecule of water. . a little oxide of copper or ferric oxide. and silver are anhydrous. of liquid. and that of strontium 6 it rates of potassium. to The which the name of perchloric acid has been given. may readily be distinguished from the nitrates. 60 (i5'5 C. rates are : deliquescent. chloric acid is set at liberty. but disappears application immediately : remains unaltered when nitrates only are present. is thus readily converted into a ferric salt when the is boiled. The chlosodium. reaction appears to consist in the resolution of 2 molecules of the chlorate into i molecule of perchlorate (KC1OJ and i of chlorite of potassium (KC1O 2 ) . 1782 at unknown. + 3 C1 2 + 3 O + 2H O + 3 2 f 8 OfOn + 4 N L 1 l ( 2( H -4X0 ( + 2 C1 2 + 2 QH 2 + 4N04 (OK)1 ' O(OK) J Many of the chlo- -Hydrochloric acid liberates euchlorine (356). the latter salt being unable to exist at so high a temperature. neither of these compounds is oxidized in the process. for example. HC10 4 = 100*5.

) is decc re- posed into the pure acid (HC1O 4) which distils over. Perchloric acid is a colourless volatile liquid. paper. a yellow mobile fluid consisting of p ire comes over. it readily separated by crystallization It is freely dissolved by boiling water. perchloric acid in the form of hydrate consists in One method of obtaining distilling potassic perehlorate with four times its weight of oil of vitriol : if the receiver be kept cool. oily liquid. I part of the salt during its decomposition evolving 39 units of heat (129. however. into contact with charcoal. the combination of chlorine with potassium evolving more heat than is reqi ired for the liberation of the oxygen in the gaseous form.he of evolution of the oxygen . colourless. the best method of preparing perchloric acid consists in boiling down a solution of chloric acid obtained by the action of hydrofluosilicic acid upon potassic chlorate.he If this be mixed with the pure acid HC10 4 in equiva! 'nt formula HC10 4 . and an impure solution of perchloric and distillation. and the temperature of the mass rises to red ess.80 PERCHLORIC ACID. and does not come over till the temperature is raised to 397 (203 C. thick. dy described. yields a heavy. it forms the white fusible crystalline substance (HC10 4 . whilst the oily hydiate remains in the -retort. of the anhydride). Potassic chloride. heat the perehlorate is resolved into oxygen and potassic chloride. is decomposed into chlorine and oxygen gases. It can tot duces frightful burns if allowed to fall upon the skin. It is It remains liquid at a temperature of ne 31 ( 35 C. of . 203). This crystallizable hydrate when heated to 230 (i 10 C. of the most powerful oxidizing agents known a drop of it brouj .H 2 0) alre. is left. . is which proportions.). be redistilled without experiencing decomposition.ht ( .H 2 O) : a large proportion of the acid.). goes spontaneous decomposition. which soon hecomes yellow owing to liberation of one of the oxides of chlori ic. but as the solid is much less soluble at ordinary temperatures. According to ROSCJC. of vitriol. This is perchloric acid liquid. Lower which when purified by If this be heated its it oxides of chlorine escape. Q - and KC1O 2 OC1 = KCl The potassic perehlorate is from the more soluble chloride.2H 2 0. and the tubes burst from . At a red crystallizes out in octohedra as the solution cools. the first portions that distil over crystallize in long silky deliquescent needles consisting of (HC10 4 . immediately produces combustion with an explosive viole ice It proalmost equal to that of the so-called chloride of nitrogen. generally atIf sealed up in tubes it gradually unc ertended with explosion. (HC10 4) first followed by a thick cily a hydrate (containing 65 '8 per cent. or almost any organic substar ce. four times volume of oil By distilling it with gives off dense white fumes.

PERCHLORATES CHLOROUS ANHYDRIDE. indeed. Diluted perchloric acid is destroy vegetable colours . 59'5Chlorous anhydride is prepared by the deoxidation of chloric . 4*070 (Brandau) Mol. The gas must be collected by displacement in dry bottles. Hel. Ann. G . wt. and this in turn is reconverted expense of the nitric acid into nitric acid by decomposing the liberated chloric acid thus . it reproduces the white crystals of Serullas (HC1O 4 . are added. acid. but they may be distinguished from the chlorates by not yielding a yellow gas when moistened with oil of vitriol. Chlorous anhydride is a dangerous compound to prepare. and silver are soluble in alcohol. nitrous acid is formed. rfOci or JO J 1 C1-0-0-0-C1 L_(OC1 Theoretic sp. gr. with evolution of oxygen and formation of a chloride. the whole is placed in a small flask. [3] vii. stable of all the acids of chlorine. : HNO [As(OH) 3 Nitrous acid. 4*1 J/ . Vol. as it is rapidly decomis In this operation the arsenious acid becomes oxidized at the posed by mercury. and if the proportion of the latter be not too large. which applied filled up to the neck with the mixture. 322). de Chimie. but the gas is then mixed with carbonic anhydride. having the general formula M'C1O 4 they are mostly deliquescent. in this of a purely sour taste. gr. None of the perchlorates are insoluble. as exposure to a with temperature not much exceeding 131 (55 C. dissolving iron evolution of hydrogen gas. 2 = AsO(OH) 3 Potassic nitrate. All the peTchlorates are decomposed by heat. when the gas is Three parts of arsenious anhydride (white arsenic) required in a state of purity.) is Sufficient to decompose it a powerful explosion. although the potassic salt requires upwards of 150 times its weight of cold water : for solution. and w-ifor Chlorous anhydride. Contact with most combustible non-metallic elements. 81 Great heat is developed when it pressure of the evolved gases.H 2 O). [~~ _"]. and the salts of sodium. barium. this object being effected by means of arsenious acid. of sp. (355) CHLOEOUS ANHYDBIDE (C! 2 a = 119). 2 UNO. and 1 6 parts of pure nitric acid. + 2KC108 = aKNOi S + Cuf + [001 loci HA OH 2] = 20 (OK) Tartaric acid may be substituted for arsenious anhydride in this operation. I '24. II. and does not form. and 4 of potassic chlorate are rubbed up into a paste with water. Observed sp. gr. + NO(OH)]. it is the most and zinc with Perchloric acid forms the salts known as perchlorates. and a very gentle heat is by means of a water-bath (Millon. combines with water. N0 (OH) = Potassic chlorate.

especially if generally the acid be m yielding mixture instance.82 CHLOROUS ACID CHLORITES PEROXIDE OF CHLORINE. a id has a similar but less irritating odour.. The ehlorites of sodiu n. 71 or 59*66 Millon. it be condensed to a red may liquid. Chlorous acid (HC10 2 =68'^) possesses considerable bleaching power.. tellurium. such as sulphur.) . termed chlorites.. posses. and strontium are also deliquescent. loo'oo . the molecule being supposed to occupy 3 volumes. Plumbic nitrate produces a acts slowly sulphur-yellow scaly precipitate in their solutions. Observed. ed unaltered in the dark. ... selenium. 3 2 3 =:ii9 100*00 .s. however. according to Mill* n. was formerly believed to be anomaloi. . The following is the composition of chlorous anhydride : its combining volume. and forms a yellow solution. this does not destroy he The chlorites maybe 1 bleaching power of the chlorites. tin. ed of powerful bleaching properties. hut mercury absorbs copper. Water dissolves about 10 times its bulk of the gas. explosion are without action upon it. zinc.. Argentic chlorite is also yellowish and insoluble distinguished from the hypochlorites by the addition of a mixture of arsenious anhydride and nitric acid . a excess. and phosphorus. (356) PEROXIDE OF CHLORINE : Chloric Dioxide (C1O 2 = 67 5. and iron .. 2*3227. By . by a powerful freezing mixture when it forms a deep brown mobile liquid which boils at a little above 32 (oC). ut by slight pressure. and forms monobasic salts. . but is gradually decomposed in 1 he Water dissolves about 20 sunlight into its component gases. for The solution oxidizes all the above- mentioned metals. I This compound gaseous at ordinary temperatures. of chlorate and 2Zn-f 4HC102 chloride. vol. which. it completely.. _>s. is Boiling-pt. such even as carbonic acid. 48 40-34 60*15 39*85 2 . or by exposure to a cold of 4 ( 20 C. gas is of a colour still deeper than that of chlorous anhydride. The gas requires great care in . it is converted into a mixture of chloride and chlorate of the metal in equivalent proportions. The pure substance at the ordinary temperature is a gas of a deep greenish yellow colour it may be condensed. owing to the formation of plumbic chlorite (Pb2C102 ).. Theoretic Sp. _ \oci_ 2*335 ). it upon bases. is liable to explode as 1 he powerfully as chloride of nitrogen.) . times its bulk of the gas.. Mol. lead. It may be preser*. Vrt... r/ocr or Cl 2 O 4 =i35) j o ' ReL Wt ' 33*75. of the Potassic chlorite (KC10 2 ) is deliquescent: if its solugeneral formula M'CIO^ tion be slowly evaporated to dryness. (r. The hlorites are decomposed by barium. decomposes the gas with Most of the metals including arsenicum has a similar effect.2 Oxygen Chlorous anhydride Cl 2 3 = = By Weight. the feeblest acids. forming a deep : yellow solution of chlorous acid (HC10Z ). ZnCl 2 f Zn2C103 + 2H 2 0. 68 (20 C. Chlorine C\. from the experiments of Millon. although it does that of the hypoehlorit Their solutions deoxidize an acidulated solution of potassic permanganate.

will be immediately produced. about 0*3 grm. the acid will and mixed in on a sheet of paper addition of a liberate chloric dioxide. and must therefore be collected by displacement. having placed glass in a add a of deep plate (fig. equal proportions by means of a spatula. and pour about 10 c. c. attended with a crackling noise. If loaf sugar and potassic chlorate be separately powdered. which will drop of sulphuric be decomposed a 2 . as thus obtained. Water. Cl Oxygen Chloric dioxide O2 CIO.) a mixture of finely powdered potassic chlorate and oxalic acid .. = = = By weight. the action being favoured by a very The reaction is represented by the following gentle heat. 35-5 or 52-59 32*0 47-41 67-5 By . with two-thirds of its weight of oil of vitriol. however. 149 (65 C.. 2. i '.) explosion. Place.. piece phosphorus the size of a pea. of oil of vitriol slowly down tiful a long funnel vessel ..PEROXIDE OP CHLORINE. Chloric dioxide may equation : Sulphuric acid. for instance. volumes of this gas furnish a mixture of 2 volumes of oxygen and i of chlorine.. (Calvert.. it is contaminated with carbonic anhydride. 293).) or determines its 145 (63 C. 293. 3 KC10 3 2C10 KC1O OCl 2KHSO? + 2S0 (OH)(OKHOH 2 2 L OCl This peroxide is also formed on heating to. its 83 little above 140 (60 C... its preparation. reaching to the bottom of the flashes of a beau- green light. Hjrdric potassic sulphate. at a temperature a (^composition being thus represented Chlorine . then the water.. and pour upon it a little FIG. Mere contact with many combustible matters at once determines its explosion. of potassic chlorate at the bottom of a tall glass. : - . vol.) Chloric dioxide acts rapidly upon mercury. 2 chlorate broken into be prepared by treating fused potassic coarse fragments. 2 lOO'QO .

Davy's euchlorine. Potassie chlorite. neutralizing t le liquid with potassic carbonate. Although one )f the triad elements. as in BC1 3 . Potassic chlorate. CHAPTER BORON : VII. OC1 aOKH oci - Other oxides of chlorine have been obtained but they have no general interest . which is evolve d on gently heating a chlorate with hydrochloric acid. and Peroxide of chlorine is not deflagrate with great brilliancy. a . consisting of a mixture of chlorine with compound oxides. in its it properties. Amorphous Boron.BF3 ) a sparingly soluble salt. they have a composition which may be explained by considering them .Cl 2 one of these . whence it derives its name. and washing the compound w: ch potassium on boric Potassic borofluoride cold water : it is When cold it is then dried at a heat a little below redne mixed with an equal weight of potassium. (KF. Boron may be obtained by the action of anhydride. is a yellow explosive gas. and in presents considerable analogy with silicon its mode of combination it may >e : obtained in the crystalline and the amorphous state. but when evaporated. acioT + OC1 f aKHO* = moT foci + + f l^cic + iT2 o. it rapidly. B= 11 : Triad. and at the same time. is ma le by saturating hydrofluoric 'with boracic acid. Water. as compounds of chlorous anhydride with chloric or perchloride anhydride.84 BORON.BF3 )+3K =8KF + 2 3. chlorite and chlorate of the metal : they yield a mixture of Chloric dioxide. 3t with in nature in combination with oxygen. O O3 Millon). by the combustible matter. 2 . or on potassic borofluoric e. alkaline acid of solutions. id heated in a covered iron crucible.s. but in comparative y small qiiantities. however. absorb properties possessed . It is always ir. (357) BORON is the characteristic element of the acid co itained in borax. 2(KF. sufficient heat will be produced to cause the mass to burst into flame. Potassip hydrate. the chlorochloric acid (aCl 2 5 . and only in a few localities.

and darker in colour. 70 or 80 grms. It must finally be dried upon a porous slab without the application of heat. After exposure to intense heat in vessels from which air is It may be excluded. and. whilst red hot. the still mixture. The mixture is then introduced into a castiron crucible previously heated to bright redness. the interval between the two being filled with recently ignited powdered charcoal. temperature crucible are digested in dilute hydrochloric acid. from which. it is precipitated unchanged on adding a little solution of sal ammoniac. the following method may be adopted small Hessian crucible is lined with the pulverulent boron made into a paste with water. and with charcoal. and it when heated with free. Pulverulent boron a non-conductor of electricity. silicon.CRYSTALLIZED AXD AMORPHOUS BORON. it is thus converted superficially emitting into boracic anhydride. 67) 150 grammes of fused boracic anhydride is coarsely powdered and mixed rapidly with 90 grms. Chem. potassic carbonate potassic fusion sets carbon is and potassic borate formed. 85 The potassic fluoride is removed by washing with hot water containing ammonic chloride in solution. If mixed with nitre and heated to redness It is it deflagrates in powerfully. Ann. forming a greenish yellow solution. which melts and protects a portion of the fire boron. first melt As below redness. Pharm. strong oxygen. Crystallized Boron. cv. also oxidized when is ignited with hydrate. The the whole exposed for a couple of hours to a heat sufficient to fuse nickel. burning with a reddish light and vivid scintillations . however. of pulverized sodic chloride that has been previously fused are placed upon the top of the As soon as the reaction is over. after which the washing may be continued with pure water until the boron begins to run through the filter. however. treated with nitric acid or with aqua regia. it becomes denser. In order to convert the amorphous into the crystallized form. as in the ordinary mode of lining a crucible : A In the central cavity a piece of aluminium weighing from 6 to 9 grammes is placed the cover is luted on and the crucible enclosed in a second. Boron fingers. . or to solutions of the alkalies. The outer crucible is next closed with a luted cover. boron exhibits a attraction for if heated in air or in oxygen. to water. inner of the is then allowed to fall the contents and when cold . washed with acidulated water till the boracic acid is got rid of. which dissolves out the . and poured. It is. Boron is not oxidized by exposure to air. whether cold or boiling. dull olive-green has been strongly ignited. easily oxidized when fused by the application of a heat required takes to still more intense than that obtained. in a slender stream into a large and deep vessel containing water acidulated with The pulverulent boron is then collected on a filter and hydrochloric acid. as thus obtained it powder. and the crucible is covered. soils the dissolved by pure water in small quantity. : Boron may be obtained in the amorphous form in large quantity by the following method (Wohler and Deville. liquid mass is thoroughly stirred with an iron rod. and the boron is pressed in strongly. before and is is an amorphous. which. of sodium cut into small pieces.

3 - . Boron.H 2 O) [B(OH) 3]. but its most abundan source is the maremma of Tuscany. pound of boron with aluminium. all its forms burns freely in chlorine . and magnesium from tht western coast of South America. and burns but imperfectly oxygen when heated to full whiteness. uncombined it state. and boric chlorid* being formed respectively. BORACIC ANHYDRIDE. whilst hydrogen is liberated. in Tuscany. Boric sesquioxide (B 2Og =7o) difficulty. in pale. are directed hi > small -lagoons or artificial basins. boric sulphide. It is found combinec with sodium as an acid borate in tihe tincal obtained from Thibet crystallized borate of calcium . whilst hydrogen is liberated. of 2 '63 . of the oxyhydrogen blowpipe. but the latter is attacked with som<. boracic anhydride.86 . generally transparent. copper-coloured. where it is met with in th . quite recently borax an< boracic acid have been found in California. opaque plates. issues in small quantity along with the jets of steam rolles or soffioni]. B3 A1 (Wohler). like titanium. on evaporation. 294. becomes incandescent. becoming coated with a layer of fused boracic anhydride. enters into direct combination with nitrogen at a high temperature . It however burns easily m when heated to redness in dry gaseous chlorine. and are hard enough to : scratch the ruby. at Monte Cerboli and Monte Rotondo. This is the onl. No acid or mixture acids has any action upon crystalline boron. but system. and even sensibly to wear away the diamond. being cono'* verted into the gaseous boric trichloride. with sulphuretted hydrogen. and accompanied by sulphuretted hydrogen (funn . a quantity of this nitride is formed as a grey coherent mass during the preparation o ? Pulverulent boron. Boron ii crystallized boron. a crude boracic acid. Crystallized boron does not fuse even when heated in the flame. of which. from which a large yield pr< According to tl ingenious suggestion of Lardarello. a comdark brown colour. (358) BORACIC ANHYDRIDE. and with hydrochloric acid it decomposes them. maintained by volcanic agency. Crystallized boron has a sp. are formed at the same time. gr. such as those shown in the wate: * fig. aluminium beautiful crystals of boron are left. the heat supplied by the fumerolles then portion -of is the borax of commerce now manufactured. but of a A quantity of scales of so-called graphitoid boron. and is converted into nitride. it assumes the form of transparent quadratic oetohedra belonging to the monoclinic These crystals when pure are nearly colourless. when ignited in contac with steam. when heated in a current of dry ammoniacal gas. These. known compound and in a of oxygen and boron. they usually contain a considerable amount of aluminium and carbon they refract light powerfully. Crystallized Boric add (HBO2.

purified borax is dissolved in 4 parts of boiling water. artificial soffioni have been formed which. The supernatant liquid. of boracic acid. seldom contains move than three-fourths of its weight of the pure crystallized acid. as at Travale. and is Calcic sulphate is deposited sufficiently concentrated to crystallize on cooling. with small quantities of aluminic sulphate and of other alkaline and earthy sulphates. The crude acid. From the last of it flows into settling vats f. FIG. heated by the vapours of several fumerolles. and it requires removal from time to time. where after the lapse of twenty-four hours more it has acquired a density of 1-07 or I'o8. in abundance in the pans during these evaporations. d.PREPARATION OF BORACIC ACID. and a small proportion of silica. About two thousand tons of the crude acid are thus pro- cured annually in Tuscany. . a peculiar organic matter. yield a large quantity of boracic acid in a manner similar to that above described. the remainder consisting principally of ammonic and magnesic sulphates. c. however. it is then transferred to a smaller longer pan. arranged for the purpose. here it stays for twenty-four hours. which contains from i^ to 2 per cent. and to the hot solution. and is run off after successive intervals of twentythese four hours into each of the four lower basins. e. selves is 87 employed in this evaporation. oil of vitriol is equal in weight to that of one-fourth of the borax employed In this process sodic added after dilution with a little water. In order to procure the acid. which is built over a fumerolle . The commercial acid is purified by adding to it sodic carbo- nate as long as effervescence occurs. In twenty-four hours the liquor is reduced to about half its bulk .four hours smaller pan. The sparingly sulphate is formed. h. By boring into the volcanic strata. 294. g. g. b. where it it is again transferred : is to a allowed to evaporate for twenty. f. and boracic acid is liberated. which circulate underneath in flues. Water from the adjacent springs is directed into the uppermost basin a. on a lower level. and purifying the borax thus formed by crystallization. is then decanted into shallow leaden evaporating pans. where in the course of twenty-four hours more the suspended matters subside.

however. fig. ir or Boron Oxygen Water Boracic acid . valued. and in thu melting of gold and silver. B2 O3 B2 = = = 48 22 or 31*43 68-57 B *<>. at a red heat. through the spectroscope i No. and the solution burns with a characteristic green flame. dried. and fused in a platinum crucible . scales soluble boracic acid crystallizes out on cooling. instead o the usual bright red of the stronger acids. 3 = = = = ) 24 27 5 f _/:. the anhydride fuses to a transparent. The following is the composition of this acid Anhydride. Many of the * Boracic acid is sparingly soluble in cold water... the crystals are washed with ice-cold water. Boracic acid that it is (Part I.. -quite which feel greasy to the touch. which. Boracic acid i - soluble in alcohol. and at a slight increase of temperature become converted into the anhydride . on redissolving the mass in 4 times its weight of boiling water and allowing the solution to cool the acid crystallizes out in a state of purity.... . it turns the paper brown as ai gives to litmus a purplish-red tint.. 81 volatile both in the vapour of water am ' marked green bands not possible to evaporate a solution o boracic acid in either of those liquids without losing a portion o alcohol so is ' the acid : if steain at a high temperature be transmitted ove . i^H.. To remove this. but 01 alkali . It clear as it cools.88 BORACIC ACID. if allowec to evaporate upon turmeric paper. forming a solutioi which has a bitterish and scarcely perceptible sour taste . pure. which remains absorbs moisture from the air and to crumbles gradually pieces. The crystals of boracic acid effloresce and Ios3 two-thirds of their water at a gentle heat. i ' would do it the other hand. in pearly-looking It is not. It gradually decom poses solutions of the carbonates even in the cold. or a viscid. Boracic acid communicates to its compounds the property of ready fusibility. : Crystallized : HBO^HjO. glass. but it is dissolved by 3 times its weight of boiling water. which are used in the glazing of porcelain. a brisk current of gaseous carbonic anhydride o of sulphuretted hydrogen will cause a separation of boracic aci< in crystals from a strong solution of borax. indeed it is chiefly on this account that i" ductile is borates are admirably adapted fo fluxes. as it always retains a little sulphuric acid.0 . when viewed seen to exhibit five well 6). 45 43-55 ico'oo 70 loo'oo BH 3 3 62 Properties.. little below.

Vol. B C1 3 BC1 3 = = = ir By weight.8H O). with a (359) Boric trichloride (BC1 3 =117-5. and other and to estimate the deficiency as boracic acid. ).6B 3 3 . 2? 3 2 106-5 117-5 90-64 100-00 Two volumes of this trichloride unite with three volumes of ammonia. Theoretic sp. All the sparingly soluble borates are dissolved by dilute nitric acid. the boric trichloride being condensed in a receiver surrounded with a frigorific mixture of A still better process is to heat boracic anhydride with phosphoric ice and salt. to determine the constituents. are so insoluble as to furnish an accurate mode of ascertaining the quantity of boracic acid present in solution by precipitation. none of the borates. gr. 4-065 . potassic hexaborate (K 3 O. those of the other cule of acid. 58 75). however. . {~r_~i . It not unlikely that boracic acid may have been overlooked in many minerals. Observed. and also a crystalline triborate (K 2 O.ioH 2 O) may be obtained in The crystals. having a density of i'35. 4-06 . and boiling it fumes strongly in the air. the acid is volatilized in considerable quantities. and become condensed into a volatile crystalline saline body. forming the ammonio~ chloride of boron (3NHa 2BC1 3 . Bel. it is usual amount of the other acids and metals..BORATES boracic acid BORIC CHLORIDE. at 65 (18 C. they A O O metals are only imperfectly soluble . strongly refracting liquid. Mol. 89 or calcic borate. Although many of these salts contain more than i moleall restore the colour of reddened litmus-paper. borates of the alkali-metals are freely soluble. This compound is prepared by passing dry chlorine over amorphous boron at a gentle heat. and is instantly decomposed by water into hydrochloric and boracic acids.) in closed tubes. or by the action of chlorine on a mixture of boracic anhydride and charcoal heated to redness. and hence. Borates. its transient green light is easily analysed by the prism..3B 3 . as its detection in small quantities is rather difficult except by the aid of the spectroscope. or 9*36 By vol. although its chemical activity is very feeble. wt. is In analysing a substance containing a borate. Its composition is the following : Boron Chlorine Boric chloride . resembling silica in this respect. If a borate be fused little hydric potassic sulphate mixed with a fourth of its weight of finely powdered fluor-spar on a platinum wire in a Bunsen gas-flame. Boracic anhydride is but very slowly volatilized by ignition. It is a colourless mobile pentachloride to 284 (140 C. it expels from their salts It enters into all anhydrides more combination with the alkaline bases in a great variety of proportions. at volatile high temperatures than itself.) .

Thus the carbonic anhydride poured out by animals as a refuse and poison ous product. Independently of that which exists diffused through the atmosphere in the state of carbonic anhydride. Vapour Density Tetrad. which ar usually regarded as organic. 3*33 unknown . It is the characteristic ingredient substances which are termed organic* that is. * As in former editions of this work many carbon compounds. with a larger proportion of foreign admixture it occurs in the form of graphite.90 CHAPTER CARBON VIII. whilsi a large proportion of the oxygen which these compounds con tained is returned into the air in the gaseous state. and from numerous other less apparent sources. The solid parts of plants. appropriating th( decompose anhydride carbon and hydrogen for their own growth and nutrition. Dyad in CO. shrubs. but foi the leaves of plants In solar compensating light both carbonic and water. constituting nearly an eighth of the entire weight of calcic carbonate. and trees owe their form and solidity to this element. it enters into the composition of the numerous varieties of calcic and of magnesic carbonate. . and still less pure in the abundant deposits of pit coal. which is mainly supplied to them from the carbonic anhydride in the atmosphere This action of plants upon carbonic anhydride is one of the means of all ordained for preserving uniformity in the composition of the air The quantities of carbonic anhydride poured forth from the bowels of the earth. CARBON: C=i2. were treated of in Pait II. . It is also met with in enormous quantities in combination. CARBONIC ANHYDRIDE I. (Inorganic Chemistry. supplies food and sustenance to the vegetable world which in its turn converts the carbon into a form suitable fo: action. as in CO 2 . peudin: briefly in the issue of the next edition of Part III. CH (360) CARBON is an elementary body of the greatest importance. and 4 Sp. It is found nearly in a state of purity in the diamond . undet a variety of forms. of substances which are produced directly or indirectly from the vegetable 01 animal creation. CARBONIC OXIDE. and more than a seventh of that of magnesic carbonate. it has been thought advisable to describe them an Appendix. to 3*55 . as diamond. woulc by degrees occasion an injurious accumulation of the this gas. Gr. and derived from the processes of respiration anc combustion.

. however. which occurs crystallized in forms belonging to the regular system. of the Brazils. is cemented spread over a revolving steel plate. met with of various tints. and the recently discovered diamond diamond fields at is the Cape of Good Hope. each of the planes of the octohedron . Each great division of anithus seen to be essential to the well-being and even to the support of the other. They have been found imbedded here and there in a fine-grained quartzose rock (Itacolumite) in Brazil. as they are Diamonds usually present themselves termed. deoxidation is effected. Plants are. and is cut and polished is by employing its own powder for the purpose. from 3-33 to 3'55Carbon is found purest state in the diamond. These crystals are generally derived from the octohedron. is generally colourless . after mixing with a little olive oil. when freed from this coating. The origin of the improbable that it was formed by crystallization after fusion. since intense heat reduces the diamond to the form of graphite. in fact. such specimens are the most prized . The gem. Gr.CARBON the maintenance of DIAMOND. so that carbonic anhydride is the chief instrument by which the force proceeding from the sun as light and heat becomes available which recombination with oxygen on the in its earth's surface. it is. but with few exceptions the gem is found scantily in an alluvial matrix consisting chiefly of sandstone and rolled quartz pebbles. and by the agency of vegetable life it is once more fitted for combustion and made a depository of fresh energy derived from the sun. in under the appearance of semi-transparent rounded pebbles. in such crystals. or lenticular. and the diamond. the faces are often convex. The fuel which has been is burned and dissipated in vapour is again reduced to the solid state. the grand agents by which. and the edges are generally rounded. while animals are the channels through is unceasingly produced. and careful Diamond proaching it the hardest body known (crystallized boron apmost nearly in this respect). of Borneo. 91 mated nature life in animals. The fine diamond dust used for this object. and the circumstances under which they are found in nature afford no clue to the process of entirely unknown. the more common The most of which are yellow and different shades of brown. under the influence of the chemical actions of the sun's rays. Sp. from which diamonds are extracted by washing sorting. enclosed a thin brownish opaque crust. famous diamond mines are those of Golconda and Bundelcund in India. it is their formation. with a cleavage parallel to (361) Diamond.

A true cut is effected by such s properly used. or indeed of carbon in any of its forms. was imbedded in a copper vessel of about the size of a teacup. but only the natural face of the crystal can be employed for this purpose. diamond is introduced into the flame of the voltaic arc. crystals with curved faces being the best . with the diamond imbedded. it appears to be mechanicalh When th< transported from one electrode to the other (280). am Th< converted into a black opaque mass. and may perhaps. though ii the intense heat of the voltaic arc. is not perfectly pure carbon i always leaves a minute yellowish ash. they are set in a convenient handle. and in cutting. being held in its position by a kind of vice. which has been founc to contain silica and ferric oxide. into which it was When it was necessary cemented with a mixture of equal parts of tin and lead. it will burn with 2 air is excluded. The diamond has a very it is may be heated intensely without change. and heating the metal till it assumed a consistence resembling that of wet sand .92 PROPERTIES OF THE DIAMOND. if diamond power brilliant lustre and a high refracting a non-conductor of electricity. many specimens emit a feeble phosphorescent light. and then plunged into oxygen gas. it it steady red light. the solder was softened by immersing the cup. : form of a cellular network. its into a suitable support. at some futur< N< time. in order to cool the diamond more quickly. for the Queen. sheets of glass. assist in determining the origin of this valuable gem. This ash has generally tin dride. heat hitherto applied suffices for the fusion or volatilization o ' the diamond. which may be seen in a darkened room. it was plunged first into warm water and then into cold water the cutting was effected by means of a cast-iron wheel revolving on a vertical axis about 2400 times per minute. loses its transparency. th< power of conducting is electricity. but a diamond with angles obtained by cleavage produces only a superficial scratch with ragged edges. The most important use to which the diamond is applied is the cutting of :. and with the production of pure carbonic anhy- The diamond. it undergoes a remarkable change . in of a while its thus diamond altered was density 2*6778 . resembling coke. crys . faces in turn presented to The Kohinoor diamond. slight pressure on each side of the cut then determines the fracture along the mark made by the diamond. however. which was cut in 1852. pencil dipped in a cream of diamond dust and oil. to change the position of the gem. Il be suspended in a cage of platinum wire. as soon as it becomes white hot suddenly acquires i begins to swell up. the diamond rested upon the upper surface of the wheel. becomes specifically lighter. and the pressure against the revolving disk was increased or diminished by adding or removingFrom time to time the face of the diamond was touched with a hair weights. After exposure tc sunshine. has each of the flat face of the disk. heated to bright redness. in a charcoal fire. a line is traced with the diamond across the glass in the proper direction . In vessels from which .

traces The particles upon which it is rubbed. once celebrated mine at Borrowdale is now nearly exhausted. like the Borrowdale graphite. is composed of small flat plates. It is likewise found in Ceylon. composed are. merely amorphous graphite is highly prized for the manufacture of Mead pencils:' where pieces of sufficient size can be obtained they are sawn into thin slices. and in several parts of the United States. or Plumbago (Sp. leaden-grey lustre.GRAPHITE. been met with abundantly in the Batougal mountains. whence its familiar name of blackIt is very friable. extremely hard. talline condition it 93 The heat of the oxyhydrogen jet xx. and wear out the saws employed to cut it. this form of graphite generally occurs in a matrix of quartz (Brodie). slate. and as it is quite 5 per and oxides of 2 to cent. Graphite occurs either massive or in six-sided crystalline plates belonging to the rhombohedral system. is fine-grained and amorphous. It has also always in rocks belonging to the earliest formation. however. and leaves lead. in South Siberia. was found to be 2' 15) is Graphite. (362) was 3*336 (Jacquelain Ann. near the frontier of China. and may thus be fitted for the manufacture of the best pencils. The Borrowdale graphite mica occurs in clay slate. united by a cementing material. OR PLUMBAGO. it forms a serviceable An application coating to protect coarse iron work from rust. Gr. in other localities it is embedded in gneiss. feels unctuous to the touch. if of good quality. manganese are The accidental however. de Chimie [3]. the other. widely different Graphite has a metallic. of which graphite is on paper like the Ceylon variety. It is never met with in a state free from admixture the foreign purest specimens when burned in oxygen : leave from which generally contains these bodies. 467). and these again into small rectanIt has gular prisms. bago. . fine-grained impurities. insufficient to produce this change. one of which. offers Carbon. in the two forms of diamond and pluman excellent instance of dimorphism . the properties in which as it displays these two dissimilar states are as those of any two elements. . unaltered by exposure to the weather. It appears they rapidly to exist in two distinct modifications. may be again reduced into coherent plates by subjecting it to enormous pressure. or granular limestone. of ash. and iron quartz. from 2^35 to Its a second form in which carbon occurs native. Graphite is an excellent conductor of electricity. Black-lead is extensively used for the lubrication of machinery. which are placed in cedar wood for usebeen found that the small fragments and the fine powder.

Chem. and mixing coarsely-powdered graphite with a fourteenth of its weight of potassic chlorate . 351) has described a method of obtaining in a very finely divided form= It consists in graphite in a state of purity. graphic acid is exposed to a temperature of between 500" and 60 and 320 C. water and carbonic oxide escaj Even if heated to redness in nitrogen. dried. and that it possesses in this form a combinii g number of 33. substance of graphitoid appearance.91 OXIDIZED PRODUCTS FROM GRAPHITE. H . Soc. consisting of C_ 2 2 4 . accompanied by an evolution of heat and light . leaving a When (260 . and diffused through a quantity of concentrated sulphuric acid.c which he terms Graphon. Brodie (Ann. If this be so. on a water bath. as this compound is termed by Brodie. . graphic acid C U 4 6 mig it be represenied as Gr 4 4 6 the first residue C 22 2 4 as Gr 8 2 O4 and the seco d C M 4 O 11 as Gr24 H 4 O n graphic acid being regarded by Brodie as analogous o state. and the pots made from this mixture are much less likely to crack when heated than those made of fire: clay only. J. H . it 3. the mixture is introduced into an iron pot. H H . if this new body further heated in an atmosphere of nitrogen. forms yello v which are insoluble in water and in acids. xii. with the symbol Gr. it is then allowed to cool. thrown into water. the hydrated oxide of silicon Si s HO 4 6 discovered by Wohler and Buff. the hydrocarbon becomes of a deep red coloi r. It now dried. which still retai: s both oxygen and hydrogen. with separation of a whi e silky plates. gelatinous mass. If the graphic acid be cautiously heated in paraffin ( 11 to a temperature of 5 18 (270 C. and n. the ammonia combining with it and forming a gelatinous body which is decomposed by acids.). the whole is then exposed for The residi e three or four days to the heat of 140 (60 C. and becomes reduced to an exceedingly fine powder. oxygen and hydrogen. it gives off gas. and subjected four or five times to tl e same treatment. and that a new compound of carbon. carbonic anhydrk Brodie considers that in these compounds the graphite retains its allotroj . de Chimie [3]. and washed chlorine is disengaged . must be well washed with water. sooty-looking substance is left. retains a portion of and carbonic oxide. this impurity may be got rid of product be * This oxidized substance may be obtained in a state of purity by the folOne part of finely powdered Ceyku lowing process (Q. . and heated to redness. it undergoes decomposition with almost explosive violenc 3. Graphic Acid (C U H 4 S ). Exposure of the mixture to the direct rays of the sun abridg 'S : the time required. and enough fuming nitric acid to render the mixture fluid. and oxygen is formed.). giving off water. increases greatly in In cases in which bulk. the graphite was originally mixed with silica. 261) graphite is intimately mixed with three parts of potassic chlorate.* If th s thoroughly. xlv. flocculent. of graphite which is of some importance to the chemist.). It is slowly attacked 1 y ammonia and by potash. appears that during this treatment the graphite becomes oxidized. and the acid at the same time gives off water and carbonic anhydride. leaving a residue containing C 66 4 U H >e ?. the clay employed for this purpose is mixed with a or blue-pots coarse kind of graphite. equal to twice the weight of the graphite The mixture is heated over a steam bath so long as any peroxide of employed. is its use in the manufacture of what are termed black-lead crucibles. gas is given off. which enters into combination with the excess of sulphuric acid. hydrogen. exceedingly bulky. H H .

it contains quantity of the saline and earthy substances. 95 by adding potassic chlorate silicic fluoride. ing to the extent to which these decomposing actions have advanced the different varieties of coal will be noticed herein after. Gas Carbon. which its supposed to have assumed present appearance and composi- tion by the combined action of heat and moisture under great The composition of coal varies considerably accordpressure. appearance of this mass vary according to the temperature and the pressure of gas in the retorts in which it has been produced. it takes up a considerable quantity of it. and oxygen. partially it decompose the gas as it escapes a portion of the carbon which held in combination is deposited. which by is heating swells up to the black powder. The cially graphitic modification of carbon may be obtained artifi- by several processes. the silica is then expelled in the form of the behaviour of the different varieties of carbon. the amorphous varieties of carbon are dissolved. and on being allowed to cool slowly. In the manufacture of coal-gas those parts of the retort which are exposed to the highest temperature. but in all cases it consists. of very dense carbon is formed. the coal is burnt in an open fire-place. as it does not yield Brodie's graphic acid when treated with potassic chlorate and is nitric acid. When cast iron is melted in contact with an excess of charcoal. On Berthelot has founded a process for the analysis of carbon. a small quantity of sodic fluoride to the mixture of graphite with and sulphuric acid . under the influence of a mixture of potassic chlorate and nitric acid. pyrographitic oxide. like vegetable matter : a small proporgeneral. and in addition. of carbon. Pit Coal is a substance originally of vegetable origin. graphite is changed Diamond into graphic acid (the graphitic oxide of Berthelot). hydrogen. even in an open the air be furnished : . possessed of a lustre resembling The density and that of a metal but containing some hydrogen. not affected by the mixture . when or ferric disulphide (FeS 2 ). if an adequate supply of oxygen from but the burning of coal. besides a variable amount of iron pyrites These saline matters are left. which always exist in the juices of plants. brown solutions being produced. and by degrees a layer .PIT COAL. This form of carbon however is not a true graphite. the carbon crystallizes out in the six-sided plates peculiar to graphite. and constitute the ashes j whilst the carbon and hydrogen are entirely converted into carbonic anhydride and water. with a variable tion of nitrogen.

These are two varieties of coal. especially the former. steady fire. whilst at the same time a considerab' e saving of fuel will be effected.96 fire. . the coal immediately begins to undergo decomposition. but it requires more labour and atteutic a On this account various contrivances ha than is usually bestowed by him. on coming into contact with the glowing embers. never complete. The latter condition is supply of an adequate quantity of atmospheric air. of these having for their object the regular supply of fuel by mechanical meai e ss s.r houses and factories may be prevented. Anthracite burns without emitting smoke and when heated gives off but little volatile matter as the proportion of the carbon to the hydrogen is much greater than in pit coal. but a large proportion of these bodies. the supply of fuel in small quantity at a time. been from time to time invented for effecting the prevention of smoke . tl e n< t so easily accomplished in the furnaces of the manufacturer as might be suppose 1. . or. whilst the carbon. howeve:. which is the more combustible element. it passes off in the gaseous form. luminous flame. becomes burned. various compounds of carbon with hydrogen being abundantly evolved in the form of gas or vapour. is more or less completely decomposed. By proper care. so that gives off a quantity of gaseous finely divided carbon or soot in susit and tarry matters. is carried up tre chimney suspended in the current of heated gases. When a quantity of fresh coal is thrown upon a hot fire. Anthracite and Steam Coal. 2nd. the volumes of black smoke ordinarily poured forth from the chimneys of oi. a portion of these hydrocarbons immediately takes fire and burrs with a bright. is CONSUMPTION OF SMOKE. if the supply of oxygen be inadequate. which are much more dense and hard than ordinary pit coal. taking care to maintain a strong. very similar to one another. The principles involved in the prevention of smoke are 1st. in order that the gases may be burned as fast as they are generated and. The regulated supply of fuel in small quantities may obviously be insured ly due care 011 the part of the stoker. (363) Consumption of Smoke. holding pension. owing to the minute state of subdivision of its particles. one cl. the hydrogen. the carbon and hydrogen experiencing a separation from each other .

the fire-door. are products as they escape. The thrown fire coal is into the by hand. Fig. F. passes off. B. and the better its manufacture. it has also the advantage of not swelling or caking together when heated. B. while the greater proportion of the carbon remains behind. hopper. represents in section the plan 296 adopted by Mr. which are carried very slowly forward by machinery connected with the toothed wheels section in continuous but very gradual supply of fuel is furnished from the W. c. cylinders. The fire- tubular. In another class of is to burn the smoke-burning contrivances. but the wear and tear of the fire-bars is considerable. C. if the quantity thus admitted is not sufficient to complete the combustion of the unburned gaseous bars. and. and allow the passage of air into the channel. the same substance as the graphite deposited from the gas. is exposed during become. and nitrogen. so constructed as to exclude atmospheric air. but in a less pure form. B. but to allow free escape for volatile matters. When the coal is heated in long closed iron (364) Coke. the essential points of which are shown in fig. since it burns without emitting any visible smoke . the . with a part of the carbon of the coal. and thus the danger of The higher the temperature to choking the draught is avoided. A object is formed in small quantity. as is 97 proposed by Juckes's apparatus. coke is often to be preferred to coal. which opens into the chimney just behind the bridge. the air becomes heated as it passes through the tubular bars. by supplying air at a high temperature to unburnt gases as they escape from FIG. a large quantity of gaseous substances. and constitutes coke. chemically. in this case consist of a series of endless chains. smoke which the the fire-place. the more dense for producing a steady is it fitted H . which coke does it II. Hills" for at- taining this object. being perforated for the admission of air. As a fuel owing to the earthy matters which are mixed with it. in front of the furnace. which is the only one of the products that will be noticed at present. but moderate quantities at a time in .MANUFACTURE OF COKE. E. hydrogen. containing the oxygen. and the amount of coal thus admitted is This apparatus fulfils its regulated by raising or lowering the door D. of the fire-grate. object well. 296. The fire-bars B. 295. H. more air can be supplied from below by raising the damper D. A. W. Coke is.

and lined with fire-bricks. A Coke may also be prepared. the walls being from 2 to 3 feet (6 to 9 decimetres) in thickness. Coke is subject to gr 'at variation in appearance and bulk. and intense heat. or entirely destitute of crystalline structure. (365) Charcoal : Amorphous carbon. very pure fo 'm of carbon is frequently observed in the fissures of the mass. before they have undergone carbonization. and the furnace left for five or six hours .98 CHARCOAL. unless the it burns less freely in this be of air abundant. furnishes in this way a very dense lustrous coke. when burned as fuel . A bituminous coal. in about bustion proceeds gradually. in he form of black fibres. distinct from that of graphite. which plays over the surface of the heap and burns off the volaThe comtile matters before their escape by a short chimney. The coke is never melted in this operation. it is customary to construct coke ovens. the door is completely closed. and the appe iranccs of fusion which it frequently exhibits are due to he for the : by heat. at the end of that time the coke is withdrawn and quenched w th water. depending on the kind of < oal >re employed in producing it it is. black is an impure variety of this kind of charcoal. and same reason. nearly always : m bulky than the coal that yields it. coke suited for the use of locomotive engines. diameter and 4 feet (1*24 metres) in internal (37 metres) tons about 3500 kilo 2^) will convert in (or height. for the purpose of introducing and wMhdrawing the charge. by a smothered combustion of the coal in heaps. in a manner sim: lar to that practised in making charcoal. 12 feet one continuous piece of masonry. like the Newcastle coal. introduced into the oven while its walls still remain red h3t. in order to economize the heat . tolerably supply In order to furnish a dense condition than when less compact. of the bituminous portions of the c( al. which splits into long columnar masses or prisms. Carbon also exists i i a third form. from above downwards forty hours after commencing the operation. however. closely resembling horsehair in appearar ce. which are usually built of brick. door in front. although with less advantage. which al^v ays retains a portion of : carbon and hydrogen some incompletely burned compounds of it is largely manufactured by heating in . as the temperature in the o^en A fresh charge is gradually falls when the door is closed. and for regulating the admission of the air. although. liquefaction. 3^ The oven has a sliding of coal into coke in forty-eight hours. several ovens are usually built together in One of these ovens. and in this state i is La ipamorphous.

and earth. vegetable matters rich in carbon. a fine powder of charcoal is deposited within them. which protects is left is it from the action of the is to cool gradually. in which After the heat has been continued for four they are consumed. provided with a air . this can be easily introduced into and withdrawn from the fixed cylinder. plot of ground is levelled in or near the forest. Tinder is another variety of carbon in the amorphous or noncrystalline coal. such as that which constitutes the visible portion The smoky products of this imperfect combustion are of smoke. however. and here the lampblack is deposited. in this condition it case. be rendered almost pure by strongly igniting in a current of chlorine. it may. the hydrogen burns which these bodies contain. even if again heated intensely in closed vessels. made to pass through a large chamber. leaving the carbon in the form of a very finelydivided powder. which is partially covered up with powdered charcoal. a stake is driven into the ground. plunged into an extinguisher or iron tightly fitting lid. logs of wood are piled up regularly round the stake so as to form a mound. the inner case with its charge is withdrawn. also. and protected from the direct action of the flame by a From this kind of iron retort proceeds a tube casing of fire-brick. an iron 99 pot. turf.MANUFACTURE OF WOOD CHARCOAL. or five hours. the charcoal manu- factured by a much ruder method. and a A quantity of brushwood having been placed round its base. The best plan consists in enclosing the wood to be charred in a second lighter case . where. and the whole. and provided with a tightly fitting lid at one end. the heap is then fired by introducing lighted fagots into an aperture left at the base of the mound for H2 . the vapours thus disengaged are kindled. The purest form in which finely divided carbon can be obtained for chemical purposes is furnished by passing the vapour of oil of turpentine or of ether slowly through tubes maintained at a full red heat . whilst still red hot. and are directed into the fire-place. set in a furnace either vertically or horizontally. always retains traces of hydrogen . form is which but the most important variety is Wood Charlargely manufactured by heating billets of wood to . connected with a condensing apparatus. whilst the uncondensible gases pass on. the walls of which are covered with coarse cloth. being the more inflammable ingredient. the end of the outer cylinder is removed. off first. but this. dull redness in cast-iron cylinders. such as resin or tar . the liquid products of the decomposition may be arrested. leaves. which is set in masonry. In countries where wood abundant. and burned in a current of air insufficient for their complete combustion .

m tinued for a The resulting charcoal retains the one which is rapidly effected. arid when the whole mass is thoroughly ignited. owing to he 1 large amount of heat which they carry off in the latent st? te.) the loss upon the original weight amounted to tot wood in the preparation of charcoal. that purpose large quantities of moisture are presently exhaled. and. which. it is then allowed to burn out. i is not sufficient to consider simply the absolute amount of heat wh ch a given weight of the fuel emits whilst burning.). of fuel. Experience shows it to be much more economical to employ dry than wood in its green conKarsten found that 100 parts of recently felled wood. the workmen regulating the admission air as circumstances require . at the moment of their formatii n. The object of preparing charcoal as a fuel is to get rid of me isture and volatile matters. it is denser purposes and more completely deprived of volatile matters. A slow combustion is found to yield more charcoal th. form of the wood. ne\er exceeding one-fourth of its weight. the earth employed to stifle the combustion is The combustion of removed. and the 33 parts of dry residue when charrad 25 parts of charcoal. and by supplying a more co n- pact fuel concentrates into a smaller space the heat which it em a condition which is often of the greatest importance in me1 lurgical operations ts. The radiat ng .lost 5yparts. )y drying at 212 (100 C. If the diameter of the heap be jo metres or more.100 : PREPARATION OF WOOD CHARCOAL. for the charring the rest. the operation is not complete in less than a month. because the heat to which it is exposed is mu*ch more intense. preferable to that made in cylinders. When quite cold. left only 14 parts of charco il. This remarkable difference in produce depends upon the decomposing action of charcoal at a high temperature upon water. being generally not more than three-fourths of the bulk of the wood. greatly reduce the temperature of the burning mass. by raising the temperature to 302 (150 C. al- demanding a high temperature. whilst the hydrogen of the water also passes off as gas. Charcoal also contains in the same bulk a larger amount of carl on than the wood which furnished it. dition. if charrsd without any preliminary drying. less left than 67 parts . it is still more of closely covered up. in consequence of which much of the carbon escapes in the gasec as state in the form of carbonic oxide. but it is much reduced in size. In the economy of material to be used as a combustible. one part of the wood is thus employed as a source of heat for Charcoal prepared in this manner is. but 100 parts of the same wood. and is con- much longer period. and the charcoal is fit for use.

particuin the glass furnace and in the porcelain kiln . these flameless coals are also the most useful. which burns with flame is therefore necessary where it is needful power of a solid communicate an elevated temperature to objects at a distance from the fire-grate. as the heat is thrown off by them into the room more completely. 100 parts of black alder (bourdaine) ried wood. charred at the following temperatures. and objects in which direct radiation can act with its full effect. instead of being carto up the chimney with the gaseous products. are especially valuable. but the per-centage of carbon in the residual charcoal was found to increase. . or to raise large masses to a uniform temperature. Wood and bituminous coals are. According to the experiments of Violette. coke. as shown in the table. consequently. In an ordinary open fire.PROPERTIES OF CHARCOAL. 101 mass of fuel is much higher than that of a gaseous the temperature of flame is very high. whilst useful larly in heating boilers. but A fuel combustible. and coal which burns with but little flame. anthracite. gave amounts of charcoal progressively diminishing . Temperature of charring. Charcoal never consists solely of pure carbon.

and has long been employed on this account as the basis of printing ink. subdivision it is a bad conductor of heat. that St 5). in the wards of hospitals. particularly colouring matters i nd many bitter principles (54). consequently a superficial charring is frequently resorted to with a view to protect wood from decay.102 ture it is POWER OF CHARCOAL TO PROMOTE OXIDATION. Charcoal Air Filters are also extensively employed to reuse. vent the escape of noxious vapours at the ventilating opening s of the sewers. . whilst most of the nitrogen remains as ammonia.he employment of trays of powdered wood charcoal in dissecti igrooms. as it allows the free passage of air. one of those substances in which chemical attraction exhibits least activity . to f 1*0tect the mouth and nostrils in an infected atmosphere. not only for decolorii ing but likewise for assisting in purifying water for dome . In a state of fine ranking next to the metals in this respect. animal matter in an advanced stage of putrefaction disappear when the putrefying substance is covered with a layer of ch ircoal. . ble material in the construction of filters. as well as its property of conde is- ing a large proportion of gaseous matters within its pores (t has been already mentioned. It certainly has a remarkable action upon putrescible substances. Lampblack furnishes the most indestructible of black pigments. to serve as foundations. dry. the carbon being dissipated as carbonic anhydride. the hydrogen as water. common practice to char the interior of tubs and casks destined to hold liquids. as in the case of piles which are driven into mud or into the beds of For the same reason it is a rivers. It will continue active for years if 1 ept . -n- house had proposed to use a respirator filled with charcoal. Finely divided charcoal is usually stated to have strong antiseptic powers. in its other forms carbon is an excellent conductor. but its conducting pOAver increases with its density. is found to exert a most beneficial in lu- ence in sweetening the atmosphere by absorbing and decomposing the offensive gases. but condenses the a offensive effluvia in its pores. So rapid is this action. and in situations where putresc mt animal matter is present. but without emitting any odoir. These properties render charcoal a valu. it continues to decay. but Stenhouse has shown that this action consists in a rapid dependent upon The offensive effluvia from densing oxygen within its pores. The diamond is a non-conductor of electricity . and . where they are destroyed b ' process of oxidation.tic purposes. The remarkable power possessed by charcoal in a finely divided st ite the power which process of oxidation charcoal possesses of con- of absorbing various bodies.

and which exhibited the properties of graphite. that the vessel crucible of pure charcoal connected with the positive electrode. Charcoal decomposes steam at a red heat . and the mercuric are. hydrogen is is liberated. in like manner. by simply agitating their solutions Avith charcoal powder. and a high temperature is required in this case also to effect the combination. These hydrocarbons belong essentially to the organic department of chemistry . its cially compounds. connected so as to form a battery of 100 pairs of 6 cells each. the whole of the charcoal powder became cemented into a coherent mass which appeared to have been fused. The simplest of these substances is light carburetted hydrogen . to the action of the battery in a smaU receiver.PROPERTIES OF CARBON. they will therefore not be discussed here. are termed car- The compounds of carbon with the metals Carbon forms a large series of compounds with hydrogen. but in the course of some experiments with a voltaic battery of intense energy. in former editions of this work will be treated of in the appendix to this volume until they can be transferred to their proper positions. or from essence of turpentine. however. The deoxidizing power of sometimes exerted at the ordinary temperature of the Schonbein found that ferric salts may be reduced to the is condition of ferrous salts. according takes place. converted into mercurous salts. C2 H2 is formed. The experiments of Berthelot have proved. acetylene. which was deposited upon the sides of the glass as a black crystalline powder . a particular hydrocarbon. carbon air. espehence the various forms of carbon are very extensively employed in the reduction of these substances to the metallic condition. 103 Carbon is usually regarded as neither fusible nor volatile . and by exposing charcoal obtained from pure sugar. formed. Despretz found on operating upon carbon points in an exhausted became filled with a dark cloud. burets or carbides. rapidly with oxygen. It to the temperature at and carbonic oxide or carbonic anhydride which the reaction had long been supposed that sulphur was the only non- metallic element besides oxygen with which carbon could be made to unite directly. that by igniting charcoal intensely by means of the voltaic arc in a current of pure hydrogen. but for the convenience of the student some few of the more simple of these bodies which have been placed in Part II. consisting of 600 cells of Bunsen's construction. and At high temperatures carbon combines will remove it from a great number of from the oxides of the metals .

The 4 volumes of oxygen which 20 volumes of air contain. or to the generous but vitiated ignorant and rash survivor who attempts to descend into the pit before it has been properly ventilated. The ' after-damp/ or choke-damp as the miners term it. 4 vols. or marsh gas. and h.104 EXPLOSION OF FTRE-DAMP IN COAL MINES. very When marsh gas is mixed with air. it w 11 larly of flames . although inflammable. loss of life to those who are engaged in coal mines. need a red heat. which takes fire on the approach of a light. + ioH 2 . phosphorus. an explosive mixture is formed. on account of the abundant escape of carbnretted hydrogen from the workings. s enabled many coal-fields to be worked which otherwise must ha e been abandoned. and escapes in considerable sometimes quantities. 2 vols. marsh gas times its it is obvious that this gas in exploding deprives ten bulk of atmospheric air of the oxygen it contains. mixed with other hydrocarbons. in from fissures in seams of coal in mines. however. as olefiai gas and hydrosulphuric acid. others. in order to succour his From the composition of comrades. or to ascertain their fate. termed by the miners fire-damp. 2 vols. quired for the combustion of different bodies varies greatly: son e take fire at a very low temperature. and 4 volumes of stea n which become condensed. or atmosphere that the explosion produces. sulphur at about 482 (250 C. CH4 + ^0 2 = 'CO. and partic t i- A produced by the combustion of the hydrocarbon s. The fatal results of an explosion of fire-damp in the mine are not. leaving 16 volumes of nitrogen reman iing mixed with the carbonic anhydride. Marsh gas. for instanc ?. 4 vols.e renders a far larger amount quite unfit for respiration. It these fatal results that r The temperature r . coal gas. essential to the existence of flames. i n instrument which has prevented many serious accidents. and often occasions accidents attended with . however. at the heat of the body.) . is often fatal to those employed in other parts of the mine. carbonic disulphide at about 4i. high temper ture is. (2i5C. pr< >duce 2 volumes of carbonic anhydride.). limited to the mechanical violence which it occasions to the sufferers. requires a much higher ter perature to ignite it than most other inflammable bodies .(367) Principle of the Safety Lamp. CH 4 It exists. was with a view of discovering some means of preventir g Davy instituted those important research -s on flame which led him to the invention of the safety-lamp. and from the deleterious nature of the resulting carbonic anhydric.

owing to the cooling effect of the metal . wire. a second wire cools the flame still further. whilst still hot. safety tube for the oxyhydrogen its for blowpipe (347) depends efficacy upon the cooling influence which the metallic tubes or channels. when the gas is mixed with 7 or 8 flammation. for the large volume of air with which it is mixed prevents the temperature from rising sufficiently high to cause the combustion to spread throughout the whole bulk of the gas the most power: ful explosion times its bulk of is occasioned air. but : employed : the flame will traverse the network as soon as the wire becomes red hot with finer meshes (about 64 to the square centimetre. Again. be placed over the flame. exert upon the burning jet of gas. the metal will be maintained at a red heat by the rapid combination of the oxygen with part of the hydrogen and some of the carbon of the gas. which. If a stout copper wire be introduced into any flame. the shorter was the length required to produce Davy found that of air and marsh . a dark space will be observed immediately around the wire. 1 . but if the same coil be previously heated to redness. Combustion may often be carried on below the point of inThe smouldering wick of a taper recently blown out affords a case in point. no explosion could be produced in a mixture gas. and a small flame may be completely extinguished by the reduction of temperature produced by bringing down a coil of wire upon it so as completely to surround the flame . even . case burns only in immediate contact with the flame of the lamp. does not take fire until the platinum becomes heated nearly to whiteness. 105 not explode when mixed either with less than 3 or with more than 8 times its volume of atmospheric air the gas in the latter . the un burned gases being cooled by its means below the be point of inflammation if a piece of gauze with large meshes it will cut off the flame so long as it remains cold. the heat of the flame is in this way prevented from passing backwards and causing the explosion of the mixed gases in the reservoir. however. or a hot slip of platinum be suspended in a current of coal-gas mixed with atmospheric air. Hemming's between the wires. formed by the interstices this protective effect. the latter will continue to burn.PRINCIPLE OF THE SAFETY-LAMP. owing to the and the influence the tube exerted upon the gas which cooling narrower the tube. and. By using wire gauze we may easily cut off the upper part of a flame. if a glowing coil of platinum foil. through a narrow tube. or is 400 to the square inch) the conducting power of the metal sufficient to cool the flame below the point of ignition.

and through to the gas below. which emits scarcely any light.* o: These principles were beautifully applied by Davy in the. enlarged flame is seen. open below. for the purpose of trimming the wick without the necessity for removing the wiro When such a lamp is incovering. mm> ) . the miner must withdraw for thoug no explosion can occur while the gauze is sound. which is merely an oil lamp n &.2 97) enclosed within a cylinder of ( FIG. 207 fine wire gauze. five or six inches (12 or 15 centim. . of fire-damp. and might easil break into holes. troduced into an explosive atmospher. until at lengt i it fills the entire gauze cylinder. the wick is generally rekindled. * Bunsen's burner acts upon a similar principle. . . It consists of a small j for the issue of the gas : this jet is fitted tightly into the bottom of a brass tul which for the poor gas burned in London may be 4 or 5 inches (10 or ia cn fc -. provided with a double top. and |ths of an inch (i6 sides of the tube near the bottom.108 ' DAVY'S SAFETY-LAMP. long. and deposits no smoke upon cold objects. when the mixture of inflammable gas and a: outside the lamp would become ignited and immediately cause a . In a similar manner the gas is may be kindled. and th Whenever this pal lamp continues to burn in the air as usual. r i explosion of the fire damp.) long. and the mixture of gas and air is kindled . whe:i the gas is in sufficient excess the lamp is entirely extinguished if it be withdrawn from the explosive mixture while the cylindc appears to be full of flame. w. construction of his miner's lamp. yet at that hig temperature the metal becomes rapidly oxidized. retted hydrogen increases.t the top of the tube. the flame is seen to eularg gradually as the proportion of carbu- . ? provided that the supply of gas be duly proportioned to that the air which mixes with it. The air enters by holes in tl e ) in diameter. i i r . itself although the wire above the gauze be red hot. and furnished at top with a cap of wire gauze. : Advantage the flame will not pass taken of this circum- stance in the laboratory to obtain a smokeless flame by the use of ordinary coal-gas A metallic chimney. the air enters at the bottom and mixes with the gas : this mixture burns above the wire gauze with a blue flame. is placed over any convenient form of burner. which passes up tightly through a tube traversing the body of the lamp. and with a crooked wire.

but it will burn with its former energy the moment that the spoon is withdrawn from the flame. about of an inch or 8 millimetres in diameter. If a fragment of phosphorus be placed in a small deflagrating spoon. burn with flame. In all ordinary cases. It is necessary to the production of Nature of (368) that the combustible be of such a nature as to be capable flame. therefore. 107 in the construction of these lamps conabout 121 meshes per square centimetre. and then introduced into the middle of the flame. the gases in the interior may be drawn off. open at both ends. tion at None of these substances are susceptible of volatiliza- the temperature attending their combustion. wooden match be held for a few seconds across the middle of the flame of a spirit-lamp with a large wick. Sulphur. and five or six attendant on is the flame inches (12 or 15 centimetres) long. an atmosphere of unburned combustible matter. it will be extinguished . ignited. of a screen. by above inserting into a flame such as that of a wax candle. although it would appear that several very the use by before its mines have been produced in this way. tapering form which flames assume. otherwise no flame is produced. as also does iron wire. If a structure of flame may be easily shown by experiment. or from 700 to In a strong current of air the 800 meshes in the square inch. unattended with flame. and they. in fact. or with some gaseous supporter of combustion. but the intermediate portion will remain uninjured. the lower extremity of a glass tube. phosphorus. serious explosions in of being converted into vapour before it undergoes combustion. It is to remark that the light and heat emitted by important . The. as well as gases. Well-burned charcoal or diamond burns with a steady glow. Flame. the match will become charred at the edges of the flame. just the wick. the various combustible Flame is. heated gas may be blown through the apertures of the gauze tains The wire gauze used temperature is sufficiently reduced to prevent the exbut such an occurrence may be easily guarded against plosion. produced whenever a continuous supply of combustible vapour or gas combines at an elevated temperature with oxygen. and ignited at the upper aperture of the tube. is due to the ascending current produced in the atmosphere by the heat Within the burning portion of the combustion. and zinc pass into the aeriform condition before they attain a temperature as high as that generated by their combination with oxygen. flame is a luminous envelope which forms a limiting surface between the unburned combustible This hollow within and the supporter of combustion without.NATURE OF FLAME LIGHT AND HEAT.

although very hot. . Phosphorus and chlorine. is scarcely more luminous than the flame of hydrogen.t becomes yellow. yet emit but little light during their combination : chlorides of phosphorus. it often happens that very little light is emitted although the heat developed may the hydrogen flame. i . or th white fumes of phosphoric anhydride produced by the combustio . zincic oxide. bodies so introduced be combustible. fired it under presis luminous when a jet of the mixed gas but feebl / although ten: a lower at burned. The increased perature. i platinum wire. light quantity a I the increase effect not probably compound only by produced but also of the the temperature greater density gases combining by sure. energy solely pure gaseous matter. although they unite 5-0 energetically as to take fire at ordinary temperatures by mere the contact. although one of the most powerful sources of heat at our command. then white. does not melt at that temperature . I luminous either by blowing a little powdered charcoal through r or by allowing finely powdered magnesia. has a shade of blue or violet (89). both the vapour of sulphur and sulphurous anhydride beir g gaseous bodies. better still. since they do not contribute to the chemi. as in the Cavendish eudiometer is . or of as is seen when oxygen and hydrogen . circumstances gives but little light flame which in ordinary may at a higher temperatme a mixture of chlorine and is A become luminous. The light from bodies feebly ignited is red as the temperature rises the ligl . notwithstanding the intense energy with which they combine . or have already undergon the flame of hydrogen may be rendere perfect combustion : . The heat flames are by no means proportioned to each other. and when is due action to of the chemical the . composes both the burning body and the product of the combustion. into the oxyhydrogen jet. however. or. . as well as phosphorus volatile bodies. without solid particles. for example. being veiy is generally stated that in all luminous flames the light emitted from solid particles highly ignited. cal changes occurring in the flame.108 VARIATION IN THE LIGHT OF DIFFERENT FLAMES. and when the heat is very intense. so that t . . the more refrangible rays of the spectrum predominate. s in emitted air. : be very great visible in clear daylight For the same reason the light of sulphur burning in oxygen is feeble. of as. a body which. like lime. is barely and that of the oxy hydrogen jet itself . necessarily reduce its hea to their It is immaterial whether th owing conducting power. hydrogen. By introducing a solid object into a feebly luminous flame. It is itself. the light becomes so intense that the eye can scarcely support i Such bodies.

the sparks being always more brilliant in the denser than in the rarer gas. plate introduced into a flame of coal gas or of a candle is usually considered as a proof of the presence of solid particles of carbon in the flame . 109 Indeed no better illustration of of phosphorus. the from red By rendering gases incandescent by the passage of electric sparks perfectly similar results were obtained. and sulphide of arsenic (realgar). although the arsenious anhydride produced is vaporized below a red heat. Frankland performed some experiments which put this Hydrogen and carbonic oxide burn in air and beyond question. where the solid scarcely volatile phosphoric anhydride is produced. there are cases where light of considerable intensity is emitted where no solid combustion. however. when particles are formed during burned in a current of oxygen. Arsenicum. furnishes a pale lambent blue flame without any sensible light. And by using atmospheric air and gradually increasing condensing syringe the sparks became brighter. a similar bright flash of light accompanies the rapid combustion. as supposed by Davy.NATURE OF LUMINOUS FLAMES. It would appear that the higher the density of the combustible or products of combustion. but to the incandescence of gaseous hydrocarbons of The deposition of black matter on a porcelain great density. solid particles are produced by the combustion. to violet. when mixed with a it is suitable proportion of nitre. the luminosity is not due to the presence of solid particles of carbon. the intensity of the light emitted is spectra of the flames being continuous very considerable. and which are all produced by the combustion of compounds of carbon and hydrogen. but it is well known that the lampblack thus ob- tained invariably contains a considerable quantity of hydrogen . In the last case. emits a sensible amount of light. as Frankland remarks. Still. furnishes so intense a white light that used as a signal light under the name of Indian fire. its density by a These results induce the belief that in ordinary flames used for illuminating purposes. and if nitric oxide be substituted for oxygen. at the ordinary pressure with flames of very small oxygen but with a pressure of from 10 to 14 atmospheres luminosity. with the feeble light emitted by the same body as it burns in chlorine. which furnishes potassic sulphate among the products. to traverse it. In like manner Franklaud urges that carbonic disulphide. the greater the luminosity of the flame. but if burnt in oxygen it produces an intensely brilliant light. this point can be given than is afforded by contrasting the painfully intense light produced by the combustion of phosphorus in oxygen. when burned in air.

the light becomes red from he reduction of temperature. the gas burns with a bl ic. feebly luminous flame . action. and meets with oxygen. a. must not be too limitc d . he ? ny contrivance which. . or by watching the effects of he wind upon the exposed gaslights at night the lengthening of In these ca . emitting lijjht and this carbonaceous matter itself. however. and they burn with a pale blue light. The supposition that ordinary luminous flames consist of gaseous matter only. Moreover. d. fig. these vapo irs rise above the wick. is still unburned. gradually burns away without residue or adjusted properly smoke. i ad the oxygen being insufficient to complete the combustion. if too much be given. in a in the part marked b flame. concentrates it into a smaller space.110 MAXIMUM OF ILLUMINATION. as may be seen by closing the central tube wh ch admits air to an argand burner. forming the central dark part. the po nt which requires the greatest attention is the due adjustment of he supply of air . the gas becomes immediately mixed with the oxygen of the ir. which can only be removed by prolonged treatment with chlorine at a white heat. without deranging the order of the comb istion. no separation of carbonaceous matter occurs here. hydrocarbons are immediately mingled with At atmospheric air.es the chimney of a lamp produces a similar effect. an effect which may be seen by blowi ng upon a common gas flame. In order to produce the maximum amount of light. and its conversion into gaseous hydrocarbons by the heat of the combustion. The greater portion of the combustible gas and vapour. however. as it comes to the surface. they are quite transparent. some of the more oxidizable hydrogen undergoing combustion and thus giving lise to the formation of denser hydrocarbons which become intensely ignited in the burning gas. The light of a flame is increased by flame becomes smoky. 298. these the lower part of the flame. the carbon passes off unburned. otherwise. is much supported by the fact that The flame of a candle is sustained by the decomposition of the melted wax or tallow absorbed by the wax. it is cooled by cont ict with portions of the air which do not participate in the chemi . and is completely burned before it has been exposed to an eleva ed temperature for a time sufficiently long to allow of the separat on : . of the carbonaceous matter.al The supply of air. here they are subjected to a high c. of the flame : temperature from the combustion of the blue port: on already mentioned . so as to raise the te n- .

and this rate of diminuwas found to hold good with the light of hydrocarbon flames generally. . the diminished. On the other hand.of mercury. It is in this Frankland (Phil. the more rarefied the atmosphere in which flame burns. for the amount of light emitted by the same candle on the summit of Mont Blanc was far less than that which it produced in the valley and by careful experiments conducted under regulated pressures.to mm> of creased from 30 to 14 inches (76o ) 355 mercury. the luminosity of all flames may be proportionately increased by augmenting the atmospheric pressure. and on the other hand. perature to the air is Ill maximum . So rapidly does this effect increase. under the ordinary pressure of 30 inches mm. In a series of expeilluminating power gradually riments upon the light of burning gas. the same volume of gas for (or 76o . The decrease in is . and without smoke. 631) found that the rate at which candles and other similar combustibles burn. than if the same quantity of gas were burned in separate jets. the more compressed sult of these complete the flame is its combustion. way that an argand burner produces a far greater amount of light with a given consumption of gas. so as to prolong as much as possible the time during which the vapours are maintained in the ignited state. Frankland found that taking the light emitted by the combustion of a given volume of gas. the observation holding good air rounding as low as 14 inches (355 mm ') of mercury. ) i inch in the pressure gave 5-1 less light. is not altered Candles burned at by variations in the atmospheric pressure. the diminution of light being directly as the diminution of pressure so that at 14 inches (355 mm *) the light emitted instead of each diminution of : tion amounting to 100 was reduced to 18*4. it was found that as the pressures demm. and other carefully devised experiments led to the unexpected conclusion that the combustion of gaseous matter is rendered less perfect in proportion as the density of the atmosphere is increased . the top of Mont Blnnc at the same rate as in the valley of Chamounix but the luminosity of the flame is greatly affected by the pressure. whilst the velocity of the current of moderate. within certain limits. even burns with a smoky flame. that an ordinary spirit-lamp which in air amount of burns in the open air with scarcely any measurable light. and when supplied with air still The remore. becomes powerfully luminous at a pressure of 4 atmospheres. in a certain burner. No reduction in the temperature of produced by a reduction of the pressure of the surwithin certain limits.EFFECT OF PRESSURE ON LUMINOSITY OF FLAMES. at 100. 1861. Trans.

from the side of which projects a brass tube. witl a chamber for the condensation of moisture from the A very convenient form of the instrument is breath. upon which is fitted a small brass jet. it is limited to a much smaller space.blowpipe is one of the most valuable and portable instruments of research which the chemist possesses he is enabled : means. ds jet is inserted to a short depth into the flame of a candle. and it often affords information which could not be obtained in any other way. and closed at its lower end. above the wick as at B. open at the narr< >w end.) long. a current of dr is from the blowpipe horizonta ly along the surface of t ic wick. to arrive with certainty and its aid. abc ut an eighth of an inch. It consists of a conical tube of in plate. The temperature of a flame (369) Theory of the Blowpipe. outside that is the brilliant p. would require much expenditure both of fuel and of time. with which the oxygen of the atmosphere finds access to the owing to the greater mobility of the particles of the air under diminished pressure. rt a. terminating in a fine uniform jet. T. of the flame. The mouth. fig. whereby the combustion is rendered more rapid. $<. 299. illuminating power in a rarefied atmosphere is attributed by Frankland. by economy at results which. and is . In the cen re parts are distinctly discernible. to the great readiness interior of the flame.112 THEORY OF THE BLOWPIPE. 300. and with strong probability. b. The mouth-blowpipe consists essentially of a bent tube. when FIG. is entirely changed in character. about 8 inches (20 cm. a. shown at fig. without its in a few minutes. and concentrating its effect by diminishing the extent of surface over which it would otherwise take place. a well-defined blue cone . which is rounded off so as to adapt itself to the lips. It is upon this principle that all blowpipes act a jet of air or of oxygen thrown into the interior of a flame. the flame loses ts luminosity. o. about an inch (25 ') in length. terminating at and exterior to that is a pale yelL w . and is directed pi o- jected laterally in t form of a pointed coi in which three is le e. be increased may very materially by augmenting the activity of the combustion. or 3 mm< .

or is volatilized wholly or partially. reversed. it may be first heated alone in a small glass tube. copper. 113 properties. and the oxide will be reduced to the metallic state is termed the reducing flame of the flame. to ascertain whether it may burns. These observations upon reduction to the flame II. At the apex. c. next be heated in a narrow tube open at both ends. The plumbic silicate contained in the and the glass glass partially decomposed at this point becomes black and opaque from the reduction of the compound of lead to the metallic state . and a fragment of any readily oxidizable metal. a. 298. the effects are c. but it can be acquired by When a substance is to be examined by the practice without much difficulty.in excess absorbed by combination with fresh portions of the combustible vapours which are constantly rising from other parts of the wick. f blowpipe. the oxide will be deprived of oxygen. taining unburnt combustible gases at a high temperature. concone. be introduced into this part of the flame. maybe best made when the globule I is exposed upon a disk of charcoal. and the transparency of the glass restored. if placed at this point will quickly become coated with oxide the oxidizing flame of the blowpipe. fig. as . products of combustion. whether it fuses easily. and if it be reduced. atmospheric oxygen at a high temperature is mechanically carried forward along with the completely formed : hence this portion of the blowpipe. Here. or changes colour. . is blackened part for a few seconds in the oxidizing flame. If a fragment of some metallic oxide. what is the colour of the metal . In this part of the flame combustion is complete. which of course have a powerful tendency to combine with oxygen. by the : are clearly defined by the surface which seems to limit the blue In front of this blue cone is the luminous portion. The different parts of this flame possess very different The blue cone is formed by the admixture of air with the combustible gases rising from the wick. oxygen again absorbed by the metal. or emits any odour. in consequence of the superior attraction of the hot gases for this element. of an ordinary flame. in order to observe It it whether melts or decrepitates. and the oxygen introduced the points where the excess of oxygen is jet is. and it corresponds to the blue portion. It should then be ascertained whether it is reduced to the metallic state. which can be conveniently supported. or whether it is brittle. such as lead. crystalline. hence this spot is termed A good illustration of the opposite actions of these contiguous portions of the flame is afforded by the effects which they respectively produce on a piece of flint-glass is tubing. flame. The art of maintaining a continual (37) ~Use blast by the mouth-blowpipe is not easily described. or malleable. sufficiently small to be completely enveloped by the luminous portion. or tin. but by placing the in the reducing flame. is the Hfouth-Bloie-pipe. such as cupric oxide.USE OF THE MOUTH-BLOWPIPE.

: and sodic carbonate. and he usually employs a pai of double bellows. : working portable blowpipe for g assmay be made as fol- A rectangular box of : inc. is which is further b. according to the >urrequires a 1. 301. proposed by Mr. e. as t is usually termed. ai d is covered with a loose lid the c . 303. about 8 inches (2O cm< ) long.her . resen * a surface across the grain. The employment of certain fluxes often aids the judgment of the operitor FIG Q02 by the colour or appearance thus )roduced. The charcoal should be sawn into slices mm in thickness. yields a trans. ) high. supplied nth to within a short distance of the prevent the return of the water in case the operator should suddenly a longer pipe. which should be about the size of a pin's head. especially for the purpose of reducing the proposed. in speaking of blowWhen either borax pipe reactions. in the manner shown at I. c. or microcosmic salt is used. uninterruptedly for long peri >ds. one of them. so as to about the third of an inch.. 2 shows it in front. fig. if it be fusible. a support of charcoal is required. or a grain of mustard-seed. parent. bent (i2 No. covered with a passing ( >wn to flap of sill ceai e to . -) wide. as shown at fiy. sses obliquely nearly to the bottoi i of the box . d. A lows fig.114 WATER BLOWPIPE. Different forms of the blowpipe have been poses for which the instrument is destined. or soda. or a coloured bead .J"l formed upon the upper surface of each disk for the reception of 4H ^BBBi MX ^ T^^ the fragment of material under examination. but when sodic carbonate is employed. is open above. c and d. worked by the foot. passes just thr< igh the covering of this chan her. or 8 ". Griffin. by a diaphragm which p. these chambers com nunicate with each other below . closed at the to] : a blowpipe jet. a bottom. whether any change be produced in the substance. a platinum wire bent into a hook at one extremity forms a more convenient support. and half an inch mm at one end so as to hold the charcoal disk. A small cavity should be P fSl . The most important of these fluxes are borax. about 14 inches (36') cm> v ide. which represents an edge view of a slip of tin plate. 302. chamber. rge supply of air to be mainta metals.icrocosmic salt. an opaque. rr. The glass-worker md FIG. according as it is heated in the reducing or in the oxidizing flame. and 6 inches (or I5 is divided into two chambers. It may by this means be ascertained whether the substance imparts any colour to the flame whether the body. a p atinum wire forms the best support. Sometimes when the substance is not easily reducible. 303.

on the one hand. The following equation shows the nature of this decomit position when chalk and hydrochloric acid are employed. it has. indeed. as may be required. in which. 115 If the box be now partially filled with water.CARBONIC ANHYDRIDE. or CARBONIC ACID CO 2 =44. Where a very intense heat is required. renews the blast as before. the advantage of giving a more intense heat than gas. carbonic anhydride Preparation. owing to the complete intermixture of the two gases. Many it is natural exist. the column of liquid will expel the air through the jet. An oil-lamp may be used when gas is not at hand . II. "1 . such as the nitric or the hydrochloric. and by means of a sliding joint. By blowing down the long pipe. CARBONIC ANHYDRIDE. Gr. g. through which a current of oxygen is directed from a gas-holder . the operator can renew the supply of air as often as may be necessary it bubbles up into the closed chamber. or as bonate. when the column of liquid. in flint glass. are placed in a retort or gasbottle. recourse may be had to the oxyhydrogen blowpipe. is poured upon the chalk. The gas-burner. by its pressure. Carbonic is ob- Fragments of chalk. 1-5224. must be effected In a platinum tube). or calcic car- this compound is heated to bright redness (which. the flame' is solid. in any desired direction. being but a feeble acid. or chloride. Gr. . can be made to approach towards or recede from the jet. it is expelled from its compounds by almost every other acid which is freely soluble in water . the latter of which escapes with brisk effervescence. Observed Theoretic Sp. tained by a much more convenient plan. and therefore of comparatively small dimensions. a spirit-lamp or gas-flame may be employed. while pure quicklime is left When behind . bonic anhydride chalk. or of marble which is a more com- pact form of calcic carbonate. e. In actual practice. c. f. and occasionally. in cases where a still stronger heat is requisite. the pressure of blow through a. CaCO 3 becoming CaO and CO 2 . and carbonic acid (H 3 CO3 ) on the other the carbonic acid is so unstable that immediately breaks up into water and gaseous carbonic anhydride. when the acid exchanges : its hydrogen for the calcium. 1*529 (371) . compounds of metallic oxides with carone of the most abundant of which is chemically termed carbonate of lime. driving the water back into the open one. producing calcic nitrate. and it is less likely to reduce the oxide of lead contained . if the result is to be accurately examined. : Molecular Volume [ Sp. CARBONIC DIOXIDE. can be raised or lowered as may be necessary. Relative weight 22 . it is therefore easily separated from its salts by the addition of one of these acids. carbonic anhydride is expelled as a colourless and transparent gas. and some powerful acid. e. diluted with 8 or 10 times its bulk of water.

t becomes necessary.Pharni. and placed of the air-pump. by upon lime-water. in the vacuum which melts at The solidified anhydride 71 57 C. the only o'6p. ether. the liquid in the tul e will speedily be frozen into a clear. according to Regnault. or with the fixed oils . transparent gas. than air (Thilorier) . transparent. 10) the expansion of the liquid. Gaseous carbonic anhydride is not inflammable. however. it freezes into a snow-whi e and if a tube containing liquid carbonic anhydrix e be plunged into a bath of the solid anhydride mixed with ethe solid (196) : >*. Limestone. an excess of evi n carbonic acid has the same effect. oyster-shells. Under the ordinary pressure of the atmosphere Properties.116 CARBONIC ANHYDRIDE. with a faintly acidulous smell and taste. agitated with the gas. whilst at is 86 (30^ C. allowed to escape into the air. 0*893 a * IO ^ and 0*779 a ^ 2 5'4 ^.) tjie If these data be correct. other Many gases. oil of turpentine. its some additional afforded is action . pearlash. Iceland spar. dride when acted on by a strong acid.) ( heavier than the liquid portion in which it is being formed. of heat four times more rapidly liquid expands by the application to Andreeff (Ann. but when generated in a confined as trans- space in strong vessels it becomes condensed to a liquid parent and colourless as water. Chem. is immediately rendered milky from tl e formation of chalk by the combination of the lime with the "ca bouic anhydride a few drops of any strong acid dissolve t ^e chalk and restore transparency to the liquid .Liquefied carbonic anhydride does not mix freely with water. but according gravity ex. .). test. naphth i. sodic carall yield carbonic anhy- Carbonic anhydride is also produced when carbon or carbonaceous substances are burnt in oxygen or in atmospheric air. When a stream of the liquefied bocy disulphide. but it is dissolve d in all C and carbonic is proportions by alcohol. carbonic anhydride is a colourless. ice-like mas i. At 32 (o C. '^ at ! 5 5 density of the liquid 0*947 at o C. although greater than that of Andreeff found tie the gas. Such a te . is not so great as Thilorier states. have the same property . therefore. whi n which. neither w: it : is 11 support the flame of burning bodies the extinction of a tap r is one of the means frequently resorted to for detecting its pr :sence.) it requires a pressure of It 38 '5 atmospheres to retain it in the liquid state (Faraday). CaCO 3 + 2HCl=CaCl 2 + H 2 O + CO 2 . and the carbonates generally. which. . bonate. then has a specific specific gravity of 0*83. boils at 108 ( 78 C.

and 760"*' weigh 1*977414 F. i is more than half as heavy again C. 304. Gaseous carbonic anhydride as atmospheric air. and in several extreme cases it exceeded 2'O per cent. increases if the pressure be increased . the liquid seldom takes up more than two-thirds of its bulk. . Soc. as much as 078 per The quantity ot cent. weigh 47*445 grains . but in some cases it fell as low as i8'6. smaller quantities its depressing It reduces both the frequency and The ill effects experienced in power of the heart's action. when diluted with air. it may be breathed without even a suspicion of its presence. inches Bar. and this occurred in a crowded schoolroom. and may be poured from one vessel into another like water. the gas escapes with brisk effervescence. If the proexceed or cent. the gas is soluble in about its own bulk of water..* but partially also to the accumulation of volatile putrescible organic particles given off from the surface of the lungs and skin. Chem. and 30 or inches of it at 60 cubic 100 grm. from its density it may easily litre at o be collected in dry vessels by dis- placement. 265. No acid is definite hydrated carbonic known. both in the form of gas and in its denser conditions of liquid and solid. was 0-33 per cent. f If the gas be simply transmitted through the water. x. in the manner represented in fig. 304. FIG. and even in much effects are very injurious.) Angus Smith found on the average. * Advan- The maximum observed by Roscoe in his experiments on the atmosphere of dwelling-houses. being. It is the combination of these circumstances which renders attention to ventilation a matter of such high importance. but appears to be convertible into a true acid by solution in water. free from water. At and its ordinary temperature. however. (Q. crowded and ill-ventilated rooms are partly due to the presence of this gas in undue quantity. oxygen in the air of these mines gave an average of 20 per cent. J. the anhydride..PROPERTIES OF CARBONIC ACID. of air it the a narcotic acts as portion 4 per 3 for poison. by producing spasm of the glottis it is prevented from entering the lungs. (Regnault). it CO the 3 +H O 2 yielding H CO 2 3 . as its name indicates. .f but solubility is when this sud- denly removed. from the examination of 339 specimens of the air in mines. 117 Carbonic anhydride in its concentrated form is irrespirable.

as a solid or fixed constituent in limestone. combined with the presence of trac of organic impurities. Black. and the preference given to a beverage. The proportion of carboi n ic anhydride in respired air varies from 3 to 4 per cent. g . and from its becoi iing fixed or absorbed by solutions of the caustic alkalies. bei. even granite and the hardest rocks are disintegrated. from the c: rcumstance of its having been discovered by Dr. and in the laj:se of time it effects changes of great importance and extent. although its usual coolness and the abundance of atmoIt is t le spheric air dissolved in it are still more important. there are mai cases in which it is produced on a very large scale in nature. t le processes for procuring the gas already described. but few of them exist which are not to a greater or less extent impregnated with carbonic acid. in 17^7. attached to a reservoir filled with the gas. insignificant as it m ty at first sight appear.. is mechanically charged with a large quantity of carbonic acid. few finely divided minerals being able to resist its gradual and as long continued is action. as The briskness of spring water. which may or icater. solution of carbonic acid in water reddens tincture of litmus but the red colour disappears if the liquor be boiled for . are yet far more extensive thun those of pure water. though in many instances extremely feeble. taken of this circumstance in the preparation of sodaFor this purpose the water. which renders the taste of boiled or d tilled water flat and insipid (345). may not contain soda or other substances in solution. This fact y be easily proved by forcing air from the lungs by means of a m tube through lime-water. absence of these qualities. Respiration in man and animals is always attended wi h the formation of a large proportion of the gas. LB partly occasioned by the carbonic acid which it it contains.118 tage is NATURAL SOURCES OF CARBONIC ANHYDRIDE. which will speedily become milky frc the deposition of calcic carbonate. owing to the expulsion of the gas. y i. The excess of the gas thus forced into the liquid occasions the agreeable briskness and pungency so much prized in this beverage. By the continuous action of water charged with carbonic acid. the solution. A. The aqueous solution of the acid possesses solvent powers which. dissolved in natural waters in many The proportion of gas instances very minute. either by absorption from t'ie atmosphere or from the soil. as it is called. 2s s- Carbonic acid was originally termed fixed air. usually about 3^ per cent. Besides (372) Natural Sources of Carbonic Anhydride. by the use of a condensing syringe. is continually proceeding. a few minutes.

The pure water of Loch Katrine. contain but small quantities. whilst the oxygen had diminished to a similar extent. - . 3. The carbonic acid met with in spring water is in many 4. in our own country. and the gas escapes with effervescence when they reach the surface. per litre. has lain down in the stream tempted by of air proceeding from it. and of Tunbridge. 119 Carbonic acid is also formed abundantly in the process 2. of fermentation. by the oxygen of the air which all waters naturally contain. Spring waters which rise in a sandy district. the oxygen gradually decreases. warm room. for example. By the operation of subterranean heat upon the limestone beneath the surface in certain volcanic districts. the surface of which is sparingly clothed with vegetation. or o o6 cubic inch. per litre. the springs in such districts are also frequently highly charged with it. and from which consequently they can take up but little organic matter. on the Continent. rose to i'34 c. quantities are discharged from open craters or from fissures and cavities in the soil. immense. is and the somewhat more than one-half in closed If such waters be kept that of the nitrogen. and has slept to wake no more. leave scarcely any residue on evaporation except a little organic matter . when first collected did not yield more than o 22 cub. and is the cause of the briskness in bottled beer. they are very free from carbonic volume of the oxygen which they hold in solution acid. centim. Many a poor houseless wanderer. and other fermenting liquors. exhibit this. carbonic In the operation of burning lime in the lime-kiln. a warm weeks in vessels for a few room.phenomenon. c. The springs of Seltzer. Pyrmont. Many accidents have occurred from persons incautiously descending into an empty fermenting-vat before the gas has had time to escape and mix with the air it is usual to facilitate the escape of the dense gas by leaving the plug at the bottom of the vessel open for some : hours. and its place is supplied by a corresponding volume of carbonic anhydride. instances derived from the gradual oxidation of the vegetable and other organic matter which it holds in solution. such as those in the northern parts of Scotland. The lake waters from the primitive districts. large volumes of carbonic anhydride are continually finding their way into the atmosphere . the anhydride expelled from the limestone by the heat escapes in large volumes.FORMATION OF CARBONIC ACID IN WATER. champagne. of carbonic anhydride per gallon but the quantity of this gas which the same sample yielded after it had been kept in a closed vessel for some weeks. often mere in a . and Marienbad. the warmth of the kiln.

by either of these contrivances the cont nts of the funnel can be admitted to a wide thermometer-tube each portion of w ich which must not be less than 30 centim. a is a cylindrical funnel of a capacity of about 30 cub. analysed. may be effected with sufficient accuracy for most purposes in the following manner : Supposing that the gas had been collected over either water or mercury. " by which the manipulation of the instrument is facilitated. and the quantity of carbonic acid contained in such waters is always considerable. whilst the quantity of oxygen which they hold in solution is proportionately The extent to which this change takes place in river reduced. 305. c. to allow of its introduction into the gas-jar . which gradually undergoes oxidation in the soil. To use the ins ru- . A or glass. as respired air. or a piece of vulcanized caoutchouc tubing compressed by a sc ew. of carbonic acid districts. become charged with organic matter. at c is a small stopcock of steel FIG. .* * The analysis of these gases or of any mixture of air with carbonic anhy- dride. such. Upon the boiird. asshown in t/ie figure. designed for effecting this transfer. such as those which rest more or chalk. it becomes necessary to transfer a portion of it from the jar in which it has been collected to the one in which it is tc be method of effecting this is shown in fig. 305. is simpler and less expensive . a d. . bee . centim. is fastened a pipette. (T cub.120 ANALYSIS OF AIR CONTAINING CARBONIC ANHYDRIDE. which is furnished at d ' ith a second screw clamp: b is a bulb of the capacity of about 16 c..) r from the u oper part of which proceeds another piece of thermometer-tube. whilst the springs of highly-cultivated less directly upon the traces. (12 inches) in length. this eat portion may Reconnected to the bulb b with a flexible joint of caoutchouc tub ng-. for example. n.

centim. those collected above the ment. the lower stopcock is closed . the plan recommended by Liebig is the simplest solution of i part of pyrogallic acid in 6 of water is prepared. occasion. the tube is again left at rest for a minute or two. h the gas should not occupy more than two-thirds of the capacity of this tube. throws or 12 drops of a solution of caustic potash (sp. the temperature and the pressure being observed as usual. and from the bulb b. and the oxygen is quickly and completely absorbed . which has been previously filled with mercury. The proportions of carbonic anhydride. On one some samples were taken from the in different points on the same day. h. (C'race Calvert. if oxygen be present. is extremity is raised above then opened. the stopcocks are both opened. which is sealed by the admission The water into the capillary tube. a. closed. e . and mercury escapes through d. It is well exhibited in the case of the Thames. c. is filled with mercury. and as soon as it c. Boussingault. is closed. The is The operator then agitates the contents of the tube by down the tube into the mercury. and the pipette. the operator. i'4) into the tube. river at low water at August. the mercury quickly displaces the air from the rest of the tube. this constitutes the body of the syringe. is begins to flow out at the open extremity of the recurved portion. h. d. or a small glass pipette with a recurved tube. is withdrawn from the jar. In order to ascertain the proportion of oxygen in the remainder. the gas is measured a third the difference between the second time. small quantity of carbonic oxide amounting to between 2 and 3 per cent. d. be transferred to the graduated tube. care being taken to bring the mercury to the same level within and without the tube . and occupies the place of the mercury in the bulb. The instrument being now full of mercury is introduced into the jar. the gas enters from e. the funnel. The difference indicates the amount of carbonic anhydride.SOURCES OF CARBONIC ANHYDRIDE. and the mixture briskly agitated the solution of potash. of the pipette. TO glass syringe may be extemporaneously prepared from a strong tube which softened in the flame of a lamp. easily ascertained in the following manner is to be carefully read off. provided with a plug of caoutchouc. and the absorption is noted by a second time reading off the volume of the gas at the proper level. of the volume of the oxygen is always formed in this operation. e. and whilst the mercury runs out into a vessel placed for its reception. becomes of an intense bistre colour. and the residue is estimated as nitrogen and third readings giving the volume of oxygen. whilst the piston is easily formed of a piece of glass rod. and as soon as the air has been displaced from the vertical portion of the fine tube. g . and its open the level of the water in the jar. and of oxygen are now The bulk of the gas in the tube. and on opening the stopcock. of about 8 or Supposing that cub. 1859. water is 121 very remarkable. and about 40 drops of the solution is by a fresh as before . b. by of a glass syringe. A . is it has thus been ascertained that a bulk of gas means up i o to be subjected to the analysis. the stopcock. standing in the jar of mercury. When a sufficient quantity has been admitted. Fresh mercury is poured into the of a little gas can now funnel. a. gr. e . as shown in the figure at i. taking mouth below the surface of the mercury this manoeuvre is : rapidly thrusting care to keep the several times re- peated in quick succession . containing the gas to be transferred. f. h. and withdrawing it.) : A . the bent limb of the pipette is introduced into the tube. the gas is expelled into the tube. pipette injected into the tube h. the tube is depressed below the level of the water in the jar. the stopcock. of : nitrogen. drawn off and recurved at one end. the stopcock.

metropolis being nearly free from contamination with sewerage products. it was in a pure condition. 2i'i C. similar experiment upon a sample of river water taken above Teddington Lock. within twenty-four hours from the time of its collection . 70 P. of river.122 SOURCES OF CARBONIC ANHYDRIDE. whilst those obtained lower down were The gases extensively impregnated with them. the results obtained are given in the following table. . in which they are contrasted with the proportions of each gas furnished by a where Temp. were expelled from each sample by boiling.

much Since a knowledge (373) Synthesis of Carbonic Anhydride. as also any carbonic anhydride that may he present . 7 123 a source of the gas. the proportion in which oxygen combines with carbon to produce carbonic anhydride has been determined with the greatest care. the heat is then to a red heat d. diamond or graphite . in a stream of dry oxygen. by the combustion of weighed quantities of diamond. d. . The apparatus employed for this purpose is indicated in fig. anhydride is produced abundantly . A represents a gas-holder filled with pure oxygen . of the composition of carbonic anhydride is a fundamental datum for the analysis of organic compounds. The carbonic anhy- oxide . oil. the front of the tube. c d is a tube of hard glass traversing the sheet-iron furnace. whilst the fore-part of the tube means of heated charcoal . this liquid will be immediately rendered milky. for removing all traces of moisture from the oxygen. is occupied by a column of cupric oxide. or tallow. c. converted into carbonic anhydride. 306. A. B a tube containing fragments of caustic potash. two candles duce about as in burning may be estimated to pro- carbonic anhydride as one man would emit by respiration during an equal interval of time. or about 1260 cubic inches (2O'6 litres) per hour.SYNTHESIS OF CARBONIC AN HYDRIDE. E. but in which no deposit of moisture is formed if the experiment be properly conducted. At c is a platinum tray containing the weighed FIG. is interesting as throwing light upon its Whenever charcoal. like wood. According to coal. if the gas. the object of which is to oxidize completely any trace of carbonic oxide which might be formed. filled with calcic chloride. contain or in Angus Smith. which traverses the column of heated cupric if water were is a weighed tube. after the combustion has terminated. be agitated with lime-water. where the carbon lies. and allowing of the gas to pass through the whole apparatus. which. carbon. of graphite. chemical nature. 306. F present. is portion of brought by The carbon burns and becomes applied to the spot. The apparatus is filled with dry oxygen by a gentle current partially opening the stopcock of the gas-holder. or bodies which. would be found to increase in weight. are burned either in oxygen carbonic air. and of charcoal.

27*28 72-72 i? 2 32 44 72-72 . 12 or 27-28 Dumas. loo'oo . although they differ entirely in properties .. but if a succe. : Carbon may again be extracted from carbonic anhydride. but before it is allowed to escape into the air it is rendered perfectly dry causing it to pass through an additional by tube.. but in their molecular arrangement.. whilst the amount of carbon burned is ascer- tained by weighing the platinum tray and its contents when the experiment is terminated. whilst carbon is liber. If a piece of pure carbon be burned in a of oxygen over jar mercury. to be a compound substance.. loo'oo . and is absorbed by a strong solution of potash contained in the bulbs of the The excess of oxygen absorbs Liebig's apparatus. Potassic oxide will be formed at the exp mse of the oxygen which the gas contains. the potassium will continue to \ urn with great brilliancy.. If a small piece of potassium. . 5). . be introduced by means of a platinum spoon into a jc r of gaseous carbonic anhydride. both synthetically and analytically. By experiments conducted upon this principle it has been determined that 13 parts of carbon require exactly 32 part? of oxygen to convert it into carbonic anhydride (Dumas and Si... the differences in properties arising not from differences in their chemical nature... shown at G. and charcoal are thus shown to be chemisame substance.. 2 Carbonic anhydride is not decomposed by such elevatk a of temperature as we can obtain in our furnaces. moisture as it passes through this liquid.. Sulphur.. ted. chlo ine.as .. it will be found after the combustion is over. and the gas has cooled to the original temperature of the oxygen. filled with fragments of caustic potash.. graphite. heated till it begins to burn in the r air. consisting of carbon and oxygen. . The increase in weight acquired by the two tubes G and H furnishes the weight of the carbonic anhydride corresponding to the carbon consumed. that the volume of the gas has undergone no permanent change the carbonic anhydride formed occupies therefore the same vol ime as the oxygen it contains. these three conditions being allotropic modifications of carbon (87). as may be seen in the black particles which are suspended in the water into which the spoon Thus carbonic complete.124 COMPOSITION OF CARBONIC ANHYDRIDE. C 2 Oxygen Carbonic anhydride C02 = = = By weight. dride passes on. .. and its composition may be represe ited is as follows : Carbon . i. cally the Diamond. plunged after the combustic a is anhydride is shown. and free oxygen. Ann. sion of electric sparks be transmitted through the gas it is part ally separated into carbonic oxide. de Chimie [3]. By . vol. H..

the other opening its for the escape of the gases. Sir G. and in a month from the commencement of operations the fire was found to be completely extinguished. with the exception of those of the alkali-metals are insoluble in water. Subsequently. and strontium.000 cubic feet. into the mine a current of jet.GENERAL PROPERTIES OF THE CARBONATES. and are deposited . and from the vast mass of heated matter. which. was regarded as monobasic. and then. cold air mixed with the spray was blown in. takes which place being represented thus. barium. obtained by forcing a stream of : air through a coke furnace into the mine. pours by the agency of the steam impure carbonic anhydride and nitrogen. one for the entrance. and extended over an area of 26 acres. Gurney.000. had been for 30 years on fire. so as to fill the entire workings with the he has thus on several occasions succeeded at a very small gas expense in extinguishing years. magnesium. but there is now no doubt that it ought to be considered a dibasic acid. closes necessity abandoned.' situate about seven 22. it forms a numerous and important class of salts called carbonates. and convert it into carbonic oxide (375). and particularly those of calcium. the conflagration the ordinary means of checking not unfrequently resists all ravages.500 cub. of gas were required to fill the mine. and many of the metals. 1851: It occurred in a seam of miles from Stirling. metres. various causes. or 226. the necessary reduction of the temperature. in such cases. nine-foot coal. fires which have raged unsubdued for very remarkable case of this kind was mentioned in the Times for The 'burning waste of Clackmannan. such as iron and zinc. water was blown in along with the carbonic anhydride in the form of a fine spray or mist. many acres of subterranean fire are thus produced. CO 2 -4. until comparatively lately. 125 and the halogens may be heated with the gas without decomwith hydrogen and exposed to a high posing it . (374) Carbonates. yet the fire was success- A May fully extinguished about 8. but if mixed carbonic oxide are formed. Gurney has turned to an Applications. every mine but the into two. many of the insoluble carbonates. and the workings are of Sir G. also remove a portion of the oxygen from carbonic anhydride. however. at different times and from of extinguishing flame. are liable to take fire. Although but a feeble acid. : Carbonic acid. may be dissolved to some extent by water charged with carbonic acid. as in cooling down the ignited mass so that In order to effect it should not again burst into flame on readmitting the air.H 3 = position CO + H 2 O. important practical account the property possessed by carbonic anhydride Coal mines. the decomand water temperature. Carbon. not so much in putting out the fire. and a continuous stream of impure carbonic The difficulty lay anhydride was kept up night and day for about three weeks.

such potassium and sodium. their solutions give with calcic salts a white precipitate..CuH 2 C.CuCO 3 [CO(OCuOE)J.. 2CuC03 . as malachite If and M' represent the M (CuH O 2 .jC03 . basic salt of lead/ such as the subnitrate or the subacetate this The instantly rendered milky by the action of carbonic acid. such other to combine tendency as dolomite. MHCO 3 3 [CO(OM) ] [CO(OH)(OM)] [CO(OM)(OM')] the MM'CO3 The following portant carbonates table represents : composition of some im- Potassic carbonate K C0 H ( 2 3 ... : cate test of the presence of free carbonic is acid is a solution of a .CO .. the general formula of the carbonates will be thus indicated as Normal salt. Trona (sodium sesquicarbonate) Amtnonic sesquicarbonate Baric carbonate Calcic carbonate .. for example. again in a crystalline form as the gas escapes slowly from the All the carbonates are dissolved with effervescence by liquid. which is a double carbonate of calcium and magnesium (MgCaaCOg) bonates are also CO ^Z (O Ca")(O Mg)" L UU J 3 a I . . with the evolution of carbonic anhydride. ( > 2[(H 4 N) 2 CO ]. Many basic 3ar- known : they are often hydrated compounds such..126 GENERAL PROPERTIES OF THE CARBONATES. and even by acetic acid the gas which comes renders lime-water turbid and possesses the other The most delicharacteristic properties of carbonic anhydride. are decomexception posed by prolonged ignition. the salt being resolved into the The carbonates have considerable anhydride and a metallic oxide.. BaCC CaCC Magnesic carbonate Dolomite Baryto-calcite MgCC MgCazCC BaCaaCC .. 2 ) atom of any two : different metallic monads.. which is immediately redissolved by an acid. . dilute nitric acid. . off is colourless.CuH 2C ] . j Malachite Blue carbonate of copper CuC03 .. '. of those of the alkali-metals and of barium. M CO 9 Acid salt. vith All the carbonates. Double salt. ioH 2 ( KHCO NaHCO 2Na^C03 . carbonates of the alkali-metals are also decomposed by acids with effervescence.. with each and form double salts. Sodic carbonate Potassic hydric carbonate (bicarbonate) Sodic hydric carbonate (bicarbonate) Na.H2 C03 2H2 . .

0-9688. in which it is but slightly soluble. whilst carbonic when reduced metals. Carbonic oxide is often produced abundantly in the ordi: nary process of combustion in stoves and furnaces this mode of its formation is important. when The chalk. and may now be collected over water. but if some deprived metal which has a less powerful attraction for oxygen. whilst the carbonic In order to remove any oxide passes off in the gaseous state. moves half the oxygen. lead.CARBONIC OXIDE. 127 CARBONIC OXIDE: 0-9678. Gr. many metallurgic operations the carbonic oxide so produced plays a conspicuous part in the reduction of the ore to the while in metallic state. The chemical changes which take place when zinc is used may be represented in the following manner: CaCO 3 + Zn = CaO + ZnO + CO. It anhydride oxide that anthracite can be employed in roasting the copper the process. will be produced. termed carbonic oxide. C + 2 O = 2 Carbonic oxide may be prepared by mixing Preparation. exposing the mixture to a red heat in a gun-barrel. the oxides of iron. splits up anhydride. Carbonic oxide. CO = 28. a new gaseous of this The bulk gas exactly equal to that of the carbonic anhydride that furnished it. and body. forming oxide of iron or zinc which remains in the retort mixed with the lime. mixed with free hydrogen. is also is new obtained abundantly when steam is transmitted over charcoal heated to bright redness. III. inasmuch oxide thus carried off as all the carbonic un burnt represents so much fuel wasted . and H CO+H . carbonic anhydride that 2. Vol. flame being essential to the due performance of The formation of carbonic oxide in an open fire is burning steadily without emitting smoke is often shown the by flickering blue flame seen playing over the glowing embers. J 4- Observed Sp. I. is may have escaped decomposition the gas washed with water containing slaked lime in suspension. In this case carbonic anhydride is first formed at the bottom of which . ores at Swansea. copper and many other heated with it. be substituted for the potassium. Theoretic Sp. MoL |"~r"h EeL wL nas been stated that carbonic anhydride is wholly (375) its of oxygen when heated with potassium. Gr. the latter of which is decomposed by the heated metal this re. being is owing to the production of carbonic is formed. and into carbonic quick-lime ignited. powdered chalk with an equal weight of iron or zinc filings. for it exercises a material influence upon the economy of combustion. the metal will deprive it of exactly half the oxygen which it contains. the carbonic anhydride will only be partially deoxidized . such as zinc ^ or iron.

Potassic sulphate. + 2KSC + >b- Another method by which carbonic oxide may be tained with facility consists in heating oxalic acid with 5 01 The oxalic acid is thus times its weight of oil of vitriol. the grate. represented Carbonic oxide may be prepared in the laboratory by passing a stream of carbonic anhydride over charcoal heated to redness in : = an iron tube. 3. from the free access of air to this part of the burning fuel. but is expressed by the anne: ed 1 symbols : Potassic ferrocyanide. thus : Sodic formiate.128 PREPARATION OF CARBONIC OXIDE. if heated in a retort with 4 or 5 ounces (140 grms. oil of vitriol. or with milk of lime. . because gas (Fownes). Sulphuric acid. Sulph. 2NaCHO 2 2 + + H SO4 =7cO~+ 2 Na^SO^ 2 S( |cO(ONa) 4. Water. If a formiate be treated with oil of vitriol.) of the yellow prussiate of ways. and the anhydride losing half : : - CO 2 + C aCO. and is resolved into a gase ms mixture consisting of equal volumes of carbonic anhydride nd carbonic oxide by allowing the mixed gases to pass throug a . case of a complicated nature. Water. when the temperature rises to a certain point the evolution of he' The reaction is in t lis takes gas place with tumultuous rapidity. Carbonic oxide. Carb. yields more than a gallon (4 or 5 litres) of the pt re Care is requisite in applying the heat. Bodic sulphate. : i vessel filled with a solution of potash. 6CCT 5.he . oxide.) of potash. V OH ) 2 = 2CO + S0 also (ONa) 2 otl er Carbonic oxide may be prepared in several Half an ounce (15 grms. its oxygen. Ammonic sulphate. pure carboric is oxide obtained. The reaction between the hot carbon and carbonic anhydride may be this. acid. but the carbonic anhydride as it traverses the red-hot coke enters into combination with an additional quantity of carbon. 6 le- prived of the elements of water. is converted into its own bulk of carbonic oxide at the same time the carbon of the heated fuel which has entered into combination with this removed oxygen furnishes an equal volume of the same gas the heated carbonic oxide takes fire as soon as it comes in contact with the air which passes over the upper surface of the fire. Ferrous sulphate.

and the purified carbonic oxide collected over water in the usual way.PREPAEATION AND PROPERTIES OF CARBONIC OXIDE. which can be mounted or dismounted in a moment. II. Properties. three times as much carbonic oxide is obtained from the same weight of oxalic acid. D a moveable gastight joint is thus obtained. having a specific gravity of 0-9678. oxide. anhydride. oxide. c. almost the whole of the carbonic anhydride present is converted into carbonic oxide. fig. and pusses to the bottom of a wider tube. of washing the gas is shown at B. 129 may be may be carbonic anhydride is absorbed.OH. at . A. obtained acid. which may be purified as above described. Carb. = CO + C0 9. lEoa -!LO =~oo fCO(OH) JCO(OH) . 307. The decomposition thus explained Oxalic acid. All attempts K. by this modification of the process. open both at top and bottom. Carb. with a faint oppressive odour. A convenient mode is : the bent tube : FIG. Carbonic oxide is a transparent colourless gas. If the gaseous mixture of carbonic anhydride and carbonic by heating oxalic acid with concentrated sulphuric be passed through a tube filled with fragments of charcoal and maintained at a red heat. 307 connected to the neck of the retort. : Water. which passes into the washing bottle. It is much lighter than carbonic anhydride.

Therefore 2 vols. of oxygen to convert them into the anhydride. then add 20 measures of rare oxygen . but if the liqxiid be boiled most of the gas is expelled unaltered.) air.130 its PROPERTIES AND COMPOSITION OF CARBONIC OXIDE. Carbonic oxide unites with an equal volume of chlorine ui der the .Cu 2 Cl 2 . If a little of solution be introduced 20 30 potash measures of the residual gas will disappear. The compound with cuprous chloride crystallizes in fatty looking scales. : bonic anhydride. A solution of cuprous chloride in hydrochloric acid. It is but very liquefaction have as yet been unsuccessful. Carbonic oxide therefore must have contained the other 10 measures of oxygen. in this soluble 100 volumes of water. consisting of (CO. and producing carbonic anhydride.2H 2 O). of carbonic oxide cor tains . the influence of sunlight. in other words half its bulk of oxygen. ures of unaltered oxygen the 20 measures of gas absorbed are car: I . or half their bulk. sparingly liquid dissolving When only 3*28 volumes at 32. 287) a certain quantity. convertii g it series of compounds : . forming carbonic oxydichloride phosgene gas. gradually absorbs carbonic oxide if agitated with it. it acts as (Bunsen). Now carbonic anhydride contains its bulk of oxygen. forming a compo md This property is sometimes employed of the formula K 2 C 2 O 2 for separating carbonic oxide from other inflammable gases in the process of analysing mixtures of such gases.) in the gas. This solution is not decomposed by dilution. be in the following manner ascertained Introduce into may the bent eudiometer (fig. burns with a beautiful pale blue light. or a )f numerous into even enters directly into c imbination with potassic hydrate when heated with it. a direct poison. leaving 10 mea. CO + C1 2 =COC1 9 Carbonic oxide has been supposed to form the radicle . but the 20 measures of carbonic oxide hav own - re- quired only 10 measures. say 20 : J measures. combining with oxygen. of carbonic oxide. or of a cuprous salt dissolved in ammonia. even although largely diluted with C. pass the electric spark with the precautions air ^ady described the 40 measures of gas will become diminishe to measures. Carbonic oxide is absorbed by potassium if the mstal be heated to about 176 (80 C. but tightness of the head. which are quickly decomposed by exposure to air. and 2*43 at 59 (15 respired. it potassic ( formiate KHO+CO = KCHO 2 [OKH + C3 = {cO(OK) Bertnelot )' The chemical composition of carbonic cude Composition. producing a peculiar sensation of oppression and It does not support combustion.

and carbonic anhydride.. widely as they differ in their properties. consist. : Carbon Oxygen Carb. of the same elements . Carbonic anhydride . Carbonic oxide of carbon that contains the smallest proporthe tion of oxygen.PREPARATION OF NITROGEN. it is evident. 16 131 of oxygen of oxygen. 12 or 42-86 16 57-14 By volume. i vol. but the proportions of the latter differ in the two cases. oxide = = CO = C O By weight. i ? i 28 loo'oo 3 Carbonic oxide. or 28 parts by weight of carbonic oxide contains and its composition may be thus represented .. relative composition of the two bodies being is the compound : Carbonic oxide .

moist When employed to remove the oxygen. which will resist a strong heat without fusion. of hard glass. and to the other is adapted a bent tube. /. A. state. or delivering the gas into a jar over water or mercury .' . The removal of oxygen from the air can also be effected 2. is filled with metallic copper in a finely divic id purpose the metal which has been reduced from the powdei jd oxide by means of hydrogen gas is well adapted.132 of oxygen : PREPARATION OF NITROGEN. has one of its extremities connected with a bent tube. if introduced into a jar is of air which standing over water. c. in which it can be surrounded by charcoal and raised to a red heat. for this fragments of fused caustic potash. The air first traverses the ti be containing the fused potash. and in two or three days nearly pure nitrogen will be left amounting to about four-fifths of the original bulk of the air.slowly in various ways. the nitrogen making its exit which by 5 and 6. by which the oxygen is co athe tube e. The tube. when cold. oxygen from a confined portion of air very rapidly and completely. filled w th state. ordinary temperatures. b. which rests 01 a sheet-iron furnace. Nitrogen may also be obtained by the action >f chlorine on a solution of ammonia (381). produce a similar effect. A stick of phosphorus. c. Moistened sulphides of the alkaline metals likewise abso rb 3. Moistened iron filings may be used for this purpose. the air which supplies iie nitrogen is driven from the gasholder. pletely removed. m i is easily regulated by the stopcock. where it leaves all traces of carbonic anhydride a id water. d. 4. over the ignited copper in a stre. and it is furnished in a state of purity by heating a solution of ammonic nitrite (38( De Luna obtains it by heating in a flask equal weights jf ). as is seen by the Many other metals in a rusty appearance which it assumes. e. exhibited in fig. such as lead shavings. metallic copper may be The method to be adopted in this case is 308 : a long straight tube. the nitrogen may be decanted into another and examined. and then passes over the ignited copper. the metal gradually becoming oxidized. larger quantities of nitrogen are required. will slowly absorb the jar at even oxygen.

or 100 cubic inches at 60 F. 100 volumes of water at o C. (377) IF a mixture be made of 4 measures of nitrogen and measure of oxygen gas. when united with water. a ordinary properties of the air. in short. of this gas at ordinary temperatures. somewhat . potassic dicliromate 133 and sal ammoniac. from liegnaulf s experimm ments. and with every act of inspiration it ' : . It is gas. such as quinine. at 15 (Bunsen). Nitrogen is a colourless. which is thus rendered less stimulating to the living system. morphine. it is never entirely absent from them.lighter than atmospheric air . it enters as a necessary component into the animal frame. intimately mixed (380). which has yet resisted every effort to liquefy it. extinguishes a taper without taking fire itself: an animal immersed in the undiluted gas perishes quickly for want of oxygen. it forms a number of highly interesting and important compounds. II. Organic compounds which contain nitrogen are frequently termed azotized or nitrogenous substances. the great bulk of which .. One very important purpose that in the atmosphere is the dilution of the oxygen. prussic acid and strychnine. and the rapidity of ordinary combustion is likewise thereby moderated. and 7 6o pressure weighs i '256 167 gramme. No two substances can offer a more striking contrast in chemical properties than oxygen and nitrogen the former one of the most It energetic of the elements. weighs 30*137 Water dissolves not more than a thirtieth of its bulk grains. Nitrogen moreover is the characteristic ingredient in ammonia . one of its compounds with oxygen. and 1*48 vols.PROPERTIES OF NITROGEN. a candle will burn in it as in atmospheric air. i litre ato C. it may be breathed like air. COMPOSITION OF THE ATMOSPHERE. which must be finely and powdered. and possesses the i The atmosphere is. absorbing 2*03 vols. 30 inches. and although it occurs in but small quantity in plants. and notwithstand- ing its apparent indisposition to enter into combination. and the potassic and spdic salts of this acid exist as natural productions. tasteless. It likewise enters largely into the composition of many animal tissues. Nitrogen is one of the most extensively diffused forms of matter. Bar. as must be evident from the facts just stated . it fulfils finds admission into the lungs. of nitrogen. but it is not directly poisonous indeed. Nitrogen also constitutes an essential part of many of the most potent and valuable medicines as well as of some of the most dangerous poisons. For example.. and inodorous Properties. mechanical mixture of several gases. forms nitric acid . the other the most indifferent.

The air was collected in A tubes of about 6 cub. in capacity. (Ann. extremity at either end. while air coiled _>d at the surface at the same time contained 20*92. that collected on the summit of the Alps. or 18. by moment. and were filled w the air for examination by opening the stopcocks. the tube was filled with air of the local! y.134 COMPOSITION OP THE ATMOSPHERE. air was collected at differ nt points of the earth's surface in glass tubes. ry contact with the flame of a spirit-lamp. the atmosphere has perceptible change in the composition of been observed since accurate experiments on the subject have been practised. by different methods of analysis. and 79*19 )f or by weight of 23*01 of oxygen. contained 2O'88 per cent. 385). 308) whilst the nitrogen was received into an exhausted flask. Air which has been freed from carbonic aqueous vapour consists. fitted with accur stopcocks. iii. are. one of these tubes was attached by a flexible tube to a small pair of bellows. centim. preser ts no sensible difference\from the mean above given. i 'id by working the bellows a few times. in one of the balloon ascents undertaken jy him and Mr. and that examini d both in town and country in various parts of the globe. [3] xxxvi. of oxygen by measure. 309. the quantity of oxygen was found by the gain in weight e:tThe results o )perienced by the tube containing the copper. drawn out to an open capilL ry When a specimen of air was to be collect d. in. : consists of oxygen and nitrogen these gases. balance of chemical actions over the face of the earth. tinually occurring upon and add a variety of other gases. aid These experiments were performed by allowing the air to stream slowly over a weighed quantity of heated copper. as at a and b. which was weighed before the experiment was commenced and after its termination.000 feet. by which the oxygen was absorbed (fig. Welsh. fig. that no difference in density. but the air brought by Ga/- Lussac from an elevation of four miles above the surface of the earth. amongst which carbonic anhyYet so wonderfully adjusted is the dride is the most abundant. and others. Trifling temporary variations no doubt occur from local causes. or 100 cub. Green under the direction of the Kew Committee of the Brit sh Association. In the extensive series of experiments te th as of Regnault (Ann.. Verver. . of oxygen by volume. They were exhausted previously to the ascent. portion of air collected by Mr. de Chimie. Brunner. which were again closed soon as the charge had entered. analyses of anhydride and careful according to the numerous Dumas and Boussingault vols. tained by Hegnault. notwithstanding their owing to the principle of diffusion (67). The capillary tubes were then drawn off and sealed. at an elevati fn of 5486 metres. do not vary more than T -^ from the quanti y of oxygen just mentioned. and the closed ends were protected f'r <ni . 1852. mixed uniformly which remove oxygen the earth's surface. Chemical operations are conwith each other. de Chimie [3]. 357). in August. on an average of 20*81 nitrogen in loo'oo 76*99 of nitrogen.

Th< 3 amount of aqueous . either of sulphurous hydrogen.. rain water and melted snow always contain a larger proportion of oxygen than the air itself. also present at all liable to extensi ve fluctuations. weighs 538*569 grain* The weight of a given volume of air at 60 F. ( 31*118 1*299500 1*299100 of Biot and Arago . according to this result. for it exactly with the density deduced from that of a mixture of corresponds and nitrogen in the proportions in which they occur in oxygen The second the atmosphere. and of some compound of carbon and hydrogen. a variable but minute trace of ammonia. In addition to oxygen and nitrogen. and 76o ram barometric - pressure. amounting to about 34 per cent... of Regnault's contrivance. and 76o pressure. 309. aiad one which could occur only in consequence of the air teing a mechanical mixture and not a chemical compound of the two* gases (64)..is a one volume of oxygen to two volumes of nitrogen. Aqueous vapour although its amount is or of sulphuretted of course. Bar.. . is therefore only -g-^ of that of an equal bulk of water at the same temperature. of Dumas and Boussingault . circumstance of great importance to aquatic animals. (378) Estimation of Aqueous Vapour. of the air dissolved. or -^-^ at o^ C. 135 The injury during the journey by small caps of glass tube fitted with corks. and frequently in towns a perceptible amount times. cubic metre of air. traces of nitric acid. mm at o C. under a at 60. analyses of the air thus obtained were executed by means of hydrogen. 20*96 of oxygen in air collected by himself from the summit of Mont Blanc. * A pressure of 30 inches Bar. .. weighs 1*2991 kilogramme. Welsh. Owing to the greater solu- bility of oxygen than of nitrogen. in a FIG. or nearly This.COMPOSITION OF THE ATMOSPHERE. eudiometer The following periments upon are results of some of the most trustworthy excalculating from the experiments Grains at 60 F. anhydride is. or a cubic foot under a pressure of 30 inches Bar. the weight of air. |sJ3i*ii7 g'J of Prout of Regnault si 131*0117^1 \3ro25 \ 1*292618 1*293187 result is probably the most accurate. 30 to. the atmo-sphere contains a certain proportion of carbonic anhydride. . 760 I at mm. Grammes o C. The same apparatus was used by Frankland found myself in the analyses of the air collected by Mr.

If the bulbs at b be filled with a stror'* < 1*25). the increase in weight will indicate the bulk of air operated upon. and the atmospheric. is filled . as shown by the dotted line which passes down fron experiment. fig. gain in weight experienced I y the tubes b and c will indicate the quantity of carbonic anh. or about of 1 8 water. vapour at any spot may be ascertained by means of the hygrometer (194). willi of fused the fragments potash. which terminates in a tube bent upwards 1o prevent the entrance of air at the bottom a known volume of air s thus drawn through the tube a. 310. gallors Th: s vessel having bee a filled with water. or it may be determined by a direct experiment in ' IG 310 ' the following - manfilled ner. it s not weighed. a. dride which has been absorbed in the operation the bent tub . whole course of the the central opening at the top. which retains all the moisture. with pumice-stone. carbonic anhydride in the air may be determined in the course if the same experiment. pressure s obtained by an observation of the barometer at the time. Tie flow of water from the aspirator is rendered uniform during tl e by making the tube whic i conveys the air sufficiently long to reach 'nearly to the bottom of the vessel. known suppose capait city be capable of contairing 80 litres. E. and the tube c. moistened with sulphuric acid. to s empty itself by slowly opening a stopcock. and a second time after it is completed. with pumice-stone moistened with sulphuric acid .136 ESTIMATION OP AQUEOUS VAPOUR IN THE AIR. The amount of moisture temperature is in tie ascertained by means of the thermometer. solution of caustic potash (sp. is cor nectedwith a vessel. but is merely interposed as a measure of precaution between the aspirator E. of . The quantity of (379) Estimation of Carbonic Anhydride. '. /. and the tube c. A bent tube. . allowed If the weight ot this tube be determined before commencing the experiment. t. gr. to prevent any ace d.

The bulbs seen at b are to be filled witb solution of caustic potash to the extent shown in the enlarged drawing. owing to the solvent action of the descending shower. Pettenkofer estimates the quantity of carbonic anhydride in air by agitating a given volume of the air for trial with a measured amount of lime-water or The lime or baryta-water used for this purbaryta water of known strength. besides side. for the purpose of absorbing gases which are transmitted through it . Angus Smith. It is more abundant in summer than in winter. the proportion of carbonic anhydride may.ESTIMATION OF CARBONIC ANHYDRIDE IN AIR. It increases during a frost. in metal and coal mines. and the quantity of lime or baryta which remains in the solution after the experiment is again determined by the solution of oxalic acid. Occasionally. is is less liable where it is generally to vary on elevated mounmore abundant. The quantity of ammonia and nitric acid in the atmosphere is materially diminished after long continued and heavy rains. and in rooms for public assemblies. pose is graduated by the alkalimetric method.000 of air. This form of apparatus was contrived by Liebig. from an examination of the air from a great number of mines. It is in continual requisition in the laboratory. It is less in amount over large bodies of water than over large tracts of land. carrying a poris amount tion of the gas with it to the earth. by means of a standard solution of tity of lime connect carbonic anhydride neutralizes and precipitates a certain quanor baryta in the form of carbonate. The before and after its action upon the air enables the operator to calculate the proportion of carbonic anhydride with great accuracy. being brought thoroughly into contact with the liquid in the narrow portions of the tubes which the different bulbs together. greatly exceed the normal amount. . The difference in the quantity of lime or baryta oxalic acid. During the night it increases.. however. De Saussure found that. its lessened after rain. The proportion of carbonic anhydride tains. from local and accidental ciralso more abundant open country. within these limits. 311. This has added contrivance to simple greatly precision in experiments of this kind. 137 dental trace of moisture from passing backwards into c. and diminishes when a thaw sets. found the mean amount of carbonic anhydride to be 0*785 per cent. fig. than in the plains. &c. and diminishes again after sunrise. The proportion of carbonic anhydride varies from 3 to in the atmosphere 6 parts in 10. in. It in densely populated districts than in the In inhabited dwellings. by placing it a little on one the gas is made to bubble up successively through each of the three lower bulbs.

( { and in towns Carburetted hydrogen Sulphuretted hydrogen r . . > traces . . P. J. . (380) THIS important compound has received the name < ammonia. ammoniac. Mo. in 100 parts by volume : Average Composition of the Atmosphere. traces of carbonic anhydride ar always obtained. . Gr. procured near the temple in Libya . COMPOUNDS OF NITROGEN. Chem. other gases and vapours are also met with. (-75C.) . Ammonia . of Hartshorn (H 3 N=i7. but ammoni .5 '04 Aqueous vapour Nitric acid \ 1*40 V traces . or otherwise carbonic anhydrid miyht be derived from them. Oxygen Nitrogen Carbonic anhydride 2O'6i 77"9. owing to the oxidation of some combustible compound of carboi 1 . The air cumstances. from the circumstance of its having been obtained froi f i a salt termed sal Jupiter Ammon. xi. COMPOUNDS OF NITROGEN WITH HYDROGEN AND CHLORINI Volatile ." ) CHAPTER X. hence its name. MeWng-pt. of towns contains in addition certain organic impurities in sus- Angus Smith has attempted to estimate their amount by measuring the quantity of a very dilute solution of potassic permanganate of known strength which a given bulk of air will Air in decolorize. -37 (-38 Gr. Alkali. In the junctions of the apparatus employed for this experiment the use of cor c and caoutchouc must be avoided (Karsten). ( sulphurous anhydride J 1 If air which has been scrupulously freed from carbonic anhydride be passe over a column of pure ignited cupric oxide. and Report on pension. Soc. Observed Sp. Nitrogen an first ( f I i hydrogen do not combine directly with each other. . . Boiling-pt. 0^59.) 0^5882. Mines. I. AMMONIA. or Spirit . J ) . / . C.) The average composition of the atmosphere in the climate of England may be approximately stated as follows. p. -103 Theoretic Sp. 1864. .138 COMPOUNDS OF NITROGEN WITH HYDROGEN. 53. 217. . (Q.

if exposed to the air. and iron exhibit this effect in a marked degree This reaction has been used as a means of estimating the quantity of nitric acid in solutions . The deoxidation of dilute nitric acid by the metals also frequently gives rise to the production of ammonia two atoms of . zinc. 381). and receives the distillate containing the ammonia into a known weight of a standard solution of sulphuric acid. also observed the formation of ammonia when nitrous acid and peroxide of nitrogen are reduced by transmitting them through a solution of hydric potassic sulphide (KHS) or of ferrous acetate. The hydrogen. rusty. is held in solution. Soc. for by dissolving zinc very slowly in dilute hydrochloric acid and adding the nitric solution in small quantities at a time. Soc. When a mixture of 2 volumes of nitric oxide and 5 of hydrogen is passed over spongy platinum or platinized asbestos Hadow has gently heated. Chem. of Schultze and Wanklyn and A still more delicate method is that of treating the solution containing the nitrate with metallic aluminium and a solution of Chapman pure caustic soda. 1862. Ammonia exists in minute quantity in the atmosphere. and indeed in almost every process of oxidation by air in the presence of moisture. the whole of the nitric acid is converted into ammonia.) Harcourt has improved upon this method (/. which contain both hydrogen and nitrogen. Chem. Q. he distils the concentrated liquid with caustic potash and a mixture of granulated zinc and iron turnings. is ]39 found during the spontaneous decomposition of moist animal matters. xv. which. at the moment of its liberation from the water by deoxidation. (Nesbit. oxygen changing places with four of hydrogen XT* M Nltncacld - : [N0 2 (OH) + 4 H 2 = NH (OH) 4 (387). become generated. 28 i . to a small extent. . Tin. and the oxidized compound retains a small quantity of ammonia. appears to enter into combination with the nitrogen of the atmosphere. i. If a current of nitric oxide be passed over a mixture of potassic hydrate and slaked lime.AMMONIA.. nitrates of potassium and calcium are formed. and thus ammonia is formed. water and ammonia are produced. while ammonia is Moistened iron filings. J.

products of the operation. also. Amongst these ' the ammoniacal liquor of the gas-works consisting o products an aqueous solution of carbonate and sulphide of ammonium . always contained in the water that is collected at the commencement of a showej than at the end of it. Barral found 3'49 parts. The atmospheric supply of ammonia is is intimately connected with tht assimilation of nitrogen by plants. in 1853 and 1854. upon this fact is based tlu usual method of determining the amount of nitrogen in organic For the purposes of manufacture ammonia is. c. on being transferred to a retort am . in short. If equal weights of quick-lime and either th< Preparation. crowded with animal life. the amount of ammonia was. circumstance which is easily accounted for by the high solubility of the gas ir water. and of animal refuse generally. 24*7 grms. 14 gallons of rain water. The proportion of Other experimenters make the quantity considerably higher. 1 found to be much higher than in rain water. . thii liquor when neutralized with sulphuric or hydrochloric acid furnishes ammonic sulphate or chloride (the sulphate or muriati of ammonia of commerce). they are decomposed. that a larger quantity of ammonia it surrounding districts. i. weather. greater.140 SOURCES OF AMMONIA. and Lawes and Gilbert. the powder. from September to February 0^927 parts the average of the last two determinations would give about I grair. also. unless present in the form 'of a nitrate or it freely. of the gas in I cubic metre of air. at Rothamsted.000. the smaller the fall. sulphate or muriate of ammonia be separately powdered and inti inately mixed. ammonia contained in rain water is liable to considerable variation : in 1. During the distillation o bones. It appears. eight million volumes of air. t\nproportion of ammonia in its atmosphere should be much higher than in tlu . ammonia is formed in con ever. and the whole of the nitrogen. in closed vessels. The proportion of ammonia ir water derived from the atmosphere is. and This amounts to about one volume of ammonia in twentyin 1850. and with the exuvia) of animals. is disengaged as ammonia . both oJ nitrogenous matters are heatec with the hydrated alkalies. of ammonia. 2 i'i grms. Boussingault has corroborated Barral's results by of ammonia in indeed it is not surprising that ir experiments upon the rain collected in Paris a populous city. in 1852. how compounds. . According to the elaborate researches of Ville. or about I gramme of ammonia in i. always ' sidcrable quantity and condenses along with the empyreumatu Almost the whole of the ammoni. found only 0^744 parts. or 0*035 c. in the year 1849. one million kilogrammes of air contained on the average. and more after a drought than after a period of rainy In the water of dews and fogs. used in the arts is is obtained however from bye products in th< distillation of coal for the manufacture of gas. at Liebfraunberg. which appear to have been conducted with every precaution to insure accuracy. Boussingault. found the average amount from March to August to be 1*142. cubic metre of rain water. o matters organic containing nitrogen. { When cyanide. Ammonia which absorb also found in clayey and in peaty soils.000 parts of rain water collected in Paris during the last five months of 1851. procured by the distillation.

monic salts a minute quantity of organic bases. the solution when poured off from the metal and cautiously 'distilled yields ammonia quite free from any organic impurity. with granulated zinc free from carbon. would yield about 750 cubic in. and traces of nitric If a mixture of ammonia and air or oxygen acid being formed. owing to the oxidation of the ammonia by the ozone. but a jet of the gas directed across the stream combustible . and water being formed chloride is used admitting of representation as follows acid . as the gas has little more of ' than half the density of atmospheric air. of collecting it may easily be effected. of the peculiar. dense white fumes of ammonic nitrite are formed.. burns with a very pale greenish yellow flame. Ammonia is extremely soluble both in alcohol and in water. (Stas. water and nitric acid are If a stream of ozonized air be passed amongst the products. Ammonic chloride. feebly of hot air issuing from a lighted argand lamp. . being only . and. 312. pungent odour of smelling salts . Water. 141 gently heated. i ounce of ammonic chloride.PREPARATION AND PROPERTIES OF AMMONIACAL GAS. is fatal to life from its irritating In a more diluted form it is a highly valueffects on the lungs. or The lime combines with the 30 gnus. equal means of the electric spark . when ducing breathed in a concentrated form. Calcic chloride. and sets the ammonia at liberty. about 12^. water. as a transparent. CaO + 2H 3NHC1 = [CaO + 2NH 4C1 = CaCl 2 + OH as thus prepared from commercial am. or by The latter mode displacement in the manner shown in fig. does not support the flame of burning bodies. the result when ammonic calcic chloride. colourless gas. able stimulant. : Lime. if fully decomposed. bulk of If the gas be the mixture be passed over spongy platinum. gives off abundance of pure ammonia.litres of the gas.) Ammonia possesses a very pungent odour inProperties a copious flow of tears it has an acrid taste. and iron wire which has been ignited in contact with the air and subsequently reduced in a current of hydrogen . an atmosphere of oxygen. which renders it necessary to collect it either over mercury. nitrogen. but absocontains invariably ammonia may be obtained by digesting a solution of lutely pure Ammonia potassic nitrite and potassic hydrate. gr. and it can be kindled readily in is Ammonia mingled with an be detonated by may oxygen. its sp. Ammonia. into a bottle containing a small quantity of a concentrated solution ammonia.

By a cold of . and then hermetically sealed . ai d sodium. produces This proa white cloud. TJ e argentic chloride re-absorbs the liquefied ammonia at ordinary temperaturi ->.) (Andreef). exerts a pressure of 6'p atmospheres at 60 (15' 5 C. brought perty is often employed to detect small quantities of ammonia slaked lime or potassic hydrate is added to the solution suspecte I to contain ammonia.75 C. which is denser than the liquid. and stopper inserted after having been Ammonia slightly greased. it is frozi n to a white.112 O'59. and turns When collected by displacement.103 ( . the gas must be allowed to pass into the bottle until a piece of dry turmeric paper held to the mouth is of the bottle is . the most powerful and forms salts. lithium.) (Regnauli 37'3 ( s ). Ammonia turmeric paper brown. 312. rapidly absorbed. FIG. and the chloride increases in weight more thf a This substance is placed in one limb of a strong tube bent to a is >. or still more readily by generating it under The easiest method is the following pressure. and slowly reproduces the original compound. immethe diately turned brown the tube then is withdrawn..). and the mixture is then gently warmed in i : into an tube a rod moistened with hydrochloric acid diluted with hal f its bulk of water be now introduced into the upper part of the tube or vessel. < . white fumes will make their appearance if ammoni i . if be present even when the quantity is too small to be dis When ammoniacal gas is required in i tinguished by the smell. Argentic chloride in powder the is exposed to a current of dry ammoniacal gai . like many other saline compounds. ammonia one-third. Any a very important class of volatile or gaseous acid atmosphere containing ammonia.). Liquefied ammonia possesses t e property of dissolving the alkaline metals. and has a specific gravi y of 0-6362 at 32 (o C. potassium. for this salt. and not over calcic chloride . obtuse angle.). has a powerfully alkaline reaction. translucent. absorbs ammonia and forms with it a definit 3 compound.. Ammwniacal gas may be liquefied by exposure to a cold f 40 (40 C. the ammonia condensed as a colourless liquid. crystalline solid. which boils at 38'5 C. neutralizes acids. state free from moisture it must be dried by passing it over quid lime. from which the metal is deposit d peculiar unchanged on evaporation of the ammonia. owing to the formation of a solid salt. PROPERTIES OF AMMONIA. . on applying heat to the chlorid and cooling the other end of the tube with a freezing mixture. forming beautiful blue solutions.

3011765 14 17 3 1 82*35 Ammonia . N decomposed into If a solution of into water 4 ammonic 3 : nitrite : decomposed represented. measures of hydrogen combine with i measure of oxygen. it is water and nitrous oxide. no change of bulk will occur. or 3 measures. 2 Other striking proofs of the composition of ammonia are afforded by the action of heat upon some of its salts . after adding 8 measures of this mixture to four of oxygen. follows If the as dry gas be subjected to a succession of electric : sparks.. the salt is the result may be thus the hydrogen of the am- . when ammonic nitrate (H 4 NNO 3 ) is heated. or 6 measures. and two-thirds. for instance. the gas is decomposed. to consist of a mixture of 2 volumes of nitrogen with 6 of hydrogen. . By . The composition of ammonia may therefore be thus represented . whilst 2 measures of nitrogen remain unacted upon 2 measures of nitrogen must therefore have been present in the ammonia in combination with 6 of hydrogen which have become condensed as steam consequently. HN 3 ioo oo - . 143 The composition of ammonia may be ascertained Composition. the 4 atoms of hydrogen in the ammonium combining with 2 of oxygen in the nitrion. and the gas produced may be shown by detonation with oxygen in a eudiometer.. the electric spark be transmitted. so as to make 12 measures in the whole. or if it be passed slowly through a porcelain tube containing iron or copper turnings. heated to bright redness. H NNO =2H O + N 3 and nitrogen 2 be heated. but on the addition of pyrogallic acid : (note 372) to the gas whilst still in contact with the alkaline liquid. the nitrogen of the ammonium as well as that of the nitric acid uniting with the remaining atom of oxygen producing nitrous oxide. By weight. since the ammonia doubles its volume when decomposed by heat... will be oxygen.. : Hydrogen Nitrogen H = N = 3 . vol. . owing to the formation of steam and its Since in the formation of water 2 subsequent condensation. and at the same time becomes dilated to double its original volume 4 volumes of ammonia become 8 . the excess of oxygen will be absorbed.COMPOSITION OF AMMONIA. condensed into half their bulk.. onethird of the volume of gas which has disappeared. consequently no carbonic anhydride can have been formed . If.. the 4 volumes of ammonia must have been formed by 6 volumes of hydrogen and 2 of nitrogen.. On agitating the residual gas with a solution of potassic hydrate.. This will amount to i measure. 2tI 2 O + 3 O.. will be hydrogen. from a Ruhmkorff's coil. 3 measures will be left.

is a reagent continually required in the laboratory. and with great regularity (Corenwinder). gr. and when wanted for the preparation of nitrogen. Carius found that wate takes 1 up about 1050 times its volume of the gas. Under certain circumstances it produces the detonating compound known as chloride of nitrogen (3 83). forming water combine with the this is an excel: When nitrogen is to be of procuring pure nitrogen. if it be left slightly alkaline. times its volume . is monium lent in this case exactly sufficient to oxygen of the nitrosion (NO 2 ). at 59 (15 C. and becoming specifically lightei The following table indicates the strength of solutions of pur 3 . at a temperature of 32 (o C. Ammoniacal Chlorine also decomposes liberates nitrogen gas. and at 77 727 (25 C. A solution of ammonia in water (381) Solution of Ammonia. 1*25. may be preserved without alteration. gr. inin bulk creasing nearly one-half. the most convenient method of obtaining the potassic nitrite for this purpose is to saturate a solution of mode caustic potash of sp. acting upon starch with nitric acid of sp.) (Carius.). 1*38. ammonia at ordinary temperatures.) 586 times its volume to Roscoe and Dittmar water saturated with ammoni according at i : i (16 C. and gently heated in a small retort nitrogen is evolved abundantly. 6o'8 ammonia of different specific gravities : Strength of Solutions of Ammonia Ammonia at 57'2 (14 C. prepared in this way. and gas is rapidly absorbed by water with considerable development of heat.) . Nitrogen may also be prepared by heating an intimate mixture of finely powdered ammonic chloride and potassic dichromate in this case the reaction is thus represented: K 2 Cr2 O 7 : .) contains 0*582 of its weight of the gas.144 SOLUTION OF AMMONIA. may be mixed with three times its bulk of a saturated solution of sal ammoniac. with nitrous acid disengaged by This solution.

which occasions the pungent smell of the liquid. destitute of odour. thereby furnishing a ready extempore method of proOn heating the liquid for a long time. first. in a concentrated form it and blisters freezes at about 40. is whole of the ammonia water in the retort. ammonia expelled rapidly by heat. is colourless and intensely alkaline the skin if . c. may be driven off. has an acrid. the curing the gas. may be employed for preparing a solution of ammonia on the small scale in the laboratory. 145 it ammonia . a small quantity of water placed. taking care that it shall not fill more than half the capacity of the bottle. E. whilst the second contains water to condense any gas that may escape through the II. a quantity of water equal in weight to that of the sal ammoniac used is introduced. which is an excellent one where a similar to FIG. liquid has to be saturated with any gas. B (which may be kept cool by immersion in cold water). Each bottle is provided with a safety L . B. applied to it yielding a gela- tinous mass. 313. are known by the name of is in the globe.SOLUTION OF AMMONIA Solution of WOULPE S BOTTLES. with the appearance of ebullition. caustic taste. Simple exposure of the solution to the air at ordinary temperatures is attended with an escape of The the gas. The retort is then connected with a series of bottles The those used for condensing nitric acid (386). The three-necked Woulfe's bottles : bottles. A. tp retain any solid particles which may be mechanically carried over by the gas . in the first bottle. 313. D. leaving nothing but Solution of ammonia is prepared on the large scale by mixing together in a capacious retort equal weights of sal ammoniac and well-burned quick-lime previously slaked and made into a paste with water. arrangement shown in fig.

in the following manner aH 3 N + K 2 becomes 2KH 2 + H 2 Tl is sulphuric acid . that of by a white precipitate with baric nitrate after dilution and saturation with nitric acid . bubbles through the liquid and collects in the bottle. the presence of carbonic acid may be detected by lime-water. has been obtained in the that of and nitrogen pound hydrogen isolated form. when a white cloud of argentic chloride is formed . safety tube. potassium is heated gently n ammoniacal gas. instead air would enter by the the from back driven c. and so that the gas rises in projects a little beyond its lower opening. however. and the equilibrium would which delivers the gas passes down through the safety tube. hydrogc n perfectly dry is liberated. and the tests for ammonia will be given at tl e same time. in the commerciil a in small quantity is very frequent impurity solution and is usually derived from the action of the ammonia en the flint glass bottles in which it has been kept. and a fusible. When. the ammonia disappears. Compounds of tl class have received the name of amides . should leave no solid residue when evaporated. more rapidly than it was supplied. may be considered either as ammonia (NE 3 ) 2 in which one atom of hydrogen is replaced by the metal potassiu . Solution of ammonia. that of chlorine by acidu- lating slightly with pure nitric acid. Ammonia is the only con(382) AMIDOGEN? (H 2 N=i6). Those who hold the latter view suppose that amidogen is capable of existing in combination with several metals and wi h a variety of bodies derived from the organic kingdom. that of lime by a whil e and that of copper or precipitate on adding ammonic oxalate in its preparation) by a used lead (derived from the apparatus Lead with black or brown precipitate sulphuretted hydrogen. chemists compound of potassium with amidogen (NH 2 ). as is the casewi h All the usi al amidogen. . to regard all these bodies as substitutio products formed upon the type of ammonia. they will be examin hereafter. iis :d AMMONIUM (H 4N=i8). compound. This compound. : N . tube open at both ends.146 AMIDOGEN AMMONIUM. which it renders milky. so that if the gas were absorbed in B. if pure. however. being The tube be restored. co iThe ammonia is decomposed by the potassiu n sisting of KH 2N. it is i ir more convenient. The ammoniacal salts will be described with those of the alkali metals. olive-green compound is formed. for of the liquid example. bottle.n or as a KH N. has not been obtained in a separate form. and adding argentic nitrate.

a bottle of chlorine perfectly free from greasy matter be inverted over a leaden dish containing a solution of I part of sal ammoniac in 12 parts of water. or and hydro- acid on an alkaline nitrite. appear to contain it. burning with a green flame. But if instead of acting on a solution of free ammonia. i'653. 2H to be mixed with a variable quantity of oxygen.C1. If a current of ammoniacal gas be directed into a bottle of gaseous chlorine it will take fire spontaneously. which is a very volatile and easily decomposed base. when decomposed by three molecules : of chlorine.CHLORIDE OP NITROGEN. which cannot be expelled from the salt by heat without entirely decomposing it (390) . By modifying the experiment. drops of ai yellow oily. so-called salts of 147 monic nitrate. Hydroxylamine. for Amammonia. however. the reaction may be employed as a means of obtaining nitrogen gas. most conveniently prepared by the action of sodium amalgam. Anderson). unites readily with acids forming crystalline salts. being also decomposed at the same time (A. Hydroxylamine NH 3 = 33 [NH 2 (HO)]. each bubble of chlorine produces a flash of light. By the action of reducing agents becoming . The full discussion of the grounds upon which this theory rests will be best postponed till we enter upon a description of the salts of ammonium. yield one molecule of nitrogen and six of hydrochloric + 3C1 2 becoming 6HC1 + 2 The nitrogen is apt acid. CHLORIDE OF NITROGEN (HC1 2 N. the hydrochloric acid as fast as it is formed combines with the excess of amif the solution be conmonia. and nitrogen is set free . whilst hydrochloric acid is formed. of The attraction existing between chlorine and Liquid. ammonia on H N HNO 3 ammoniac is on this view regarded as ammonic chloride H 4N. and tin .! N N .look ing She/ liquid gradually collect on the surface of the liquid and fall to the (H 4NC1). example.NO 3 Sal on nitrates a base is formed having this composition : it may be regarded as is intermediate between chloric ammonia (NH 3 ) and ammonic hydrate (NH^OH). for when a stream of chlorine gas is transmitted through a solution of ammonia. + 3 nitric acid. when formed by the action of is not accompanied by any separation of the elements of water. H 4N. Gr. dense white fumes being generated by the union of the hydrochloric acid with undecomposed ammonia. is feeble the compound commonly known by the . or nitrate preferably the ammonic salt. Sp. while nitrogen is liberated centrated. Two molecules of ammonia. L2 . a little water . nitrogen very name of chloride of nitrogen is always obtained by indirect (383) means.G1 3N ?) .

as usual. and one of the most violence dangerous compounds known. The analysis of this body is attended with great difficulty. t is of which has been a substitution product obtained from ammonia. and hydrogi n (HC1 2 N.148 OXIDES AND OXACIDS OF NITROGEN. It is very volatile. in this case and ia the analogous instances of the explosion of the oxides of chlorin :. OXIDES AND OXACIDS OF NITROGEN. with the resins. but during the expansion and sudden separation of the two gaseous elements. On explode when touched with strong acids. five distil ct compounds of nitrogen with oxygen have been obtained. but a combination of chlorine. so that it is not easy to effect their direct union . t le composition of which is given in the following table : . . it is and highly probable that it is not simply a chloride >f nitrogen. The exemitting a flash of light when the detonation occurs. and the fixed oils. body remains liquid at 16'6 (27 C. such as oil of turThe alkalies likewise pentine. general. Little or nothing is known of the cause of these remarkable reactions. The new as the salt in the and sink formed. for it explodes with tremendous when heated to between 200 and 212 (93 and 100 C. not during an act of combination. indirectly. phosphorus. whilst the chlorine slowly disappears substance known as chloride of nitrogen. A obtaining this body consists in suspending a fragment of sal ammoniac (say 1*5 or 2 grammes) in a solution of hypochlorous acid are gradually oily drops of the so-called chloride of nitrogen is dissolved. but is possesses a peculiar penetrating odour. this liquid is the safer method of bottom. but.C1 3 N). the hydrog< n more or less completely displaced by chlorim . light is emitted. nitrogen. liquid . cause its immediate explosion. somewhat analogous to the corresponding explosi e (439) compounds obtained by the action of iodine on ammonia II. (384) The attraction of nitrogen for oxygen is much feefr er than that of either carbon or hydrogen for oxygen.). the other hand. it invariably breaks or that is sudden so porceglass any plosion lain vessel in is which it may be contained : hence a leaden saucer liquid chloride als:> used in preparing the compound. or of the light and heat emitted when the chloride explodes by slight elevation of temperature.). or with sugar. The explodes violently at ordinary temperatures when brought into contact with many inflammable substances. it does not with metallic bodies io.

even decomposition at this temperature. 44 or 28 14 28 . with a dangerous explosion from the The crystals are dispressure exerted by the liberated gases. 241).). and the tube bursts. forms transcrystals. N : . a uniform current of perfectly dry chlorine gas is passed very slowly over crystals of well-dried argentic nitrate . till the decomposition has commenced.). xxviii. :* Argentic nitrate. the salt is at first heated to about 203 (95 C. N 2 = 4 Oxygen. and the tem- The operation perature is then lowered to about 140 (60 C. who find that nitric anhydride may be readily prepared by passing the vapour of nitrylic chloride over dry argentic nitrate heated to a temperature of about 150 (60 to 70 C. 4AgNO 3 + 2C1 2 give * It is possible that nitrylic chloride (N0 2 C1) is first formed thus 2C1 2 = 2AgCl + 2N02 Cl + 2 and then that this chloride decomposes a second molecule of argentic nitrate . The chlorine displaces the nitrion (NO 3 ) from the argentic nitrate argentic chloride is formed. de Chimie [3]. 85 (29'5 C. 149 In 100 parts.NITRIC ANHYDRIDE. the nitric anhydride is condensed in The decomposition may be represented in the following crystals. manner. which brilliant. Nitrous anhydride Peroxide of nitrogen Nitric anhydride NO =30 N O3 = 76 N = 92 2 2 28 N 2 S =108 28 + 16 + 16 + 48 + 64 + 80 Dinitric 63-64 46^67 36-85 + 36*36 + 53*33 + 63-15 -f- f~.). is colourless a very unstable compound. By surrounding the receiver *.~] \_~^] P j 30*44 25*93 69*56 | { + 74'7 ? (385) Nitric Anhydride or Pentoxide (N 2 O 5 C. and requires attention to a number of minute precautions. Vol. Boiling-pt. they melt perature.. derived from the right at 85 and boil at 113. and nitrion breaks up into nitric anhydride whilst oxygen escapes. AgN03 + NO2 C1 = AgCl + 2 O 6 th s is rendered more probable from the experiments of. undergoing Sometimes the crystals.. Mol. with a freezing mixture. 113 (45 This substance. -Fusing-pt. Nitric anhydride. o. Nitrogen. weight. Nitrous oxide Nitric oxide . for the details of which the reader is referred to Deville's paper (Ann.) . is one of considerable delicacy. Odet and Vignon. By w. solved rapidly by water. emitting much heat. : + .. and producing ordinary hydrated nitric acid.). In order to procure the anhydride. O N0 2J parent. ) (NO.. though it is probably not quite so simple Argentic chloride. if kept in sealed tubes become decomposed at the ordinary tem- rhombic prism.

150

PRODUCTION OF NITRIC ACID.

Nitric anhydride can also be prepared by cautiously adding phosphoric anhydride to nitric acid cooled by a freezing mixture and subsequently distilling the mixture (Weber).
Deville ascertained the composition of nitric anhydride by estimating the quantity of nitrogen which a given weight of the

compound furnished after removal of the oxygen by passing the vapour over finely divided metallic copper at a high temperature; 100 parts by weight of the anhydride were thus found
to contain 25 '9 of nitrogen; the deficiency, 74' i, is oxygen; or 28 parts of nitrogen are united with 80 of oxygen.
(386)

NI.TRICACID; Hydric Nitrate, HNO S [NO 2 (OH)] =63 ; of Liquid at 59 (15 C.) 1-530, a 32 (o C.) 1*559; Boiling-pt. 187 C.) ; Comp. in 100 parts, N 2 O 5 , 85^72 ; (86 H 2 O, 14' 28. The most important of the compounds of oxygen with nitrogen is that which when in combination with water was formerly called aquafortis, and is now designated nitric acid It was known to the alchemists, but its true composition was first determined When nitrogen is mixel by Cavendish in 1785. with 12 or 14 times its bulk of hydrogen, and a jet of the mixel gas is allowed to burn in air or in oxygen, the water which is formed has a sour taste and an acid reaction, owing to tli3
Sp. Gr.
.

this

simultaneous formation of a small quantity of nitric acid. 1 1 case the nitrogen burns by the aid of the heat develope 1 during the combustion of the hydrogen, and the oxidized com-

pound combines
increases
its

at

once with the water formed, which
stability.

muc

i

was, indeed, owing to tli3 accidental production of nitric acid in the course of his exper ments on the formation of water by the combustion of hydrogei , that Cavendish was induced to institute the train of research s.
c

chemical

It

which terminated in this important discovery. If a mixture of 2 volumes of nitrogen with 5 volumes t oxygen be introduced into the bent eudiometer (fig. 287), the tul of which is filled up with an infusion of blue litmus in distille
water, and a series of sparks be transmitted through the gaseoi mixture by means of an induction coil, the two gases will combic
<

f
3
1

s
3

The heat f gradually, and the litmus solution will be reddened. the spark determines the combination of the gases just at tli 3 spot through which it passes, but the action does not exten I In like manner, if a number of sparks from tl) 3 further. electrical machine be passed between two metallic points, ovt r
moistened litmus-paper, a red spot will be produced upon tl to the formation of a minute of nitric aci paper, owing quantity the combination of the and of the air j by oxygen nitrogen
3
I

i

PREPARATION OF NITRIC ACID.

151

During stormy weather, and indeed presence of aqueous vapour. whenever a flash of lightning passes through a moist atmosphere, the same compound is produced in appreciable quantity, so that
it is

rare to meet with rain water in which traces

of

ammonic

may sufficiently delicate processes. Ammonia likewise yields nitric acid under certain circumstances by slow oxidation (380). Nitrates of potassium and sodium occur in the form of an
if
it

nitrate

not be detected,

be

examined by

on the soil, especially in tropical climates, as in some of India and Peru. The compound formed with potassium parts constitutes the nitre or saltpetre of commerce. The nitrates of the alkali-metals are ofteji present in the water of wells in towns
efflorescence

or in the vicinity of cemeteries, the nitric acid being in these cases produced by the oxidation of azotized animal matters, as they undergo decomposition during the percolation of their aqueous
solution through the
It
soil.
is from one of these nitrates that the acid is Preparation. obtained for chemical When potassic nitrate is always purposes. heated with a powerful acid, such as the sulphuric (H 2 SO 4 dihydric
,

sulphate) a true double decomposition occurs. hydrogen change places, forming on the one

The potassium and hand hydric potassic

sulphate

(KHSO 4),

and on the other hydric

nitrate, or nitric acid

(HNO 3 ). The hydric potassic sulphate remains in the retort, whilst the more volatile nitric acid distils over, and may be condensed in the usual manner. The method of procuring nitric
acids which

acid offers a good example of the general principle upon which admit of being distilled without experiencing de-

composition are obtained from their metallic
acids,
it

salts

;

the ordinary

must be remembered, are salts of hydrogen. In preparing on the small scale, equal weights of nitre and oil of vitriol are placed in a glass retort, and the distillation is proceeded with in the manner shown in figs. 143 and 144, Part 1^.365.
nitric acid

During the distillation red fumes appear in the retort, arising from a partial decomposition of the acid, and the formation of some
is

of the lower oxides of nitrogen, whilst a yellowish corrosive liquid condensed in the receiver this liquid is hydric nitrate, or concentrated nitric acid (HNO 3 ) ; it fumes strongly in the air, and
:

emits a powerfully irritating and acid odour.

On

the large scale, iron retorts,

fig.

314, coated with

fire-clay

on the inside

of the upper part, where they are exposed to the acid vapours, are employed for the distillation, and sodic nitrate is substituted for potassic nitrate, as it is a

cheaper

and likewise yields 9 per cent, more nitric acid than potassic nitrate. or retorts are arranged in pairs in a furnace, so that each fire heats two cylinders, as shown in the section, I. The cylinders are supplied with a
salt,

The cylinders

152
moveable
lid, c, d, at

PREPARATION OF NITRIC ACID.
each end.
c,

The
is

nitrate

is

through the opening at
fitted accurately to
ifter

which

closed during the distillation

introduced into the retort, A, by a stone lid,

the retort
i.

is closed.

the aperture ; and the oil of vitriol is added by a funnel at e, As soon as the acid is introduced, the funnel is with-

Fio. 314.

2.

drawn, and the opening at e is closed with a plug. The nitric acid as it distils over passes through the pipey, and is condensed in a series of stoneware bottle:*, The acid collected in the first receiver is alwajs the first of which is seen at B. contaminated with sulphuric acid, and that in the last is rather dilute, as watt r is placed in it to condense the nitrous fumes.

Upon the large scale it is customary to employ a proportioa of sulphuric acid smaller than that used when the distillation is performed in glass vessels, for it is quite possible to effect a complete decomposition of the nitrate by heating it with one-half il s
Under these circumstances, however, i weight of oil of vitriol. is needed to expel the last portions of aci( , higher temperature and a considerable quantity of the nitric acid is thereby decon The residue in the retort, when the smallt r posed and wasted.
quantity of sulphuric acid
is

used,

is

dipotassic sulphate

(K 2 SO 4
is

,

which

is

much
is

less soluble in
:

water, and consequently

muc

i

more

but in the iron cylinder of the mam of no moment, because the saline mass can easil y be detached by the use of iron tools when the distillation is at a i end.
difficult

of removal

facturer this

The cause of

these differences in the result of the process<

s

adopted on the large and on the small scale lies in the fact th: sulphuric acid by its reaction upon potash gives rise to two di ferent sulphates, one of which contains twice as much potassiui
as the other
;

t
'-

i

acid sulphate consisting of a 4 , being hydric potassic sulphate, while the common neutral sulphate, r SO 4 .dipotassic sulphate contains 2
(

the

KHSO

K

.

and sulphuric acid are mixed in the proportion f i molecule of nitre, to i of acid), the hydr c potassic sulphate is obtained, and nitric acid distils readily ; ha .f
nitre
<

When

equal weights (or

PREPARATION OF NITRIC ACID.

153

the hydrogen only of the sulphuric acid being displaced by potassium the change is represented in the following equation
: :

Sulphuric
Nitre.
acid.

Nitric
acid.

Hydric potassic
sulphate.

-f

[N0 2 (OK) + S0 3 (OH) 3 =

N0 (OH) + SO
2

2

(OH)(OK)

;]

but if the nitrate be mixed with sulphuric acid in the proportion of two molecules of the former to one of the latter, the decomposition takes place in two successive stages ; in the first of these,
half the nitre only is decomposed, hydric potassic sulphate being furnished in the first instance as before, and a gentle heat only is needed for the distillation of the nitric acid so produced.

The following equation represents this
Nitre.
acid.

first

stage of the change
Nitric
acid.

:

Hydric potassic
sulphate.

Nitre.

KHSO 4
[>N0 (OK) + S(X(OH) 2 = N0 (OK) + ~S0 2 (OH)(OK).]

.

NO

2

(OH)

+

But as soon as the first half of the nitric acid has passed over, the temperature begins to rise, and the hydric potassic sulphate reacts OD the undecomposed nitre ; the second half of the nitric
then formed, but is at the same time partially decomposed, to the high temperature, and this is particularly the case owing towards the end of the operation finally, the whole of the potasacid
is
:

sium remains in the retort in the form of the sparingly soluble neutral or dipotassic sulphate. This second stage of the decomposition
is

exhibited in the subjoined equation
Hydric potassic
sulphate.

:

vrjf,.

Nitric
acid.

Dipotassic sulphate.

KNO,
[N0
2

+

KHS<3

4

(OK)

+ S0 3 (OH)(OK)

= .HNCT + K^SO^ = NO (OH) + SO (OK)
3
2 2

2 .]

Similar equations would represent the reactions with sodic nitrate, substituting the symbol Na for K, wherever the latter
occurs.

The acid which is obtained by the foregoing Properties. is of a process yellowish or red colour, owing to the presence of some of the lower oxides of nitrogen these may, if necessary, be
;

got rid of by mixing the acid with an equal bulk of oil of vitriol, and submitting the mixture to distillation. If the first portions be collected, and a current of air be passed through the

dry

154
liquid, gently

NITRIC ACID

PROPERTIES.

warmed and

sheltered from strong daylight, a pure

and quite free from the lower oxides of nitrogen. It is, however, so unstable in this concentrated form that it cannot be redistilled without exacid remains behind as colourless as water,

periencing partial decomposition. exposed to the sun's light a similar decomposition is produced ; oxygen gas is evolved, and the acid becomes coloured owing to the formation of lower
oxides of nitrogen. When pure, nitric acid is a colourless, limpid, fuming, powerfully corrosive liquid, which freezes at about ~ 6 7 (-55 C 0- It begins to boil at 187 (86 C.), but the temperature rises gradually, owing to the decomposition of the
liquid;

When

continues to rise slowly till point the acid in the retort

oxygen and nitrous fumes are evolved; the boiling-point it reaches 250 (121 C.), at which distils unchanged, and has a com-

position approaching to (2HNO 3 ,3H 2 O).* Owing to the facility with which the acid parts with oxygen, it is If it be continually employed as an oxidizing agent.

dropped into hot finely powdered charcoal, the charcoal burns mixed with a litde oil of vitriol, and poured into oil cf vividly
;

turpentine, the mixture bursts into flame. Sulphur and iodine are oxidized by it, and phosphorus almost with explosive violence.

Nitric acid
stroys
all

is one of the most corrosive substances known, it deanimal textures rapidly, and if slightly diluted stains tha

skin, wool, feathers, and all albuminous bodies of a bright yellow colour. Nitric acid acts violently upon tin or iron filings, esif they be previously moistened with a few drops f and attacks most of the other metals except gold, plat num, rhodium, and iridium. The action of nitric acid upon tl 3 metals varies with its temperature and degree of dilution but s energy is most manifest when diluted to a specific gravity of fro: a i The pure concentrated acid, HNO 3 is in fact wit! '35 to i '25. out action upon tin, iron,, bismuth, and many other metals \i The presence of nitrous acid in tl e ordinary temperatures.

pecially

<

water

;

:

i

,

nitric acid greatly increases its oxidizing power, as, owing to tl e instability of nitrous acid, this compound parts with its oxygc u

At a temperature of o very readily. C.) the acid, wheth T concentrated or dilute, is without action on copper, but it di s-

(18

solves zinc rapidly.

The chemical acti< n (387) Action of Nitric Acid on Metals. of nitric acid upon the metals is a process of considerable ii iLike hydrochloric, sulphuric, and other acids, the composition of nitric a id of constant boiling point, varies with the pressure (note, p. 30).

NITRIC ACID

ACTION OF ACIDS UPON METALS.

155

portance, but in order to study with advantage the effects to which it gives rise it will be useful to consider the action of acids

upon the metals from a general point of view. It has already been stated that the metals unite directly with many of the nonmetallic elements, such as chlorine and oxygen. Antimony, for
example, will take
fire

spontaneously
will

if

allowed to
in

fall

in fine

powder into

chlorine,

and iron

burn

oxygen

if first

heated
to

to the point of ignition.

The

metallic oxides,

when presented

the acids, become quickly dissolved ; cupric oxide is brought into solution by diluted sulphuric acid, zincic oxide quickly disappears

when

agitated" with hydrochloric acid, dissolved by acetic acid.
-

and plumbic oxide

is

rapidly

But a metal will not unite directly with an anhydride. Union between a metallic oxide and an anhydride may, however, occur,
though, even then, the action
of water.
is much favoured by the presence Sulphuric anhydride, for instance, does not act upon iron, but the anhydride is immediately absorbed by caustic potash, and in like manner, carbonic + SCX becoming 4 ;

KHO

KHSO

anhydride

is

When

rapidly absorbed by slaked lime. the metals are presented to the acids other
;

phenomena

a brisk action frequently takes place, accompanied by the evolution of a gas, and it is very often stated that the metal first becomes oxidized, and is then dissolved by the acid.

are observed

however, necessary to assume that the metal undergoes oxidation as a preliminary step, for the reaction may be explained on the supposition that the metal simply displaces the
It is not,

hydrogen of the

acid.

When,
is
;

for example,

dilute sulphuric acid, the metal

placed in rapidly dissolved, whilst hydrozinc
is
2
.

gen escapes in the gaseous form

H SO4 + Zn yielding ZnSO4 + H
2

A

similar result

is

obtained

when

iron or tin

is

dissolved in hydro-

chloric acid, ferrous or stannous chloride being produced, whilst hydrogen is given off, the reaction in the case of iron being re-

When an presented by the equation 2HCl4-Fe FeCl 2 + 2 oxide is employed instead of a metal, the hydrogen, instead of
.

=

H

escaping as gas, is eliminated in the form of water ; for instance, in the action of zincic oxide upon sulphuric acid, the change may

be represented as

ZuO + SO 4 ZnSO 4 + 2 O ; and again with O. oxide and cupric hydrochloric acid, CuO-i-2HCl CuCl 2 2 The ordinary action of metals upon sulphuric acid, in which

H

=

H

=

+H

the components of the acid are united by powerful chemical ties, but where the is, as we have just seen, comparatively simple ;

elements of the acid are but feebly held together, as is the case with nitric acid, the actions are often more complicated. When,

156

NITRIC ACID

ITS

VARIOUS HYDRATES.

for example, silver or copper is dissolved in nitric acid, hydrogen may as before be displaced from the acid by the metal which
; but, owing to the facility with which nitric acid parts with its oxygen, no hydrogen is set free, the latter being oxidized at the moment of its liberation at the expense of the

becomes dissolved

oxygen of the nitric acid one of the lower oxides of the nitrogen is formed, and occasions the disengagement of ruddy fumes instead of the colourless and inflammable hydrogen. The exact nature
;

when allowed

of the decomposition, however, varies in different cases ; silver to become dissolved slowly in the cold in an excess

of diluted nitric acid produces nitrous acid (HNO,), which re-

mains in solution; Ag2 + 3HNO 3 giving 2AgNO 3 + H 2 O + HNO 2 and the metal is dissolved without evolution of gas a simi ,ar effect is also produced by palladium. With metals which attack the acid more vigorously, such as copper or mercury, nitric arid of moderate concentration (sp. gr. 1^25 to 1*3) disengages nitric
:

oxide

in

large

quantity:

for

2NO + 3(Cii2NO 3 )+4H 2 O;
centrated
dantly;
(sp. gr. i '42),

but

if

example, 3Cu + 8HNO 3 yields the acid be more highly conis

peroxide of nitrogen

disengaged abin-

Cu + 4HNO 3 yielding Cu2NO 3 + 2NO 2 + 2H 2 O. And when

the decomposition occurs at a high temperature, free nitrogen is usually disengaged in considerable quantity, the acid undergoi ig complete deoxidation; 5Cu+ i2HNO 3 5(Cu2NO 3 ) + 2 + 6H C 0. If the metal, like zinc, has a still more energetic action, the

=

N

dilute acid yields nitrous oxide
3
2

4Zn + ioHNO = N OH-4(Zn2NO
for instance,
3

amongst the gaseous producl s
3 )-f

;

5H 2 O.

When zinc
2

or

tir is
s;

used with a stronger acid, ammonia

is

4Zn + 9 HNO :=4(Zn2NO 3 )-f-3H O + H 3 N,
Nitric Acid.

found amongst the produc

the a n-

monia combining with the excess of acid employed.
(388)

Hyr rates of

When

concentrated nit

-ic

exposed to the air it absorbs moisture, and if 70 parts of the concentrated acid be mixed with 30 of water it emits a s< nis

acid

sible

amount of

heat.

Under

nitric acid of considerable stability appears

these circumstances a hydrate of to be formed witl a
)

composition approximately represented by the formula (2HN< such an acid has a sp. gr. of 1*424; it boils at 3H 2 O)
:
:

g,

2^0

(121 C.), and may be distilled, under ordinary pressures pA weaker acid when heated parts with its parently unaltered. water till it arrives at this density, and a stronger acid, wt an distilled, loses acid until reduced to this point, the liquid in he
retort eventually, in both cases,

Although

when

acquiring a density of 1*4:4. does not vary sensibly in composit on distilled under the ordinary atmospheric pressure, llos oe
this hydrate

COMMON IMPURITIES OF THE
found by conducting the
distillation at

ACID.

157

reduced pressures, that the

density of the acid in the retort, and consequently the proportion of water, varies with the pressure under which the distillation takes place.

Strength of Nitric Acid
HNOs
in 100 parts

(J,

Kolb}.

by weight.

158
the acid with water

NITRATES.

till of a sp. gr. not exceeding 1-42, and then or with 2 distilling 3 per cent, of potassic dichromate. Nitric acid is monobasic; that is to say, each atom of Nitrates. nitrion (NO 3 requires one atom of a monad metal like potassium
)

to neutralize

it

;

the salts which
.

it

forms are termed

nitrates.

These salts may be procured Their general formula is M'NO 3 without difficulty by dissolving either the metal itself, or its oxide, or its carbonate, in nitric acid more or less diluted. Many of the
nitrates, including those of potassium,

sodium, ammonium, barium,

lead, and

Others combine with 6 molecules silver, are anhydrous. of water of crystallization; among these are the salts of magnesium,
zinc, nickel, cobalt, iron,

and copper

;

portion of the water

is

different,

calcic

whilst in others the pronitrate retaining 4H 2 0,

If crystallized at a high temperaO. and strontic nitrate 2 and strontic nitrate m.iy ture, cupric nitrate retains only 2 O, No acid nitrates are known be obtained in the anhydrous form.

5H

3H

to exist, but several subnitrates or basic nitrates may be cured ; that is to say, salts may be formed which contain

pro-

mere
:

than one equivalent of basyl for each equivalent of acid radicle such, for instance, as the hydrated basic nitrate of copj er

(Cu2NO 3 ,3CuH 2 O 2 ).
The following
nitrates
:

table

gives the composition of

some of the

Potassic nitrate

...

...
...

...
...

...
... ... ...

Sodic nitrate

...

Ammonic

nitrate

...
...

...
...

...
...

H NNO
4

NaNOs
g

Baric nitrate
Strontic nitrate
Calcic nitric

............ ............
... ...
...

Ba2NOs
Sr2N0 5H 2 Ca2N03 .4H 2 Mg2NOs ,6H 2 O Zn2N03 ,6H 2 O Fe2NO ,6H 2 Cu2N0 3 ,6H 8 Pb2NO
3< 3

Magnesic nitrate
Zincic nitrate

... ...

...
...

"...
...
...

Ferrous nitrate

...

...

Cupric nitrate

.........
... ... ... ...
...

... ...
... ...

Plumbic

nitrate

...
... ...

Argentic nitrate

Mercurous nitrate

...

Hydrated plumbic subnitrate Hydrated cupric subnitrate ... Hydrated mercurous subuitrate

......
...

AgNO HgN0 ,H
g 3

2

...
...

...

Pb2N03 ,PbH 2 Cu2NO3 ,3CuH. \ 3HgN03 ,Hg2 0,] 2 O
i'

Most of the nitrates fuse readily when heated, and at an elevated temperature they are all decomposed. From the nitra es of the alkali-metals, nearly pure oxygen escapes at first, an< a
i

formed, but afterwards the nitrite undergoes decomp( sia mixture of oxygen and nitrogen passes off, and the ox de tion, of the metal is left. When thrown on glowing coals, the nitra ,;es
nitrite is

DETECTION OF NITKIC ACID.
:

159

are decomposed with deflagration if paper \>Q moistened with the solution of any nitrate, allowed to dry, and then ignited it will burn with the rapid smouldering combustion characteristic of

This property is also touch-paper. some other acids, of which the chloric
acid

is

exhibited by the salts of the most important.

All the nitrates, when heated with sulphuric acid, evolve nitric but there is no ready method of precipitating nitric acid ;
its

from

solutions, since all its

compounds are more or less soluble

in water.

Various indirect methods have been proposed for its ascertaining presence one of the best of these consists in the solution, if acid, with potash, and evaporating neutralizing
:

nearly to dryness, then adding a few copper clippings, and heating the mixture with a little oil of vitriol ; if nitric acid be present, the characteristic red fumes of peroxide of nitrogen will make their appearance. A quantity of these fumes, too small to be be detected visible, may by suspending in the vessel a piece of

paper moistened with a mixture of starch and solution of potassic iodide, which will become blue from the formation of a compound
of the starch with the liberated iodine.

The most

delicate test

for nitric acid, however, is ferrous sulphate ; if a small quantity of this salt be dissolved in the solution to be tested, and oil of
vitriol

be cautiously poured down the side of the tube containing the mixture so as to form a distinct stratum below it, a brownish
red coloration will make its appearance at the line of contact between the two liquids if nitric acid be present this depends the is circumstance that the nitric oxide which formed by upon the deoxidizing action of one portion of the iron salt, becomes
;

dissolved with the distinctive

brown
;

colour, in the solution of the

unaltered part of the ferrous salt the deoxidation of the nitric acid which occurs may be represented in the following equation
:

Ferrous
sulphate.

Sulphuric
acid.

Nitric
acid.

Ferric
sulphate.

Nitric oxide.

,

.

oTeSC^

4 3H^SO 4 4 2HNcT =
3

3 (Fe 2 3SO 4 )

4 ^NO 4

^5.

If a few drops of hydrochloric acid be added to a solution which contains free nitric acid, or a nitrate in solution, the liquid
is

This effect, however, acquires the power of dissolving gold leaf. produced by hydrochloric acid in solutions of the chlorates,

bromates, and iodates, so that the absence of these acids must be proved before applying this test (353, 431, 437).
The
other acids
accurate quantitative determination of nitric acid when mixed with is a matter of considerable One method consists in the difficulty.

conversion of the acid
the

into ammonia, and the subsequent determination of amount of ammonia found (380). Another, which, when the quantity

ICO
of nitric acid

TESTS FOR NITRIC ACID

NITROUS OXIDE.

.

is very small, furnishes excellent results, is that proposed by Pugh It is based upon the determination of the amount (Q. J. C/tem. Soc. xii-35). of stannous chloride which is converted into stannic chloride when the solution is heated with nitric acid in presence of an excess of hydrochloric acid.

A

quantity of the concentrated solution containing the nitric acid to be determined is introduced into a strong tube, and a known volume of a solution of stannous chloride in a large excess of hydrochloric acid is added, the strength of the tin solution having been ascertained by the use of a standard solution of
certain

Care is taken to employ an excess of the tin solution. fragment of marble is dropped into the tube so as to produce a quantity of The tube is then carbonic anhydride sufficient to displace the atmospheric air. carefully sealed and exposed for about a quarter of an hour to a temperature of 338 (170 C.). It is allowed to cool, and the contents of the tube are next transferred to a glass and diluted with 90 or TOO cub. centim. of water; a f?w drops of a weak solution of potassic iodide and starch are then added, and the amount of tin still remaining in the form of stannous salt is determined by the addition of a graduated solution of the dichromate, until the liquid becomes blue The reaction upon which this process deper ds from the liberation of iodine.
potassic dichromate.

A

may

be thus expressed

:

HN0
:

+ 4SnCl 2 + pHCl = H 4NC1 + 3

4 SnCl 4

the nitrogen of the nitric acid being wholly converted into ammonia during Hie the difference between the amount of the dichromate originally operation
required to peroxidize the quantity of tin solution employed, and that actuary consumed after the experiment is over, yielding the data for fixing the quant ty of nitric acid: 393*3 mgrms. of the dichromate represent 63 of nitric a :id

(HN0

3 ),

or

54 of the anhydride (N2

6 ).

This

method, however,

is

i

ot
er

applicable for determining the nitrates in water analysis as the organic

mat

present interferes with the result.

NITROUS OXIDE, Protoxide of Nitrogen, or Nitrogen Monoxide; N 2 O = 44- [ON2] Mol. Vol. [_"_ ~J; Eel. wt. $.\ ;
(390)
j.

Theoretic Sp. Gr. 1*5224; Observed Sp. Gr. 1*527. Preparation.If a mixture of equal parts of nitric and sulphuric acid, dilut

'd

with 8 or 10 parts of water, be digested with metallic zinc, metal displaces the hydrogen of the sulphuric acid, which at

t ie
t ie

moment
less

of

i atom of oxygen. But to obtain the gas in a pure state it is far better to heat ammonic nitrate (H 4NNO 3 the salt furnished by neutral zing pure nitric acid with ammonic carbonate) in a glass retoi t ; the salt quickly melts, and at a temperature of between 392 a id 500 (200 and 260 C.) apparently begins to boil, although in

gas is united with
2.

liberation deoxidizes the nitric acid, and a coloi rslowly given off, composed of 2 atoms of nitrog :n
its

,

reality it is

undergoing decomposition, being resolved into

1

he
re

gaseous

nitrous oxide and aqueous vapour.
carefully watched,

The temperati
rise so

must be

and not be allowed to

high as

to occasion the production of white vapours in the retort, becai se the decomposition is then apt to occur with explosive violen ;e.

PREPARATION AND PROPERTIES OF NITROUS OXIDE.

161

Ammonium is a commay be explained as follows with of when the ammonic nitrate is nitrogen hydrogen ; pound of the ammonium the combines with part of heated, hydrogen
The
reaction
:

the oxygen of the nitrion, forming water, whilst the remaining atom of oxygen unites with the two atoms of nitrogen, forming
nitrous oxide.

The
:

result

of the nitrion and of the
nitrous oxide

that the whole of the nitrogen, both ammonium, is liberated in the form of
is

becoming 2H 2 O + N 2 O[NO 2 (ONH 4 ) = 3 ounce or 30 grms. of the salt furnishes about 2] 2 cubic or rather more than 8 litres of the gas. inches, 500 L. Smith a modification of the foregoing process adopts 3. for preparing the gas he decomposes sal ammoniac (H 4 NC1) by means of nitric acid (of sp. gr. i'2o) at a gentle heat. The gas which is obtained in this manner is not pure, but is contaminated with small quantities of chlorine and of nitrogen the chlorine may be removed by allowing the gas to bubble up through a solution of potash. Advantage may sometimes be taken of this of action nitric acid on sal ammoniac to destroy an excess of chloride in solution in the course of an analysis. ammonic

H NNO
4 i

ON + 2OH

:

;

Properties.

Nitrous oxide

is

a transparent, colourless gas,
:

with a faint sweetish smell and taste

100 volumes of water at

(o C.) dissolve 130 of the gas; at 59 (15 C.), 77 vols.; at 75 (24 C.) only 60 vols. (Bunsen). Owing to this considerable diminution in solubility with the rise of temperature, it

32

and

should be collected over

warm

water.

Under a pressure of 50

atmospheres at 45
of sp. gr. at 32
(

(7

(O

C.), it is reducible to a colourless liquid, It boils at about C.), of 0*9004. 133

and may be frozen into a transparent When the liquid nitrous oxide 146 ( 99 C.). was mixed with carbonic disulphide, and exposed to evaporation
92
C.)

(Wills),

solid at

about

vacuo, Natterer obtained a reduction of temperature which he estimated at 220 ( I4OC.) ; this is a lower point than has hitherto been attained by any other means. The gaseous nitrous oxide has a specific gravity of 1*527, which coincides with that of
in

This gas possesses the qualities neither of carbonic anhydride. It supports the combustion of many an acid nor of an alkali. bodies with a brilliancy resembling that which they exhibit when
It is, however, at once distinguished from greater solubility in water. glowing match bursts into flame when plunged into nitrous oxide sulphur when

burned in oxygen.
its

oxygen by

much

A

:

kindled burns in

with a pale rose-coloured flame. A little nitric oxide is commonly formed during such combustions, and is manifested by the occurrence of ruddy fumes, due to adit

n.

M

162
mixture of
bottle.
this

ANALYSIS OF NITROUS OXIDE.
gas with

the oxygen of the air as

it

enters the

after the discovery of nitrous oxide, Davy ascertained that it may be respired for a few minutes it then produces a

Soon

:

in many singular species of transient intoxication, attended to muscular instances with an irresistible propensity exertion, and the has hence often to uncontrollable laughter ; gas acquired the

largely used as an to pain during surgical .anaesthetic for producing insensibility for this purpose it operations, especially the extraction of teeth in order to facilitate transbottles iron in is condensed wrought

popular

name

of laughing-gas.

It

is

now

:

port.

If nitrous oxide be passed repeatedly through Composition. a porcelain tube heated to bright redness, the gas is decomposed into a mixture of oxygen and nitrogen, 2 volumes becoming ex-

An easy panded permanently into the space of 3 volumes. method of analysing nitrous oxide consists in mixing it with hydrogen, and passing an electric spark through the mixture. If 4 measures of nitrous oxide be mixed with an excess of hydrogen gas, say with 6 measures of hydrogen, in the bent eudiometar will be produced and on (fig. 287), 10 measures of mixed gas steam will be formed the oxid athe electric spark, by transmitting tion of the hydrogen, and will be immediately condensed, whilst the 10 measures will become reduced to 6: but the contained in the nitrous of oxide cannot be it oxygen quantity once inferred from this change of bulk: before this can be done, it is needful to ascertain how much hydrogen is left in the mi cture. This may be effected by mixing the 6 remaining measur ;s with 2 measures of oxygen, thus making 8 measures, and aga n Steam will again be formed, ai d transmitting the electric spark.
;

immediately condensed the 8 measures of the mixture will nc w be reduced to 5 ; 3 measures of the gas will therefore have disi appeared, two-thirds of which, or 2 measures, are hydrogen measure of the gas now left must consequently be oxygen whi< h
: :

was added in excess, and the remaining 4 measures are nitroge i. Of the 6 measures of hydrogen originally added, 4 have therefo -e combined with oxygen derived from the nitrous oxide and sin & 4 measures of hydrogen require 2 measures of oxygen for co iversion into water, the 4 measures of nitrous oxide must ha e contained 2 measures of oxygen. It appears, also, that nitro is
;

its own bulk of nitrogen, since the 4 measures >f the gas originally employed furnish 4 measures of nitrogen ; tl is nitrogen is moreover so combined with 2 measures of oxygen,

oxide contains

PREPARATION OF NITRIC OXIDE.

163

into the space of

that the 6 measures of the two gases when united are condensed 4 measures, or into two-thirds of the bulk which

they occupied when separate.

The composition
Nitrogen

is

therefore

:

.

...

...

N =
3

Oxygen
Nitrous oxide

......

=

By weight. 28 or 63*64 16 36'36

By
... ...

vol.

2'o

ro
2'o

N

2

= 44

loo'oo

...

The

specific

hydrogen being
mination of
standard
its

j

gravity of the gas found by experiment, 22*066 (or 1*527 referred to air) confirms this deter-

composition.

Hydrogen being taken
... ...
...
...

as

the

2 vols. of nitrogen weigh
1 vol.

...

28
16

of oxygen weighs

...

2 vols. of nitrous oxide weigh
i

...

...

44

close to consequently that found by experiment. The proportion of nitrogen contained in the gas may also be ascertained by means of potassium ; for if potassium be heated in
22, a

volume would weigh

number very

nitrous oxide, it burns vividly, and is converted into potash, leaving a volume of nitrogen equal to that of the gas employed.
Salts of Nitrogen Monoxide, or Hyponitrites. By the action of sodium solution of an alkaline nitrate, it is speedily reduced to the nitrite, which, in its turn, undergoes further reduction, yielding amongst other products,

amalgam on a

NONa, a salt of which nitrous oxide appears to be the anhyrendering the solution slightly acid with acetic acid, and adding argentic nitrate, the silver salt, NOAg, is obtained as a yellow pulverulent presolution of cipitate insoluble in water, and almost insoluble in acetic acid.
dride.

sodium hyponitrite,

On

A

hyponitrite is alkaline to test paper, and when strongly acidified with acetic acid and heated, evolves nitrous oxide (Divers).
sodic

(391) NITRIC
oxide,
Vol.
[

OXIDE; Nitrosyl ; formerly Deutoxide, or Bin-

of Nitrogen,

NO = 30*
wt.
15.

}-^r\

&Pi.

@r r
'

39

'>

Atomic
acid

J;

Rel.

Preparation.

If nitric

be

diluted with twice

its
-

gravity of about i metallic mercury contained in

bulk of water, so as to reduce it to a specific 2, and be poured upon copper clippings or
a retort, a brisk action speedily
if

occurs

;

a gentle heat being applied,

necessary, until

it

com-

* The vapour density of

this

(H =

i

vol.) instead of

N

compound

is

anomalous,

NO yielding

2 volumes

2

2

as

would be

requisite if the

compound followed the
would

usual law.

It

is

become normal,

possible that at a sufficiently low temperature its density as is the case with nitric peroxide.

M

2

164

COMPOSITION OF NITRIC OXIDE.
the retort becomes
if

mences

;

filled

with red fumes, and a gas

is

disengaged, which
colourless
1

collected over water will be found to

be

20

c. c.

i ounce, or 30 grins., of copper by solution in about ; of the diluted acid would yield nearly 420 cubic inches,

If the heat be too high the or about 7 litres of nitric oxide. is apt to be contaminated with nitrogen. During this degas as be metal the displacing hydrogen regarded may composition

from one portion of the acid to form a nitrate which is dissolved, whilst the hydrogen, in the moment of its liberation, decomposes another portion of the acid, forming water and setting nitric The following equation shows the reaction oxide at liberty. which occurs between 3 atoms of copper and 8 molecules of
nitric acid, resulting in the

formation of nitric oxide, 3 molecule s
:

of cupric nitrate, and 4 of water
Copper.
Nitric acid.

Cnpric nitrate.

Nitric oxide.

Water.

8HNO3
8N0
2.
2

=

3(Cu2NO?)
3

(OH)

=

(0 2 Cu)"

-T~zNO+ 4H 2 O. CND + 4 OH 2 +
~~i
.

| JJJ

Nitric oxide gas may also be obtained perfectly pure digesting hydrochloric acid with iron filings till it will dissolve

by no

more, decanting the clear liquid, and adding to its own bulk < f hydrochloric acid on placing the solution in a retort, and adding potassic nitrate, the nitric oxide is immediately evolved in large
:

quantity (Pelouze).

ceding case
Ferrous
chloride.

;

it

may

The reaction is not so simple as in the be represented as follows
:

pn
Nitr oxid

-

Hydrochlor.
acid.

Potassic
nitrate.

Ferric
chloride.

Water

Potassie
chloride.

;
.

A
retort

simple modification of this method consists in placing in a 30 grms. of commercial nitre, 240 grms. of ferrous sulphat ,
1
1

and pouring upon them 250 cubic centim. of diluted sulphuric aci Such a mixture wi (i measure of acid to 3 measures of water).
give about 7
litres

nitric oxide cannot I e Composition. ascertained by detonation with hydrogen; for equal volumes f hydrogen and nitric oxide burn quietly with a green flame o i
<

of pure nitric oxide. The composition of

the approach of a burning body. heating charcoal strongly in it ;

Davy analysed
i

nitric oxide I y

2 volumes of the gas

treatment furnish bonic anhydride

i

volume of nitrogen, and
but
carbonic

by th volume of ca
its o\v

s
:i

:

anhydride

contains

volume of oxygen

;

nitric oxide

must therefore have consisted

f

PROPERTIES OF NITRIC OXIDE.
I

165
i

volume of nitrogen united without condensation with

volume

of oxygen.
Nitrogen
... ...

Oxygen
Nitric oxide

= NO =
O

N =

By weight. 14 or 46*67 16 53-33

By
...

vol.

i I

vol.

...

vol.

30

IOCTOO

...

2 vols.

specific gravity accords with the determination that the unite without condensation. gases
Relative weight of
I

The

vol.

of Nitrogen

... ...

i

Oxygen

= =

14 16

2 vols. of Nitric oxide

...

30

The

relative weight

of one volume of the

compound would

therefore be 15 while experiment gives 15^0 14 (L'O^, air being

taken as unity). Potassium burns when heated in the gas, potash being produced. If the experiment be conducted in such a manner as to
allow the residual gas to be measured after the combustion is over, 2 volumes of nitric oxide will be found to leave i volume

of nitrogen. the gas.
Properties.

A

similar result

is

obtained

when

tin

is

heated in

and cannot be
liquefy
its
it.

Nitric oxide has a strong disagreeable odour, It has hitherto resisted all attempts to respired.
dissolve
is

Water does not
;

more than one-twentieth of
to a red heat without under-

bulk of this gas.
it

Nitric oxide

the most stable of the oxides

of nitrogen

may even be exposed

going decomposition, but a succession of electric sparks converts and it, if it be moist, into a mixture of nitrogen and nitric acid
:

in contact with moistened iron filings, or a moist sulphide of one of the alkali-metals, it is slowly converted into nitrous oxide.

burning bodies, such, for instance, as a lighted taper, or phosphorus just kindled, are extinguished when plunged into the gas ; but if the phosphorus be burning vigorously the temperature will be sufficiently high to enable it to decompose the gas and it will then deflagrate with a brilliancy equal to that produced by its combustion in oxygen. If a thin bulb containing a few drops of carbonic disulphide be placed in a jar of nitric oxide, closed by a glass plate, and agitated briskly, so as to break the bulb

Many

and diffuse the vapour through the gas, a mixture will be obtained which on the approach of a flame burns with an intense whitish
blue light. Nitric oxide
is

sulphate, forming a deep reddish-brown liquid.

completely absorbed by a solution of ferrous All the ferrous

166

NITROUS ANHYDRIDE.

according to Peligot, 4 molecules molecule of nitric oxide, the solution in. This property, the case of the sulphate containing (4FeSO 4 ,N 2 O 2 ). as has been already mentioned (389), is employed for the purpose This liquid of detecting the presence of nitric acid in solution.
salts exert a similar action, and,

of the salt of iron absorb

i

when

absorbs oxygen rapidly from the air or from gaseous mixtures ; heated, most of the nitric oxide is expelled from it unSolutions of stannous and mercurous salts also absorb changed.

but they undergo change, and the gas cannot again Nitric acid likewise absorbs the be expelled from them by heat. gas rapidly; if the acid be concentrated, the solution becomes reddish brown ; if 'more diluted, it is green ; if still weaker, the
nitric oxide,

solution
little

is blue, but if diluted below a specific gravity of 1*15, of the gas is absorbed, and the acid remains colourless. Nitric oxide is neither acid nor alkaline in its characters. It

has, however, a very powerful attraction for oxygen, and to this circumstance one of the most characteristic properties of the gas

any gas containing uncombined oxygen, dense red fumes are formed, which are free ly soluble in water, producing an acid liquid. Formerly this circumstance was employed to determine the quantity of oxygen in gaseous mixtures ; but the method is now abandoned, as t! le
:

is

due

when mixed with oxygen,

or with

absorption is not uniform, owing to the formation in uncertain It may, quantity of a mixture of the soluble oxides of nitrogen.

however, be used with advantage as a qualitative test to demo strate the existence of uncombined oxygen in a gaseous mixtui
Nitric

i-

e.

oxide

also unites with half its

the two gases are mixed, and nitrous oxychloride
(394)-

volume of chlorine wh NOC1 is form

;n :d

(392) NITROUS ANHYDRIDE:
tion.
i.

(NO O
-,

.

Prepar 7-

an exhausted flask 4 volumes of niti tc oxide with i volume of oxygen, both in a perfectly dry sta e, brownish-red fumes of nitrous anhydride are formed, which a1 a temperature of o ( 18 C.) become condensed into a very volat le blue liquid, which emits a red vapour.

By mixing

in

Nitrous anhydride may also be obtained nearly in a stf 2. of purity, by heating in a capacious retort i part of starch wi H parts of nitric acid of it can be dried by passi sp. gr. 1^25 it over calcic chloride, and then be may liquefied by transmissi
:

te

th
ig >n

through a U-shaped tube surrounded by a mixture of ice and sa t. A small quantity of water converts the anhydriue Properties.

NITRITES.

167

into nitrous acid, but a larger quantity quickly decomposes it hence the presence of a small into nitric acid and nitric oxide
:

quantity of water converts the blue into a dark green liquid, but a larger quantity decomposes it with effervescence nitric acid is
:

formed, and
represented:
Nitrites.
is

nitric oxide escapes.

This last reaction

may be thus

H O + 3N 2 O 3
2

form nitrous anhydride with water decomposed by facility, yet nitrosion (NO ) forms with the metals of the alkalies these salts, permanent compounds

Though

give in its uncombined

2HNO3 + 4NO.

:

which have the general formula
nitric oxide

M'NO

2,

are called nitrites.

If

be placed over a solution of caustic potash, and small of quantities oxygen be 'added, potassic nitrite is produced in the and if nitre, or sodic nitrate, be heated to redness until liquid ;
the gas which
will be
is

evolved begins to contain nitrogen, the residue
nitrite.

found to be composed chiefly of potassic or sodic
nitrites are soluble in alcohol,

These

from the corresponding
nitrites of

nitrates,

and may thus be separated which are insoluble. The normal

sodium, silver, and lead are anhydrous. A considerable number of double nitrites of potassium may be formed. Lang has, for instance, among others, described the following
:

Nitrite of potassium

.........
and barium ... and zinc ...... bariutn and nickel...

'

2KN0 ,H 2 2KN02 ,Ba2N02 ,H 2 2KN02 ,Zn2NO 2 ,H 2 O
2

If the nitrite either of potassium or of sodium be dissolved in water, and argentic nitrate be added, a sparingly soluble argentic nitrite is precipitated, which may be purified by crystallization

from hot water.
solution

The addition of cold
decomposes the

dilute sulphuric acid to a

and the liquid then becomes of a brownish-red colour on adding a solution of ferrous The nitrites may thus be distinguished from the sulphate. nitrates, since the latter do not change colour when similarly A very minute treated, unless concentrated acid be employed.
of
nitrite
salt,

trace of

any

nitrite

may be

detected by mixing a dilute solution

of potassic iodide, free from iodate, with starch and a little diluted hydrochloric acid (sp. gr. i'oo6) ; the liquid to be tested, after being acidulated with hydrochloric acid, is then to be added
to the test mixture,

when the blue colour

of iodide of starch will

Acid solutions of appear, if any trace of a nitrite be present. the nitrites destroy the blue colour of indigo at ordinary temperatures, acting in this as in the preceding cases by its oxidizing
powers ; but in other instances it shows reducing powers equally marked. Acidulated solutions of the nitrites, for example, bleach

168

PREPARATION OF PEROXIDE OF NITROGEN.

potassic permanganate, and slowly reduce potassic chroraate to a Auric chloride is reduced to metallic green salt of chromium.

gold by these

salts,

and mercurous
nitrites

salts give a

grey precipitate of

reduced mercury.

The presence of
of

in

the well waters of
the

towns

is

common

ammonia

occurrence, probably owing to or of nitrogenous organic matter.

oxidation

of

Ammonia becomes

oxidized to nitrous acid
air in the presence

when

it is

in contact with atmospheric

platinum wire
in

;

if

a coil

of platinum black, or of a coil of heated of red-hot platinum wire be heli

a jar of air moistened with a few drops of a strong solution of ammonia, white fumes of ammonic nitrite will be

formed.

The contact of

metallic copper

is still

more

effectual ia

promoting the formation of nitrous acid from ammonia, when free oxygen is present; if a small quantity of finely divided metallic copper be shaken up with a few drops of a solution of ammonia in a bottle containing air, the oxygen will be absorbed in a few minutes, and nitrous acid will be found in the liquid. Even bright slips of
copper effect a similar oxidation of the ammonia, oxide of copper being simultaneously formed. The cause of these phenomena is obscure. According to Schonbein,the white fumes produced during the spontaneous oxidation of phosphorus in air consist, not of phos-

phorous anhydride, but of ammonic nitrite formed by the actio of the ozone upon moist air.
alkali -metals, as

i

Schonbein has shown that the solutions of the nitrates of tha
well
as

some other

nitrates,

may be

reduce

I

slowly to nitrites

by stirring or agitation with a rod of zinc or the reduction cadmium, being accelerated by heat.
(393)
acid,
2

c f

PEROXIDE OF NITROGEN
4

;

Nitric peroxide or Hyponitn
I

c

N O =9

2,

or

NO = 4 6
2

TCNTO 21
|

,_(JMU 2 J

^l

;

Melting.pt. 14

(-10

C.

,

and Troost ; Boiling-pt. 7i'6 (22 C.). Preparation.- The red fumes which appear on mixing nitric oxide wit i The pej atmospheric air consist mainly of peroxide of nitrogen.
Deville
I.

oxide

may be procured
nitric oxide

in
i

volumes of

and

prismatic crystals by passing tw of oxygen, both perfectly dry, int

> >

tubes previously dried with scrupulous care, and cooled down b a mixture of ice and salt. (Peligot, Ann. de Chimie, III. ii. 61

/
)

These crystals melt at 14 F. C.) ; at the ordinary ten perature of the air they form an orange-coloured liquid, whic boils at 7i'6 (22 C.), and produces a deep brownish-red vapou It is remarkable that after this compound has once been melte

(10

i

.

I

28 C. tube surrounded and fig.PEROXIDE OF NITROGEN. which the temperature rises. may tals.). Towards the latter part of the distilla- tion the anhydrous perif it oxide comes over. It. lead. it is decomposed. or mercury. it 169 This substance is does not freeze even at 6'3 ( 2i'3 C. (-10 C. salt. a minute trace of water is sufficient to prevent the formation of the crystalline compound. similar to that obtained by the The peroxide of nitrogen was distillation of plumbic nitrate.). the peroxide is condensed to a liquid which is green. deep red fumes. as by shown in 315. liquid peroxide is digested with a metal.N 2 O 5 .). the reaction is But when the as follows: K + N O4 =KNO + NO.. Miiller).) it is It emits a tint dense brownish-red vapour.) (82 as It has a specific gravity of i'45'j F. with potassium. nitrate of the metal is formed. and at ordinary temperatures boils 7i-6 (22 C. and plumbic oxide is left: 2 2PbO + 2N29 OA + O. decomposed by water with singular facility . for instance. consisting of a mixture of peroxide of nitrogen and free oxygen are produced.. and freezes at 40 (40 C. 2 3 No nitrite is formed under these circumstances. owing to the presence of a little moisture. such as potassium. does not form specific salts. and long possess hence was termed hyponitric acid. yielding KNO 3 + KNO + H 2 2 O. small glass retort. and the receiver be changed. . be obtained in crysThe melted peris oxide at o nearly colourless C. however.H 2 O).) : (-18 at it becomes yellow at 14 is red. 315. the to considered properties of an anhydride. but : is immediately decomposed by bases into a nitrate and 2 nitrite NO 4 + 2KHO. becomes deeper in (38 C. and nitric oxide is expelled . till at 100 almost opaque. If dry plumbic nitrate (Pb2NO 3 ) be heated strongly in a 2. occasioning in its stead the production of a green liquid (probably N2 O 3 .. If (Pb2NO s 2(Pb2NO 3) = the red vapour be to pass through a made bent ice FIG.

blue. or 30^44 By . green. 1-58 at 154 and 1^57 at O 4 is entirely dissociated into peratures above 154 the 2 2 The molecule of nitric peroxide is. i vol. and finally colourless an effervescence being occasioned during the whole time from the it escape of nitric oxide in the liquid. The nitric oxide on of mixing with the oxygen of the nitrogen as usual. found it as low as 171 whilst at 170 . M N (77 C... or one-half the molecilar : weight experiment gives 38'294 at z6 it 'j. Playfair and Wanklyn have shown it to be probable that at low temperatures the compound has the formula N 2 O 4 but that tiller as the temperature rises it assumes the constitution NO 2 hnds at 82 Chem. 2 .. vapour.. at ioo'i . formula NO =T 3 j is I '59 I - Deville and Troost (Compt. reproduces the peroxide li< The different tints assumed by the uid during dilution appear to be owing to the solution of the n trie oxide in varying proportion in the nitric acid produced by the Peroxide of nitrogen combines directly decomposition. yellow. The relative weight being 23. .. differently constituted at different temperatures. and Mitscherlich.. and of many burning bodies . . . 69-56 2 2 46 loo'oo . showing that at tem- NO compo- Nitrogen N Oxygen O 2 4 = = By .. It supports the combustion of a taper. (Ann. gr. 28 or 30^44 64 69-56 92 lO'OOO 2 4 2 .. its sition is By weight. This vapour has a peculiar. the experimental number bting 22740 at i83-2... but probably the calculated density for the higher. r8 at 8o'6 . 3 . becon ing successive!)' orange. N i83'2. finally.. nitric acid in 2 abundance is fori aed H O + 3NO =NO+2HNO air. 2*08 at 6o'2.170 PEROXIDE OF NITROGEN. gravity of the vapour is only 1*84. And the relative weight would be 46. suffocating odour. the of the cxxii. rend. gravity to be 2^65 at 267 . therefore.. at some temperature not stated. po assium takes fire in it spontaneously. If water be added gradu illy to the liquid peroxide. vol. At higher temperatures Nitrogen consists of: N O2 Oxygen =14 = 32 By weight. Ixiv. sp. 2 4 =[^_ J theoretically . 15) O would (28 C. Pharm. passes through various tints. . give 3' 18.) to be 270. at low temperatures.) the sp.. 257) found the specific i'68 C.

(394) Nitrylic Chloride. reduced by the addition of water) . Argentic phosphate. together with other compounds. KN07 [N02 (OK) -f HCISO. Hydrochloric acid.31 by the action of water it is decomposed into hydrochloric and nitric acids.Cl(OH) + = = KHS0 4 S02 (OH)(OK) + + - NO^Cl JST0 2 C1. Peroxide of nitrogen by be distinguished from nitrous acid a neutral solution of potassic of to power imparting may same reagent by sulphocyanide a red tint closely resembling that produced in the ferric salts . I ". Phosphoric oxyirichloride. produce one of the most corrosive compounds in the range of chemistry or may give rise. of vapour.3 2 . SOj. and forms a crystalline its compound with it (2H. Nitrylic chloride.gr. gr. tinction exhibit properties entirely different from either. + 3 NO C1. in a few minutes. The important influence of proportion upon the products of chemical combination of is exhibited in a striking light compounds nitrogen oxygen. Nitrylic chloride. may. which may be breathed with impunity .) . nitrous oxide. 2 of liquid. [3 N0 2 (OAg) + POC] a = PO(OAg) 3 Hydric potassie sulphate. as in nitric acid. as in the case of the . Nitrylic chloride boils at 41 (5 C. N0C1 1 + "HP + OH a = "HcP += HC1 + "~HNC N0 (OH)] 2 . Nitric acid. of vapour. to a stimulating and intoxicating gas. sp. however.] This body appears to be produced. wt. Water. while the intermediate combinations with The by these same elements. whilst each one of the true combinations of nitrogen with oxygen exhibits characters distinct from those of either of its components.] S : Or by the action of chlorhydrosulphuric acid on potassic nitrate Potassic nitrate.NITRYLIC CHLORIDE. broad disof mixture the results also be may easily traced between A The properties of the atmoare the the chemical qualiresults of simple admixture sphere ties of oxygen appearing to be simply diluted by its apparently inert companion. or Chloride of Nitryl.N 2 O SO 3 4 . according to the quantities in which they are united. is also absorbed by concentrated sulphuric acid.SO 4 . 2'8ip9 rel. 2*63 . theoretic sp. Chlorhydrosulphuric acid. the decomposition proceeds further. C1 = 8l'5. by the action of dry hydrochloric acid on dry nitric peroxide. 171 It hydrochloric acid. NO2 C1. 4075. is a liquid of a pale yellow colour prepared by the action of phosphoric oxytrichloride on plumbic or argentic nitrate N0 : : Argentic nitrate.) and does not solidify at 24 (. and forms several chlorinated compounds (394). C. nitrogen (just as the sweetness of sugar is : and those of true chemical union. and the liquid becomes colourless. 405 note).

or it is immediately decomposed with formation of mercurous chloride and nil ric oxide . When chlorine L ~j . de Chimie [3]. but the sblut contains hydrochloric acid and the products of the decomposition of nit -ic similar decomposition ensues when it is peroxide in presence of water.) it is may be regarded as nitric peroxide in which one-half of Below 1 9 replaced by the equivalent quantity of chlorine. producing chloronitric gas. and abundant ruddy fumes. Ann. red fumes pass off' in abundance. mixed with nitric oxide in the gaseous state. mixed with an alkaline hydrate. In this reaction 2 molecules of nitric ai id decompose 6 of hydrochloric acid. they combine. immediately. . and which boils at about 32 (o C. a transparent. long mistaken for peroxide of nitrogen. If a mixture of flask part of concentrated nitric acid and 3 parts of hydrochloric acid be placed in a and subjected to a gentle heat in the water bath. but as the decomposition advances the quantity of . in the early stages of t ic decomposition of aqua regia. but the red fumes pass on. Soiling-point 19 ( - 7 C. wt. Cl. NOC1 [NOC1] Theort Rel.). These vapours. \ ''<? is se 2 volumes of nitric oxide and I of chlorine prodi ce orange-coloured gas 2 volumes of the new compound. being liberated the chlorine in the nascent state acts upon the metals and dissolves : them. (Gay-Lussac . NOCL 1 or N 2 2 C1 4 [" j JJJJl . they decompose each other free chlorine. and yield a de: . the product is nearly pure chloi o- Aqua chloronitric nitric gas. but when the two acids are mixed. while free chlorine escapes fn m the open extremity of the tube. ~~! C1 2 I . 203. 2-2663. reduced to a red liquid resembling the chloronitric compound in odour ud aspect. the " King of Metals/' Both platinum and gold are insoluble in either acid separately. and may be condensed as a heavy red liquid in a tube receiver surrounded by a mixture of ice and salt. as it is .172 : AQUA REGIA. above this temperature it is it gas with a suffocating odour of aqua reg ia. sp. Molecular Vol. and free chlorine : f~ I j_ 2HNO. AQUA REGIA Nitro-muriatic Acid. or nitric dioxytetraMoride. i regia. N/)2 C1 4 + 4 Hg = 2 Hg Cl + a deep lemon yellow-coloured Water decomposes m A : 2 2 N 2 2 Nitrous oxychloride or chloronitrous gas. xxiii. under certain circumstances. if transmitted through a bottle cooled by immeygnn in melting ice. + 6HC1 = 2NOC1 2 + 4H 2 + ("won + 4 OH 2 + 2N02 (OH) + 6HC1 = iJnXr JN U^I (. red gas with which the chlorine of nitrogen.).) The is mixed consists of oxychlorides Chloro-nitric gas. It cannot be formed over mercury. deposit a little volatilized hydrochloric acid and water. may produce be ch arid chloronitrous gas . The name of aqua regia was given by the alchemists to a mixture of nitric and hydrochloric acid. 2 _J Chloro-nitric gas the oxygen ( is 7 C. water. The gas cannot be collected over mercury.gr. is At a temperature of o ( 18 C. 3275. fuming liquid. from the power that it possesses of dissolving gold. it immediately decomposed by this metal. or nitric oxydichloride. red. appearing to dissolve it.

by its action perchlorides liquid is when the tated. of Vapour (SS)=r ~j. or NITRIDE OF BORON BN.).)i. and decomposed by an alkali. Mol. Most of the sulphur used in England is . porous mass is left. when boiled with diluted hydrochloric acid and well washed. boron combines with nitride may also be obtained by transmitting a current of dry nitrogen gas over finely-powdered charcoal. such as those of lead or copper. 1904. (3940) BORIC NITRIDE. (395) THIS element is the representative of the hexad nonmetallic elements. In a current of steam 2 ammonic borate BN + 2H NH B0 4 2 . at . exposed to a full white heat in a porcelain tube. Dyaff. 239 (i 15 C. and Hexad in Sulphuric Acid [S vi O 2 (OH) 2]. which feels like talc when rubbed upon the skin. heated in hydrogen or in chlorine without change . Observed Specific Gravity of Vapour at r~] . yields boric nitride as a white. it upon by concentrated acid or alkaline solutions . Neither of these chlorinated compounds exerts any solvent action on gold or platinum. Melting-pt. as in H 2 S.SULPHUR. with 4 parts of fused It may boracic anhydride. Tetrad in Sulphurous Anhydride [S iv O ]. As already menBoric nitrogen at a red heat with great avidity. s = 32.) Boiling-pt. It completely converted into also decomposed when heated is with easily reducible metallic oxides. : tioned. light. Combining Volume below 1500 (816 C.) . infusible. 836 (446 C. 6-617. CHAPTER SULPHUR : XI. Gr. 2^2144. of the metals are formed in solution. amorphous. MoL ^. above 1904 (1040 C. and heating it to full redness in a covered platinum crucible . it is KBO a K 4- + H : 3KHO + BN 3 N. nitric oxids being evolved. Aqua regia is largely employed as an oxidizing agent . 173 nitrous oxychloride NOC1 increases. 32 . but is but very slowly acted fused with potassic when hydrate it 2 is converted into ammonia and potassic borate. the whole of the nitric acid may be By decomposed and expelled. a white. which. wt. Vol. and in 2 1V Triethyl-sulphine Iodide [S (C 2 H 5 ) 3 I]. It may be insoluble powder. = 64. Theoretic Sp. likewise be procured readily by mixing i part of anhydrous borax with 2 parts a mixture of I part of pure of sal ammoniac.awd in Sulphuric Dioxydichloride [S vi O 2 Cl 2]. 2'23. the oxide of the metal corresponding in composition to its perchloride is precipiboiling the solutions of the metals in aqua regia. and a pure solution of the metallic chlorides with excess of hydrochloric acid will be formed.) Rel. 900 (482 C. with excess of hydrochloric acid.

copper. where it occurs in the native or uncombined state in beds of a blue clay formation. at this temperature sulj:lmr i volume of wl ich yields a deep yellow vapour of sp.). constituting i oil known as flowers of sulphur. the sulphates of calcium. . Sulphur is still more extensively distributed ia the oxidized condition in the form of sulphates . and zinc.174 PROPERTIES OF SULPHUR.it a which dense liquid it may be distilled. and bi rns with a blue flame.). or common sulphur translucent. : heated to about 1832 (ioooC. and that at this high temperature the vol ime occupied by an atom of sulphur vapour corresponds with tha of . gritty powder. mag- nesium. 6'6\>j Bineau found that when sulphi ris contains 3 atoms of sulphur. and w" icn . and a necessary ingredient in the muscular tissue of indeed always contained in the albuminoid or proteid compounds. obtained from Sicily. or in transparent yellow crystals. Sulphur is likewise an essential constituent of many bodies of organic origin volatile oils . the form of which is derived from the octohedron with a rhombic base. Many of sulphur with the metals occur in great abundance as natural productions. lead. .) (Regnault) . barium. it is a bad tasteless conductor of heat.). arid . Native sulphur is found either in amorphous masses. Sulphur is highly inflammable. it enters into the composition of several foetid it is is animals. consequently occurs in commerce either as grasped with a warm hand frequently crackles and falls to pit ces from the unequal expansion . Properties. and strontium being abundant natural productions. especially the sulphides of iron. It is insoluble in water. and when heated in the ait' it takes fire at between 455 and 500 (235 and 260 C. Sulphur a harsh. Ferric disulphide (FeS 2 . found abundantly in most volcanic districts. emitting pungent suffocating fumes of <ul- At 239 (115 C. is less than the unmelted sulphur. In the latter condition it is a so id. or in round sticks. it is an insulator of electricity. of a characteristic yellow colour. iron pyrites) furnishes a large proportion of the sulphur consumed in the manufacture of oil of vitriol. gr. peculiar odour. the boiling point b< ing higher temperature about 836 (446 C. stretching from the southern It is also coast of the island towards the base of Mount Etna. forming a yellow phurous anhydride. brimstone.) it melts. yellow. the vapour becomes dilated to three times the bulk that an equal weight of the vapour occu )ies at 900 (482 C. and particularly in of the compounds those which border the Mediterranean. brittle substance. and is with a slight. md becomes negatively electric by friction.

175 an atom of oxygen .EXTRACTION AND REFINING OF SULPHUR. burn vividly when heated in its vapour. especially when the action is favoured by heat. of sulphur with the metals are termed sulphides they were known formerly as sulphur ets* responding to each oxide. and is then drawn off into cylindrical wooden moulds. Sulphur combines readily with chlorine. magnetic pyrites. fragments of ore are now piled up until the heap is about 8 feet metres) high. lateral neck . the fagots (2 '5 . prepared from pyrites (FeS 2 ). furnished with a short. When distilled sulphur is is in closed vessels. When the proportion of sulphur in the matrix is large. and over this one of brushwood in the centre is placed constructed a wooden chimney. which communicates with air-ways left between of which is at . and sulphur often displaces oxygen by double decomposition . The compounds . many of which. with bromine. Feg S 4 remaining. iron. and with iodine. Extraction. which it is applied in the arts. the sulphur melts. as a preliminary step in the roasting of copper pyrites to prepare it for smelting. i atom of sulphur is therefore equivalent to i atom of oxygen and consequently to 2 atoms of hydrogen or of chlorine. and with at the top charging large aperture a short wide tube. wide. Huge heaps of the ore are arranged in the form of a truncated square pyramid. the fire is kindled in the centre by dropping . and slopes downwards through the walls of the furnace into an earthen receiver of a form similar to that of the retort from the bottom of the receiver a short pipe carries : : off the It is. with a layer of powdered ore. in which it is cast into the usual form of roll sulphur. and silver. the mineral is sometimes and by this means about one-third of the sulphur . if in a state of fine division. but if the fire be urged. kept cool. and will furnish about 20 tons of sulphur. this observation has recently been confirmed by Deville and Debray.' When the construction of the heap is complete. and the melted sulphur into a vessel containing water. masonry be allowed to become hot. and forms 'flowers of sulphur'. the base it contains volatilized is more usual is about 30 feet (or 10 metres) in the side. a capacity of 4 or 5 gallons (18 for them with the crude sulphur. the earthy impurities are removed by simply melting out the sulphur from them . A layer of powdered ore the bottom. the sulphur is condensed in powder. like copper. but when the proportion of sulphur does not exceed 8 to 12 per cent. of 2000 tons of pyrites. which proceeds from the side at the upper part. to conduct the operation in the open air. and requires rectification before it is fit for many of the purposes to This second distillation is conducted in retorts. runs down. generally of iron. however. which but it and condensed. performed upon the spot where it is obtained. For this purpose a long brick furnace is arranged so as to contain a double row of upright earthenware retorts. and lastly the whole is covered. the fumes are If the walls of these chambers be received into large chambers of brickwork. It also enters rapidly into combination with most of the metals. it is found to be more advantageous to subject the mineral to a rough distillation. still very impure. for a depth of 12 inches Such a heap contains upwards (30 centimetres). each of a or 22 litres) the retorts are furnished with. and the process be conducted slowly. each Generally a sulphide exists coratom of oxygen in the molecule of the oxide being replaced in the sulphide by an atom of sulphur .

into these cavities it drains. and sulphur begins to ooze from the surface. viz. the still fluid portion may be poui ed off. is in the production of sulphuric acid. ployed to some extent as a medicine. The first form is with a rhombic base. acid it is applied to the bleaching of silks and flannels. Its cryst ds undergo 'no change in the air they fuse at 239 (115 C. if the cr ist be pierced with a hot wire. and although to the eye the crystals retain their prismatic o ittl transparent brownish-yellow needles. if an octohedron of sulphur be placed in a liquid. owin^ to the formation of prismatic crystals. the transparency disappe: rs. numerous hemispherical wells or excavations. the density of ordinary roll sulph ir.). it loses its transparency.o and 230 (104 and 110 C. (87) reuce of allotropy it may be obtained in several distinct modi(396) : fications of form. it melts at 248 (120 C. this is observed. as in the preparation of matches . The second variety is obtained by melting 2 or 3 kilogramn es of sulphur. from its used to facilitate the combustion of many ties are bodies.). and large quantiIt is emconsumed in the manufacture of gunpowder. the native crystal of sulphur. This form is :iot According to Brodie.176 lighted fagots diffused VARIOUS FORMS OF SULPHUR. consisting of minute rhombic -octohedra. When covers. an amount of heat is emi ted . and is daily ladled out and cast into moulds. he line. down the chimney in the course of a few days the heat becomes throughout the mass. or (if the surface of he crystals be scratched) in a few hours. Uses. Sulphur has been already as a out affording pointed striking illustration of the occur. are made in the superficial layer of ore. especially in certain forms and when converted into sulphurous of cutaneous disease . of disulphide. and has a density of 2*05. these have a specific gravity considerably less octohedral sulphur. and allowing it to solidify on the surface . for the reception of the sulphur . the octohedon It may be obtained artificially by allowi ig the solution of sulphur in chloride of sulphur. fitted with .. p: is- : they lose their coherence. belonging to the oblique matic form . or in carbonic It is semi-transparent. other hand. Various forms of Sulphur. or in different allotropic states. an amber yellow colour. its chief consumption.). however. Sulphur is ready inflammability it is extensively employed in the arts . and the solid mass beneath will be found to be lined w th : an rgS. to evaporate spontaneously. Mitscherlich has ascertained that in the passage of the p 'ismatic into the octohedral form. permanent in the air in a few days. temperature of which is slowly raised to a point between 2 . The process of roasting sueh a heap occupies five or six mouths. and an opaque crumbling mas is On he produced.

which is higher temperature. by immersing the prisms in a solution of carbonic disulphide. even when this solvent is already saturated with sulphur (Ann. 308) that this deepening the melted in colour of sulphur is due to the formation of another of modification sulphur.) now suddenly cooled by pouring it in a slender stream If it be into cold water. and tolerably the temperature rises.) 239 it and 284 it (140 C. of heat be steadily continued. 177 which would raise 4'O9 (2 27 C. if the apanalogous case of the melting of ice. to the elevation of temperature which it has experienced. the larger : Magnus has shown is the quantity of this black sulphur which is the formed details of the process required for isolating it are given at length in the memoir above referred to. the greater part of it assuming the If this ductile sulphur be heated to 212 brittle condition.) upon sulphur is very peculiar.) the more once liquefies. though it never becomes as fluid as sulphur when first melted at the temperature at 248 (120 C. transparent. density. giving out again the heat which it had absorbed.) during the change. the temperature of an equal weight of water This conversion of the prismatic into the octo- The forms. from a pale amber to a deep brown. (Pogg. (260 C. xcii. Annal. notwithstanding continued accessions of heat from without. and then suddenly cooled. the (loo C.). red variety of A sulphur was also obtained by Magnus.). In a few hours it becomes yellow and opaque. is produced by the action of a still even more remarkable than the preceding The influence of heat begins to melt at about C. 124). it also increases in octohedral form. the temperature again plication has it attained to nearly 500 and when rises. of only i'957is present.ALLOTROPIC FORMS OF SULPHUR. de Chimie [3]. xlix. which is black . to Berthelot (Ann. a soft tenacious mass is produced. deepens. the colour limpid liquid .). and at last nearly black and opaque. as in the After awhile. and between 248 (120 forms a yellow.). (110 C. and returns to the brittle form. xlvi. de Chimie [3]. becoming darker in proportion. third variety. which may be drawn The colour of the cooled threads varies out into elastic threads. which Mitscherlich proved to be produced only when a minute quantity of some fatty body Ductile sulphur has a sp. becomes brown.) these changes are very decided . hedral variety may be effected suddenly. At 356 (180 C. it suddenly returns to the tempe- rature rising to 230 II. 435) (397) According N . gr. so that heat is becoming absorbed. the more frequently the sulphur is heated up to about 599 (315 C. it gradually as : becomes more and more viscid the temperature at this point for awhile becomes stationary. It (115 C.

pentine likewise dissolves sulphur freely. rest. then suffered to cool very modification. phide at the ordinary temperatures also dissolved freely b chloride of sulphur. and as the liquid cooL' the sulphur crystallizes out first in the prismatic form.178 there are VARIOUS FORMS OF SULPHUR. and submitted to 2 or 3 successive sublimations it becomes converted into the electronegative condition. iji on 3 3 of disodic sulphide. and is rendered entire! The electropositive variety may also be slowly soluble in carbonic disulphide. especially when heated. the various modifications of which sulphur is two principal forms which are more stable than the These are the octahedral. solvent for sulphur. If maintained at 230 (110 C. it is somewhat less stable when of sulphur by decomposing it with water. and the white precipitate hydrogen. among susceptible. It is this form which is always deposited from cold solutions of sulphur . if the prepared from the chloride be obtained thus by digestion in carbonic disulphide.) for some time. and a negative variety. the solutio retains i . . amorphous powder is left. as he terms it. then with alcohol. Crystalline sulphur. it gradually with simultaneous development of heal. the electromost permanent condition of sulphur. in octohedra . or. and chlorine. ' converted into the electronegative form by contact with certain electropositiv substances. Electropositive sulphur is deposited at th negative electrode of the battery during the electrolysis of sulphurous or su Other modifications of the insoluble form of sulphur.). afterwards as the temperature continues to fall. are mor3 The most stable variety is that obtained by electronegative than sulphur itself. obtained from the alkaline polysulphides by the addition of an acid. Vitreous sulphur i s . . of sulphur when cold. such as the thiosulphates (hyposulphites). like oxygen. In the so-called electronegative or octohedral condition sulphur is soluble in This variety is deposited at the positive electrode of tho voltaic battery during the electrolysis of an aqueous solution of sulphuretted To this variety. whether the solvent be alcohol. a yellow purified precipitate This amorphous sulphur is muca or orange-yellow. If amorphous sulphur be heated to 572 (300 C. passes into the octohedral modification. bromine. disulphide. with greater facility than the foregoing one into the soluble variety (for examplt by exposure to 212 (100 C. ' The black sulphur of Magnus is also insoluble in carbonic disulphide. Boiling oil of tui it is ' : . . benzol. : form.) for some hours). in which cas3 a portion of the sulphur becomes dissolved. . The electropositive variety is obtained when sulphur is separated from it* combinations with elements which. as by digestion for some days in a solution of liquid ammonia. also belong. which is insoluble in carbonic pulverulent. and the remainder is rendere I soluble in carbonic disulphide. of either the octohedral or the prismati is soluble in. carbonic disulphide. about 3 times its weight of carbonic disul. or chloride of sulphur. . may be obtained by decomposin tlie oxidized compounds of sulphur. more readily oxidized by the action of hot nitric acid than the crystallin3 . b acids. which pan piiuric acid. the or electropositive form. carbonic disulphide. the prismatic form. i '5 per cent. and crystallizes out again in octohedra by th Benzol is an excellen spontaneous evaporation of these liquids. with carbonic disulphide. ami treating flowers of sulphur first then a second time with the disulphide . at a low temperaturt slowly. or in one of hydric potassic sulphite (KHSO S ).

179 but partially soluble in carbonic disulphide. the electropositive varieties becoming modified as they are dissolved : the hot solution as it cools de- posits minute transparent prismatic crystals of the electronegative variety. gr. (398) HYDROSULPHURIC ACID. centim. is It is formed in small sometimes called hydrosulphuric acid. [SHJ Mol Vol. Sulphur is also frequently liberated in the ductile form from the native sulphides of the metals during their solution in aqua regia. not wholly changed into the crystalline form of sulphur. 2 . the sulphur is condensed in red drops. and received into vessels in which the temperature is not considerably reduced. about half an ounce Preparation. termed an sulphuretted important compound commonly hydrogen hydrogen. COMPOUNDS OF SULPHUR WITH HYDROGEN. Theoforms with Sulphur 1*1764.) of water now poured a fluid ounce (about 30 cub. but is always usually employed. H S = 3 4. it may. and even after it has lost its vitreous and tenacious character by exposure to the air.} in a bottle together with about 6 or 8 ounces (200 cub. it is changed into the amorphous form. retic 17. Sp. Chloroform and ether dissolve sulphur less freely than alcohol. which remain liquid for many hours.) of sulphuric acid is in through the funnel tube. but which. i. All the varieties of sulphur are soluble to a small extent in boiling anhydrous alcohol. the sulphur is separated in solid flocks. When sulphur is distilled in small quantities. Observed. as it possesses feebly acid properties. Dihydric Sulphide. when the gas is the iron and hydrogen change places. be reconverted it is by fusion into ordinary sulphur. 1*1912. ferevolved abundantly . in small fragments. quantities prepared for use with an metallic sulphides dilute and ferrous acid. centim.COMPOUNDS OF SULPHUR WITH HYDROGEN. When nitric acid is used. Sulphuretted Hydrogen. however. soluble in carbonic disulphide. If vitreous sulphur be left in contact for 24 hours with an aqueous solution of sulphuretted hydrogen. ferrous of sulphide (FeS). sulphuric acid being sulphide when sulphur is heated in hydrogen by decomposing one of the gas. QT^J Ret- to/. i'955 being left when it is treated with carbonic disulphide. a pale buff-coloured powder of sp. and from the thiosulphates (hyposulphites) when decomposed by concentrated hydrochloric acid. is placed (15 grms. Gr. : rous sulphate is formed and dissolved and sulphuretted hydrogen N 2 . For ordinary purposes.

ordinary stopper. may thus be kept in a serviceable condilion without the trouble or loss of time consequent on the frequ . various small tubes are conne( ted ' together by long pieces of canized caoutchouc tubing. open at both ends.180 is PROPERTIES OF SULPHURETTED HYDROGEN. gr. ratus. this tube is ground so as to close the neck of the bottle air-tight. the ferrous sulphide is contaminated. a convenient arrangement for disengaging a continuous Fig. > ul- When the gas is re2. but is made to fit. 2 molecules of antimonious chloride and 3 of sulphure ted + 6HC1 = 2SbCl s + 3 H 2 S. wl ich would be needed unless his 'he expedient were adopted. 317. The appa- which requires to be requently dismounted in order to be charged afresh. 8 a piece of stout glass tube. 316 shows The cork through which the tubes current of the gas from ferrous sulphide. B or c. 316. the apparatus may then be arranged as in fig. Sb 3 S. in order to remove any parti les is 304 of the acid or of the metallic salt which over. quired in a state of purity . I may have As the compound of antimony with sulphur it is been mechanically car ied a sesquisulphide (Sb. 3:7. S ). s molecule of hydrogen and furnishes .nt renewal of the corks. i part of powdered antimoni >us sulphide is substituted for the ferrous sulphide in this cas it : * necessary to employ parts of hydrochloric acid of sp. pass FIG. into is not fitted at once into the bottle. as at a. IT. promixed with cured in this manner is usually iron with which metallic on the duced by the action of the acid evolved. and to apply a gentle heat to she In either case the mixture . 318. like an FIG. requires 6 molecules of hydrochloric acid for its decomposit on. such as is shown in fig. . 318. FIG. gas requires to be washed before collecting it. The gas which is proFeS + H 2 SO 4 =H 2 S + FeSO 4 free hydrogen. .

Hydrosulphuric acid is a transparent colourless gas. Under a hydrogen is pressure of about 17 atmospheres. and has the smell and taste of the gas... sulphur being precipitated. weighing at 60 and 30 inches rather more than 37 grains. When exposed to the air. according to Regnault. and iodine . extremely mobile liquid.) . of a very offensive odour. bromine.. and this action is favoured by the presence of a base which fixes the newly- formed acid. is slowly oxidized. depositing sulphur if the supply of air be insufficient for complete combustion. 2 * Potassium caunot be substituted for tin in this case. Hydrosulphuric acid is also immediately decomposed by chlorine. Its density a little exceeds that of atmomm Bar. Composition. or hydriodic acid being formed by the union of the hydrogen with one of the halogens above mentioned. whilst the hydrogen of the sulphuretted hydrogen water. The solution is feebly acid.). The proportion of hydrogen in a given volume of the gas may be ascertained by heating some granulated tin in a small retort filled with sulphuretted hydrogen and inverted in a vessel of mercury the sulphur combines with the tin. or 100 ' cub. spheric weighing i'5475 grm.* In sulphuretted hydrogen i volume of sulphur vapour and 2 volumes of hydrogen are therefore condensed into the space of 2 volumes. resembling that of rotten eggs. I 320194-12 5-88 a 34 loo'oo . 181 Properties. and the composition of the gas may be : thus represented Sulphur : Hydrogen = H = HS= S 2 2 By 2 weight. vol.COMPOSITION OF SULPHURETTED HYDROGEN. and burns with a pale. and jven when diluted with from 600 to 1200 times its bulk of air is rapidly fatal to the lower animals. By . because. bluish flame. it is partially decomposed into sulphur and free hydrogen.) dissolves 4/37 times its bulk of sulphuretted hydrogen. i litre at o C. sulphuretted reducible to a colourless. freezes to a transparent mass at a temperature of 12 2' 8 ( Water at 32 (o C. 76o air. and 26*6 at 75'2 (24 C.. whilst the hydrogen which remains occupies the same space when cold as the original gas. this solution becomes turbid from separation of sulphur. in.. which. If transmitted through tubes heated to redness.. . although .).. it 86 C. and hydrochloric. forming If the oxidation of sulphuretted hydrogen takes place in a moist atmosphere.) (Bunsen). It is highly poisonous when respired in a concentrated form. 3-23 times its bulk at 59 (15 C. hydrobromic. It is inflammable. boils at 79'6 ( 62 C. a little sulphuric acid is formed.

Sulphuretted hydrogen is in continual requisition in tl e laboratory as a test for the detection of certain metals as it giv -s characteristic precipitates with many metallic salts . sulphuretted hydrogen is generated in large quantities in stagnant sewers and cesspools. decomposes the gas. it aid . when cupric sulphate in solution is treat< d with sulphuretted hydrogen.a?H 4 2 2 2 O. hydrosulphate of potash (K 2 O. In this way soluble sulphides are formed in : many springs. Hydrosulphuric aciil. as in the analogous case are. and is capable. being K H however. of the chlorides. because the hydrogen of the acid is exactly equivalent o the oxygen of the base. the dipotassic sulphide which is formed absorbs enters into combination with another portion of the gas. dipotassic sulphide and water. causir g the odour observed on exposing such compounds to moist air. the sulphate loses oxygen. thus CaSO 4 -2O 2 =CaS. and the liquid becomes ac d from the liberation of sulphuric acid: CuSO 4 + S + ^H O = : H The larger number of the metallic sulphid :s when thus formed combine with water at the moment of the ir 2 H SO + CuS. whilst sulphide of the metal remains. giving to them their peculiar sulphureous odour and.182 HYDROSULPHATES. sulphate (H 3N) 2 2 S.H 2 S. in a somewhat similar manner. combines readily with bases for example. produces an insoluble metallic su lphide for instance. for example. hydrosulphate of potash. an abundant black precipitate )f hydrated cupric sulphide is formed. (399) Hydrosulp hates and Sulphides. if the gas be passed into a solution of potash or ammonia.H 2 S) may be regarded . generally regarded as containing sulphides of tl e metals. one atom of calcic sulphate. by the abstraction of 4 atoms into calcic of oxygen.is S-1-H 2 O. for instanc 3. Sulphuretted hydrogen is formed spontaneously under a Whenever a soluble sulphate remains variety of circumstances. or as Moreover. OB SULPHIDES. though a feeble acid. of forming water and a metallic sulphide f >r example. such as those of Harrogate. ammonia. becomes converted sulphide . which combines with the elements of the decaying substance. sul2 : K phuretted hydrogen in cases in which it occasions a precipitate n the solution of a metallic salt. of Such solutions formed. precipitation. it is : or hydrorapidly absorbed. in contact with decaying animal or vegetable matter. The sulphides thus formed are readily decomposed by acids sufli- even the carbonic acid absorbed from the atmosphere being cient to occasion the liberation of sulphuretted hydrogen. 2 O.

in the course of analysis. solutions of the alkaline sulphides have indeed been employed for The results of oxidaremoving oxygen from gaseous mixtures. but as this gas is liable to carry over particles held in mechanical suspension.^H 2 O + 2S 2 . and many of them absorb oxygen +K rapidly when exposed to the air in their moist condition . salt When in any the attraction between the metal and the too great to be overcome by the action of hydrothe sulphide may be obtained if we simultaneously acid. 4FeS. intermediate between the hydrosulphuric acid and the ordinary sulphide e. but if mixed with a solution of dipotassic sulphide. Potassic sulphhydrate.coloured precipitate. like nickel sulphide into sulphate . Hydrosulphuric acid is usually stated to have a strong disposition to combine with the soluble sulphides. and with those of antimony an orange. with those of arsenicum. this may easily be alkali-metal present salt-radicle is effected by adding a soluble sulphide to the solution of the salt to be decomposed if ferrous sulphate (FeSO 4) be exposed to a cur: rent of sulphuretted hydrogen it will experience no change . Many metallic solutions. 316. yield no precipitate with : sul- phuretted hydrogen and it is therefore commonly employed. fig. to separate those metals which are thrown down by it in the form of insoluble sulphides. Dipotassie sulphide. it is first allowed to bubble up through a layer of water in a Woulfe's bottle interposed between the generator and the -liquid to be submitted to its action. : Hydrosulphuric acid. whilst others. a black precipitate ofhydrated ferrous sulphide (FeS. such as those of zinc. 183 with the compounds of lead it gives a black. corresponding with the compounds in the oxygen series indicated by the formulae : .HYDROSULPHATES.<rH 2 O) is immediately produced. when acidulated. some being converted. NiS. while potassic sulphate is formed in the solution: FeSO 4 2 S. iron. ^H 2 O = K 2 SO 4 + FeS. a yellow. OR SULPHIDES. For this purpose a current of the gas is transmitted through the solution on which it is designed to act.^H 2 O. as shown at c. are simply converted into free sulphur and a metallic oxide .-H O + 3O 2 2 becoming 2Fe 2 O 3 . sulphuric an to the salt-radicle. are most conveniently represented by regarding them as double sulphides of the metal and hydrogen. and to form definite compounds with them. however.g. The sulphides thus formed are very commonly hydrated compounds. rH O + 2O 2 = NiSO 4 -l-rH 2 O < tion vary. and manganese. These compounds. like ferrous sul: phide.

a brov n or black tinge occurs upon the paper after the lapse of a few The pr >minutes. 2H 4NHS + MnSO 4 =(H 4N) 2 SO 4 +MnS + H. which m ty be obtained by boiling equal weights of slaked lime and powdered sulphur in water. 2H 2 S + 2l2 =4HI + S 2 Traces of soluble sulphides . in this reacti* >u the sulphuretted hydrogen converts the iodine into hydriodic whilst the acid. (400) ir HYDBIC PEBSULPHIDE. hydrate. ? or "2^5 ?) it is (SH ' ^-P' r ' f -Liquid. may be detected in neutral >r alkaline solutions by the magnificent purple colour which they form on the addition of a solution of sodic Whi u nitroprusside. may be accurately determined by mixing the liquid to be tested with a small quantity of a cold solution of starch any slightly acidulated with acetic acid. if sulphuretted hydrogen be evolved. hydrogen and the dyads or tetrads. and when decomposed by a metallic for salt.184 . heated before the blowpipe. S. double sulphides belongs the ordinary test-liquid (H 4NHS). KKO. or Persulphide of Hydrogen (H2 S 2 i"]6g. the hydrosulphuric acid is set at ii liberty . most of the sulphides emit the odo of sulphurous anhydride. This evolution of sulphuretted hydrogen distinguishes them from t le No such double sulphides are formed with simple sulphides.. ammonic hydric sulphide. 3CaH 2 + 6S 2 whilst the excess of undissolved sulphur is separated >y . These compounds emit a strong odour of sulphuretted hydrogen. Many of the sulphhydrates and sulphides are easily detected by the odour of sulphuretted hydrogen which they evolve when moistened with hydrochloric acid. Potassic Anhydrous potash. portion of free sulphuretted hydrogen. "KHO . ^RO To this class of . very minute trace of the gas may be detected by enclosing a piece of paper A moistened with a solution of plumbic acetate in the upper part of the tube or vessel in which the suspected sulphide has beoii mixed with acid. and enters into solution . example. which is used in the laboratory under the name of hydrosulphate of ammonia. PERSULPHIDE OF HYDROGEN. or of a soluble sulphide u solution. owing to the formation of plumbic sulphide. In order to procure this co n- usual to begin by preparing a calcic pound pentasulphide (CaS 6 ). such as the metals of the earths proper and of the iron group. calcic pentasulphide mixed with a corresponding amount of calcic th osulphate (hyposulphite) is : CaS 2 3 + 2CaS6 + 3H 2 formed. liquid becomes turbid from the separation if sulphur. and adding a standard sol i:s tion of iodine dissolved in potassic iodide until the starch assum a blue tint from the action of excess of iodine . Tests.

(401) SULPHUR CHLORIDE S 2 C1 2 =I35. hydric persulphide sub- sides as an oily liquid. and is immediately decomThe latter circumstance renders it necessary in preparing posed by alkalies. Rel. this compound to add the calcic pentasulphide to the acid. and much more readily when heated. in the S C1 the shown chloride. since a portion of sulphur derived from the calcic thiosulphate (hyposulphite) formed in preparing the pentasulphide is always precipitated along with the persulphide. which would produce an evolution of hydrosulphuric The sulphur which is a precipitation of finely divided sulphur. in precipitated employed in this manner from an alkaline pentasulphide was medicine under the term of lac sulpkuris formerly contact with Oxides of manganese and silver decompose hydric persulphide by mere the liquid. 185 On pouring diluted with twice its bulk of water the deep yellow liquid into hydrochloric acid previously and gently warmed. J . 470 . Bolling-pt. it cannot be purified by distillation. wt. having a smell In acid it burns with a blue flame. to the acid and pentasulphide.SULPHUR CHLORIDE. Vol. and not the acid . fig. : and taste resembling that of hydrosulphuric many . of Liquid. Gr. 28o'4 (138 C. owing to its instability. . 67*5 Sp. of its properties it presents a striking it possesses bleaching powers. and.). and becomes dissolved composition is not known with in it. preparing 319 arrangement 2 2 may be adopted. 319. r68 of Vapour. In ordinary temperature. filtration. freely. . is very analogy with hydric peroxide (348) prone to spontaneous decomposition into sulphur and sulphuretted hydrogen it is rendered more stable by the presence of acids. producing a violent effervescence. Mol. so that its Hydric persulphide dissolves sulphur certainty. compounds with each other Chlorine . owing to the dis- engagement of sulphuretted hydrogen. in which a steady current of washed and dried . r (scn L scij' . and sulphur form two combine they gradually at the FIG.

owing to its action on the externally : . Gr. however. disagreeable. even denies its existence as a separate body. emits fumes on exposure to the air. Carius. viz. 1*625) may be formed by saturating the preceding compound with chlorine: it is a deep-red liquid. as well as to that of oxygen which they contain. of a It peculiar. . vol. the others are less important. cvi. ig known and employed on a large scale in. wt. Sulphurous anhydride Sulphuric anhydride . 2H 3 N. and they show the application of the law of multiple pioportions to the case of the sulphur. . penetrating odour is thus formed. mixed with some of the polythionic acids. kept cool resulting chloride tillation it may be purified from excess of chlorine by redisfrom powdered sulphur a yellow volatile liquid.186 chlorine is OXIDES OF SULPHUR. of Liquid. and of comparatively recent discovery.. S02 =^ S03 = 64 80 . bottom. Some of these acids of sulphur are interesting. ~j 50-00 40-00 ^J + + 50-00 6o'oo = = ice loc Sulphur. brought into contact ammonia it . and is slowly decomposed into hydrochloric and sulphurous acids.H 3 N. Mol.. in allusion to the multiple proportion in which the si 1- phur enters their composition .the arts . sulphur). (402) only of sulphur are CoMPpUNDS OF SULPHUR WITH OXYGEN. and free sulphur It acts powerfully on mercury when in the electropositive form. Two oxides known in the anhydrous state. | Sulphur.-at list is oxyacids of sulphur. many. Oxygen. combines in two proportions. and is decomposed in the direct rays of ihe It is partially decomposed by sun into the chloride S 2 C) 2 and free chlorine. inasmuch as they exhildt a combining ratio different from any which we have as yet co isidered.S 2 C1 2 and4. Pharm.. t ic The following table exhibits the composition of the vario is. Sulphur dichloride (SC1 2 = 103 Sp. When dropped into water it falls to the atmospheric moisture. : Mol. passed into the retort containing melted sulphur. boiling it. forming the compounds . regarding ihe red liquid as a mixture of the chloride S 2 C1 2 with a higher chloride (SC1 4 ) not yet isolated.S 2 Cl 2 An oxychloride of sulphur (S 2 C14O 3 ) is obtained in crystals by transmitting moist chlorine through the chloride. with and dissolves sulphur freely . 291). the must be collected in a dry receiver. . which fumes strongly in the air. i n of as constituting the polythionic series (from iro\v. forms numerous oxidized acid compounds: two of them (sulphurous acid and sulphuric acid) have been lo.. Qti< >v. Chi in. the existence of which The five compounds which stand last on the present kno^ are often spok n. with it. in his elaborate examination of these compounds (Ann.

ment furnishes an easy proof of the composition of the gas . Vol..10 C... required in a pure state.. Theoretic Sp. H S0 2 2 . and the gas has been allowed to regain its original temperature...... Sul- SO 2 = 64. two or three ounces (about 90 grammes) of concentrated sulphuric acid may be boiled in a glass retort with half an ounce ( 5 grms. when the combustion is terminated..10 (-76 C. then the sulphuric whose compounds.pt.. . with the exception of some of the hyposulphites (thiosulphates).. I . producing a gaseous oxide.. acid.. acid. but the density of the gas is doubled. Tetrathionic Pentathionic .. ["~|~|. The result of the reaction in the case of copper is 1 indicated by the following equation : The gas should be washed in the usual way by allowing it to bubble up through a bottle containing a small quantity of water.)..). i... sulphurous anhydride is always prepared by depriving oil of vitriol of part of its oxygen... or ... When Preparation. . Sulphurous anhydride in : is the sole product if the oxygen be dry. wt. (403) SULPHUROUS ANHYDRIDE : f phur burns in oxygen with a lilac-coloured flame... 1-38.) of copper clippings or of mercury. The composition of sulphurous anhydride may be represented the following way By weight... the volume of the gaseous product will be found to be the same as before the This experiexperiment.. Boiling-pt. of Liquid......... shall first acid...) .. at 60 (i5'5 C. Sulphur . . S 2 = 32 or Oxygen .. . Gr... 2 2 Sulphurous anhydride S0 2 64 . have as yet received no practical applications...... of Gas.... .. .. By vol... HS HSO HS HS 2 2 2 2 3 2 4 H 2 SS = 66 = 82 = 98 = 114 = 162 = 194 = 226 = 258 v examine the sulphurous acid. 2^247.... In order to effect this... Observed. = 32 50 50 100 ...... .... ... Sulphosulphuric acid Dithionic Trithionic ..... . Meltinff... ... for it is thus shown to contain equal weights of sulphur and oxygen.. 14 (.. H H 2 S03 S04 2 3 3 6 6 6 6 Hyposulphuvous Thiosulphuric .SULPHUROUS ANHYDRIDE.. briefly noticing the other acids..... 2-2144. Eel.... We (formerly Sulphurous Acid] Mol. Hyposulphurous Sulphurous acid Sulphuric acid acid. ...... 187 Hydrosulphurous acid .... 32.

188 to retain SULPHUROUS ANHYDRIDE PREPARATION. and is occasionally met with in springs of volcanic districts. carbonic anhydride 3. it freezes at 105 ( 76 C. emitted abundantly from the craters solution in the Sulphurous anhydride.ed ibe he >m This gas has a pungent suffocating odour. by transmission through a tube surrounded b. According to Millon and Commaille. that of burning sulphur. cooled by a freezing mixture . accumulates in his . however. limpid liquid. be sulphuric acid and any impurities which might in the gas. every trac of arsenic in the sulphuric acid. and the liquid is preserved by drawing off and sealing the tube at narrow portion in the flame of the blowpipe. . S 2 + MnO 2 =SO 2 + MnS. Cu 2 $ is produced during this operation. insoluble residue. Sulphuric acid may means of charcoal or dry accompanied by one-half be more economically deoxidized by sawdust. washed and dried by means of concentrated sulphuric acid placed in she a bottle. the presence of unimportant. the anhydride is poured into it through a small t funnel. a mixture of ice and salt. 320 show^ a method of liquefying sulphurous anhydride. forming a trs tisr parent. which is surrounded b freezing mixture of ice and salt. c. with i obtained by heating a mixture of 3 parts of part of sulphur.timate mixture of 4 parts of flowers of sulphur and 5 of finely powdered peroxide of manganese. H SO 2 3. A. without removing it fi the freezing mixture. Sulphurous anhydride dissolves in water yielding a solution of sulphurous acid. in closed tubes at Fig. 1 ke Properties. may be condensed to a colourless. or in the copper dissolved.) it exerts a pressure of 2*54 atmospheres. and collected in the receiver. transparent. such as the preparation of the alkaline sulphites. quickly extinguis ies the flame of burning bodies. when diluted it produces the symptoms of It is not inflammable. B. one of which is shown at E. which read ily * According to Maumene. in .). which dissolves bitumen . The gas is generated in the flask. which is Iso ' . transmitted through the pewter worm.* mechanically suspended 2. 2CuO + S 2 becoming is Cu 2 S + S0 2 Sulphurous anhydride of volcanoes. For most purposes. by heating in a flask an ir. and ordinary catarrh. : what similar result is cupric oxide . heavier than the liquid 60 (i5'5 C. . which renders it quite irrespirable ii a concentrated form . crystalline solid. colourless. Sulphurous anhydride may also be procured readily by the oxidation of sulphur for example. D. but the gas in this case is its C + 2H 2 SO 4 =2SO 2 + CO 2 +2H 2 O. 321 : the tube having been pla in the freezing mixture. fig. after which a mixture of cupric sulphide nd oxysulphide is also formed. a certain quantity of cuprous sulphide. the liquefied compound is stored up for use small tubes. is volume of carbonic anhydride . sulphurous anhydride and mangaA somenous sulphide are produced .

takes up. 320. half the oxygen of presence the sulphurous anhydride uniting with the hydrogen of the sul- Sulphurous phuretted hydrogen. gas must always be collected either over mercury. SO 3 in the form of cubical crystals a 2 procuring the pure acid of sulphurous acid (SO 2 i5H 2 O. whilst sulphur is deposited. or in bottles by displacement. water and pentathionic acid being formed For complete decomposition. the dry gas easily applied. anhydride and sulphuretted hydrogen. 189 water. equal volumes of sulphuretted hydrogen and of sulphurous anhydride would be requisite. Water. the latter method is the C. from the high density of the (double that of oxygen). : H according to Bunsen. crystalline hydrate or SO 2 8H 2 O. Pierre) may also be obtained at a low temperature at 39 (4 C. gas. Schonfeld . Dopping succeeded in aqueous the.). and gradually absorbs oxygen from the air. in the of moisture.) . decompose each other. 321. On cooling a saturated of the gas to 32 solution (o C. FIG.). at 32. 43-5 times its bulk at 59 (15 C.) this hydrate melts and is decomposed. which conthe verts sulphurous into sulphuric acid. . lecomposes again at a very gentle heat into the anhydride and The solution has a taste and smell similar to that of FIG.PREPARATION OF SULPHUROUS ANHYDRIDE. 68'8 times its bulk of gas. and 32 at 75 (24 Owing to the solubility of sulphurous anhydride in water. ioSO 2 +ioH 2 S=5S 2 .

With the alkalies Sulphurous acid is a weak dibasic HI id. and their colour is discharged. may be preserved fresh for years.ioH O) [SO(ONa) 2 . new flannel. affords a practical illustration of the effect of an alkali upon goods which have been bleached by sulphurous acid. and suspended in closed chambers in which sulphur is burned in an open dish the sulphurous anhydride is absorbed by the damp goods. and then sealed of the to the action gas. would be injured by chlorine. and the colour will be restored in . sponge. It is wine: a often used to check fermentation in cider. and other articles which Uses. . The articles to be bleached are moistened. The acid . isinglass. for the sulphurous acid may either be expelled by a stronger acid. but those of barii m. It is pro(397). it is always obtained by burn ng air. and calcium. one of which is represented by the ordinary disodic sulphite (Na 2 SO3 . decompose the colouring matters. appears to act by forming colourless compounds with certain It does not. however.ioOH 2]. . The following table shows the composition of some of :he sulphites : . and in this case it sulphur.190 INDUSTRIAL APPLICATIONS OF SULPHUROUS ACID. and is insoluble of Much form bable that a large proportion of native sulphur has been formed in consequence of this reaction. or it may be neutralized by an alkali. as well as silken goods. colouring matter. or in home-m ide little sulphur being burned in the cask before filling it with the liquor. It is. or a metallic sulphide. The sulphites of the alkali-metals are the o ily ones which are freely soluble in water strontium. when it is the reproduction of the yellow colour washed with an alkaline soap for the first time. principally as a preliminary step in the ma: lufacture of oil of vitriol that sulphurous anhydride is made u >on 1 the large scale. Sulphurous anhydride is a powerful antiseptic and is also highly Meat which has been exposed valuable as a disinfecting agent. up in metallic canisl ers filled with nitrogen to which a little nitric oxide has been added to remove the last traces of oxygen. forms two kinds of salts. while the other class is represented by :he hydric potassic sulphite (KHSO 3 ) [SO(OH)(ONa)] often caHed the bisulphite. are dissolved to some extent by an aqueous solution of sulphurous acid. the sulphur thus deposited is in the electropositive in carbonic disulphide. in (404) Sulphites. like chlorine. Sulphurous acid possesses considerable bleaching is extensively employed in bleaching straw and wool. and powers.

by the metals which. which should be closed by a glass plate.2OH 2] [SO(02 Ba)"] [SO(02 Mg)". of iodine. phuric acid. 191 Sulphurous acid H S0 2 8 [SO(OH). The sulphites.2OH2 ] Hydric-potassic sulphite (bisulphite) KHSO NaHS03 . PbSO.2H 2 BaSOs '. : arsenic acid green salt of cipitated reduced to arsenious acid. MM'SO.. iron.SULPHITES. Gold.SOS [SO(OM)J [SO(OH)(OM)] / salt HMSO. the precipitate is soluble in excess of the sulphite.. which is soluble in hydrochloric acid. are prefrom solutions containing excess of hydrochloric acid in is the reduced state. in the upper part of the vessel. Magnesic sulphite Plumbic sulphite Argentic sulphite MgS03 3 H2 . and tellurium.] Normal Acid salt M. its of sulphurous which known by best test for detecting small addition of a fragment of zinc and a drop or two of hydrochloric acid to the solution . the sulphurous acid is deoxidized. A solution of sulphurous acid dissolves like zinc. General formulae. tin. absorb oxygen from the air .. and is decomposed and cadmium. evolve . and chromic acid to a chromium. the gas last named may be detected by suspending a piece of paper moistened with a solution of plumbic acetate.. when moist. . and sulphuretted hydrogen is given off. but the solution thus obtained gives a white precipitate of baric sulphate on the addition of a solution of chlorine. Sodic sulphite Hydric-sodic sulphite (bisulphite) Calcic sulphite 4 HO Baric sulphite CaSOs . decomposed by a strong heat. or of bleaching powder. [SO(OM)(OM )] Potassic sulphite K S0 2 H 2 3. traces of sulphites consists in the phur combines with hydrogen.ioOH s] [SO(OH)(ONa)4OHj] [SO(0 2 Ca)". [SO(OH)(OK)] [SO(ONa) 8 . selenium. Double salt . the ferric salts are reduced by them to ferrous salts . and solutions of these salts are often used as deoxidizing agents for example. the sul- The peculiar pungent odour. the They are also decomposed by sulwith evolution or hydrochloric is acid. solutions of the Salts of silver in solution give a white precipitate with soluble sulphites . 3 OH 2] [SO(02 Pb)"] [SO(OAg)J Many of the sulphites are acid being gradually expelled. and it is partially reduced to metallic silver when the liquid is boiled : a characteristic reaction is the formation with baric chloride of a white precipitate of baric sulphite. 2 [SO(OK).

but this method is never employed. and some olher quantities.000 tons are The acid is occasionally met with uncomconsumed. and represented in the annexed equations ferrous : sulphurous acid. however. is speedily resolved into ferrous sulphide and tetrathionate . [SO 2 (OH) 2 ]. o: in Preparation. since which period the mode of conducting it has under one several modifications and improvements. sulphites are readily formed by transmitting a stream of sulphurous acid through water in which the oxide or the carbo- The nate of the metal is dissolved or suspended. it so that the intervention of some third substance becomes neces- . magnesium.192 SULPHURIC ACID PREPARATION. union between the two gases. concentrated nitric acid. the latter. Iron. metals. most abundant constituents of the c ust When sulphur is boiled in aqua regia. ferrous sulphite and thiosulphate (hyposulphite) being first formed. that when sulj hur is burned in air or in oxygen. if made to combine with half as much more oxyge as instructive. the product is sulphurous anhydj ide.FS<O + + H O = FeSO 4 + H SO + g 2 3 S2 . This gas. are amongst the of the earth. it is gradually oxidized and converted nto sulphuric acid . (405) Dihydric Sulphate (H 2 SO 4 = 98) which This constitutes one of the most substance. does not easily take p ace. barium. made by a process first employed by Roebuck. of chemical manufacture. It has i The changes which occur D. is rapidly heated with a solution of sulphurous acid. however. excepting for On the large scale t is experimental purposes in the laboratory. acid. free sulphur. In Great Britain alone upwards of 100. The sulphates of calcium. the tetrathionate in its turn is converted into hydrogen with hydrochloric dissolved if sulphate. is converted into sulphuric anhydride. in this process are remarkable and been already mentioned. rect already contains. FeS 4 O 6 = FtS 4. though in princip e it continues the same. particularly in those of volcanic regi< >ns. as is and whilst 3FeS 2 O 3 further. about the year i' 46. is made in enornous important products SULPHURIC ACID. the carbonates being decomposed with effervescence. annually bined in thermal springs. for example.

mixed with twice its bulk of occurs. and containing a mixture of oxide of copper oxide of chromium. if water be presented to them.SULPHURIC ACID PREPARATION. that the two gases unite rapidly when transmitted through a tube heated to incipient and sesqui- redness. the two gases combine. sulphurous anhydride. The following acid : table represents the composition of sulphuric Sulphur s = Oxygen . a very gradual combination If pure and dry oxygen. 193 sary . Wohler has also observed. obtained by precipitation. and sulphuric anhydride (SO 3 ) is produced. be transmitted over spongy platinum (65) heated in a tube.

and may go through the before. The nitric oxide is thus again liberated. and in a few minutes the inner surface of the receiver becomes coated with a white crystalline deposit. composition of which sulphurous anhydride.2SOS = (NO) 2 S 2 O7 ]. Weltzien found that sulphuric acid (H 2 S0 4 ) combines directly with nitn as anhydride (N a Ot). and the interior of which is moistened with sulphuric anhydride (S03).* body has been the object of H. sulphuric acid also forms with nitric peroxide a white crystal! ne H . in all proportions without er be la Provostaye procures it by the action of liquid sulphurous anhydride on liq id he considers it when anhydrous to consist of (SO nitric peroxide S . 2 6. and slightly moistened in the interior. . and may be sublimed without decomposition. from which oxygen is carefully excluded. but they often involve very complicated considerations. represented by the formula (2lI 2 0. in proportions which n: ly be represented by the formula or H(NO)S0 4 Z O. on cooling.SO. and he found the crystalline compound to have a composit an which may be represented by the formula [N2 O8 . and I molecule of sulphuric N0 NO H reconverted by again absorbing oxygen from the air. amorphous substance is formed . pound he regards as the essential constituent in the crystals above describ 'd.2X0 2 ).. they absorb moisture and ei Concentrated sulphuric acid. and this co 11true composition of this crystalline * The much discussion and numerous experimental inquiries. of crystals actually occurs.N2 According to he $ same chemist..2SOS .2N( a ). A. and nitric oxide from the bottle. a acid remains in i molecule of nitric oxide escapes. nitric peroxide. iu fusible at i63'4 (73 C. a forms a crystalline compound similar to the foregoing . which. sulphurous anhydride air. no deposition the formation of the crystalline body and its destruction are simultaneous if in the air has carrier of the operation be properly conducted. in the proportion of I molecule for every 2 molecules of nit 'ic oxide absorbed . . large excess. Pharm. yielding brisk effervescence . d. by the aid of heat. same round of compositions and decompositions. as sulphuric acid on the large scale. which appear to contain water of crystallization. it is decomposed with + 2 S04 + x-iH 2 . fnsh sulphurous anhydride and these in their turn are decomposed by the water as crystals are formed.). the solution crystallizes. dissolves th< nitrous fumes.it m in id change. are made to pass ruddy fumes of nitric peroxide (N0 2 ) are immediately formed by the combination of the nitric oxide with atmospheric oxygen. the addition of wa immediately liberates red fumes of nitric peroxide from it. compound. Rose states that by passing pure dry nitric oxide into a glass vessel. . hard. whilst sulphuric acid is dissolv If the anhydrous crystals be exposed to the air. + S0 2 + a-H 2 0. liberating nitric oxide. contains the . which is consistent with the analysis of Briining. and water enter. is peroxide. into nitric been consumed : the oxide of nitrogen thus acts the part oi a In the manufacture of oxygen to the sulphurous anhydride. filled with ing apparatus. Oil of vitriol rapidly absorbs both nitrous anhydride and nitric peroxide. There are many other methods by which this curious substance may De obtained. this combines with another molecule of in the presence of a small quantity of water. Water imr ediately decomposes it. It fuses at a high temperature. a white. fig.194 SULPHURIC ACID THEORY OP ITS FORMATION/ Into a large three-necked receiver. c. Briining has shown that during the formation of this compound sulphun us anhydride is liberated. As soon as this crystalline mass is treated with water.3S0 8 . forming a white crystalline mass. into the . rectangular prisms. B. till the whole of the oxygen solution: the nitric oxide. Chem. 322. cxv. even when the peroxide is pres nt two substances in a proportion which may be Ann. atmospheric from the retort.

which pass on with the sulphurous anhydride. c. The general arrangements adopted are shown in FIG. and the mutual reaction of the atmospheric oxygen. 10 Ib. fig. c. 15 150 to 300 feet in length. represent furnaces in which the sulphur is burned 323. supplied from upon the square inch by means of jets. constructed of sheet lead. d. by suitable flues. interposed in the current of the mixed gases. the sulphurous anhydride is procured by burning either sulphur or iron pyrites (FeS 2 ) . A. consist o2 . or and 20 from wide. Vapours of nitric acid are thus liberated.) is placed upon tbe floor of the chamber. provision being made for an abundant supply of atmo- spheric air. in the current of heated gas an iron pot. 323. 5 or 7 broad. or about 4 or 5 metres high. is placed. they are sometimes partially intersected by incomplete transverse leaden partitions. to the depth of 2 or 3 inches (6 or 8 cm. These chambers are often 12 or 15 feet high. and sulphuric acid is formed in large quantity. b. to condense the acid . Water with a view of effecting their more intimate admixture. d. and supported by a strong timber framework. F. and from 50 to 100 metres long . In a properly managed chamber. 2 by the sulphurous anhydride to and then the changes already pointed out succeed each other rapidly. The nitric acid from the nitre speedily becomes deoxidized the state of nitric oxide (3SO 2 + 2HNO 3 + 2H 2 O = 2NO + 3 H SO 4 ). into immense chambers. sulphurous anhydride. c. A. the gases which pass off by only of nitrogen aud nitric oxide. which has been previously charged with a mixture of sodic nitrate and oil of : vitriol.. the boiler. 195 (406) In the manufacture of sulphuric acid. E.MANUFACTURE OP SULPHURIC ACID. F. the and sulphurous anhydride oxygen being supplied in quantities the exit flue. and nitric oxide is further facilitated by the injection of steam at a pressure of about c.

oxide in Gay-Lussac has taken advantage of the solubility of nitric oil of vitriol. gr. the brown a . i'6o does not usually contain more than o'6 per cent. The sulphuric bers it is is acid which collects at the bottom of the cha n- in too dilute a condition for many not found advantageous to allow it concentration greater than 1*60. gr. till it has acquired a density of the be carried beyond this point in concentration cannot 1*720.re has been reduced by one-half. during the whole operation some a . as the concentrated acid then beg ins to distil over.id is transferred into glass retorts. This improvement consists in conducting the spent gases into a leaden tower filled with fragments of coke. Indeed. the bottom of the tower to a reservoir from which it is agzin raised by a forcing-pump to the top of a second similar tower at the nitrous entrance of the chamber. flows off at nitrous and thus becomes charged with the vapours. . for their at just sufficient air entering mutual combination. 1720 forms the brown acid of commerce . avoided when the presence of nitrous compounds must be platinum is employed. which upon the old plan amounted to from oneeighth to one-twelfth of the weight of the sulphur consumed. as to attain a degree of and retain the nitrous fumes.r- extensively employed in the manufacture of the so-called sup phosphate of lime for manures. into platinum stills .* At this point it is sufficien ly strong for the manufacture of salt-cake. When required in a still more concentrated form. because the temperature required would endanger evaporated in shallow leaden pans the melting of the leaden pan and its corrosion by the ar This acid of sp. as is practised in many woi iss. in these it is again further heated ui til white fumes of oil of vitriol pass over. fresh atmospheric the other end along with the sulphurous an- hydride. when it becomes liable to abscrb technical purposes. where it is deprived of the compounds by the sulphurous anhydride as it enters By this contrivance the quantity of niv. through which a stream The acid of concentrated sulphuric acid is continually trickling. or even by formerly requisite from the furnace. of nitrous acid (Mr. is id. two-thirds. otherwise the metal is .id * The crude acid of sp. but it requires concc ntration for other purposes with this view it is drawn off a ad . to economize the consumption of nitre in the process. or. it . and for other coarse purposes. Allhusen). It is useless to carry he operation beyond this point. these vessels.196 MODE OF CONDENSING THE NITROUS FUMES. gradually corroded .

SO 3 : instead of 18*36 per cent. . H SO4 2 it is obtained. gr. effected H 2 O. always 189) [3].SULPHURIC ACID. the true compound ebullition. passes over with the water. contains a slight excess of water beyond that required by the the concentrated vitriol of commerce. 1*848 is Marignac. but if heated to partially decomposed in the manner stated by De of sp. of water. if the concentration of the acid be by a temperature not exceeding 500 (260 C. he always 19-62. De of it finds that de Chimie xxxix. it and The acid that remains is in the retort after oil has thus been boiled down. and a similar observation was made by GrayPlayfair states that.) (Vre). is 197 therefore preserved. Specific gravity. formula obtained Lussac. Strength of Sulphuric Acid of Different Densities at 60 * (i 5 5 C. Marignac (Ann. which returned to the leaden chamber.).

Sulphuric acid does not evaporate at the ordinary temperature of the air. mixes with water in all proportions. ture. which have accidentally fallen into it.198 moisture. gr. occasioned by its charring dish. and if a drop of the diluted acid until the acid concentration . Bineau stales that just above the boiling-point of the acid the vapour has a of 2' 15. This by some chemists is supposed to be produced at le ir >y le the separation of the compound into aqueous vapour and anhydri results differ but slightly table. until it chars or destroys the cohesion of the fibres .) a molecule of the compound occupies t space of 4 volumes. and the mixcold. from those of Ure. the water gradually evaporates which is left behind acquires a certain degree of on approaching a fire or other source of heat. sometimes of a dark brown colour. advantage is very often taken of this which enables it to be employed in a variety of cases property. So powerful is the attraction of the acid for moisture. laboratory. as : may be seen from the anne: ed temp. a id the remaining liquid boils at 64O'4 (338 C. fall upon a cloth. 59 (15 C. separate. It SULPHURIC ACID.) Specific . that if it he freely exposed to the air for a few days in a shallow made by the absorption of aqueous In the vapour. The acid of commerce is as a desiccating agent (66 and 185). always pouring the acid into the water. such as straw or wocd. m 878 (470 C. further portion of the water De Marignac finds that the true sulphuric acid (H 2 SO 4 ) wh heated emits a small quantity of the vapour of the anhydride. it frequently doubles its weight action on fragments of organic matter. which would represent 2 volumes of the anhydri le and 2 volumes of steam (i molecule of each) condensed into fie space of 3 volumes. and not the water into the acid. but it continues to expand by heat un il sp. and the acid becomes mere and more concentrated. is the dilution should therefore be performed gradually.). a is expelled. even when very much diluted. this is one cause of the destructive action of sulphuric acid upon linen. has a less volume than the two liquids when Great heat is given out at the moment the mixture when . which would reduce the density of the vapo to 1*692.

). 199 After by the process of dissociation (see note. Vol. till it ceases to lose weight. an acid of still higher concentration than oil of vitriol is Such an required. salts are ZnO. brown. [SO(02 Zn)"J. p.and orthophosphoric acids do to Their formulae would then be H 4 SO6 [SO(OH) 4 ]. and Zn g SO e (408) = ZnS04 known. until the density is reduced to I "j 8. the acid has been frozen.). fibrous mass. and this circumstance. gave rise to the name of oil of vitriol. formerly called anhydrous sulphuric acid.) till it ceases to give off water. In preparing the Nordhausen acid. SO g = 8o .heat be applied to the retort. this fuming Nordhausen acid be placed in a glass retort. For the purpose of dissolving indigo in the process of dyeing Saxony blue. be procured by evaporating a dilute acid in vacua at 212 (iooC. which solidify into a This silky-looking.). congelation immediately occurs. may On dropping into the cooled acid a crystal of the acid previously frozen. ReL wt. Theoretic If Sp. and it begins to boil at 379 (193 C. 2ZnO. If water be added to sulphuric acid. and is hence known as Nordhausen oil of vitriol. white fumes pass over. and is then distilled in earthen retorts . but when frozen reaches 32 (o or it does not become liquid till the temperature C. Observed. is the compound The residue in the .NORDHAUSEN SULPHURIC ACID.) . vitriol. white. the sp. and metaphosphoric acid. Another hydrate (H 2 SO 4 . by which the concentrated acid of commerce is still frequently known. of Vapour. but it be cooled much below this point without solidifying. gr.H 2 0) Hydrate of Sulphuric Acid. according to Graham. The density of this hydrate is l'6z. Nordhausen Sulphuric Acid. 3-768 . Zn 2SO B = ZnS04 . 107). aiul crystallizes in splendid rhombic prisms. H SO 6 g [S(OH)J : their corresponding zinc . and which is convenient as distinguishing it from more diluted acids. a definite hydrate is formed. of which is l'95l . fuming liquid passes over. a dense. in Saxony. The concentrated till acid of commerce does not 29 usually freeze it has been cooled to about (34 C. from this property it is often termed glacial sulphuric gr. about 1*9. acid is principally prepared at the town of Nordhausen. taken in conjunction with the oily consistence of the concentrated acid. it melts at 51 (io 0< 5 C. and a gentle.2H 2 0) may. found that this hydrate may be obtained by heating a more diluted 400 (2O4'5 C. j~ j. and the temperature rises to 51. These two hydrates may be regarded as separate acids bearing the same kind of relation to sulphuric acid as pyro. 40 . Part T. Mol. of sp. 0> It freezes at 47 (8 3 C. ferrous sulphate is dried at a moderate heat to expel its water of crystallization.). 3*01 . Gr. (409) Sulphuric Anhydride. acid. furnished with a receiver which is kept cool by ice. (H 2 S0 4 .). or fuming The old name for ferrous sulphate was green sulphuric acid. It Graham acid to begins to boil at about 400 (205) giving off a weaker acid.

. and becomes reconverted into the first variety. Sulphuric anhydride. Mercury when heated in . according to the proportion of sulphur . i volume of sulphur vapour and 3 of oxygen being condensed in the anhydride into the space of 2 volumes of vapour..200 SULPHURIC ANHYDRIDE. however. after oil the anhydride is of vitriol. but when once it has been solidified. It has a specific gravity of 1*946 at without charring the skin. green. and is very deliquescent 55 *4 (13 C.S0 3 =Na2 SO. and baric sulphate is formed. forming solutions which have a brown. C. i 60 100 . it passes rapidly into the other form. Na2 S0 4.. is converted into mercuric sulphate with liberation of sulphurous Phosphorus takes fire in its vapour.).). the two combine with incandescence. all retort. 3 2 S03 =80 . at which temperature it is slowly volatilized. whilst disodic sulphate remains in the retort after which. sulphuric anhydride exists under two modifications one of which melts at about 65 (i8'3 C. = = 32 48 By weight. Sulphuric anhydride its expelled. the vapour. Sulphuric anhydride combines with sulphur. The specific gravity of this vapour was found by Mitscherlich to be 3*01. setting sulphur free.). consists of ordinary may also be obtained from hydrogen an earthen retort. OR ANHYDROUS SULPHURIC ACID... if distilled in hydric sodic sulphate red heat. 01 by fusion at a high temperature .+ S03 . It is tough. is decomposed into 2 volumes of sulphurous anhydride and i of oxygen. Sulphuric anhydride in some cases combines with the anhydrous bases if its vapour be passed over baryta heated nearly to redness.. or blue colour. forming a colourless vapour which. which melts at a dull in the form of water . fumes in the when air. and The anhydride forms with oil of vitriol a Compound (H 2 SO 4J SO 3 ) (35 C. it of the anhydride. According to De Marignac. the blue anhydride. ductile. possesses no acid properties. S0 2 (OH) O S0 (OH) 2 1 that crystallizes in plates which fuse at 95 The composition of the Nordhausen acid approximates to this. which is 2*764 for : Sulphur S 3 Oxygen Sulphuric anhydride .. . and boils at about 95 (35 if The solution has all the properties of The anhydride melts at 65 (i8'3 C.). like wax. .. thrown into water the heat emitted is so intense that it hisses as : a hot iron would do. and can be moulded in the fingers. and is produced by distillation. and is deprived of the (NaHSOJ. or 40 By volume. passed through ignited porcelain tubes.). which does not melt below 212 (100). or somewhat higher than its calculated amount. yields white fumes : SO 3 + H 2 O. ordinary sulphuric acid.

= HC1. and forms a liquid termed chlorhydrotulphuric acid (HC!. It also combines with hydrochloric acid. and is Williamson obtained it by the action of phosphoric decomposed by water.COMMON IMPURITIES OF SULPHURIC compound containing the smallest proportion. We are therefore acquainted with the following definite compounds of sulphuric anhydride with water. Compound. chloride chloric acid upon sulphuric acid H 2 SO.SO S ). 201 and It likewise dissolves iodine. the anhydride : starting with . ACID. [S0 2 (OH)C1].). with one-tenth of its weight of iodine forms a green crystalline compound. + PCI. which boils ab 293 (145 C.SOS + HC1 + POC1 S hydroand phosphoric oxytrichloride being formed at the same time. . . .

but in some cases it undergoes decomposition when boiled with them even silver is dissolved by it. for instance. platinum. The more oxidizable metals are dissolved by this acid when diluted with water. required pure. or with sulphur.202 the SULPHATES. boiling takes place with violent (p. : concentrated acid is also decomposed when boiled with charcoa. acid sulphate of potassium. undiluted acid. such as the basic sulphate of coppei termed (CuSO 4. may Sulphurous detected in the acid.2CuH 2 O 2 ). displacing from their salts all acids which boil at i lower temperature than itself. as. bismuth. Sulphuric acid is one of the most energetic o1 the acids. rhodium. and constitute important and well-known minerals such as gypsum (CaSO 4 . sulphurous anhydride being evolved. the acid must be re-distilled with a this salt decomposes any nitrous acid which may be present conducted with much The distillation requires to be 143). and lead.2H 2 O). may be obtained. furnish the sulphates of the metals. such as sulphates. sulphurous anhydride being formed. or hydric potassic sulphate (KHSOJ in a few instances basic salts. the sulphide. which. whilst the ebullition takes place tranquilly from the sides. mercury. and tellurium are acted upon Gold. in which case the insoluble matters collect at the bottom. and by the acid in a similar manner. whilst the metal unites with sulphion (SOJ. whilst the sul- feebly upon metallic bodies : phate of the metal is 2 dissolved in the excess of sulphuric acid thus: 2 Ag2 + 2H 2 SO 4 ==Ag SO 4 + SO 2 +2H O. so as to apply the heat to the sides only of the retort. antimony. and manganese are acted upon in this way. by exposure to the weather. as sulphate. Sulphates. and the sulphates of barium Some are formed by the spontaneous 01 strontium. arseni- cum. tin. or ty The soluble sul roasting. Many of the sulphate. The salts formed by this acid an With the alkalies it forms acid salts. (411) Sulphuric acid in its concentrated form acts but in the cold. iridium are not acted upon by sulphuric acid even when boiled with it. Copper. forming a sulphate zinc. occur native. : the danger may be concussions and sudden bursts of vapour avoided by distilling it from freshly broken crystals of quartz . nickel. the as care. iron The cobalt. shows the presence of these impurities by of constriking a characteristic purplish-red colour at the point be sometimes acid tact of the two liquids. lead. or by using a gas-burner in the form of a large ring. hydrogen being liberated. may also hydrochloric acid and potassic When little ammonic sulphate. artificial oxidation of the sulphides. . of iron and copper.

nickel. but it exhibits some singular anomalies (567).K 2 SO 4. even in small quantity.6H O) isomorphous with those just mentioned. which retain 6 : molecules of water of crystallization. Many of the sul- phates are formed as residues during the preparation of the volatile acids by the action of sulphuric acid on their salts. silver.SULPHATES 203 phates of the metals may be readily prepared by dissolving the metal in dilute sulphuric acid. and under some circumstances as low as 2H 2 O.2H phate (gypsum) sulphates of zinc. lead. such as potassic sulphate or ammonic sulphate peculiar double salts are thus formed. and so on. such as sodic sulphate. sulphate may after having be easily recognized. Sodic sulphate crystallizes usually as (NagSO^ioHgO). the carbonic oxide escaping as gas. 7H 2 often smaller if the solution be allowed to crystallize at a high temperature. heated in the flame of the blowpipe . strontium. it is piece of platinum = BaS+4CO. part with their acid When . which. The suland of both barium. or the oxide or carbonate in cases in which the metal is not readily attacked by the acid. which partially loses its acid : the sulphates of zinc. copper. magnesium. 4 and nickel. C) Neither plumbic sulphate nor the sulphates of the metals of the alkalies and alkaline earths are decomposed when heated to redness. . Potassic sulphate is thus obtained during the preparation of nitric acid from saltpetre. but the other sul- phates ignited. if. cadmium. sodic sulphate as a residue from common salt in the manufacture of hydrochloric acid. at others 4. heated with without difficulty when strongly charcoal the sulphates are all decomposed those of the metals of the alkalies and alkaline earths being converted into sulphides. the proportion of water being sometimes 5. cobalt. evolve sulphuretted hydrogen. are anhydrous. Cupric sulphate crystallizes with 5H 2 O. may be obtained by precipitating a soluble salt of the metal by means of some soluble sulphate. The contains . except magnesic sulphate. when moistened Baric with hydrochloric acid. The insoluble sulphates. mercurous and mercuric sulphate. iron. cobalt. and silver require an intense heat to decompose them . usually crystallize with water in these salts is but the number of molecules of O. and which are still isomorphous with magnesic sulphate (535). Calcic sulCaSO O. phates potassium. but it forms double salts containing 6H 2 O such as : (CuSO4. The sulphates of the group isomorphous with magnesic sulphate contain i molecule of water which admits of displacement by a molecule of some anhydrous sulphate. such as those of barium and lead. been mixed with a little charcoal and folded in a foil.

and evolves hydrosulphuric acid . . the baric sulphide. when moistened with hydrochloric acid.204 SULPHATES. is converted into baric chloride. The sulphates of the metals of the 3 = +H alkalies and alkaline earths may also be converted into sulphides tube. is more important sulphates Neutral salt The composition of some of the shown in the following list : General formulas. Sulphuric acid is and In this sulphide. by heating them to redness in a glass or porcelain passing over them a current of dry hydrogen gas. K SO + 4H =K 2 4 2 2 S +4H 2 O. way potassic sulphate is reduced without difficulty to water being eliminated. dibasic. BaS + 2HCl BaCl 2 S.

possessed of great reducing power due to the presence of zincic hyposulphite.HYPOSULPHUROUS ACID. may NaHSO by dissolving metallic zinc in a concentrated solution of sodic hydric sulphite. HCHO rj H (CO(OH) containing tetrad sulphur in the place of the carbon. absorbs oxygen with great rapidity. the only one of any practical importance . but insoluble in alcohol. A solution of sodic of either potassic or sodic carbonate. it solidifies to a mass of slender It may be purified by needles of the sodic hyposulphite. phurous acid. a sulphate of the alkali-metal which may be dissolved by water. unless a large excess of The sulphates which are insoluble in water and acid be present. This acid. should be the vessels filled with the employed quite operations liquid. (413) HYPOSULPHUROUS ACID or Hydrosulphurous acid. is the true hyposulS O 3 . alcohol. discovered by Schiitzenberger. on pouring In all these solution in water and reprecipitation by alcohol. of a deep orange yellow colour unstable than the sodic salt. and adding about three times its volume of This precipitates the remainder of the sulphate. [SSO(OH) 2 ]. 2 . dissolving zinc in aqueous sulphuand a yellow solution is obtained. H SO 2 . Of the re- maining acids of sulphur. The acid is probably analogous in constitution to formic acid. causing considerable elevation of temperature. produces a similar but less complete decomposition. when boiled with the insoluble sulphates. HYPOSULPHUROUS ACID H 2 S 2 O 3 =ii4. On treating the sodic salt with oxalic acid a solution should be carefully excluded. HSHO . rous acid On is no hydrogen evolved. hitherto called . be obtained Tolerably pure sodic hyposulphite. in acids may be entirely decomposed by fusion with an excess or potassic carbonate. rapidly losing is its colour and depositing sulphur. being insoluble carbonate of the other metal is left. separating it from the zincic sodic sulphate which crystallizes out. usually known by that name. is and the soluble air very exposed to the air in a moist state. The sodic salt in water. and when of : hyposulphurous acid it is much more obtained. and off the solution and allowing it to stand in a cool place for some hours. T L or /rk (bO(OH) > (413) THIOSULPHURIC or SULPHOSULPHURIC ACID. the acid 3 3 H being thiosulphuric acid. 205 all the sulphates are insoluble in alcohol. whilst an formed.

Rose none of the hyposulphites can be obtained all the anhydrous form. A a solution of sodic sulphite with powdered sulphur .5H 2 O . b. has been shown by Pape to be an error. thai salt. sulphosulphuric. instance. dered sulphur.H 2 O This. for removing the last traces of chlorine from the bleached pulp employed in paper-making . acid. instead of being should be Ba"S 2 H 2 O 4 Ba"S 2 O 3 . PbS003 PbSS03 Na2 S003 Na2 SS03 [S02 (0 2 Pb)"] [SS"0(0 2 Pb)"] [SO2 (ONa) 2 ] [SS"O(ONa) 2 ] Sodic thiosulphate or hyposulphite (hyposulphite of soda Na S 2 O 3 . . well washed with it is after this operation. so that their true formula should be 2 2 3 M H of the barium salt. therefore be regarded as sulphates in which I atom of oxygen is replaced by i atom of dyad sulphur. hyposulphurous.. the surface of the photograph is freed from the unaltered argentic compound by immersion in a solution of the hyposulphite. and it has been proposed by Percy as a solvent in the separation states that of argentic chloride for metallurgical purin poses. possessed salts by this This application has arisen from the power compound of dissolving those argentic haloid which are insoluble in water. 1*672). the sulphu . to light. forming with them soluble double salts . Plumbic sulphate Plumbic thiosulphate or sulphosulphate Sodic sulphate Sodic thiosulphate or sulphosulphate . whilst the portion which has been blackened by light is left unacted upon.. still better plan consists in digestin. water. Sp. is manufactured to some exten from impure sulphide of sodium (prepared by fusing together ii a covered crucible equal weights of sodic carbonate and pow 2 . however. for . the thiosulphuric. by transmitting through solution of it a stream of gaseous sulphurous anhydride until i ceases to be absorbed the liquid is then filtered and evaporated . or by converting sodic sulphate into sulphide. the picture be no longer liable to alteration by exposure Besides is employed to a considerable extent as application in photography. the sodic hyposulphite an antichlore. its if. Gr. the of them retaining at least i molecule of water which cannot be expelled without completely decomposing / S O 4 .206 is SODIC THIOSULPHATE. calcining the sulphate with carbon). and may be called thiosuL phates or sulphosulphates. or dithionous Its sodium salt has been largely employed in the fixing of photographic pictures. sodic thiosulphate crystallizes in striated rhombic prisms termi nated by oblique faces. th( lead salt dried at 100 The salts maj containing Pb"S 2 3 O .

baric sulphate is precipitated. 4Na2 S 3 . however. Na 2 SO 3 + S becoming Na 2 S 2 3 When heated in closed vessels the hyposulphite first loses water. is 207 gradually dissolved and forms a colourless solution. their solutions are decomposed below temperature of 212 into free sulphur and sulphites of the earths. Baric thiosulphate (BaS 2 O 3 . but at a higher temperature it becomes decomposed and blackened. forming the argentic sodic thiosulphite.H. salt acidulated with hydrochloric An alcoholic solution of iodine is rendered colourless by . this precipitate may be dried at 212 (100 C.5H 3 O).O) [SSO(O 2 Ba) be 2 ] may obtained in small brilliant crystals by mixing dilute solutions of baric chloride and sodic thiosulphate. AgCl The + O = an intensely sweet Solutions + O . which on evaporation yields crystals of sodic thiosulphate.. the black These salts also give a sulphide of mercury being deposited. and in the refuse from the ball soda of the alkali works they consist chiefly of a mixture of calcic sulphide with lime and calcic carbonate. sulphuric acid is added to baric thiosulphate.) without change. Calcic thiosulphate is formed spontaneously in large quantity in the refuse lime from the gas-works. and The thiosulphates of calcium SrS 2 O 3 . be prepared . O O= 3 Na2 S0 4 +Na2 S . and the odour of sulphurous anhydride is OH emitted . owing to its partial a solution of mercurous conversion. but if the solution be filtered. H 2 S 2 O3 becoming decomposed into S + SO 2 + H 2 O. soluble thiosulphates are easily recognized by the facility with which they dissolve argentic chloride. 5 and strontium (CaS 2 O 3 .6H. to obtain the acid in the form of a hydrate either from this or from any of its salts . for example. and is then resolved into sodic sulphate and pentasulphide . when. the clear liquid speedily becomes milky from the separation of sulphur. of the thiosulphates give a white precipitate of plumbic thiosulphate in solutions of the salts of lead . which readily obtained from them by double decomposition // with sodic carbonate. of brown precipitate. i atom of sulphur and i molecule of water combining with i molecule of sodic sulphite . consisting cupric sulphide. into plumbic sulphide nitrate is immediately decomposed by a solution of the thiosulphates at ordinary temperatures in a similar manner.BARIC THIOSULPHATE. It is impossible.O and by transmitting sulphurous may anhydride through the sulphides of calcium and strontium the suspended in water. when heated . which yields a solution of Na 2 S 2 3 NaCl NaAgS 2 3 taste . are now employed is as valuable sources of sodic thiosulphate. with a solution of a cupric acid.

399) : Sodic thiosulphate.0 . .2H 2 O) is used for gilding the daguerreotype the positive proof obtained in photoplate. " * 6 = Na S O + AuNa 2 4 6 3 2S 3 O 3 + 3NaCl. but on adding baryta-water manganese is precipitat . the precipitate : : must be cipitated redissolved. i'347. Auric chloride. in a small quantity of water. and the solution on evaporat on below 41 (5 C. which are very soluble in water. (414) HYPOSULPHUBIC ACID : Dithionic acid. or Hyposulphite of gold and sodium (AuNa3 2S 2 O 3 . It is difficult to prevent the formation of a little of the latter. such as the baric disodic hy >oand the corresponding silver salt (AgNaS. hyposulphuric acid sulphate acid : is liberated. a tetrathionate of the metal being produced (416).-. which is readily resolved into sulphi ric this when and sulphurous anhydride H 2 S 2 O6 = H 2 S04 + S02 . sodic tetrathionate. and baric sulphate and hyposulphate are formed MnSO 4 f salts are easily separated . which belong to the oblique system.2H 0) 6 ..| S02 (02 Mu)" . needles. and again pre- It crystallizes in groups of colourless by alcohol. MnS 2 6 + 2BaH 2 = BaS04 + BaS 2 2 6 + 2MnH 2 2 . Sodic tetrathionate.4H 2 0).Ba)" + 2 Mn(OH 2 )' The baric sulph . Aurous trisodic Sodic chloride. tion of this double salt is explained by the following equatioa (Fordos and Gelis. When sulphurous anhydride be obtained 162.te being insoluble is readily removed by filtration.1 s i- 1. de Chimie [3]. is i-e be allowed to rise. ric concentrated by evaporation in vacuo leaves an inodor us strongly acid liquid of sp. xiii. and if the liquid be kept cool. Dihydric = and may 2 This acid is more stable than thiosulphuric aci Cir /r>T_r\ liSUo^UilJ in solution in water. with o: ly 2 molecules of water. and may be filtered from the b. but insoluble in It may be mixed with dilute sulphuric or hydrcalcohol. becoming t ic MnSO4 two .S. . dithionatf . solutions of I part of auric chloride and concentrated mixing sodic chloride. + 2Ba(OH) 2 = S0 2 (0 2 Ba)" + O. The forms chloric acid without the evolution of sulphurous acid. 4Na2 S 2 O 3 + AuCl 3 H. thiosulphate.208 HYPOSULPHUR1C ACID. manganous sulphate .d as hydrated protoxide. 6 may S0 2 (OAg) .O. Ann. Many double hyposulphates 1 smlphate (BaNao2S 2 be obtained. the gas is rapidly absorbed. mangano If the temperatv hyposulphate is formed Mn0 2 + 2SO 2 yielding MnS 2 6 . gr. is formed instead . Aurous trisodic thiosulphate. j is is transmitted through water in which finely divided peroxide of manganese suspended. admixture with an excess of thiosulphate. Mn0 + S0 2 2 . and for colouring It may be prepared in a state of purity by graphic printing.4H 2 O): at higher temperatures it yields permanent crystals.) leaves the baric hyposulphate in prismatic efflorescent crysl ils (BaS 2 6 . By the cautious ad lition of dilute sulphuric acid to a solution of this salt until a precipitate ceases to be formed. of sodic thiosulphate 3 parts on the and hyposulphite of sodium and gold being formed addition of alcohol the latter salt is precipitated.

but if heated with it. The action of sulphurous escapes and potassic trithionate (K 2 g 6 ) anhydride on potassic thiosulphate also yields the same salt it crystallizes in Solutions of the anhydrous four-sided prisms. sulphur is deposited.J S = S + SO(OH) 2 + S0 (OH) 2 a When J (S02 (OH) are heated in a closed tube. which soon becomes black. 2H 2 S 2 6 + 2H 2 4H 2 S04 In the cold. It is very unstable. and a new. baric iodide thionate. and white with : mercuric nitrate . When baric thiosulphate is suspended in water. r . with argentic nitrate they give a yellowish-white precipitate. Dihydric trithionate. Dihydric tetrathionate . ii. (415) TRITHIONIC . but its solution gradually undergoes spontaneous 4S 2 S 6 decomposition into sulphur. sparingly soluble salt. acid remains in the liquid. and sulphuric acid . : recrystallization . These reactions distinguish the hyposulphates from both the sulphites and thiosulphates.TRITHIONIC ACID PENTATHIONIC ACID. whilst sulphur sulphurous phuretted hydrogen acid is . sulphurous anhydride gradually S is formed. terminated by dihedral summits. whilst a sulphate of the metal remains behind. When in solution they may be oxidized at a boiling heat by chlorine or by nitric + 2= acid. sulphui-ous acid. two molecules of sulphuric acid being formed.S03 + ioH 2 S = 2H 2 S 5 6 + 5S 2 4. The solid salts when heated emit sulphurous anhydride. boiling the solution. the trithionates OH is SOJOH) 2 4. HS 2 4 6 =226 is (SOa (OH) S S . and from a solution of this salt a pure solution of tetrathionic acid may be prepared by the addition of a quantity of sulphuric acid just sufficient to precipitate the whole of the barium . sulphur is left. sulphurous anhydride (416) expelled.SO. baric tetraseparated in hydrated crystals which contain 2 molecules of water The tetrathionate is purified by I 2 + 2H a O = BaI 2 + BaS 4 6 .SOS (OH)J be digested with powdered sulphur for three or four days. is sublimed. 2 H H S + H. sulphur is deposited. and sulphuric escapes. trithionates give black precipitates with mercurous nitrate. and iodine [JS0 (OH)J 4 added.i8H 2 O. HSO 2 8 g =i94 S I If a saturated solution of hydric potassic sulphite (KHS03 ) L . sulphurous anhydride is . and the liberated trithionic acid has even been obtained in prismatic crystals. 209 The hyposulphates are all soluble in water. they present no appearance of decomposition when treated with sulphuric acid. sulphurous anhydride By "1 (417) PENTATHIONIC ACID: . its solution is being readily decomposed into tetrathionic and trithionic acids. evolved. Potassic trithionate may be decomposed by means of tartaric or hydrofluosilicic acid. is 2BaS 2 O s + is formed. till the yellow colour which the liquid at first acquires has disappeared. and a new acid remains in ioH. but no deposit of sulphur occurs. ACID. and sulphate of the metal TETEATHIONIC ACID. A solution of L lS0 (OH) 2 of suldecomposed by transmitting through it a current the liquid .2H 2 O. the acid may be concentrated in vacua over sulphuric acid.

It may be distilled unchanged from caustic lime or baryta : il but by admixture with water it is hydrochloric acids . wt. Kel. o 2 liquid. 3S0 2 C1 2 = 2SO . even in the cold. Vol.SC1 . (418) Thionylic chloride.Pb8 2P04 + 3S02 C1 2 [ 3 S02 (0 2 Pb)" + 2 POC1 3 = P2 2 (02 Pb)"3 + 3S02 Cl a ]. yield sulphurous anhy- The hyposulphates emit no odour dilute sulphuric acid in the cold. immediately decomposed into sulphuric am H 2 S04 + 2HC1. possessing an extremely It may be mort pungent odour. 67-5 If equal measures of Jioiling^pt. gr. of Liquid. Baric pentathionate (BaS 5 6 . S0 2 C1 2 + 2H 2 = (80( I3) may be obtained with iodine. \^6'6 (77 C. It is readily prepared by the strongly refracting liquid. and having an irritating effect upon the eyes. Rose obtained a fuming. as of sulphur . but they probably are to be regarded a. : dilute sulphuric acid produces with the thiosulphates. easily prepared by distilling an intimate mixture of phosphoric chloride or ol phosphoryl chloride with plumbic sulphate . = r BS i j 8. Sp. be mixed together. The sulphites. which boils at 293 (145 C. Kosi compounds of sulphuric anhydride with chloride or iodidi (420) BOBIC SULPHIDE : B. or Chlorosulphuric Acid. and can be separated by fractional distillation from the phosphoric oxychloride formed at the same time [S02 + PC15 = POC1 8 + SOC1 ?].2H 2 0) may be obtained in silky deposited. Mol. in its solution. even when heated with it. By transmitting th> vapours of sulphuric anhydride into chloride of sulphur cooled by a freezing mixture.S. r ^r j. an odour of with dilute sulphuric acid. These bodies were considered by H. affords a simple means of distinguishing between most of these acids. Gr. An analogous compoum and by Berzelius. i'66 . or Sulphurous chloride SOC1 2 is a colourless. of vapour. action of sulphurous anhydride on phosphorous trichloride. 1-818 . with of sulphurous anhydride whilst but evolve sulphurous anhydride by the aid of heat dride even in the cold. as does not form salts. oily-looking compound (S0 . . sulphurous anhydride and chlorine. and containing 2 atoms o chlorine or of iodine in place of the third atom of oxygen. and precipitating the salt from mercurous nitrate gives a yellowits aqueous solution by the addition oi' alcohol : precipitate and argentic nitrate a yellow quickly becomes decomposed and turns black. . plumbic phosphate and sulphury] chloride being formed (Carius) the reaction with the phosphoryl chloride is as . no change occurs in diffused daylight.water. 8 6 bodies formed on the type of sulphuric anhydride. 4*671 Observed.). precipitate. both perfectly dry. of Vapour. they evolve no odour. Theoretic. This substance ought not to be called an acid. (419) Sulphuryl Chloride. 4703 . which Tests for the Adds of Sulphur. S02 C1 2 =I35. When concentrated sulphuric acid is poured upon the sulphates. but under the influence of bright sunshine they unite and become condensed into a colourless liquid.SO C1 .). 4-481). scales by neutralizing the acid with baryta. 3 2 sp. boiling at 180 (82 C.). an odour of sulphurous anhydride attended with a deposit of sulphur.210 BORIC SULPHIDE. The action of sulphuric acid upon the salts of the various oxy-acids of sulphur. g is obtained by passing th BSJ . follows 3PbS04 + 2 POC1 3 .

as well as in the fixed and volatile oils. Nitrogen sulphide combines with the chlorides irritates the of sulphur in several proportions.) of Mol 38. and is converted into vapour. It is readily decomposed by water with the formation of boracic and hydrosulphuric acids. of high refracting power. (421) NITBOGEN SULPHIDE: SN or S 2 N2 is . the yellow liquid is filtered from the amrnonic chloride which is produced. colourless be obtained in a state of purity. of Liquid. Carbonic disulphide takes up about -g^ of its weight when boiled with it . in which it is insoluble. :2B . 2' 6 2 96 . Sp. pungent taste. The reaction which attends the formation of the substance is very complicated and has not been completely ascertained. Gr. Ann.S 3 4. of an acrid. or Bisulphide of Carbon..2B2 Sg + 6CO. water does not dissolve it. This to redness is in an earthen retort. peculiar. the sulphur melts. the latter is removed by digesting in cold carbonic disulphide. Observed. C. From time is to time this cork is fragment of sulphur dropped into the retort.). 2-6447 . n Vapour. heated to redness 2 3 volatile in sulphuretted hydrogen. liquid. (422) phocarbonic Acid. Boiling-pt. mucous membrane of the eyes and nose most painfull}'. beautiful golden-yellow rhombic crystals of nitrogen sulphide mixed with crystals of sulphur are formed. and a the cork being immediately replaced . in benzol. It is heavier than water. xxxii. and explodes when heated to 3I4'6 It has a faint odour. 389). ether. though only in small quantity. The gas is transmitted till [3]. vessels properly cooled. Nitrogen sulphide detonates powerfully by percussion. but it is soluble in all proportions in ether and in alcohol. SulCS 2 =76. B. Rel. wt. and oil of turpentine dissolve it very sparingly . de obtained. (Fordos and Gelis. but by redistillation it may It is a very volatile. and allowed to evaporate spontaneously. by passing dry ammonia through a solution of sulphur dichloride in 10 or 12 times its volume of carbonic disulphide.CARBONIC BISULPHIDE. and a foetid. by the use of suitable apparatus constructed on this principle. the vapour of sulphur being It is yellow when first formed. Theoretic. adheres strongly to paper if rubbed on it. Chimie This compound the brown colour of the precipitate first formed disappears . It is now manufactured on a very large scale. compound may be prepared by heating fragments of charcoal bright Vol. into the tubulure of which of the a porcelain tube passing nearly to the bottom retort the tube is closed at its upper extremity Jued : withdrawn. alliaceous odour. Disulphide of carbon has not p2 . but slowly decomposes the compound. ii8'4 (48 C.6H 2 = 3H 2 S + 2H g BOs It has been thought that boric sulphide is the source of boracic acid and sulphuretted hydrogen in the Tuscan lagoons. 211 vapour of carbonic disulphide over a mixture of carbon and boracic anhydride + 3CS 2 + 30 . and driven over red-hot coke. contains an excess of sulphur. (15 '5 CARBONIC DISUIPHIDE. and (157 C. both in this country and in France. which at this elevated temperature combines with the carbon. in oil of turpentine. 1-272 at 60 . and the disulphide thus produced may be condensed in \vith a cork.) ['~ ~] . It is a white solid. alcohol.

bromine. and of growing importance. Indeed. It is one of the best solvents of caoutchouc. vol. especially in economizing the after as last portions of olive oil left in the pulp of the fruit much to the ordinary prohas been employed as a . and does not injure the grain . and may be substituted for ether as a solvent for some of the It has been used on a very large scale by Deiss organic bases. for the purpose of ascertaining the proportion of oil which the ground seeds contain Part III. also been which contain as possible has been obtained by pressure.. the construction of hence it has sometimes been employed in thermometers destined to measure very intense degrees of cold. (Richardson and Watts' Technology. so that special precautions fire against should be taken when using it. It has used as a solvent for extracting bitumen from minerals instead of subjecting them cess of destructive distillation and it 138)- Carbonic disulphide offers one of the best illustrations of the analogy in properties between oxygen and sulphur an analog} : . for the relief of these symptoms the use of a solution of ferrous carbonate in carbonic acid water has been found in some degree effectual. on exposure to air the disulphide quickly evaporates. and. The vapour of carbonic disulphide It coma. weakness. as a solvent for extracting oils and fats. a small quantity of the disulphide enclosed in a tight chamber with the grain. Iodine. i. great depression followed by when breathed produces is indeed very poisonous. It dissolves sulphur freely.) (Frankland). CARBONIC BISULPHIDE. It burns with a blue flame.212 hitherto been frozen . and chlorine are likewise readily dissolved by the disulphide. by spontaneous evaporation. when its vapour is mixed with hydrogen or carbonic oxide it takes fire below 420 (2i5'5 C. it. the applications of the disulphide very numerous. solvent in the analysis of oil seeds. Phosphorus is also freely dissolved by it. Advantage has been taken of this poisonous property to free grain infested with weevils from the insect . in a few hours kills both the larvae and the eggs (Doyere). leaves it in rhombic bctohedra. and hence much care is requisite in preventing its escape into It prothe apartments in which the workpeople are engaged. and loss of memory. depression. p. duces in those more or less exposed to its fumes. and may be obtained in crystals from the solution by slow evaporation. in the arts are at a comparatively Carbonic disulphide is highly inflammable and readily ignites low temperature. producing sulphurous and carbonic anhydrides.

213 as though far from being so complete that of the different halogens with each other.. alkali-metals. corresponding : in composition to analogous salts which contain oxygen Carbonic disulphide. it contains 2 atoms of sulphur in the place of 2 atoms of oxygen. and forming with them sulpho-salts.. these substances possessing the power of uniting with the sulphides of the basic metals.. is yet in some respects of a It is to be remarked that sulphur is the only striking character. vol. S 2 CS 3 + 2HC1=H 2 CS 3 + 2KC1. The sulpho-carsolution at ordinary temperatures. . when Aqueous kept.) with strong solution of obtained by digesting hydrogen ammonia at a gentle heat. forming such for instance as potassic sulpho-carbonate (K 2 CS 3 ). i? 2 2 64 84*21 76 loo'oo . and sulphuretted hydrogen evolved thus: CS 3 + 3H 2 2 K O= K CO + 3H 2 3 aqueous bonates when decomposed by hydrochloric acid form a yellow oily liquid. owing to their conversion into sulphides. may be regarded as the analogue of carbonic anhydride. 2 Solutions of the sulpho-carbouates of the alkali-metals give a brown precipitate with solutions of the salts of copper they and : K yield. The compound of carbon and sulphur so obtained affords a good instance of the class of combinations which Berzelius has called sulphur -acids. Carbonic disulphide CS2 = = = By weight. The soluble sulpho-carbonates are easily converted.. non-metallic element excepting oxygen with which carbon can be easily caused to unite directly. with dilute solutions of argentic nitrate and of corrosive sublimate.. combines with the sulphides of the which are called sulpha-carbonates. by boiling their aqueous solutions. speedily. .CARBON SESQUISULPHIDE. K CO 2 3 . 12 or 15*79 By . and form a brown liquid containing carbonate CO 3 + and sulpho-carbonate of the metal. + 3CS 2 2 6KHO =K 2K 2CS i + 3 H 2 0. more or less red precipitate. into carbonate of the metal. which. which contains 3 atoms of sulphur in the place of the 3 atoms of Carbonic disulphide salts oxygen in the corresponding carbonate. for example. solutions of the hydrated alkalies gradually discolour the disulphide.. sulphuretted hydrogen. (423) CAEBON SESQTJISULPHIDE C 2 S 3 is carbosesquisulphide (C ? S 3 H. water being decomposed.. the composition of the compound being as follows Carbon Sulphur : C S2 .. containing the elements of carbonic disulphide a similar decomposition takes place slowly in the . and with lead salts they give a All these precipitates blacken.. yellow precipitates .

(425) CARBONIC OXYSULPHIDE COS is a colourless. . ether. It is freely soluble in carbonic disulphide. The potassic and sodic nitrosulphates are rather more stable. it This salt is a singularly unstable compound. is not known in the form 2 S0 3 2NO and sulphurous anhydride may be mixed with . produces a similar decomposition probably a double decomposition occurs . and have a pungent bitter taste. from which the sulphur may be separated by sodic Carbon sesquisulphide is also produced when a mixture of carbonic sulphite. and sulphuric acid remains in the liquid. No insoluble nitrosulphates have been formed . xv. and in which neither a sulphite nor a nitrite can be detected the usual tests. the dry ammonic nitrosulphate be heated a little above 230 (115 C. Nitric oxide = 142. is HYDROGEN CARBOSESQUISULPHIDE C 2 S S H 2 formed when carbonic disulphide is treated with sodium amalgam and the product acted on with red solution is thus produced. 408). and carbonic disulphide. A remarkable series of salts has been described by Fremy (Ann. then mixed with four or five times its bulk of the solution of ammonia. S03 2 S04 + 2 0.S04 + CuS0 3 2NO. in solutions of salts of barium. but the presence of a free alkali increases its stability.214 NITROSULPHURIC ACID. due to the escape of nitrous oxide. and dried in vacua over sulphuric acid. . whilst the cupric : nitrosulphate is immediately resolved into nitrous oxide and If cupric sulphate. If an attempt be made to liberate the acid by salt. The nitrosulphates of the alkali-metals are neutral to test-paper. Sulphazotised Acids of Fremy. 2'ic>46. a precipitate of carbon sesquisulphide and sulphur is produced. whilst the liquid is artificially kept cool. Sulphurous anhydride combines with the elements of potassic nitrite and water in several different proportions. sp. over mercury. some months. by The solutions of these salts produce. It is an amorphous disulphide and water is exposed to sunlight for brown powder. CuS04 + (H4N) 2 S08 2NO becoming (H 4 N). de Chimie [3]. formed by the action of sulphurous anhydride upon a solution of potassic nitrite containing a large excess of free alkali. a precipitate . for instance. combustible gas of produced in numerous reactions. when the substance A is precipitated. as. insoluble in alcohol. and beautiful snow-white rhombic crystals of ammonic nitrosulphate [(H 4N) 2 S03 2NO] are deposited . they may be collected on a filter. through which sulphuretted hydrogen water. washed with a little ice-cold solution of ammonia. the gas is If a concentrated solution of ammonia be gradually and completely absorbed. is passed and the liquid poured into dilute hydrochloric acid. and forms compounds which crystallize readily. gr. and readily decomposed when heated to about 392 (424) (200 C. the gas is in great measure absorbed. when dissolved in water begins to undergo decomposition at ordinary temperatures. takes place. and a current of nitric oxide be slowly transmitted. H each other in a dry state without entering into combination. Mere admixture of the solution of the ammonic nitrogiving the addition of another acid to the H 2NO H N sulphate with that of many metallic salts. it is decomposed with explosive evolution of nitrous oxide.). but if a strong solution of potash be thrown up into a jar containing a mixture of 2 volumes of nitric oxide and I volume of sulphurous anhydride. and forms salts with the metals. (427) Compounds of Sulphurous and Nitrous Acids .). (426) NITROSULPHTJBIC ACID of the free acid. when a mixture of carbonic oxide with excess of sulphur vapour is passed through a red-hot tube and by the action of sulphuric anhydride on carbonic disulphide and in a much purer state by the action of sulphuric acid on potassic sulphocyanate. and passing chlorine through the liquid . they give no precipitate with baryta water. such for instance as cupric sulphate. saturated with sulphurous acid. brisk effervescence.

Premy was unable to procure remarkable that if no sulphany such compound which contained sodium. CHAPTER THE remaining halogens. grain grain in each gallon. : The subjoined formulae Potassic sulphazite will sufficiently indicate the derivation of these salts : from potash. analogues of chlorine. of Vapour [ 80 . and be considered. i45'4 (63 C. varying from one-third of a.S 5 N2 H 6 16 4K 2O. so fipMfios. Molecular Vol. It has also been found in a silver ore from Mexico.BROMINE. likewise contain bromine in quantity sufficient to render its extraction from them a source of profit. Many saline springs. azotised salts are formed. such as those of Kreuznach and Kissingen. XII. sea. Potassic sulphammonate is easily formed by mixing a strong solution of potassic sulphite with one of potassic nitrite j the sulphammonate is deposited in beautiful silky needles.) . bromine. These compounds are all decomposed by boiling their solutions. of Vapour. Rel. Atomic Vol. wt. in South America in both cases the bromide of is mixed with silver chloride of silver. iodine. +3H O 2 3 -|-8SO 2 +3H 2 sodic nitrite be substituted for potassic nitrite. and it is abundant in the mines of Chanarcillo. 9\5 (o C. Observed. per litre. 215 which contains the new acid.) 3*187. Bromine exists in minute quantity. or from 4 to 14 mgrms. Monad as in HBr. in bittern. Melting-pt. Indeed.) .S 4 N 2 H 6 N 14 or 3K 2 O+N 2 2 3 +3S0 2 +3H2 2 i sulphazotate sulphammonate It is 3K 2 0.S 8 N 2 H 6 O22 or 3 or 3K 2 or 4K20+N 2 K. named owing to its irritating odour (from was discovered by Balard in the year 1826. the mother-liquor of sea-water after the less soluble salts have been extracted by crystallization. (428) BROMINE. of Vapour [ J . = 8o. nitrous and sulphurous anhydrides sulphazate 3K20. few deposits of sodic chloride exist in which traces of bromine have not been discovered. 5*536 . Indeed. Gr. may now I.0+N O3 + 4 S0 2 +3H O 0+N2 3 +5SO.water in to about one : . as bromide of magnesium. H . J2'5 Boiling-pt. the waters of the Dead Sea contain bromine in larger quantity than this it appears to be combined with magnesium. a stench). fluorine. and ammonia and sulphuric acid are amongst the products some of them even experience a similar decomposition at ordinary temperatures. . 5'54 ( . Theoretic Sp.S3 N 2 H 6 12 3K 20. the BROMINE: Br. of Liquid at 32 C. water.

which receiver containing water. giving it a beautiful and characteristic : This yellow liquid when agitated with ether. the liquid is evaporated to dry ness. yellow colour. The chlorine unites with part of the bromine. and the saline mass is gently ignited t0 decompose the bromate. of repeated charges bromine. parts with its bromine. and may again be employed in a repetition of the process upon a fresh When the solution of potash has. where it forms a beautiful golden yellow layer. In order to obtain bromine. from the brine. the yellow colour and of bromide immediately disappears from formation bromate of potassium which remain dissolved in the water . since from the manner in which potassic bromide is formed. All the soluble bromides are decomposed readily by chlorine. It is then mixed with peroxide of and distilled in a retort with sulphuric acid . taking care to avoid an excess of this gas. the mother-liquor Extraction. forming of bromine. which is partially decomposed and dissolved receiver. and bromine is set free MgBr2 + Cl 3 =MgCl 2 + Br2 . which is dissolved by the ether. In this operation a small quantity of chlorine passes over with the bromine. sition is of the may ice. the ether rises to the surface.216 EXTRACTION OF BROMINE. after all the salts separable by crystallization have been removed. chloride it is always contaminated with a portion of potassic chloride. after a time. and furnished with a glass stopcock at the bottom. the attraction of chlorine for the metals being more powerful than that of bromine. the bromine dissolving in the liquid. dense manganese red vapours of bromine pass over. whilst the ether. been nearly neutralized. is subjected to a current of chlorine. by quantity of bittern. rises to the surface despoiled of its bromine. and if the mixture be placed in a glass globe closed at the top by a stopper. is The mother-liquor drawn agitated with a solution of potassic hydrate. which would occasion inconvenience by forming a compound with the liberated bromine. be collected in a The decomposame nature as that attending the liberation of chlorine from sea salt by means of oxide of manganese and suland kept cool by phuric acid : aKBr + MnO 2 + 3 H 2 SO 4 = 2KHSO 4 + MnSO 4 + 2H 2 O + Br3 . In the foregoing operation magnesic chloride is formed. off by opening the and the ethereal solution containing the bromine is stopcock. . 3Br2 + 6KHO = KBrO 3 + 5KBr + 3H 2 O. while the bromine is condensed in In order to obtain bromine free from chlorine it by the water in the red drops.

forming compounds termed bromides (430). its compounds with silver furnishes a material of considerable value in photographic operations. even gold combines with it. though but slowly . Bromine is a red liquid. When swallowed operates as a powerfully irritating poison . Bromine is soluble in water. hydrobromic Bromine combines directly and ether still more abundantly. it also forms a hydrate (Br . HYDROBROMIC ACID. which produces a mixture of bromide and chloride with bromate of barium this mixture must be heated to redness in order to convert the bromate into bromide of barium. 9'5 ( i2'5 C. fig. MoL 40*5. which dissolves nothing but the bromide. Observed. even it diluted with extremely irritating to the air. at 59'o (15 C. The baric bromide is obtained by evaporation of its alcoholic solution. In smell it resemis bles chlorine. . gr. Bromine boils at I45'4 F. (63 C. It has a sp.) : very volatile. as in the case of antimony and of tin . the act of combination occasionally being attended with ignition. bining with hydrogen. it acts rapidly on the organic tissues. and with many of the metals. consisting be detonated by the approach of flame. at This is a of equal ordinary gaseous body measures of hydrogen and bromine vapour united without change of bulk. Gr. 2'8o2^> r j. solution of bromine with phosphorus. and emits dense red vapours resembling peroxide of nitrogen in colour (Part I. yielding a solution of a yellow colour . to the extent of 3*2 per cent. 2731. The aqueous is decomposed by sunlight into dissolves bromine freely. The mixture of bromine vapour and hydrogen cannot temperatures. of 2*98 at 59 (15 C. Hydric bromide (HBr = 8i) . Theoretic Sp. Bromine resembles chlorine in its property of com. will colours.) it forms a red crystalline properties of bromine greatly resemble those of It bleaches chlorine. to be nearly opaque. if largely is nose and fauces. Its not vapour support the flame of many vegetable The a burning taper. and renders the skin permanently yellow. 81). so deep in colour as Properties. and the residue digested in alcohol. (429) wt.). Rel. though they are less strongly developed.) (Pierre).). ioH O) crystallizing in octohedra 2 which are not decomposed even at 59 to 68 (15 to 20 C. 217 must be saturated with baric hydrate. and when exposed all to a temperature of solid.HYDROBROMIC ACID. or by the electric spark. Vol. and when heated with black oxide of manganese and sulphuric acid it yields pure : bromine. acid and Alcohol oxygen. forming a very powerful acid. and when respired.

which is decon of its t.218 HYDROBROMIC ACID . and the ' ' closed by a cork. In the bend p. Properties.PROPERTIES. and posed by the water at the momei hydrobromic acid escapes by the be) t t tube.. ment may be easily performed with the aid of a tube bent as ia fig. Hydrobromic acid gas may be procured abundantly by decomposing potassic bromide with a concentrated Preparation.. wh 'n . partial deoxidation. Hydrobromic acid is a colourless gas. i.... forming the tri-bromide. a mixture of hydrobromic acid. the is product impure. 324. arising from the union of the newly produced gas with the aqueous vapour... a red-hot platinum wire becomes acid the formation of the apparent by the immediately may be made white fumes. bromine.. c on aj >plying a gentle heat at b. or 98-76 1-24 By volume. composition (73 : Bromine . and 2.. Faraday succeeded in liquef : ing the gas under strong pressure. Hydrogen . possessing the usual irritating action of acid gases on the lungs it is not in'flammable and extinguishes flame. when the follow- ing reaction occurs : This experiphosphorous and hydrobromic acids being produced.. the br< mine distils over and comes inlo tube is .... a few fragments of phosphorus ani moistened glass are placed.)... in the mixture. 2 Hydrobromic acid gas very soluble in water. . formation. and in a bath of solid carbon c anhydride and ether. by suspending If moisture be present. which melts at 100 The acid has the followii g C. but the two elements to unite slowly.. It may also be obtained by decomposing phosphorous bromide by means of a small quantity of water. brcIG 324 mine is poured into b. since this acid itself undergoes purpose. Br H HBr is = = = 80 i By weight. If sulphuric acid be used for the solution of phosphoric acid. i i Hydrobromic 81 100-00 . forming... acid . sulphurous anhydride passing over. contact with the phosphorus. he even obtained it in the form of a soli I. .

bromine being set free and hydro- without change. The bromides. as it acquires a yellow tinge with an amount of bromine too small to be acid observed with ether. when oil heated with black oxide of manganese and vapours of bromine. at water. taking care to avoid an excess. yield red has a similar effect. p. KHO + HBr yielding H The bromides are all solid at ordinary tem(430) Bromides. argentic bromide is in- soluble in cold nitric acid. forming argentic bromide (AgBr). Mercurous nitrate when added to dissolved by a large excess of soluble in dilute solutions of the bromides gives a white precipitate of mercurous bromide (Hg3 Br2 ) which is soluble in chlorine water with liberation of bromine. 219 concentrated. bromide of the metal and water being produced . for instance. but the bromides of gold and platinum undergo decomposition. a small quantity of carbonic disul- phide may be advantageously substituted for ether. the presence of sulphuric or of sulphurous must however in this case be avoided. Oxy bromides may be formed re- . chloric acid produced. a fuming solution of greater density than hydrochloric acid. and are partially volatilized. and when in solution may be recognized by the yellow colour of bromine which is produced by the addition of a few drops of chlorine water. 1*486 (HBr. immediately. peratures. and plumbic bromide (PbBr 2 ) respectively. If the quantity of the bromide is very minute. most of them are fused by a moderate heat. it boils at 259 (126 C. gr. strong nitric acid of vitriol. The action of hydrobromic acid upon the metallic oxides is analogous to that of hydrochloric acid. of the acid . but is ammonia. and the compounds of bromine thus formed almost always correspond both in number and composition with the chlorides of the same metal. plumbic bromide on the contrary is nitric acid. which on standing separates as a yellow layer of liquid. On agitating this yellow solution with ether. soluble in Most are all of the bromides are readily decomposed by chlorine. the bromine is dissolved by the ether. Bromine often combines with the same metal in more than one proportion. solution of sp. 225). They the top of the colourless aqueous portion. 5H O) contains about 47 per cent. hydrobromic acid and potassic hydrate form potassic bromide and water KBr + 2 O. Both argentic and plumbic nitrate give a white precipitate with solutions of the bromides. .BROMIDES. Cuprous bromide is only sparingly soluble. and A may be distilled it decomposes Chlorine (See note.).

it forms a ic < e- touating oily-looking liquid. irritating odour.220 BROMIC ACID. Compounds of feeble bleaching powers may also be obtained by treating bromine with solutions of the alkalies. be obtained in a pure state by this of chloric acid (353).H2 O) . HBrOs =i29. means. with the exception of bromic acid. it is said. sparingly soluble it is also only slightly soluble. resembling chloride of nitrogen in appearance and properties. may. Water dissolves it. to Bromide of Nitrogen may be obtained by digesting potas bromide with the so-called chloride of nitrogen .nd plumbic bromate retains i molecule of water (Pb2Br03 . while oxygen is evolved. but must be prepared by decomposing argentic bromate with bromine. however. Any solid bromate. By the action of heat. a carbonic oxy dibromide (COBr ) ana o- gous to phosgene may be obtained by the action of brom ae vapour on carbonic oxide in the sun's rays. : Perbromic acid. whilst oxygen is liberated. - 2 2 2 they are brown-red liquids and little investigated. There appear to be two bromides of sulphur. been prepared are monobasic. The Potassic bromate. When heated with hydrochloric acid these All the salts of bromic acid which have as yet precipitates evolve free bromine. nearly unknown. Kammerer by decomposing Bromous Hydric perbromate (HBr04 =i45) was obtained by perchloric acid by the gradual addition of bromine (432) chloride (BrCl 3 : P). . reddish-yellow liquid. potassic bromide be ng formed. ' | JQ/QJTX oxyacids of bromine are. Argentic and mercurous bromate are anhydrous j. be formed by agitating finely powdered mercuric oxide with bromine and water. which is v?ry unstable. and The this salt yields the acid by a process similar to that employed in the preparation It cannot. is easily obtained by transmitting chlorine gas through liquid bromine it is a volatile. w ith a very pungent. is procured by acting on bromine with caustic potash. and this compound has never been obtained in the form of anhydride. potassic bromate is decomposed. Hydric Inmate. Bromine forms a compound with boron (BBr3 ) analogous boric chloride. A hypobromous acid (HBrO). when mixed with concentrated sulphuric acid and heated. . gives off red fumes of free bromine. sembling the oxychlorides and the bromides of the alkali-metal* form double bromides with the bromides of those metals which yield acids with oxygen. S Br and SB . (431) BBOMIC ACID. to its solution. with potassic bromide. forming a deep yel ow solution possessed of considerable bleaching power. togetiier bromic corresponds to chloric acid in composition. According to Schiel.

The liquid thus obtained which is dissolves about one-half of the ash. burnt. algae. of Vapour ^ . 127. Boiling-pt.). 225 (io7C. In the mineral kingdom. is now mixed with one-eighth of its bulk of oil of vitriol. notwithstanding. Molecular Vol. is burned in : shallow excavations. Observed. 4*947. mains. Stanford distils the able : sea-weed in closed retorts. Atomic and Comb. the now examining. sodic carbonate. sponges. wt. and allowed . or kelp. having been dried in the sun. and all that can be separated by a double sulphate of potassium and crystallization is removed . and with zinc in Silesia. is still third element in the group which we are denser than bromine. IODINE: 1=127. This liquor. Vol. and potassic chloride are thus extracted. Sp. existing in the solid It was accidentally discovered in the year 1811. Monad as in HI. bromine. Eel. and store it and other marine plants. thus it occurs combined with silver in Mexico. at a low heat . then evaporated in open pans. 8716. since the fuci. The iodine remains in the mother-liquor. it also exists in small quantity as iodate in These. of specific gravity from 1*33 to 1*38.IODINE. owing to the volatility of the sodic iodide at a red heat.weed. the following is an outline of the process adopted in procuring it The sea-weed. Gr. is The half-fused ash. Meltiny-pt.) . rarely Triad as in ICL. 347 (175 C. 87884. Glasgow. 221 11. Theoretic Sp. Iodine exists in the ocean in quantities still smaller than It is. extract it up in their tissues. which still retains disodic sulphide. of Solid. which rebroken into fragments and treated with boiling water . by Courtois in the waste liquors produced in the manufacture of sodic carbonate from the ashes of sea. from kelp made on the coasts of Scotland and Ireland . Gr. besides sodic thiosulphate and some carbonate. form at the ordinary temperature. when as varec or kelp. sodium. or iodine ley. give an ash which is technically known containing a small quantity of iodine in the form of sodic iodide. o (433) IODINE. the crude Peruvian sodic nitrate. from sea-water. ^ ~^j . obtained with less difficulty. iodine has been found in one or two rare ores. Iodine is at present largely manufactured at Extraction. of Vapour. the loss of this salt would be considerif the temperature were allowed to rise too high in order to prevent loss of iodide by this process and also to obtain a valuable variety of charcoal and other products.

). whi hydric sodic sulphate and manganous sulphate remain in The process resembles that for chlorine or bromine retort. The is liquid transferred supernatant next to a stoneware or lead- en if retort. heated with peroxide of manganese. whi :h . formi ig chloride of iodine. at a low temperature iodi ic distils over. mixed with able a consider- quantity of deposited sulphur. the iodine is liberated. and combines with part of the iodine. a quantity of powder :d having black oxide of manganese is introduced through the tubulure. sulphurous sulphate anhydride. which. The liquid retains an excess of si 1- When this mixture phuric acid. : is st t le . c. shown at is to facilitate the tubulure. been heated to about 140 (60 C. and is condensed in the globular receivers. d. are usually made of earthen\vare and are of considerable si: e. cylindrical a. . The process must be conducted slowly. chlois disengaged. the addition of the sulphuric a( id occasions the decomposition of the sodic carbonate and thiosi 1phate. rine In the foregoing process. b. clearing of the neck of the retort in case it should become obstructed by the formati >u It is purified of crystals. 325. which still remain in solution. which causes a loss. to stand for twenty-four hours carbonic anhydride. as well as of any diso< ic sulphide that may be present. of lead. c. If the temperature be allowed to rise as high as 212. and sodic crystal- FlG 3 2 5- lizes out. the head of the retort.322 EXTRACTION OF IODINE. supported in a sand- bath. b. The object of the seco id by a second sublimation. is luted on with clay. the sodic chloride retained in the ley is decomposed. and all the sodic iodide. and the contents of the reto 't. and gently heated from te- neath by a sm ill fire. fig. and sulphuretted hydrogen gases escape. is of for: n. forming sodic sulphate which is removed by crystallization.

yielding a magnificent purple vapour.PROPERTIES OF IODINE. a beautiful blue colour shows itself. Iodine. an iodide of the metal being formed. it is sensibly volatile. hence its name (from ioti$i}q. Iodine attacks many ing iodides .). feeble. Lugol's Solution. . of water. and very perties solutions of the iodides. forming A red solutions. . in is but it allows the to of iodine tion disulphide opaque light. ether. when taken internally. of the metals rapidly. particularly in glandular swellings. as chloride of iodine. and colour. but in small quantities it is a very valuable medicine. disconsists cine. and in certain forms of goitre. a 223 is The crystalline form of iodine an octohedron . emitting an odour like that of chlorine. whilst the iodine is set free is taken of this in the of fact iodine. : forms David Price recommends the use of a solution of potassic nitrite as a . hydriodic acid. generally obtained in bluish-black in lustre. to which a minute Iodine It stains the skin and' strong soluquantity imparts a beautiful rich violet colour. dissolve it freely. may be distinctly recognized. There are various modes of applying this test consists in part of iodine. iodine. are Alcohol. and boils at about 347 (175 C. carand likewise dissolve benzol bonic tetrachloride. iron or zinc is readily dissolved water. but if the iodine be in combination. formby it in presence of The compounds of : iodine with the metals and with hydrogen are decomposed by adchlorine. when dissolved in one million parts the simplest a little cold starch with the mixing liquid which paste is suspected to contain iodine . with due precaution.coloured). if it be present in an uncombined form. most organized substances of a brown Water dissolves it in very corrodes them. It is a non-conductor of scales. especially when in a electricity. and prevents the action of the test. Properties. Chloroform. forming a yellow solution. it is of a deep brown colour. in large doses acts as an irritant poison. avoided. is also soluble in carbonic disulphide. but much weaker. rhombic base but it is moist condition. with. violet. ascertaining vantage presence The most delicate test for it it. when uncombined. when heated it fuses at 225 (107 C). is the intense blue colour which i yields with starch by its means. forming brown solutions. gradually Its bleaching prosmall quantity. in solved 44 parts of water. which was formerly much used in mediof 2 parts of iodine and 3 of potassic iodide. and even by bromine. resembling plumbago and At ordinary temperatures. this colour does not appear until a drop of chlorine : water or of solution of bleaching powder be added to iodine free set it the an excess of chlorine must be. the less refrangible heat rays to pass freely.

the following Place in a small retort 10 parts of potassic iodide with 5 of water. the volume of the is Mol. and possesses a powerfully acid irritating odour. Water dis- easily prepared by sut and passing a current of sulphv retted hydrogen gas through the mixture until the brown coloi r of the iodine disappears hydriodic acid is formed and sulphur s The liquid gradually becomes clear f deposited in abundance. Theoretic Sp. When iodine is Vol. fc Hydriodic acid gas is not combustible. The colour fades away if the solution be heated. Hydric dipotasnc phosphate. the liquid to be tested being slightly acidulated . and 20 of iodine .224 HYDRIODIC ACID. it is better mode is not. nor does it suppoi combustion. 4-4288. but falls. HI = 128 . partially restored again as the temperature Solutions of the alkalies. as well as of sulphurous acid. and may be collected. and this is decomposed b/ water into hydriodic and phosphoric acids. it is often convenient to substitute for the freshly starch. and a colourless acid gas produced. whilst a fresh portio i of hydriodic acid is liberated by the action of the phosphoric acid on the potassic iodide.i Potassic iodide. made and allowed paper may paste. usually prepared in this manner. ^J. left at rest. such be preserved for an indefinite length of time. 4^443. . Hydriodic acid. j d Phosphorus. It fumes in the air. paper which has been smeared with the to become dry. . destroy the colour. As starch paste cannot be long kept without undergoing decomposition. and reducing agents generally. heated in hydrogen. and may then be decanted from the precipitate 1 A pending iodine in water. w . (434) HYDRIODIC ACID. Observed. substitute for the chlorine. then drop in cautiously : A i part of phosphorus cut into small fragments. Gr. Rel. sulphur : the decomposition consists simply in the displacemei t . no inconvenience arises from the presence of the nitrite in slight excess. It is reduced under strong pressure to i yellowish liquid. wt. The final result is exhibited by the following equation : of the reactio. SKI + j I 2 + P^ + 76H^O = 4K^HP?4 + SSl. solution of hydriodic acid may be 51 C). and is ready for use at any moment. Ths iodide of phosphorus is first formed. by displacement. Hydric iodide. Hydriodic acid gas will be evolved abundantly. gas becomes doubled. 64. however. and apply a gentle heat. which freezes at 60 ( solves the gas with great avidity. is sulphuretted hydrogen. in dry bottles. If kept in a dry place.

p. : formed... both in this case and in the analogous one of the solution of hydrobromic acid. the oxygen dis- Most of the iodides are decomposed by placing the iodine.. and are less fusible and volatile than the The iodides of gold. absorbs oxygen.. especially if placed in a strong light. the constancy of the boiling-point. with almost equal rapidity .. (127 dissolves iodine freely.. with its iodine... iodide is formed.. Iodine . chlorine and bromine.. when it consists of (2HI. may be By .. and at 261 C.. Q . as well as by nitrous acid and conIodine is also centrated nitric acid. whether it be in the gaseous Bromine and nitric acid act similarly and form or in solution. forming a brown solution by exposure to the air. Hydrogen Hydriodic acid = H = I 127 i or 99*22 o'78 i I . 2H 2 S + 2l 2 becoming This liquid may be concentrated till it acquires a density of 1*7. platinum. it. and combines decompose it. and violet vapours of iodine are obtained... causes similar to those traced in hydrochloric acid. and palladium are decomposed by heat into the metal and free iodine. water is tion of iodine . many other oxidizing agents also Mercury decomposes it gradually. consequently its decomposition By weight. .).IODIDES. silver. with liberation of iodine. The composition of hydriodic acid may be ascertained by Potassic heating potassium in a measured volume of the gas. HI 128 lOO'oo 2 (435) Iodides. such as zinc and iron. but the greater number of the iodides are converted into oxides when heated in the air. with evolution of hydrogen and formation of a metallic iodide.. and the liquid becomes brown from the liberaif the decomposition be permitted to proceed the Chlorine effects iodine is ultimately deposited in fine crystals. The iodides of the metals are all solid at ordinary temperatures.nH 2 O. but it was found to be partially decom- posed by varying the temperature of evaporation.. A solution of hydriodic acid dissolves many of the metals. ii. (Note. with oil of vitriol and peroxide set free when an iodide is heated of manganese. 225 of the sulphur by the iodine.) Hydrofluoric acid evidently furnishes a true hydrate. thus represented : vol. Water * Eoscoe has shown that. and dependent upon apparent definite character of the hydrate.. 30... its decomposition instantaneously. as well as the is accidental. corresponding chlorides and bromides. and hydrogen remains equal in bulk to half the acid gas employed . . Bineau)..* It then distils unchanged It is a powerful acid.

yellowish-brown liquid. magnificent ruby red crystals.) and boils at c 2i4 (ioiC. in alcohol and in ether. The soluble iodides of the metals are decomposed by water. Two compounds of iodine with (436) it chlorine. which is nearly insoluble in ammonia but freely soluble in sodic thiosulphate and in potassic cyanide. the plumbic iodide is deposited in very beautiful With argentic nitrate a buff-coloured lustrous golden scales. arsenic. having the ap- pearance of iodine. auric chloride salts the iodides give foi ir lemon-yellow precipitate palladious iodide (PdI 2 ) and with of palladium a brown determining the produced. solution of corrosive sublimate (HgCl 2 ) they give a beautiful salmon-coloured precipitate. soluble freely CHLORIDES OF IODINE.226 dissolves CHLORIDES OP IODINE. argentic iodide is formed. which is slightly soluble in boiling water. some of them are insoluble. and antimony. yellow precipitate of plumbic iodide. Mercurous nitrate gives a green precipitate in solutions of the With plumbic nitrate they yield a bright soluble iodides. since palladious chloride is in water. especially if the lead salt be present in excess . and exhibit colours of great The iodides of some of the metals which form acids brilliancy. Trichloride of iodine. If a mixture of ferrous sulphate and cupric sulphate be added tc a solution of any iodide. apparently without change. may metallic be obtained by the direct action of hydriodic acid upon the oxide. which undergo spontaneous subli . with oxygen. a protochloride obtained. 3 is procurec It form: by acting upon iodine with excess of dry chlorine gas. (1C1) and a trichloride (IC1 3 ) may bt protochloride. which solidifies on standing. volatile. or by the action of iodine and water upon the itself. it melts at 77 (25 C. or iodous trichloride (IC1 ). which is sometimes used quantity of iodine present in a solution is which occurs mixed with chlorine. such as those of tin. as obtained b} distilling i part of iodine with 4 parts of potassic chlorate. when in solution. which almost immediately changes to a brilliant scarlet in . a white precipitate of cuprous iodide (Cu 2 I 2) is obtained. With . or iodous chloride (IC1). the greater number of the metallic iodides freely. to a mass of dark lustrous crystals. This chloride when hot dissolves iodine readily and deposits it in beautiful crystals. metal These iodides. on cooling. is t The very irritating. are characterized With a by the reaction with starch already mentioned (433). this is mercuric iodide : it is soluble excess both of potassic iodide and of corrosive sublimate.): it dissolves.

iodic acid to iodate. The neutralized liquid contains sodic iodate and chloride.). I 2 O 5 =334. in This body may be obtained I 76^04. chlorine gas escaping.OXIDES OP IODINE. 100 parts. which causes an effervescence. the iodic (HIO 3 ) and the periodic acid (HIO 4) besides some other oxides but imperfectly known. whilst potassic iodate is formed and dissolved in the the chloric acid which is set free in the first instance by liquid : the nitric acid imparts its oxygen to the iodine.. and passing a current of chlorine gas through it till the iodine is dissolved . in suspending iodine in water. the liquid is then attended neutralized by sodic carbonate. Alkaline solutions decompose it. prepared may 2. : bonate in the following manner Sodic : chloride. which is dissolved by water unaltered it is decomposed on the addition of the alkaline caracid. in closed bottles : the vapour it is extremely irritating to the If exposed to the air attracts moisture. be in several be may procured by ways. Baric Q2 . Liebig's plan of preparing iodic acid consists 3. and is dissolved by water without experiencing decomposition. [I-O-O-O-O-O-IJ . ffOI />//-) This It acid corresponds in composition to chloric and bromic acids. TT\ Hydric HIO 3 =i76. 227 mation eyes. and Bromides of iodine. by a precipitation of iodine. and iodine is precipitated as in Liebig's method of preparing iodic acid (437). Iodine has a more powerful (437) OXTDES OF IODINE. mixed with and iodine be of chlorate may 5 parts potassic parts of water and a little nitric acid . chlorine is thus evolved in abundance. Iodine also combines with bromine.O 23'96. which may be again dissolved by passing chlorine through the the iodine is liquid. Equal long boiling of iodine in concentrated nitric acid. viz. and forms with it two compounds which by their action upon water furnish well-defined acids. by cautiously heating Iodic acid . forms compounds with it which are possessed of properties similar to those of the chlorides of iodine. It I. IODIC ANHYDRIDE. and this undergoes a similar decomposition (Millon). attraction for oxygen than either chlorine or bromine. 338 (170 ^ | C. Comp. . while the iodic acid liberates a fresh portion of chloric acid from the chlorate. repeating the series of operations until all converted into iodic In this case the chlorine combines directly with the iodine and forms trichloride of iodine.

there * are three iodates of potassium. and is then decomposed by a quantity just sufficient to combine with the barium : the iodic acid is dis- solved by the water.4BaO. oxygen gas. 2(Ba2lO. the triiodate. and may be separated from the insoluble baric sulphate by nitration. With the exception of the iodates o is barium salt consisting of Ba2lO 4. those of strontium.) it is (371 Its solution is destitute of 3 molecules of anhydride to i molecule of base . astringent taste many organic bodies decompose it. Some iodates contain i molecule. an iodide of the meta formed. the diiodate . iodate. KIO 3 + 3H 2 SO3 = KI + 3H 2 SO 4 . and then the iodine may be detected by the stare) test in the usual way. and owing to this circumstance litmus-paper is first reddened and afterwards bleached by it. an abundant precipitate of the sparingly soluble baric iodate is formed. leave a basic periodate the example. The iodates of the metals of the not heated too strongly. and free iodine.. is next added . potassic last : 2KI + 3O 2 but if the attraction of the metal be greater for oxyger than for iodine.I 2 O 5 . The aqueou solutions of the iodates are decomposed by sulphurous acid . and bariun O (Ba2lO 3 . . Iodic acid may be obtained aqueous solution in crystals C.) it is converted into the anhydride. 2KIO 3 . the All the iodates are decomposed two being anhydro-salts. an oxide is left behind baric iodate. or KI 3 O 8 . + 5O 2 + 2l 2 if . which is washed from adhering of sulphuric acid salts. Iodic acid offers some anomalies in its combination lodates. by heat if the metal have a stronger attraction for iodine than for oxygen. C.H 2 O) if precipitated from hot solutions. an iodide of the metal is formed and oxygen is for evolved . odour. the violei vapours of the latter escaping along with the oxygen . the normal iodate . and has a sour. .228 chloride IODIC ACID IODATES. some 2. for example. and : (170 C. > crystallizable compounds with sulphuric acid and with man - other acids.I O 2 (130 or by raising the heat to 338 5 by spontaneous evaporation of its composed of HIO 3 at a temloses two-thirds of its water. for example : : is converted into baryta. retain 2 whilst the iodates of lead and silver are anhydrous argenti iodate is insoluble in dilute nitric acid. 01 following formulae : K I 4O n 2 . KIO 3 J 3 O 5. yielding 2BaO alkaline earths. Iodic acid form H : . Th calcium salt retains 6H 2 O. 2KIO 3 becomes instance. and some with bases. and at about 700 : decomposed into iodine and oxygen.) it perature of 266 becomes HIO 3 . they may be represented by the KIO 3 . fo ' the alkali-metals the iodates are but sparingly soluble.

a grain or less. By evaporation of the solution. causes. NaI0 4 . and indeed often detonate without any the explosion is remarkably sharp and sudden assignable cause fumes of iodine are produced. is decanted. and a faint light is emitted.3BaO. but red. 2AgI0 4 . 229 r lO(OH) n (438) PERIODIC ACID . thus formed must be washed with absolute alcohol.5H 2 0. The normal sodic salt. sodic and decomposed into a basic argentic periowhich is dissolved. if from hot solutions.i. Analogous precipitates are formed with salts of calcium. The hydrated basic Na3 0.Ag2 0. and the precipitate washed with water. but are dissolved freely by dilute nitric acid. This acid corresponds in composition to the perchloric: the anhydride is at The acid is obtained by passing a current of chlorine present unknown. if precipitated from cold. this salt is when treated with water date. of lead. giving periolate. which contains an excess of iodine held in solution by ammonic iodide. a black powder is obtained. and the insoluble powder is placed upon filtering-paper in quantities of Two comand allowed to dry spontaneously.PERIODIC ACID IODIDE OF NITROGEN. rise to a sparingly soluble basic sodic The reaction which occurs may be represented by the following symbols Sodic iodate.3H 2 0. : Sodic hydrate.3H 2 is when crystallized contains periodate.Ag 2 0. gas through a solution of sodic iodate to which caustic soda has been added in the proportion of 3 molecules of free alkali to i molecule of sodic iodate an : unusual decomposition takes place. periodates are most of them sparingly soluble in water. Basic periodate of Sodic m Water ' . pounds (NI3 and NHI 3) appear to be formed together under both these compounds. the precipiIf the of iodine be precipitated with concentrated aqueous solution of ammonia.2H 2 0. a cold saturated solution of iodine in 2 absolute alcohol'should be mixed with twice or thrice its bulk of a saturated solution of tate ammonia in absolute alcohol . rn. The brown supernatant liquid. with solutions of normal baric salts. . which are somewhat soluble in alcohol and in ether. the black powder consists of a body which may be reprealcoholic solution . which dissolved in dilute nitric acid. or of silver. a precipitate of a basic periodate 2(Ba2lO4 ). By digesting iodine for half an (439) IODIDE OF NITROGEN. which is insoluble. HI04 =i92. the periodic acid may be obtained in deliquescent oblique rhombic The prisms HI0 4 . the liquid becoming acid.2NaI04 . and periodic acid. when dry. explode these circumstances upon the slightest touch. the argentic periodate is then dissolved in boiling nitric acid . : Stahlschmidt finds that in order to obtain the compound NHI in a state of purity. Hydric periodate . and precipitated by the addition of argentic nitrate . hour in a cold solution of ammonia.H 2 0. 2AgI04 . a normal argentic periodate (AgI0 4 ) crystallizes as the liquid cools. The hydrated argentic basic periodate is pale yellow.:o Chlorine.

gradually losing iodine by exposure to the air. both in their uncombined state and in their compounds they indeed form one of : the best defined natural groups of simple substances. or ammonia in which the 3 atoms of hydrogen have been displaced by 3 of iodine. to be struck with the close analogy presented by the three ele- mentary bodies. chlorine. and iodine ar hydrogen from any of its organic com pounds. also capable of displacing extremely soluble in water. bromine. furnishes I molecule of ammonic iodide. of hydriodic acid. the union occurring without change o bulk. All thes elements have the characteristic peculiarity of combining with . has been obtained . hydrogen in the proportion of i volume of the gas or vapour with ? i volume of hydrogen . . fusing-point. A Sulpkuryl Iodide S02 I 2 analogous to sulphuryl chloride. sented by the formula NI3 . It is impossible not (441) Natural Relations of the Halogens.230 NATURAL RELATIONS OF THE HALOGENS. means of ascertaining the relative quantities of nitrogen and iodine i contained in the body under examination molecule of the black powder (NHI g ). but in which a certaiji number of atom of the halogen have taken the place of a corresponding numbe of atoms of hydrogen. when treated with 2 molecules of sulphuretted hydrogen. bromine. sulphuretted hydrogen also effects its decomposition quietly but The results of the reaction last mentioned afford a completely. bromine. and iodine. elements rise as the atomic weight increases. which follows : Elements. but compound is unstable. and 2 atoms of sulphur : ] : the (440) Iodide of Sulphur S2 I 2 is a crystalline brittle steel grey solid. chlorine. . as and boiling-point of thes is shown in th . and the compound formed being powerfully acid an< Chlorine. . but potash and the acids accelerate the decomposition . producing substances which correspond in compositioi with the original body. Iodide of nitrogen becomes slowly decomposed in water . and strong nitric acid destroy it rapidly . < The table specific gravity. ammonia retards.

When in the liquid form. in the inverse order of that of the same halogens for hydrogen and the metals. three elements have the same salts atomic volume and when united with the same metal the which they furnish are isomorphous . * The attraction of these three halogens for oxygen is. gaseous. potassic chloride. nor the acid in solution. is decomposed by free chlorine or bromine bromic acid and the bromates are also unaffected by : free chlorine . . and perbromic acid by acting upon perchloric acid with bromine. The following table exhibits some of the corresponding compounds with hydrogen and oxygen which are formed by the halogens. iodine solid . Hydrochloric acid. all crystallize in cubes. bromine liquid. Neither iodic anhydride. for example. though chloric acid is only partially converted into bromic acid by the action of bromine upon it. of these elements also forms a powerful monobasic acid with 3 and with 4 atoms of oxygen. the . however. and iodide. chlorine is bining number increases. but iodic acid is tion of chloric or bromic acid easily obtained by the decomposiby free iodine. broEach mide.NATURAL RELATIONS OF THE HALOGENS. the properties of bromine being indeed intermediate between those of chlorine and iodine. 231 The intensity of their chemical activity decreases as the comAt ordinary temperatures.

Theoretic Sp. and this circumstance prevented chemists from adopting generally the views which had a short time previously been put forward The nature of chlorine. Monad. Vol. Q . Rel. is little satisfactory is known concerning of its it in its free state. Rel. free fluorine may be obtained in the following manner as a colourless gas which has no action on perfectly dry glass. The air must be completely expelled from the tube by converting a portion of the iodine into vapour . general nature. the fourth member of the group. permanent over mercury. No entertained According to Kammerer (Chemisches Cen1862. in an experiment made in this manner. 1*315 . are the to compounds corresponding closely analogous ones of the three elements of the haloid group which have been already described. however. HF = 2o. however. the only compound of fluorine which exists abundantly in nature. tralblatt. maintaining the elementary discovery of iodine. Aug. 523). or calcic fluoride (CaF 2 ). is with the exception of cryolite (6NaF. as (442) HF. (443) HYDROFLUORIC wt. decided them. wt. and the little cylinder of argentic fluoride broken . by Davy. o'689 Atomic .). the iodine had entirely disappeared. 19 . . and assisted materially in fixing the opinion now entertained respecting the compounds of fluorine. the tube is then to be hermetically sealed. was obtained. 10 . but of which our knowledge is in a much less satisfactory condition.Al 2 F c ). tion on this hypothesis. Gr.232 FLUORINE. in Theoretical Density. particularly in the phosphates of calcium and certain kinds of mica. Vapour. FLUORINE: F=i9Theoretical Comb. since its doubt. It exists too in minute quantity in the bones of animals. and rapidly absorbed by a solution of potash. At the end of this time. and from it all the preparations of fluorine are obtained. and especially in the teeth. and a colourless gas. III. ACID: Hydric of anhydrous fluoride. Small quantities of calcic fluoride are contained in a variety of minerals. Into a perfectly dry glass tube iodine is introduced. Fluor-spar. together with a thin closed glass cylinder containing well-dried argentic fluoride in excess over the iodine. p. MANY unsuccessful attempts have been Its made at various times to isolate fluorine. after of which the tube must be exposed for 24 hours to a temperature from 160 to 180 (71 to 82 C. frame is so irritating and deleterious. and that its action on the that is human chemical activity is so powerful.

to the powerfully corrosive action upon glass. fig. 326. is mixed with 2 or 3 parts of oil of vitriol occurs is at ordinary temperatures no evolution of vapour . For leaden poses. the head. but in union with hydrogen it forms a very remarkable acid. 3 26 foregoing method was long believed to be anhydrous . c. the - still and receiver be of platinum. and a reaction takes place similar to that which occurs in the preparation of hydrochloric acid : CaF2 + H 2 SO 4 = 3 HF + CaSO 4 Owing fluoric acid . and is cooled by immersion in a mixture : it of ice and salt. The concentrated acid obtained by the FIG. free from silica and the metallic sulphides.PREPARATION OF HYDROFLUORIC ACID. 233 is ^ ~~\ No compound of fluorine with oxygen known. the fluor-spar be pure. distillation in the be conducted a retort. xxiv. 434) have proved that it contains water. a. and a colourless gas of an extremely irritating nature was set free it produced dense fumes on escaping into the air. may the convenience of removing the charge after the operation is over. in a concentrated form. had but little action on perfectly dry glass. but a transparent gelatinous mass On the application of a gentle heat dense acid fumes formed. accurately by an overlapping grooved joint into the body. Vol. The heat may be : conveniently applied in an equable manner by placing the body of d is the rethe retort in a shallow iron tray. it He an distilled with excess of anhydride : phosphoric the water was thereby removed. When should a perfectly pure acid is required. In order to procure hydrofluoric acid in solution Preparation. but the researches of Louyet (Comptes Rendus. fits b. i part of finely powdered fluor-spar. it is exerted by hydroneces- For ordinary pursary always to prepare it in metallic vessels. and was : . if of an extremely deleterious nature arise. which it deprives of its silicon. it is found advantageous to make the retort in two pieces. filled with sand ceiver for the acid to the neck consists of a leaden pipe fitted by grinding of the retort. a head and a body .

it ought never to be preserved in the concentrated form.that caused by quenching a red-hot iron. should be conducted with the greatest care. p. lead. xlvii. (See note. The liquid acid is highly dangerous. which i. excepting platinum and some of the metal. the equivalent of hydrofluoric acid is expelled by the application of a freezing mixture of ice and salt. 225. gr. which boils (16 C. mobile.). and gold. colourless liquid. In order to detect a fluoride in a compounc which is suspected to contain it. in order to prevent the wa? i . de Chimie [3]. and does not solidify at 30 34\5 vitriol is acid obtained by distilling fluor-spar with oil o: a densely fuming. which ( 67 (i9'4 C. silver. resembling.). Tests. a colourless mobile liquid of sp. and with the evolution of so high a temperature caustic action as to produce a hissing noise. gently warmed for a few minutes. Fremy (Ann.). according to Gore. gr. volatile. but by the addition of water the density may be in creased to 1*150.). the glass being cooled with piece of moistened filtering paper. Potassium.234 PROPERTIES OF HYDROFLUORIC ACID. so as to expose a portion of the glass this etching is then inverted over the platinum capsule. The and remains unfrozen at 4 ( 20 C.HF) to distillation careful desiccation. 0^9879 at 55 (i2'8 C. and special provision must be made for carrying oft" the fumes from the operator.). the anhydrous acid is obtained in the form of a colourless. In its concentrated form it has a specific gravitj of 1*060. 7) fluoride of potassium and hydrogen to the double prefers subject the salt is first rendered anhydrous by .2H 2 O).). associated with it. the material is reduced to a fin< action powder and mixed acid . When poured into water it combines with ii with great avidity. and may be distilled un Diluted hydrofluoric acid graduallj changed. Anhydrous hydrofluoric acid. thrown into the strong acid. i'i5c (120 C. a few characters are next traced witl a point through the wax. boils at 248 whilst undergoing solution displaces hydrogen. the meta (HF. from its at about 60 The preparation of this acid upon the skin. in a platinum capsule with strong sulphuri< a slip of glass is warmed and rubbed over with beeswax so as to coat it uniformly . and mercury . the smallest drop occasioning a deep and painful burn. rapidly condensed by water. Fremy (KF. Indeed. and by afterwards applying a strong heat. decomposes it with explosion. : also obtained the anhydrous acid by decomposing plumbic fluoride by dry hydrogen. The acid of sp. is Properties. very volatile liquid. i Hydrofluoric acid is easily recognized by its corrosive upon glass.) dissolves the metals. boils at C. beyond which point further dilution is attendee with a regular decrease in density.

The double fluoride of potassium and hydrogen (KF. titanic. the tageously for etching on glass graduations on the glass stem of a thermometer may be made : with great precision and facility . and the tube is plunged into a long leaden tube filled with the diluted acid . it is ren- dered more opaque. such as the tantalic. insoluble precipitates : are produced. Fluorides. if the liquid acid be used the lines are trans- Most of the compounds of the metals with on the application of heat. Calcic fluoride is so transparent as to be perceived with difficulty . consisting of the fluorides of these metals. since argentic fluoride is soluble but with salts of lead. and form compounds which may often be obtained in crystals that are soluble in water. for instance. When ignited in a current of steam many of them are converted fluorine fuse easily into the corresponding oxides. will be be very found to be corroded in the parts exposed if the traces faint. or on the addition of ammonia. and hence the origin of the terms fluor-spar and fluorine (from fluo. in the course of a few minutes the scale is effected is permanently engraved when the engraving by the vapour of the acid. but they are not so readily attacked by nitric acid. and tungstic . but on heating the liquid. in water. the traces are white and : opaque.FLUORIDES. but parent. vessels in The solutions of the soluble fluorides : corrode the glass which they are contained they give no precipitate with argentic nitrate. the glass tube is first coated with engravers' etching varnish. the glass. magnesium. Many metallic fluorides combine with an additional atom of hydrofluoric acid. on cleaning off the wax with a little oil of turpentine. If heated with chlorine. to flow).HF) has been already mentioned as a convenient source for preparing anhydrous hydrofluoric acid. from becoming melted. whilst chlorides of the metal are prosoluble. many of the fluorides are decomposed. Double fluorides of the alkali-metals with the fluorides of the electro-negative metals which form acids with oxygen may likewise be obtained with facility. or only is formed. whilst hydrofluoric acid large number of the fluorides are insoluble. A They are all decomposed when and evolve hydrofluoric acid. weak solution of hydrofluoric acid A is often employed advan- in this way. vitriol. they may be rendered visible by breathing upon : the surface of the plate. the divisions are traced through the varnish with a fine point. molybdic. sparingly heated with oil of duced. 235 If fluorine be contained in the mixture. barium. and calcium. Many insoluble metallic anhydrides.

TiF4 +2H 2 O. and give rise to new by the excess of hydroTitanic compound acids. remarkable that the mixture does not dissolve either gold or platinum. 34'o. readily dis- which has not been strongly ignited . (444) vol. and fumes densely in the air. wt.. |_ Boric fluoride. Observed. : By .. which dissolves 700 times its volume of the gas witl considerable rise of temperature. gr.. B F3 . n'o 57-0 or 16-18 2? 3 2 83-82 68 o - ico'oo . and the boric fluoride passes of as a colourless gas which may be collected over mercury. forming a fuming oily acid liquit of sp. Hydrofluoric acid. . 68'o) Trifluoride of boron (BF 3 Theoretic Sp. is thus converted into fluotitanic*acid TiO 2 + 6HF becoming 2HF.. Tj. and intensely ignited in i wrought iron tube closed at one end. are thus dissolved by hydrofluoric acid. Boric fluoride does not support combustion . fluorides of the metals being formed. B ( 4 \ O BO BO BO <2 Ca)" + 2BIV i Calcic borate remains in the tube... decomposition occur: chloride. but it is... 2*312.. when mixed with solves silicon Silica yields a similar nitric acid.236 BORIC FLUORIDE^ OR TRIFLUORIDE OF BORON. .not of sufficient practical importance to require notice here the compounds which it forms with silicon will bf : described hereafter (452). = boric It is best prepared in the following manner 2 parts of fluor-spar and i of fused boracic anhydride. Mol Boron forms with fluorine a body analogous to the . Numerous other compounds of fluorine have been prepared. charring organic matte of vitriol This solution has been callec . for instance. 2*353. i'77 which as powerfully as oil is very corrosive. compound (2HF. or Rel. anhydride. are intimately mixed. gr. both ii flue powder. Th< composition of the boric fluoride Boron Fluorine is the following By weight. but they are . it has an irritat It is rapidly absorbe( ing odour.SiF4 ).. . anhydrides. vol. whilst the oxygen of these compounds the produces water with the hydrogen of the hydrofluoric acid : metallic fluorides so formed are dissolved fluoric acid. according to the equation 3CaF 2 3 CaF2 ^ + -f 4B 2 O3 = = 3 3(Ca2BO 2) + 3 BF 3 . by water.

which rempins behind. produced of two molecules of boric fluoride on three of action the by O When heated. if consist only of fluorine and calcium.BF 2 3 ). largely diluted with water. that if boracic acid be added to a solution of potassic or ammonic fluoride. 2 3 . its composiwater. of cream : : the fluorine unites with the hydrogen of the sulphuric acid. of fluor-spar. and concentrated sulphuric acid. is completed. and then concentrating it in platinum vessels B 2 O 3 .COMBINING PROPORTION OF FLUORINE. the specific gravity the of liquid becoming reduced to 1*584. Although the chemist has hitherto been unable to isolate fluorine in a state of purity. and forms calcic experiment On weighing the crucible after the sulphate. for each molecule of boracic acid. and contains two molecules of water. the calcic sulphate will be found to amount to 17 '436 it is grammes. tion being is also easily preacid with boracic acid. at this density it distils unchanged. 7*436 grms. boric fluoride escapes. musty . whilst the calcium combines with sulphion. and is expelled in the form of hydrofluoric acid. 20 being the quantity of calcium equivalent to one atom of hydrogen.2H 2 O. (H = i) though since it is a dyad its atomic weight is 40 (13) but 68 1 : 2O : : 17*436 : x( = 5*128) . and the mode of proceeding offers an instructive illustration of the resources of chemical analysis in such a case. of calcic sulphate must consequently contain 5*128 of calcium it . When pears to consist of a molecular compound of hydrofluoric acid with boric fluoride and is formed in the following manner : 8BF3 -f 4 H 2 So strong is = 2HB0 + 6(HF. keeping pared by saturating hydrofluoric the mixture cool. yet its combining proportion has been determined with precision . the excess of acid is expelled by the heat of a lamp the temperature is raised very cautiously. three of potassic or fluoride ammouic hydrate are liberated and a boro- produced : (445) Determination of the Combining Proportion of Fluorine. the tendency to the formation of this compound in dilute solutions. Now known that 68 parts of calcic sulphate contain 20 of calcium : and 48 of sulphion. therefore.6HF. Borofluoric acid until dense fumes rise from the liquid. of this powder are accurately weighed into a counterpoised platinum crucible. 237 It appears to consist of B borofluoric acid. 100 parts. is added in quantity sufficient to reduce the whole to the consistence : after standing for some hours.. one-fourth of the boron is in the form of boracic acid.6HF. Pure fluor-spar is reduced to an The method of operating is as follows impalpable powder. 10 grms. and another compound is separated This acid apfound in solution termed hydrofluoboric acid. and the crucible and In this operation the whole of its contents are finally heated to bright redness. and dried. also perfectly pure.

of calcium in 100 parts. which these elements form with the same bodies are isomorphous ' might be arranged thus in series : Carbon Silicon Tin Zirconium. OR SILICIUM. The acid liquid. a gaseou. I atom of hydrogen thus ascertained to CHAPTER SILICON. : Qty. which is partially soluble ii water.SiF 4 2 conium forms a solid tetrachloride. tion of fluorine The combining proporbe composed of 51-28 of calcium and 4872 of fluorine. possessing striking similarities in composition and constitution to organic substances. of Fluorine in 100 parts. of fluorine. yields a sparingly solubl< . is The quantity of fluorine equivalent to be 19. wise exhibits a similar resemblance to titanium and tin in its power of forming an oxide with 2 atoms of oxygen.2H 2O.238 SILICON. a mixture of fluor-spar with fine quartzose sand o. when neutra lizcd with a solution of caustic potash. In order to obtain the element in its uncom ground bined form. indicate that silicon is very nearly allied to carbon. as in SiCl 4 . These element. : : Equiy. . SrF 2 . is the It mos is the abundant term component of the earth's essential constituent of Bilex or flint. flints is heated with concentrated sulphuric acid . is then found directly by the following calculation : Qty. and hence the origin of th< silicon. SrF 2 .SnF4. Titanium These elements Silicon all lent in their most usual combinations to belong to the class of tetrads. .. a hydride SiH 4 analogous to marsh gas CH 4 and the numerous compounds which may be obtained.TiF4 2 H 2 O). of calcium. tetrafluoride of silicon is formed. in when solid combination with oxygen crust. (446) SILICON presents a certain analogy with boron in its Silicon liketendency to unite with flourine and with nitrogen. : Si = 28 Tetrad. The double fluorides production of a volatile liquid tetrachloride. producing an acid solution. Equiv. but in properties it is nearly The tetrad character of silicon. OR SILICIUM : XIII.g. Zir (e. being equiva 4 atoms of hydrogen. : 51-28 20 48-72 19. the existence o allied to silicon. SrF2 . and in its H 2 0.

and mixed of Potassic fluoride is of its weight potassium. reduced and partially combines with the excess of potassium. be prepared by heating potassium or sodium in porcelain trays. the silicon undergoes a remarkable change in properties. the : silicon much burns brilliantly in the nitre. Silicon is not acted upon by nitric or sulphuric acid. and is which fuses from the intense heat. The brown powder just described. becomes much denser. Silicon may be obtained in two distinct modifications. converted into forms a superficial 2. parts with a trace of hydrogen. Amorphous Silicon. and coating over the unburnt silicon. and darker in colour.AMORPHOUS AND CRYSTALLINE salt. It may even be fused with nitre or with potassic chlorate without undergoing oxidation . and After such ignition. is hastened by the addition of a little potassic carbonate. It is a non-conductor of the fingers when touched. 2KF. even when urged in the blowpipe flame. in a glass tube. substituted for potassium in this experiment. although it is rapidly dissolved if treated with a mixture of nitric and hydrofluoric acids. but if the heat be urged to whiteness. silicon presents the appearance of a dull brown powder. and soils When heated in the air or in oxygen silica. which is protected by lining it with thin plates of mica and passing a current of the vapour of silicic chloride over it.SiF i -f 2K 2 = Si -J-6KF.. The mass. but is readily soluble in hydrofluoric acid. whilst silicon is tion of hydrogen. . arising from the decomposition of the water by The washing with cold water is conthe excess of potassium. the amorphous and the crystalline modification. in which electricity it sinks. it burns brilliantly. and resists the action of pure hydrofluoric acid. in the proportion Silicon may also of i part of sodium to 2 of the silicofluoride. with when cold. viz. and heated. is treated water. the mixture then deflagrates briskly. may be heated strongly in air or in oxygen. . SILICON. which produces a copious evoluformed. insoluble in water. as Sodium may be advantageously long as anything is dissolved. and ceases to give any alkaline reaction with testthen finally well washed with boiling water. if heated intensely in a closed platinum crucible.SiF 4 a glass or iron tube with eight or nine-tenths in dried. the oxidation. and in a warm solution of caustic potash. even though the temperature be may much lower : by fusing with potassic carbonate alone. without taking it has become sufficiently fire heavy to sink in oil of vitriol. When procured by the processes above 1. shrinks greatly. tinued until it it is paper . however. 239 This p classic silicofluoride is to be thoroughly aKF. described. Crystalline Silicon.

powdered cryolite. in both cases silica is dissolved by the melted alkaline carbonate. n) that tie really only modifications of tl 3 octohedral form. the much resemble this graphitoid modifiwho obtained the and described Deville cation by Wohler. which have plates. When heated in a current of hydrochloric acid. * Silicon appears to have the same sort of tendency to combine with alum to unite with iron. owing to the formation of a platinum silicide. xv. W. . and is placing a portion of and completely oxidized . and tht - nium that carhon has . by silicon in crystalline plates. . H. but it is gradually dissolved by a mixture of hydrofluoric and nitric acids. the sodic chloride becomes volatilized. it may be fluoric acids/* ? heated to whiteness in a current of oxygen without undergoing change. a sp. . 65). a volatile liquid.t and a metallic lustre. in which two parallel faces are much larger than any of tl e other faces. silicon is easily formed. The alloy is easily formed by heatin aluminium in a Hessian crucible with from 20 to 40 times its weight of di potassic silicofluoride. < reaches the platinum. Miller has shown (Proceed. According to Deville (Ann. Fused silicon may also be pro cured when the mixture of sodic chloride with reduced silicoi (obtained by igniting sodium in the vapour of silicic chloride detached as far as possible from adhering fragments of porcelair is placed in a crucible lined with charcoal. while two other parallel faces are either too small to be observed. In this form silicon is a conductor of electricity. xlix. the silicon into a platinum crucible lined with lime and protectec by an outer clay crucible: the whole is then intensely heated iie a wind furnace. fusing the two together for a quarter of an hour. r of so-called graphitoid silicon are are altogether wanting . whilst hydrogen gas is liberated. and exposed to intens heat in a forge . silicon requires for its fusion a temperature between the melting-pom In order to fuse it he introduce of cast iron and that of steel. disits The properties of carbonic anhydride. the crucible is spoiled. de Chimie [3]. gr. silicon chloroform. treating the glass black mass with hydrochloric acid. and the silicon . by treating an alloy of silicon and compact form of silicon aluminium in succession with boiling hydrochloric and hydrowhen the silicon remains behind in the form of Ii. f Prof. If the lining of lime cracks.240 GRAPHITOID AND CRYSTALLIZED SILICON. although it is oxidized but very slowly when fused with potassic hydrate. and th silicon is fused into globules in the midst of the melted mass These globules frequently show well-marked indications of crys. of 2'49. / i allowing the crucible to cool slowly. . i of with aluminium obtained also be part 5 o: by fusing may of and 10 free from lead. silicic hydrotrichloridc (SiHCl3 ) is formed (451). plates Roy. and then with hydrofluoric. Soc.

heat. II. by Brodie from graphite Si. terminated by three-sided pyramids. steel-grey colour. Deville and Caron have in this way (Ann. It may be obtained mixed with quantity R . Crystals of silicon may likewise be procured. first in hydrochloric. and with less difficulty. and have cast it into large cylindrical bars without sensible loss by oxidation. Silicon forms but a single oxide. and 4 of The mixture must be maintained at a red pure granulated zinc. to a current of the vapour of silicic chloride the aluminium is volatilized as aluminic chloride. it must then be allowed to until the slag is completely melted cool slowly. 241 they have a dark. silica. by exposing pure aluminium in porcelain trays. (458) . Wohler has. and the zinc which runs from the pasty mass in which the silicon is retained may be employed again in a similar the zinc which still adheres to the silicon may be reoperation moved by digestion. p. cut into small pieces. Ixvii. or silicic anhydride. the well-known compound. Si 3 H 4 O 5 ? silicium for the element . and a lustre like that of specular iron ore now and then the silicon is found : : It may also be crystallized in regular double six-sided pyramids. discovered a remarkable series of compounds into the composition of which both oxygen and hydrogen enter: one of these he calls silicon (Si 6 H 6 O4 ?) reserving the term another he has named leukon. The mass of zinc thus obtained contains long needles of silicon formed of octohedra. and the silicon obtained in the fused condition. These bars exhibited a brilliant surface. operation the whole of the zinc may be expelled. de Chimie [3]. and introducing a mixture of 3 parts of potassic silicofluoride with i part of sodium.SILICIC tallization HYDRIDE. heated intensely in a porcelain tube. and afterwards in boilIf a very high temperature be employed in this ing nitric acid. 4 scribed a remarkable gaseous combination H and Buff have deof hydrogen and a large silicon. but below the temperature necessary to volatilize the zinc. leaving the silicon in crystals : which have a reddish lustre . by heating an earthen crucible to redness. obtained in regular six-sided prisms. 94). inserted one into the : other much of the zinc may be extracted by partial fusion at a low temperature. derived from the octohedron. 440) fused several hundred : : grammes of silicon under a layer of potassic silicofluoride at a temperature near that at which cast iron melts. they are hard enough even to cut glass like the diamond. these bodies are possibly analogous to those obtained (note. Wohler (447) SILICIC HYDRIDE . however. which was not altered by exposure to the air.

a its brown also surface. a cold plate of porcelain or of glass be introduced into a jet air. in contact with sodium. when allowed to burn in ] emits white fumes. but becomes so when diluted with hydrogen. but in practice it is obtained by the fc Observed. of any considerable elevation of tempera- A ture are necessary to insure the maximum production of the Hydride of silicon may also be obtained by decomposing impure silicide of magnesium with cold dilute hydrochloric acid . Mol. 35 of dried sodic silicon uoride. when a wire or plate of aluminium combined with silicon is placed in a solution of feeble sodie of a voltaic and the avoidance hydride. wt. of Vapour. and 10 of fused sodic chloride . which is immediately covered. . (448) CHLORIDE OP SILICON. a coating of silicon being depcand the gas is found to have lost its self-lighting powe: sited. In this state it is not spontaneously inflammable at the ordinary temperature. and thrown into a red-hot Hessian crucible. of free hydrogen as a spontaneously inflammable gas. The the electrolytic gas is colourless . and heated in a cover< d crucible . 5-939. with 20 parts of sodium in small fragments. It is of silicon is deposited upoa decomposed by transmission through film tube heated to redness. and subjected to a current neither chlorine nor carbon separately can decor >f i- . Theoretic Sp. 2 C. Pure silicic hydride has been obtained by the decompositio i of an organic silicon compound called triethylic silicoformia e a glass . but is withovt action upon the solutions of lead and of platinum . the silicide is obtained by mixing intimately 40 parts of fused magnesic chloride. in dry chlorine : which it is ignited.) Boiling -$'. SiCl4 =i7c .). This gas precipitates many metallic solutions. Gr. consisting or amorphous silica. the precip tates in most cases contain silicon. orwhen mixed witii air under reduced pressure. Silicic chloride. or if gently heated. Vol. chloride and made the positive pole large surface of aluminium battery. the heating is to be continued till the vapours of sodium cease t3 1 burn. argentic nitrate. 5-882 of Liquid.SILICIC HYDRIDE. . 1-5237 at 32 (o C. such as cupric su phate. and palladious chloride. |~j~] ' Rel. This compound may be formed by heatir * 'S^ (59 silicon in chlorine . 85 . it f f c the burning gas. the charred mass in fragments is transferred to a po celain tube. these are mixed in a warm dry tubt. lowing indirect method : Finely powdered silica is made t p into a paste with oil and charcoal.

4 I? Silicic chloride SiCl 4 = 170 silicic locroo Water immediately decomposes hydrated silica. 327. a tube fused into the bend of the tube also be kept cool E. whilst silicic chloride is formed . but together they effect its decomposition easily. of apparatus by which the chloride may be readily a porcelain tube. irritating odour strongly in the Chlorine Silicon air. chloride. which with its contents is exposed to a red heat in the furnace : silicic chloride distils over into the bent tube. and FlG. and forming hydrochloric acid. Fig. with . The product is received into vessels cooled with a freezing mixture. washed with water in B. acid. A depositing moist atmo- R 2 . conveys the chloride into a bottle. carbonic oxide escaping. a pungent. SiO 2 + 2Cl 2 + C 2 =2CO-fSiCl 4 . very volatile. 8 353 16-47 By vol. dried by 327 shows a form : D is transmitting it over pumice and sulphuric acid contained in the tube c. Q t which may by ice.CHLORIDE OP SILICON. colourless liquid. Silicic chloride is a transparent. 243 pose silica. which contains the mixture of charcoal and chlorine is liberated from the flask A. allowed to pass through the tube D. silica prepared . and fumes Its composition is the following it is : C1 4 Si = = 142 28 By or weight. E r where it is condensed by immersion in a freezing-mixture of ice and salt .

).3SiCl 2 of hydrochlorate of chloride of silicon or chloroleukon (Si a H. for the formula al ove given corresponds to 3 volumes instead of 2 volumes of vapour. which fumes powerfully on exposui-e to the lir.Cl M Hi. known the siliceous deposit obtained from the as tabasheer. Si 2 I is obtained by the action of finely divided metallic silver on the tetriodide. and burns with a greenish. Boiling-pt. or I volun e of the vapour of disulphide of silicon and 2 of the tetrachloride united wit) out condensation . 8 is passed over heated silicc i. If its vaj nir highly be mixed with oxygen. posited in Water decomposes the form of a brown amorphous crust exhibiting a metallic lus tre. heated in its vapour. by pass ng hydrochloric acid over heated crystallized silicon and condensing the product in a tube surrounded by a freezing mixture by fractional distillation ^he silicon chloroform is separated from the silicic chloride. exhibits the same peculiarity. Sp. (Sp. G>: of Vapour.8 (l2O'5 C. It is The triiod'de formed by the action of iodine on silicon at a high temperature. but resume their opacity joints on drying : of the bamboo. for SiS 2 2SiCl 4 = = By volume. 3O7'4 (153 C.he 95 . 7'42). ' Wohler and Buff (Ann. 98 (35 37 C. luminous flame. Two iodides are known the tetriodide SiT4 a sub(450) Silicic iodides. It is a colour ess : mobile liquid. fe( bly suffocating odour. i 2 . Gr. which melt at 2/.)* and 2SiS4 SiCl v Also a chlorinated silicic sulphydrate SiCl s HS . causing of silica in opaque lamellar plates. of . it immediately with great elevation of temperature. This body mixed with silicic chloride constitutes . the deposition sphere also decomposes the chloride. .)] is analogous in properties to the chloride: it nray be formed in a similar manner.) to a yellowish liquid. and emitting a vapoui of It is highly inflammable. a The vapour density of this compound is anomalous. whilst half its silicon is d. depositing silica and emitting hydrochloric acid. 7*25 . if The the metal produced. of Vapour 4^64 . this is one of the best methods be of obtaining silicon. Sp. Gr. It is obtained [3]. Two compounds between the sulphide and the chloride of silicon have been obtained (Pierre) having the formulae SiS2 . which boils at about 392 (200 C. (449) Silicic Bromide [SiBr4 . and but liquid chloride does not act on potassium.ric spark. 6 It cr) stallizes in colourless hexagonal prisms (451) SILICON CHLOBOFOEM SiHCls . silica being deposited. de Chimie = 4HCl. Vapour. The liquid may be boiled with sodium without undergoing decon position. lee kon : and hydrochloric acid being formed 2SiHCl 4g When hydriodic acid mixed with hydrogen * 3H 2 = 6HC1 + Si H 2 2 . Gr.) 2-813. whilst hydrochloric acid and silicic chloride are formed. 5-24 . If passed through a tube heated to redness. it explodes violently on the transmission of the elei . (Sp. of Liquid at 32 (o C. Boiling-pi.244 SILICON CHLOROFORM. depositing a white film upon surrounding bodies.).. it is decomposed inl > a mixture of silicic chloride and hydrochloric acid. 269). which like the mineral hydrophane become transparent when immersed in water. stance crystallizing in colourless transparent octohedrons. potassic chloride is silicon is set free . Theoretic.2SiCl 4 .

and boiling at 428 (220 C. pounds of silicon so powerful is the attraction between fluorine and silicon that hydrofluoric acid separates silicon from its most In order intimate combinations.. wt. 3*598 . it is not inflammable. and according to Natterer it The gas is dissolved and solid at 220 ( 140 C.. is deposited as silica in a hydrated form : .. as : odour is shown in the following equations CaF2 +H 2 S0 4 = and 4 "HF+SiO 2 =2H 2 The composition of the gas may be thus represented Silicon : Si Fluorine Silicic fluoride . 104 (452) FLUORIDE OP SILICON . and renders it opalescent.SiF 4 a stream of gaseous silicic fluoride is transmitted Two through water. It is a colourless. strongly refracting liquid of sp.. with a suffocating peculiar.. Silicic tetrafluoride SiF4 Rel. which adheres becomes partially . and this given off. Theoretic Sp. but extinguishes a lighted taper . and in jars which have been perfectly dried at a high temperature. equal parts of finely powdered fluorspar and siliceous sand. with twelve times their weight of oil of vitriol. 2HF. Silicic very firmly to the glass. On the application of heat. Silicic tetrafluoride fumes strongly in the air. mixture of solid 245 silicic iodide with liquid silicic iodoform SiHl3 is produced. F4 SiF 4 = = = By weight.). pungent. Hydrofluosilicic Acid. = 144. acid is is liberated. i? 4 2 76 104 73*1 . and forms with it a volatile crystalline compound. such as silica and glass. Gr. 52 ..) it must therefore be collected decomposed by water over mercury. under strong pressure it was liquefied by Faraday . fluoride combines with twice its volume of ammoniacal gas. vol.). Observed.. When (453) SILICOFLUORIC ACID . gr.. or powdered glass. it is decomposed and partially dissolved. 3*362 at 32 (o C. the slightest trace of moisture on the surface of the jar causes a deposition of silica. = . a colourless gas. molecules of water react on 3 of the fluoride.SILICIC FLUORIDE. loo'o . hydrofluoric immediately attacks the silica. Vol. and produce the silicofluoric acid which is dissolved. \~ The to prepare silicic fluoride. fluoride is : Mol. 28 or 26-9 By . one of the most remarkable com^]. whilst one-third of its silicon. are mixed in a capa- cious flask or retort. y6o .

: the latter acid. :>). water. as shown in as it 328. in order that the orifice of the tube may dip beneath the fig. reacting on t le and silicic fluoride.SiF. so if allowed to evaporate upon it free tilized.SiF4 4tJ 2 O + 6KF4-SiO . so that the liquid finally becomes a gelatinous this is mass . In the preparation of this acid the end of the tube from which the fluoride is escaping must not come in contact with the FIG. by the deposited be obviated This may by placing a little mercury at the bottom of the vessel. In solution it forms a very soi r. consists dissolving hydrofluoric acid. leaving hydrofluoric silica of the glass. may . but it dc es . ANHYDRIDE 2'8. in loopa. silica is precipitated. salts of With tate. be thus represented: In the second case: 2KHO + 2HF.n is required in quantity. 2*2 Comp. 46'66. Cryst. Each bubble surrounded rises is by a siliceous envelope. 53'34- Berzelius represented this compound a^ a . as in water produces silicic fluoride the ordinary process for making that gas. 328. otherwise it will speedily become obstructed silica. 2'5 Si.SiF = 6KHO + 2HF. ts. but if and the wh< -)- SiF4 . when silica in dilute to free from the deposit of silica from adhering it silica. submitted to pressure in a linen cloth. O. 3y which means the solution of silicofluoric acid is separated when thoroughly washed pure hydrate obtaining the acid. con- stitutes a of it A more easy method of . 4HF+SiO =2H 2 O salts. = 4 A dilute solution of silicofluoric acid p o2 duces transparent jelly-like precipitates in the salts of the alkj limetals . Amorphous. does not attack glass. becomes volaacid. Gr. or Silica. mercury. Silicofluoric acid combines with bases to form in le excess of base be employed. case the action 2 In the fi 'st 2H O + 2 KF. barium the acid gives a white crystalline preci ri- (454) SILICIC Sp.246 SILICOFLUORIC ACID. of the fluorine is separated as a metallic fluoride. it is frequently employed as a precipitant of potassir na. which. Silicic dioxide (SiO 2 =6 2*3 . saturated solution of silicofluoric acid A fuming liquid.

Carnelian is a red or brown ferric oxide. silica has the aspect of a white divided Finely earth. however. 1857) have. a to transparent glass. and it will be employed in this work. Amethyst is a purple variety coloured with an oxide of iron is (ferric acid ?) . * The experiments of Colonel Yorke (Phil. the crystalline and the In the crystalline state it has the higher specific- Pure crystalline silica occurs in rock crystal and in some forms of quartz. Pure crystallized silica is and of a vast variety of minerals. and although insoluble. and in Preparation. when converted usual : tion of finely divided and in decomposing fused potassic carbonate by the addisilica. in two modifications. would then produce 2 volumes of vapour as silicic molecule of chloride. pipe Native silica flexible. reasons which render it more probable that i contains only 2 atoms of oxygen. varies with the nature of the sodic carbonate losing a larger proportion than potassic carbonate. which consist of a mixture of the crystallized and amorphous varieties. if that of are. and that it corresponds in composition to carbonic anhydride : for example. lithic from an excess of the different carbonates. opal upper variety calcedony. which may be drawn out into fine. Flint is a variety containing of in the chalk and found . Trans. it possesses the power of uniting insoluble in water. instead of forming an exception to the general rule. is all acids except hydrofluoric. Silica constitutes the principal ingredient of all sandstones. crystallized in six-sided prisms. Silica found nearly pure in agate and calcedony. shown that the proportion of carbonic anhydride expelled by equal weights of silica base . and carbonate^more than sodic carbonate. as it does upon the theory of Berzelius. 247 trioxide. giving oxygen be 8.* This view has the advantage of greater simplicity. Silica occurs amorphous. where equal quantities of silica were employed. According to the experiments of Dumas. and in hardness it approaches the colourless . however. chiefly consists of the amorphous variety of silica with a varying quantity of water. transversely striated. and 53*3 of oxygen. and terminated by six-sided pyramids. gravity. There it the atomic weight of silicon as 22. perfectly transparent It fuses in the flame of the oxyhydrogen blowprecious gems. 100 parts of silica contain 46*7 of silicon. . elastic threads of the amorphous variety. and it enters largely into the composition of felspar. into vapour. Calcedony in alternate layers of different colours constitutes onyx. it is found that the whole of the car- bonic anhydride is expelled when the proportion of silica is to the carbonate as 60 to 138.SILICIC ANHYDRIDE.

takes When all the mineral has been introduced the mixture is place. an excess of alkali is always used. may heating colourless quartz to redness. but it becomes less soluble in proportion to the excess of silica. powder. the mineral is rendered friable by this treatment. silica. gaseous Perfectly pure silica may also be procured by passing the silicic fluoride into water. it is well washed as long as anything is dissolved . and decanting the strong acid. by continuing the heat. till at soluble in length a point is reached at which water or in the common acids. When it is proposed is no longer indeed. and quenching it in water. yielding SiO 2 + Silica likewise be obtained nearly pure by 2(2HF. if washed and ignited furnish silica of snowy whiteness. without becoming sensibly moist. on being digested with water the mass slowly dissolves with the exception of a portion of the impurities. in which it is entirely and in sufficient quantity. tained. manner give a very white powder. silica. as is : PREPARATION OF PURE SILICA. it is As thus prepared. state of purity fused at a red heat. and are easily attacked much more (455) by solvents than the crystalline Insoluble. deposited in white hydrated flocculi. variety. heated strongly for some minutes. and is then common flints treated in a easily reduced to a fine powder . . due to the escape of carbonic anhydride. is converted into a white earthy-looking powder no longer soluble in soluble if the acid be dilute acids : after being digested with oil of vitriol to remove traces of titanic anhydride. Hydrates is of Silica. the silica is separated as a gelatinous hydrate. as the resulting compound is then easily attacked by acids. as silica when once deposited. it the basis silica. like charcoal and other perfectly pure. of glass. if then dried and ignited. and although however. . 3SiF4 + 2ll 2 O. a decomposition of the gas and one-third of the silicon it contains is oxidized and occurs. shown by the usual process for obtaining it in a A mixture of potassic and sodic carbonates is and one-third of its weight of ground flint. on each addition a quantities brisk effervescence. porous bodies. it forms to obtain pure therefore.248 with bases. which. If the solution in hydrochloric acid be evaporated.SiF4 ). which is nearly pure All the artificial forms of silica are amorphous. is or some other at siliceous mineral in fine added in small a time to the melted mass. which the siliceous material may have conA larger quantity of silica than that above indicated would still yield a mixture which might be fused by a strong heat . similar silica. which. generally in water. such as ferric oxide and titanic anhydride. absorbs aqueous vapour rapidly from the air. and is then allowed to cool .

which corresponds nearly to the days over sulphuric acid. the silica is precipitated in a gelatinous form in proportion as the alkali is neutralized. of silica may be cent. and if hydrochloric acid be gradually added to a solution of an alkaline silicate in water. whilst water is The coagulation is retarded by hydrochloric acid. 204). containing.59 (15 C. Its coagulation is also effected in a few minutes by the addition of i^/j^y part of any alkaline or earthy carbonate in solution. the whole of the silica is retained in solution but it may be precipitated from this acid solution by the of an . gradual addition of a solution of potash. but solutions of gelatin. is immediately cause a gelatinous precipitate when solution of silica gradually added to one of gelatin in excess.-| O lSi(OH) 3 J . and the whole then solidifies. shrinks. From the solution of alkaline silicate in excess of hydrochloric acid. with a feebly acid reaction. Graham obtains a pure solution of hydrated silica. Alcohol and sugar. changing the water in the outer vessel at intervals of 2 4 hours. nitric. obtained a transparent. which had a composition represented by the formula 3H 2 O. a modification of it exists which dissolves completely at the moment of its liberation from some of its compounds For instance. if a dilute solution which are already in solution. soluble alumina. by the action of moist air upon silicic ether. and acetic acids are without action on the solution. is SILICA. after exposure for two f water. : By evaporation in vacuo at . p. are without action. rather greater than that of carbonic acid. if the liquid be down in a flask. small quantities of caustic potash or soda. considerable difficulty in obtaining a defiit easily loses a portion of its water at low temperatures. and colourless. Sulphuric. inch (i centimetre) in depth be subjected for 4 or 5 days to dialysis. The solution is tasteless. 100 parts of silica require 1*85 of potash (K 2 0) to neutralize this effect on litmus. A boiled concentrated solution prepared in this till the quantity way and containing 5 of silica reaches it is 14 per per cent. for however. alkaline silicate be poured into a considerable excess of hydrochloric acid. and soluble ferric oxide.). by subjecting the liquid to dialysis in If a stratum of liquid 4 tenths of an a hoop dialyser of parchment-paper (62).SiO 2 2 * There is.2SiO 2 . The solution is not easily preserved for many days.HYDRATES OF even in the gelatinous form. 1861. the hydrochloric acid and the soluble chlorides will be found to have diffused so completely that the liquid in the dialyser will give no precipitate with argentic nitrate. and by separated from it. 21*99 formula H 0. as it becomes converted into a solid transparent jelly which. Trans. (Phil. the precipitate obtained consists of loo of silica and 92 of gelatin. In open vessels apt to gelatinize on the edge. the silica is left behind in the form of a transparent glassy mass of great lustre. but not by caustic ammonia nor by neutral nor acid salts. Ebelmen. and is moreover a very hygroscopic substance. so as to neutralize the acid . even in closed vessels. glassy hydrate.f and a compound which gave * [SiO(OH) a ]. gum and caramel. limpid. 249 almost insoluble both in water and in acids. f f-(Si(OH). but it is slowly coagulated by a few bubbles of carbonic anhydride. nite hydrate of silica.

and the change is accelerated by the presence of 2 or 3 per cent. the other between 6'6 and 7 per cent. obtained in the insoluble form. corresponding to the formula H 2 O. on drying the ordinary gelatinous hydrate of silica in vacua over sulphuric acid without the aid of heat.t which would contain 6^9 per cent. between the upper greensand and the gault the proportion of hydrated silica in these deposits varies very : A 5 to as much as 72 per cent. of water. very large quantities of silica are dissolved.3SiO 2 . From the occurrence of a mixed ether consisting of of water. When by that of a high temperature. ~ (SiO(OH)n JsiO o _ lsiO(OH)_ . Fuchs obtained two hydrates of one containing from 9-1 to 9'6 per cent. the composition the hydrate doubtful. i'i6). which. flints in their unground condition in strong may be dissolved solutions of caustic alkali (sp. very white and light hydrate of silica occurs naturally in abundance in beds situated at the base of the chalk formation. when made into a paste with water.* which requires 9'! per cent.SiO ). being most abundant in the A mixture of this material with slaked upper portion of the deposit (Way). as the liquid cools. lime. as boiling springs of Iceland.).4SiO 2 . (C 5 H n 3C H . ranging from of soda. (150 Finely divided hydrate of silica is also dissolved by the alkaline carbonates these carbonates are only partially decomthe silica which is dissolved. gr...J 2 5 4 it basic acid. gradually converted into the soluble Even variety by long digestion with solutions of the alkalies. on analysis was procured by Doveri. if the solution be Insoluble silica digested with may be them under pressure and 200 at a temperature of between 302 C. are deposited as "petrifactions" on surrounding objects exposed in the basin or in the stream. agreeing nearly with the formula H 3 O.250 similar results SOLUBLE AND INSOLUBLE SILICA.. is in a few weeks converted into a silicate of lime. It appears to be owing posed by : and 392 to the solubility all of silica in solutions of the carbonates that in spring and river waters contain in minute quantity on evaporation the silica almost silica is solution . greatly. though from as appears that the the facility silicic is with which of really a tetrabasic its hydrogen escapes is water. silica. and the action of the alkaline liquid is aided is the case with the Geysers or of the Yellowstone River in America.

so abundantly diffused over the surface of the earth. and quartz and agate the crystallized Silicates. Silica also exists 251 in the soluble form in a class of minerals which are hydrated siliceous compounds found zeolites.. M'4 Si0 4 2 Si02 Acid silicates Silicate of calcium 2(Mg"Si03 ). in the formulae of the silicates I . (456) The silicates are most abundant natural All the forms of clay. The combinations with bases which are of most usual occurrence belong to one or ocher of the following classes. [Si(02 Cu)"(OH) 2 ] [Si(O2 Fe)" 2] M" 2 Si04 Metasilicates Forge cinder Wollastonite (MgFe)" 2 Si04 Fe" 2 Si04 Ca"Si03 Picrosmine ...2Si0 2 [SiO(0 2 Ca)"j [2SiO(02 Mg)". swell up to a this transparent jelly.SiO2 .OH 2 ] M' 2 Si03 .. . and the difficulty of crystallizing it by artificial means. . The composition may In the above formulae M' stands for i atom of any metallic monad. Nov. in the cavities of the amygdaloid rocks.of many of the ordinary varieties of glass be approximative^ represented by mixtures of different or-j (silicates which have this formula. compounds are found in the form of crystallized minerals. orthosilicates M .j M"Si03 . and M" for i atom of any metallic dyad. acid admits of modifications which differ in basic power. productions. are compounds of this description. hydrochloric acid. combines with bases in several different proportions .. . Meerschaum ( . 4 2 with an intermediate class formed by the combination of one M SiO (Phil. such as calcium. many of which are double silicates of very complex Silica most of its It is highly probable that silicic. atom of each of the two. In most cases... anhydride.(Si02 .H 2 (CaMg)"Si03 Mg" 2 Si0 4 .H s O) Ca" 2 Si04 . such as potassium. and a large number of other common minerals.SILICATES. . The zeolites... Mag.. however... . The zeolites represent the hydrated silica in silicic a crystalline form.. M"Si03 1 Silicates Augite . mica.. hornblende. if finely and treated with powdered. gelatinous mass consists of hydrate termed of silica... silica These observations on the various conditions under which may be rendered soluble derive their interest from the extensive formation of crystallized silica. of those the type . like phosphoric composition.. 1859) proposes 4. felspar. Odling to call the silicates of the type SiO 3 metasilicates. : the orthosilicates being regarded as the normal M' 4 Si04 salts Orthosilicates or Dioptase Olivine Cu"H Si04 .Si0.

priated to the element for itself. when fused a clear colourless bead. it. whilst the anhy- drous normal and acid by any acid except the detected by fusing them with sodic or potassic carbonate. The mixture is . and then heating the residue with acid. The freedom of silica from bases when may be ascertained by its being volatilized without residue evaporated in a platinum vessel with excess of pure hydroPure but is fluoric acid. . an evolution of hydrogen takes place. or which contain excess of silica. silicates. precipitate alkalies . to this Wohler has given the name of silicon. insoluble in water. salts bonates and the of all the volatile any percepdecomposes the caracids when ignited with them silica. undissolved in the form of a white powder. yields a colourless bead of glass. (457) If coarsely-powdered calcic silicide be digested in fuming nitric in a vessel kept cool by immersion in water. and those which contain the largest proportion of base. tartaric. the bead is generally more with silica slowly. for as silica is not volatilized to tible extent by the heat of a fumade. that the ordinary vegetable acids. Most of the silicates are fusible their fusibility is increased by mixture with each other those which contain readily fusible oxides melt at the lowest temperature. present. and a new compound is gradually formed . and in general the basic silicates fuse more readily than those which are normal in comAll the silicates are position. the silica remains of the earths are not decomposed The silicates may be hydrofluoric. such as the acetic. and evaporating to dryness . Borax dissolves a spongy mass in the clear bead . produces a similar result. have not hitherto been satisfactorily classified. which is objectionable. the oxalic. some time in a dark place until The mixture is to be agitated frequently and kept no more gas is given off. . action is At a high temperature. on treating the product with hot water. because it has been already approacid. with the exception of those of the alkalies The hydrated which contain a large proportion of base. are those most easily decomposed by acids silicates . when fused with sodic carbonate upon platinum foil before the blowpipe. and the silica from its combinations with the and a current of gaseous carbonic anhydride. custom of representing them as compounds Their diversified forms of the bases with the anhydride silica. . silica is not attacked by fusion with micro- cosmic if salt. the it reversed .252 shall adhere to the SILICATES. hence even the sulphates yield up their bases to the whilst the sulphuric anhydride is expelled. or even the gradual absorption of carbonic acid from the atmosphere. however. left as any earth or base be or less opalescent. which. forming The acid character is so feebly marked in silica.

and afterwards takes fire with slight explosion and the emission of sparks. The solution the liquid rapidly decomposes with evolution of hydrogen gas. and evolves hydrogen. especially in the presence of alkalies. Soc. Chem. which has a brown colour due to the presence of silicon. has a similar effect. S5 2 H 2 3 JO [ (SiHOj . in contact with water. washed. 322). and the insoluble material between blotting-paper. 268). even palladium. who has changed Friedel and its name to leukon. gold. carbonates dissolve it rapidly with brisk effevescence. and dried in the dark in vacuo. If heated with water in a sealed tube to 384'8 (196 C. Salts of copper. (Si 3 H4 O5 ?). Chim. agent.LEUKON. with evolution If exposed to the sun's rays under water. do not act upon It may be heated in air to 572 it. precipitating gold and palladium in a metallic It also throws down reduced selenium form. Leukon undergoes oxidation. The acids. 253 be diluted with collected. and base. carbonic When heated it deepens in disulphide. and instantly bleaches a solution of potassic permanganate.) without alteration. white). Pharm. In the dark it may be preserved without alteration. but if hydrogen. 7 or 8 parts of water. but at a somewhat higher temperature it takes fire.' Wohler (Ann. forming a silicate of the ammonia also decomposes it with slow evolution . either in a moist or dry of exposed to diffused daylight it slowly becomes paler. pressed over sulphuric acid.) it is speedily converted into white flakes of silica. de Chimie [3]. characteristic reaction is the rapid manner in which it is dissolved by solutions of the caustic alkalies. Ammonia. from neutral solutions of their salts. cxxvii. and a white residue is left. even when boiling . insoluble in water. exerts a strong reducing power. but it has been further examined by Wohler. which Wohler has termed leukon. whilst hydrogen escapes of hydrogen. vii. 276) describe this body as a snow-white powder when dry. phosphorous chloride. as it might be fitly termed in allusion to g a bright orange-yellow mass. lii. heated without access of air. with rise of temperature and copious evolution of hydrogen. into a mixture of silicon decomposed but Leukon is slightly soluble in water. silver. Silicone (Si 6 If leaving silica. Laden'burg have shown that this body is the analogue of the unknown formic anhydride. still lower oxide . colour. silicon formanhydride . but undergoes immediate decomposition. leaving a residue of silica and silicon in C. its colour. Buff. however. is O 4 ?). it evolves hydrogen. state. with the exception of the hydrofluoric. (300 C. or silicic chloride.S1LICONE then to .). sufficiently light to float The caustic alkalies and their upon water. If heated in a closed crucible whilst silicic it is and silica. whilst pure hydrogen is liberated. Wohler and Buff (Ann. Silicone is not attacked either by chlorine or by fuming nitric or sulphuric Its acid. but hydrofluoric acid dissolves it completely. it immediately begins to evolve hydrogen. hydride (447) is liberated. although it sinks in ether. burning with scintillation. emitting a phosphorescent light. at temperatures above 32 (o C. H amorphous 212 (100 The decomposition begins even at shining brown flakes. Silicone acts as a powerful reducing the alkali-metals dissolve it more slowly. This compound was first described as a hydrated oxide of silicon.). (458) Leukon. and tellurium from solutions of selenious and tellurous acids in hydrochloric Wohler and acid. and osmium yield with it dark silicates of a suboxide. in allusion to its asnect (from \evKos. The carbonates of in very dilute solutions. think it probable that this solution contains a of silicon than the one above described. alcohol. [2]. Friedel and Ladenburg (Bull. or chryseon.

vanadium. fibrous compound This nitride may be heated to redness in full When heated to chlorine without undergoing decomposition. being placed There is not the same great resemblance amongst the metals. SiS 2 =92. arsenicum. but at the same sulsilica decomposed. and a current of dry hydrochloric acid gas passed is formed and in part condensed in the over it. folds of blotting-paper and dried in vacuo over sulphuric acid. : CHAPTER XIV. SiS 2 + 2H 2 O becoming SiO 2 + 2H 3 S. when heated bluish. corresponding compounds are much more striking than between . SILICIC SULPHIDE: A disulphide corre- sponding in composition to silica is formed by transmitting the vapour of carbonic disulphide over a mixture of finely divided silica is and carbon. (SiHClJ U-tube. in nitrogen light. becoming coated with a of the two elements. crystallized gas. silicon chloroform . whilst the portion which passes on is immediately decomposed by the water into hydrochloric acid and leukon 2SiHCl 3 + 3H 2 = 6HC1 + Si 2 2 Os The voluminous white precipitate thus obtained is to be quickly pressed between . redness in a current of steam.254 PENTAD ELEMENTS. antimony. air. the two elements combine with a red glow . the phuretted hydrogen and soluble silica being formed may be obtained as a jelly by evaporation. PENTAD ELEMENTS. the analogies being rather insignificant in some cases The similarities between the though strongly marked in others. a white earthy-looking disulphide. between the elements of this group as exists in the case of the (461) typical it THE pentad been described : will halogens. nitrogen. the remaining members of the group. Leukon is best prepared by placing crystallized silicon in a wide glass tube connected with a U-tube cooled by a mixture of ice and salt. has already be only necessary in this place to consider phosphorus. whilst the apparatus terminates in a bent tube dipping into ice-cold water the silicon is to be raised to a barely visible red heat. (459) SILICIC NITRIDE or NITHIDE OF SILICON may be obtained by the direct action of nitrogen upon silicon at a very high temperature . H . is which absorbs moisture rapidly from the the result is : this compound time is completely soluble in water. bismuth and tantalum. or when compact or pulverulent silicon strongly heated in an atmosphere of sulphur. element. silicon. ammonia is disengaged silica is abundantly and (460) formed.

and are scarcely apparent in bismuth. in the In a large number of their compounds these elements exist tervalent or triad condition representing three atoms of hydrogen they are also sometimes quinquivalent or pentads.RELATIONS OF THE PENTAD ELEMENTS. The following table exhibits some of the corresponding com- pounds of the 5 triads just mentioned. with the members of this group in the proportion of 3 atoms to related to this atom of phosphorus. gradation of properties is observed in these elements. arsenicum and antimony form gaseous hydrides in which 3 volumes of hydrogen combine with \ a volume of the : vapour of the other element the compounds which are formed occupying the space of 2 volumes these gaseous compounds exhibiting a tendency to alkalinity. and then antimony. and 2 to 5. they are weaker in arsenicum. as is shown in the correspondence in form . and those of mispickel (FeSAs). is connected with the phosphorus group by its bination with hydrogen (H 3 N). hydrogen i .between crystals of iron pyrites (FeS 2 ). the next follows arsenicum. sulphur being isomorphous with arsenicum. and form derivatives much Each of these elements unites resembling those of ammonia. group by the composition and oxides and chloride although no compound at is Nitrogen. and phosphorus is the particularly in the three intermediate ones A : least dense. and by its formation of anhyAn interesting drides with 3 and with 5 atoms of oxygen. isomorphous relation exists between the members of the sulphur and those of the phosphorus group . The acid properties of the oxidized compounds are most marked in fusible volatile . then in phosphorus. Bismuth is also its character of of bismuth and com- already pointed out. in the order of their atomic weights. forming compounds in which the acid character is less and less marked as the atomic weight of the combustible element The isomorphous relations of arsenious anhydride increases. which differ very widely from another. the 255 one elements themselves. most and nitrogen. arsenicum. ammonia The compounds with hydrogen follow the same order : is a powerful base and requires a high temperature for its decomin arseposition. phosphuretted hydrogen is a very feeble base : . as present known. with oxygen in the proportion of 2 atoms to 3. Phosphorus. still weaker in antimony. and the corresponding tribasic phosphates and arseniates also offer some of the Chlorine unites most striking exemplifications of isomorphism. or antimony. and antimonious oxide have long been known.

although manifest in some of its derivatives.256 PHOSPHORUS. niuretted hydrogen the basic character is not perceived. . simple exposure decomposed by hydride is whilst the at'raction of bismuth for its hydrogen is so feeble that unknown. Ammonia. each of these three hydrides being the than to heat preceding one. and the same thing is true of more easily antimony .

and heated to incipient redness in an iron stantly. but it is now obtained almost exclusively from the bones of animals. Calcic sulphate. and after it has it is become fire. This latter compound is readily soluble in water. the residue is then washed with water. phosphorus it less It is S . Iii order to prepare it. in combination with the whole of the phosphoric acid. or 3 parts of crude acid or 20 parts of water. acid. and is present in the form of alkaline and earthy phosphates in the urine and excrements of animals. with water . whilst the remaining third is left as an acid salt. in symbols : H4CaaPO 4 ). [P 2 2 (0 2 Ca)" 3 + S0 2 (OH) 2 =P <OH) 4 (0 2Ca)" + 2SO 2 (O2Ca)"] The acid solution is evaporated to the consistence of a syrup. fig. under pressure. 257 the brain and nerves are composed. It is likewise contained in albumin and in fibrin in small proportion. The mixture for bone-ash by any 2 of concentrated sulphuric of sp. The reaction may be thus expressed Acid calcic Tricalcic phosphate. and is conthe rises when redness. or from native calcic phosphate. is transferred pot. retort (a. whilst hot. the ammonia and is volatile products the bone black employed this in are collected. and 18 after being allowed to stand two or three days. is is placed upon a strong linen filter. and the washings In this process the sulare added to the filtered solution. in vapour. 'Separated from the calcic sulphate by pressure . stirring conto an earthern sisting of a mixture of equal parts of borax and fire-clay. phosphate. Extraction. 329). con- The mass. covered externally with a thin paste.refining. but now the gelatin of the bones is first extracted by heating them. 1*550. with a view of rendering full II. Sulph. two-thirds of the calcium are removed by it and the acid liquid as insoluble calcic sulphate. useless for purpose. gr. and is frequently described as superphosphate of lime (calcic-tetrahydric diphosphate. is added in such acid quantity as partially to decompose phuric the calcic phosphate .PHOSPHORUS EXTRACTION. solid Phosphorus was originally prepared from the contained in urine. then mixed with from one-fourth to one-half its weight of charcoal. 4 Ca^2PcT + 2H^O^ = H 4CaaPO 2 2 4 + iCaSO^ . or the bones are distilled in closed ness vessels. then gradually heated to porous. whilst sugar. bones were formerly always burned to whitesalts by calcining them in an open fire for some hours. burned in the obtained open Three parts of powdered of these methods are mixed with acid.

258 densed in the PHOSPHORUS wide EXTRACTION. its phosphorus. In this operation it is convert the into found necessary to normal phossuperphosphate phate of calcium. reproretort. superphosphate. or it may be fused. by duces the charcoal. phosphorus. gases to a chimney. open at both ends. . which may be regarded of two stages. with a solution of bleaching powdei . copper tube. tricalcic phosphate. when heated. and car bonic oxide being produced : 3 Ca2PO 3 +ioC=P +Ca 2PO 4 4 3 + loCO * > 2 (O 2 Ca)" 3 -fioCO. it is warm water. does not part with The when heated. and then under a solution of potassic dichromat * Phosphorus may also be obtained by heating an intimate mixture < (' charcoal and tricalcic phosphate or of bone-ash to bright redness in a current hydrochloric acid gas. therefore as consisting during the whole operation.] With fused under a view to render the phosphorus perfectly pure. since bone-ash. the first being the decomposition of the super- phosphate into calcic metaphosphate : H 4 Ca2PO [P 2 whilst 2 = Ca2PO 4 (OH)/0 2 Ca)''=P 2 stage + 2H 2 O. (0 2 Ca)'' + 2 OH 2 . fires under ammonia. tricalcic phosphate oxide which remains in the whilst carbonic anc phosphorus pass off in the gaseous condition. dipping into the water This vessel is provided with a smaller contained in the receiver. for conveying away the uucondensed tube. and squeezed through wash-leather.] s the second consists of the decomposition of th< calcic metaphosphate. b. carbonic oxide and hydrogen being liberated along wit < f i vapour of phosphorus while 2(Ca 3 2P04 ) calcic chloride is formed : + i6C + I2HC1 = P4 + i6CO + 6H 2 + 6CaCl 2 . 329. is decomposed into water and calcic metaphosphate the latter being acted upon . FIG. Gaseous matters escape.

of which 100 cubic inches calculated at 30 inches Bar. Phosphorus is a soft. it takes fire still more easily. and emits In closed vessels it dense white fumes of phosphoric anhydride.) (Schrotter). becomes hard and it fumes in the air. but when touched with a wire or a glass rod it suddenly solidifies. in dilute it 259 of phosphorus sulphuric to be acid. : 0> It fuses at in 5 (44 2 C. both in the solid It is extremely inflammable. If it contains impurities. therefore. as the burns it. colourwaxy-looking solid. brittle at low temperatures emitting white It has a specific gravity of r83 vapours of an alliaceous odour. would weigh about 135 grains. only slightly soluble in ether. occasioned by melted phosphorus are deep and often extremely severe. The easy fusibility moulded into sticks with facility. it will long continue fluid at ordinary temperatures if undisturbed. Phosphorus is a non-conductor of electricity. and 60. by phosphorous disulphide fall : chloride. and 50 (10 C. to evaporate slowly in a current of hydrogen or carbonic anhydride. which. it is melted under water and run into tubes. from the difficulty of extinguishing the flame. in which it is allowed to enables solidify. according to Deville. if melted under an alkaline liquid and allowed to cool.PROPERTIES OF PHOSPHORUS. boils at about 550 (288 C. however. taking fire in and the liquid state. in oil of turpenIt is also freely distine. less. the finely divided phosphorus left on the evaporation of the solvent absorbs If the solution be allowed oxygen so rapidly that it takes fire.). so that great caution is required in handling It is better always to cut it under water. and by carbonic when filter its solution in the allowed to upon paper in the open disulphide is air. solved by chloride of sulphur. no alteration in the relative volumes of the two is effected by a temperature of . which two intense green lines. but more so in benzol. such as oxide of phosphorus. one of which appears to coincide with one of the lines of barium s 2 a . Properties.). Phosphorus burns with a brilliant white flame. Phosphorus is insoluble in water. giving off a colourless vapour. An atom of phosphorus. gives off a volume of vapour equal to one-half that of an atom of hydrogen and. semi-transparent. the phosphorus may be obtained crystallized in rhombic dodecahedra. The vapour of phosphorus when mixed with hydrogen to the gas the property of burning with when examined spectroscopically exhibits gives green flame.: . at the open air at a temperature very little above its fusing-poirit.). 1904 (1040 C. and in the fixed and essential oils.

it then appears to be It has a sp. may be obtained by heating very pure phosphorus to near its boiling-point and it. test of the presence of phosphorus. light. de Chimie [3]. at all temperatures above 32 (o C. gr. hypophosphites. into a flask . for when exposed to the air. The transparent variety has been already when kept exposed to light under water. . and undergoes a slow combustion. who prepares it by the action of heat on ordinary phosphorus for this purpose the dry phosphorus is introduced from which the air is displaced by means of a current of carbonic anhydride. in a darkened room a pale greenish light may be observed (hence its name. attended with the production of the white fumes and the garlic odour Phosphorus already mentioned . The red form of phosphorus has been carefully studied by Schrotter (Ann. a stick of phosphorus no when exposed to its action (Graham). the open end of this tube dips . assumes a second form. white and opaque. Red or amorphous Phosphorus. consisting of small plates . xxiv. is attached . by the spontaneous sublimation of in the Torricellian vacuum when exposed to the rays phosphorus suddenly cooling of the sun. bearing). whilst a fourth or viscous modification. but by simple fusion and slow cooling is again becomes transparent and colourless. always preserved under water. A third form it obtained by suddenly cooling melted phosphorus . $opoc. and to the neck of which a long narrow tube. naphtha vapour. or be diluted with some other gas. phosphorus. 406).) it gradually combines with oxygen. The luminosity of phosphorus is prevented by the admixture of certain inflammable vapours and gases in minute quantity with the atmosphere. analogous to viscous sulphur. of 1*515 white phosphorus becomes reconverted into the vitreous : variety by a temperature not exceeding 122 (50 C. it is perfectly black and opaque. Phosphorus (463) Different modifications of Phosphorus.). bent downward. -rrVo f turpentine. or -^VT of vapour of oil of longer appears luminous It is remarkable that in oxygen the luminosity is not observed until the temperature rises to 59 (15 C. if air be mixed with either -^-^o of its bulk of olefiant gas.). and is somewhat less fusible. A fifth form occurs in the shape of red which are obtained scales.260 RED PHOSPHORUS. from <pwq. into Marsh's apparatus. assumes several different forms under the influence of causes apparently trifling. give rise to this phewhich is sufficiently sensitive to serve as a qualitative is common amorphous when introduced nomenon. and phosphites. mentioned this. unless the gas be rarefied.

takes fire spontaneously when exposed to the air. then expelling the air by a current the open of carbonic anhydride. This oxidation occurs so slowly that it was at first imagined that amorphous phosphorus underwent no change by exposure to the air.RED PHOSPHORUS. the cation from ordinary phosphorus may be effected by grinding the mass to fine powder under water and boiling it with a solution of caustic soda as long as phosphuretted hydrogen is formed. phosphorus upon which two or fragments three bulbs have been blown. almost all the phosphorus becomes converted into the solid amorphous variety. the : digestion being repeated so long as any phosphorus is dissolved. phosphoric acid is formed. and by maintaining the heat for 30 or 40 hours steadily between 446 and 464 (230 and 240 C. and from its deliquescent character the powder becomes damp. the change may be produced much more rapidly. however. and fresh disulphide added. 261 into a little mercury to prevent access of atmospheric air to the interior of the flask. be heat watched may readily phosphorus by by placing a few dried in a of welltube. apparatus : then poured upon the mass in the flask. The purifiplace.). if not quite free from unaltered phosphorus . which in the finest specimens rivals that of vermilion. whole mass suddenly passes back into the ordinary with form. great development of heat. The red powder of which the undissolved portion consists. any dissolved phosphorus will be left behind. and sealing one end of the tube. but does not do so if quite pure. When the change appears to be is the allowed to cool carbonic disulphide is complete. and allowed to stand for some hours this is poured off. It absorbs oxygen slowly. Heat is next applied to the flask by means of an oil-bath : the phosphorus melts readily. which may be known by allowing a few drops of the decanted liquid to evaporate spontaneously in a watch-glass . for if the red powder be heated up to the point at which its re-conversion into the transparent variety takes siderable scale. with a conchoidal fracture. By heating the phosphorus more strongly during its preparation. but the phosphorus then assumes the form of reddish-brown friable masses. and is not unattended with danger . accompanied by the sudden formation of a large volume of phosphorus vapour. The higher the temperature at which the transformation is effected. This form of phosphorus is manufactured at Birmingham on a con- The process occupies some weeks. the oxidation being more rapid if the powder be moist . and afterwards dried. the deeper is the colour of the product. The residual red phosphorus is then thoroughly washed from sodic The changes produced in hypophosphite. .

which ultimately solidify to a transparent colourless mass. and powdered glass . as they do not contain any phosphorus. used to destroy cock- . the amorphous variety may be swallowed with impunity the vitreous phosphorus forms the active ingre. and differs Red remarkably in phosphorus. but in addition to this risk. and then tipped with a mixture. or are gummed and dusted over with sulphur. but less readily. although they frequently remain liquid for some hours. Of these evils. having a specific gravity of V 4. these take fire when rubbed upon the phosphorized surface. whilst the matches themselves are tipped with a composition consisting of a mixture of potassic chlorate. but not by moderate friction upon any other substance. or in benzol. the ends of the pieces of wood are first dipped in melted paraffin. those employed in the business are liable to a distressing form of caries of the lower jaw. in which the chief ingredients are an emulsion of phosphorus in glue. or amorphous phosphorus. the first is greatly lessened. and the second altogether avoided. dient in the phosphorus paste frequently roaches and other kinds of vermin. from the highly inflammable and explosive nature of the ingredients used .) . the red powder. When friction being sufficient to produce the effect very slight peroxide of manganese and peroxide of lead act in a similar way. and potassic chlorate or black oxide of mangaprincipal consumption nese. matches. phosphorous The density of amorphous phosphorus chloride. by the use of amorphous phosphorus. : detonates. when taken Although vitreous phosphorus acts as a powerful irritant poison internally. according to It may be heated in Brodie. It is not soluble either in Carbonic disulphide. The The manufacture is attended with considerable danger. odour. but on continuing to raise the temperature it distils over in colourless transparent drops. antimonious sulphide. arising from the action of the fumes of phosphorus when inhaled. An ingenious plan for diminishing the risk of fires from the use of lucifer matches consists in separating the phosphorus from the other combustible ingredients . as it is commonly called.262 RED PHOSPHORUS. has been obtained distinctly crystallized in rhombohedrons. phosphorus it becomes red. at this point it melts and bursts into flame. On applying heat to the end being made to dip into mercury. a mixture of amorphous phosphorus with half its weight of powdered glass is attached by means of size to the rubbing surface for kindling the matches . the temwithout red the upon phosphorus application of heat : perature rises. of phosphorus is in the manufacture of lucifer In the usual mode of preparing these matches. \ It many of its properties from the waxy-looking stick may be exposed to the air without emitting any exceeds that of the vitreous form. rubbed with potassic chlorate but the phosphorus does not take it fire. the open air without change till the temperature reaches 500 (260 C. burning with the dazzling brilliancy of common phosphorus and emitting Chlorine acts directly dense fumes of phosphoric anhydride.

and copper. when it is allowed to burst upon the If the bubbles be allowed to light. hydriodic acid being formed and phosphuretted hydrogen liberated. breaks pi'oduces a beautiful white wreath anhydride. Phosphuretted hydrogen. PH 4I. Atomic and Mol. a The gas so obtained has the remarkable phosphate being formed.PHOSPHIDES OF HYDROGEN. The first is gaseous. phosphorus reduces to the metallic state . is generally prepared by heating fragments of phosphorus with a strong solution of caustic potash. with evolution of phosphuretted hydrogen . . PH 4I = HI + PH 3 3PO(OH) 3 ] 3HPH O . . H P=34. . rise into a jar of oxygen. platinum. 1*314 (Dumas) 17. the rapid gyratory movements communicated to the air allowed to escape into the air* in bubbles. of fire property taking spontaneously in atmospheric air or hydrogen in oxygen gas . composed of a number of ringlets if it contained in a bubble. each bubble of phosphoric revolving in vertical planes around the axis of the wreath itself. Gr. however.as .. : Phos- phamine. as it ascends . may be in a state of purity by the decomposition of phosphorous acid heat. are also reduced gradually when a stick of phosphorus is immersed in their solutions. 3 H PO + H P 3 4 3 [4 POH(OH) 2 =PH 3 + by hypophosphorous acid gives an analogous result. 2 3 3KPH 2 O 2 + H 3 IWhen "potash [P4 + 3OH + 2 is used. P 4 + 3H 3 O + 3KHO becoming 30KH = 3POH (OK)+PH ]. metal is then formed. owing to the gradual decomposition of the hypophosphite when boiled with ezi^ss of free alkali. Salts of palladium. action of water on phosphonic iodide. 263 Owing some of the soluble compounds of the metals to its strong attraction for oxygen. None of the compounds (464) PHOSPHIDES OF HYDROGEN. 3 : : H H HP . a stick of phosphorus placed in a solution of auric chloride or of argentic nitrate becomes speedily encased in reduced gold or silver. 1-1764. 4H PHO 2 . . surface of a still sheet of water. at ordinary temperatures. thus tracing before the eye. free is also evolved. wt. Observed. the second liquid. or with cream of lime hypophosphite of the . Phosphuretted hydrogen gas : Phosphorous trihydride Theoretic Sp. 2 P. H3 PO 4 + H 3 P [>POH 2 (OH)=PH 3 + becoming 2 2 It can also be very conveniently prepared by the PO(OH) 3 ]. and 3 P. a brilliant flash of attended with a slight concussion. of phosphorus with hydrogen is possessed of acid characters these compounds are three in number viz. Phosphuretted hydrogen gas yielding 3 Q ^J. accompanies the bursting of each bubble. Preparation.with admirable distinctness. 3 Eel. obtained Vol. and the third solid.

. Owing to the spontaneous inflammation of the gas it should be made in small vessels containing but little atmospheric air. 3 P.. that of mercury is yellow.. as that of . phosphonic iodide (H 3 P. such as ether. it is slightly soluble in water and when liquefiable under pressure transmitted through solutions of certain metallic salts such as those of lead. but the addition of so small a quantity as f its bulk of the vapour of nitrous anhydride confers TO. or some- pure It is times even at diminished. oxygen explodes at a temperature of 302 (150 C. such as charcoal. naphtha. 05 3'o 2 o - . the bodies. as well as by chlorine. is it is wholly absorbed by a solution of chloride of lime. decomposed by sulphurous acid. Phosphuretted hydrogen is a highly inflammable colourless gas. Those of lead and copper are black.. and that porous On the other hand. has a density of 277 .264 PHOSPHURETTED HYDROGEN PROPERTIES. if the pressure be suddenly this gas half a phorus and 3 volumes Its composition space of 2 volumes. or pi'iS 8*82 By . . . and phosphoric acid is found in solution. gas phosphorous not self-lighting. copper. cation of a basic character is. according to Bineau. = 34 loo'oo . bines with certain of the acids in definite exFor proportions. common In temperatures. A mixture of the gas with air or with bromine. however. to which it is analogous in composition but it is without action Some indiupon either red or blue litmus.). .. shown it comfor by it. from acid and from obtained phosphonic iodide. destroys this self-lighting power . with a very disagreeable alliaceous odour.HI or. and iodine. which fuse at a moderate heat. for its vapour. also remove it. Graham has shown that the addition of small quantities of the vapour of some inflammable bodies. PH 4 I) is formed by the union of equal volumes of the two gases. condensation. vol. and oil of turpentine. its compound with hydriodic acid. it is absorbed and decomposed phosphides of the metals are produced and are precipitated. it crystallizes in cubes. or mercury. The combining volume of phosphuretted hydrogen is the same ammonia.Wo is this property upon it. Properties. Solutions of the salts of gold and silver are reduced to the metallic When the gas state. which in the act of combination do not undergo ample.. represented : volume of the vapour of phosof hydrogen are condensed into the may therefore be thus Phosphorus P Hydrogen Phosphuretted hydrogen H H 3 = = 31 3 By weight.

This com- pound is easily prepared by introducing into a small retort 127 parts of dry iodine ground up with powdered glass. This compound exists at ordinary temperatures as a volatile liquid. and that also destroyed by exposing the gas to a great degree of cold. through a bent tube immersed in a freezing-mixture of ice and salt: a colourless liquid of high refracting power is thus condensed. These compounds are decomposed by water.. to its condensation in the liquid form. (465) . long remained without explanation. with escape of phosphuretted hydrogen gas. and into the non-self-lighting gas (H S P) . in the case of the exposure to sunlight. 265 and if air be excluded it may be sublimed without alteration. de Chimie [3]. then adding 20 parts of water . and 31 parts of phosphorus in small fragments. Thenard. evidently due. which neutralize iron. condensed in crystals in the neck of the retort. Solar light quickly decomposes it into the solid phosphide (HP 2 or P4 ) and into the gaseous phosphuretted hydrogen. traced a few years ago by P. These crystals are deliquescent. hydriodate of phosphuretted hydrogen is cool. whilst the gas lost its self-lighting power . Phosphuretted hydrogen combines with the perchlorides of many of the metals. of igniting spontaneously when mixed with free oxygen. as a careful analysis indicated little or no difference in composition between the self-lighting gas and the other variety. (Ann.) + 6PH 'P "H C(PCP"'Fn" jp[p. and but slightly inflammable phosphide (HP ). which does not solidify at -4 (-20' C. remarked. 2 If a little of the vapour of this liquid be allowed to diffuse itself through H .PHOSPHIDES OF HYDROGEN. in certain cases. It takes fire the instant that it comes into contact with air.. solid. which by exposure to light is decomposed into a yellow. and are decomposed by water into hydriodic acid and phosphuretted hydrogen gas. to decomposition of the inflammable compound. to the presence of a minute quantity of the vapour of another phosphide of hydrogen (H 10 P B ). that when the spontaneously inflammable gas was exposed to the sunlight for a few hours. and in the case of the application of cold. and burns with the intense white light of phosphorus. if it be kept A similar compound may be obtained with hydro bromic acid. organic compounds are obtained and possess powerful basic properties. j.). which takes fire the it comes in contact with uncombined oxygen. The true cause of the phenomenon was. however. the vapours which come off consists of the compound mixed with an excess of hydriodic acid . and acids. which does not possess this property. Hofmann and Cahours have shown that by displacing the hydrogen in gaseous phosphide of hydrogen. this power was effect is This is Liquid phosphide of hydrogen may be prepared by conducting the gas which disengaged by the action of water upon phosphide of calcium (Ca 2 P2 ). titanium. for instant that xiv. antimony.Hp 5 2 4 = 3 It had long been. Liquid Phosphide of hydrogen: H^P. or H 1Q P6 ? pi! 2 -pir -i | The ( singular property which phosphuretted hydrogen possesses. a solid yellow compound was deposited in small quantity upon the sides of the vessel. 5. by ethyl and other analogous hydrocarbons. such as those of tin.

4*79. decomposed by a large excess of water. phosphorus (467) CHLORIDES OF PHOSPHORUS. colourless. Rel. forms two compounds. and chloride . i64'8 (73-8 C. 319) . PC1 5 So strong is the chemical attraction between these . the operation may be conducted same manner as in the preparation of the chloride of the trichloride distils as a very volatile. the solid phosphide. phosphorus contained in a retort in the . Oxygen. Sp. is it yielding 2 3 + 3HC1 Trichloride of phosphorus converted into the pentaalso H PHO absorbs oxygen and . and is itself soluble in benzol and in carbonic disulphide alcohol and ether decompose it with evolution of great heat. + [PC1 3 3OH ? =POH(OH) 3 + 3HC1] . carbonic oxide. a trichloride. Gr. It is not soluble either in water or in of calcium with hot hydrochloric acid. Chlorine. sulphur : It is also immediately giving rise to various organic compounds. the other of a green colour . or any other combustible gas.). it confers upon it the property of taking fire spontaneously when mixed with atmospheric air or with oxygen. they do not differ from each other fire in composition. and forms phosphorous and hydrochloric PC1 3 + 3H O. elements. of these chlorides. 68-75.) . PC1 3 = 137-5. Mol Vol. of Vapour. wl.). fuming liquid. or Terchloride of phosphorus Phosphorous chloride. Observed. and the solid yellow phosphide of This substance is readily prepared by treating phosphide hydrogen is formed. This liquid is sometimes prepared by causing the vapour of phosphorus to pass over corrosive sublimate placed in a long tube. and of two of their derivatives : In 100 parts. and gently heated but it may be obtained more conveniently by transmitting a gentle stream of perfectly dry chlorine gas over dry and melted . . (fig. PC1 3 and a pentachloride. "With chlorine. HP . one of a yellow. freely. The solid yellow hydride of phosphorus takes at about 302 (150 C. and when heated with a solution of potassic hydrate it dissolves with There appear to be two varieties of liberation of phosphuretted hydrogen gas.266 CHLORIDES OF PHOSPHORUS. at a boiling temperature furnishes the oxytrichloride. 4*7575. Sulphur I37'5 208-5 I53'5 169-5 22-54 14-86 20'lp 18-28 77-46 85-I4 69-38 62-84 . The liquid phosphide is im(466) Solid Phosphide of hydrogen 2 . \~^~]. Boiling-pi. acids. hydrogen. that phosphorus immediately takes fire in an atmoThe following table shows the composition sphere of chlorine. Theoretic. mediately decomposed by hydrochloric acid. 18-88 (468) Trichloride. It dissolves phosphorus transparent. absorbs chlorine with avidity. alcohol. Trichloride of phosphorus Pentachloride PC1 3 PC1 5 Oxytrichloride Suiphotrichloride POCI 3 PSC1 3 = = = = Phosph. of Liquid 1*616 at 32 (o C.

and is immediately decomposed by a large excess of water into 3 phosphoric 4 and hydrochloric acids. Pentachloride of by the union of equal volumes of In a large number (Cahours). " I I Observed. Mol. proportion of equal volumes of as was long since indicated by .).parts of phosphoric chloride. but it may be fused under pressure at a temperature of 298 (148 C. 5 * The vapour volume of this compound phosphorus may be supposed to be formed chlorine. or Oxy- H PO + 5HC1 rj . Vol. and allowing chlorine to enter so long as it is absorbed . when the following reaction occurs: 3PC1 5 + 2(HBO .) whilst still solid. is anomalous. forming [PC1 5 + 4OH 3 =PO(OH) 3 +5HC1]. T ^]. 52*1.w ^. -^. tile.3'654. It combines readily with ammonia and burns in the flame of a It is very lamp. is Vol.H 3 O) = 3 POC1 3 + 6HC1 + B 2 O 3 [3PC1 + The oxychloride is readily 2B(OH) 3 =3POC13 + 6HC1 + B 2 O 3 ]. Mol. producing chlorine and phosphoric anhydride. deliquescent. (470) Phosphoryl chloride. I obtained by placing dry phosphorus in a flask provided with a stopcock. of Vapour.).1I i -I. at 572 (300 C. or it may be formed This compound* by treating trichloride of phosphorus in a large glass flask with an excess of chlorine. + H 2 O = POC13 + 2HC1. Phosphoric oxytrichloride may be obtained with facility by Gerhardt's plan of distilling i part of crystallized boracic acid with 4^. 230 (110 C. 5*298. no condensation occurs. Rel. which below 212 (100 C. 7&'75'> &P- (j!> '- of Liquid. solution It forms the pentachloride is obtained in a a white crystalline solid. POC1 3 = 153-5.) formed when the vapour of water is allowed to mingle slowly with that of the pentachloride. and the vapour of the trichloride of cases where two bodies combine in the their components. This compound is Boiling-pt. (469) Pentachloride or Per chloride of phosphorus . fuming which is limpid. PC1. voladecomposed by the further addition The reaction is The oxychloride is a as follows : of water into phosphoric and hydrochloric acids. Pentachloride of phosphorus is also now prepared on a considerable scale by dissolving phosphorus in carbonic disulphide and transmitting dried chlorine in excess through the solution which is cooled artificially during the operation . liquid. Phosphoric oxy trichloride . Gr. 5-311.PHOSPHORIC OXYCHLORIDE. Gay-Lussac. Theoretic. Observed. Phosphoric PCl 5 =2o8'5. exhausting the air. on evaporating crystalline volatilizes the state. PC1 5 + 4H O chloride of phosphorus. wt. Theoretic Sp. hydrochloric acid and oxychloride of phosphorus being the result. of -Vapour. 3*605. 267 chloride.

and a trisodic sulphoxyphosphate may be obtained in six- sided tabular crystals which contain i2H 0. viz.. but containing It is obtained by decomposing phosphoric chloride sulphur instead of oxygen. 5-878.parts (or 2 atoms) of iodine.268 BROMIDES AND IODIDES OF PHOSPHORUS. P O or by passing oxygen gas into boiling + 3PC1 5 2 5 =5POC1 3 .parts of iodine in When the solution is concentrated by disulphide. but the two are not isomorphous. 5*8647. but it does may The oxychloride may also be prethe pared by heating pentachloride with phosphoric anhydride. (471) Phosphoric sulphotrichloride. Bel. PSC! 3 - H procured still sulphide to chloride of phosphorus chloride is by the gradual addition of powdered antimonious = 3PSC1 8 + aSbCl. 257 (l25C. 84*75. Vol. thin flexible prismatic crystals of the iodide are deposited. Phosphorous iodide. condensed. particularly the oxychlorides and anhydrides of the organic acids. not answer quite so well phosphorus trichloride. (o (J. colourless liquid. The Diiodide (PI 3 = 285) may be prepared by dissolving i part (or I atom) of phosphorus in carbonic disulphide. 2-925. Pentabromide and Oxybromide of phosphorus. Theoretic. may be formed by similar methods. Two iodides of phosphorus be formed. analogous to the corresponding compounds with chlorine. 1*631. exchanges its chlorine for oxygen . 242). It may be with sulphuretted hydrogen: PC1 6 + 2 S. they are white and insoluble. [^]. and strontium may be formed by double decomposition with the sodium salt . sodic is formed. and is decomposed by water. .)]. of Vapour. of a bright orange colour. This iodide melts at 230 (110 C. is a compound corresponding to the oxy trichloride. 347*5 ( I 75'3 C. = 169-5 \-P. and subsequently cooled by a freezing mixture. BoiUng-pt. which. yielding PSC1 3 + 2 HC1. dark .. at 32 (472) BEOMIDES OF PHOSPHOBUS.). or Triiodide of phosphorus (PI 3 =4i2). Sulphotriphosphoric chloride 3PC1 5 + Sb 2 S 3 more easily : a fuming. Gr. de Chimie [3]. Observed. calcium. Crystallized oxalic acid for in this be substituted acid boracic operation. i evaporation. or Sulphochloride of phosphorus. The following equation explains the changes which accompany its production PSCl g + 6NaHO . whilst hydrochloric acid passes off in the form of gas. The composition of this salt is 2 analogous to that of the trisodic phosphate.@ r of Liquid. Mol. xxx. Corresponding compounds with barium. by dissolving carbonic part of phosphorus and 12-5. leaving boracic anhydride in the retort. and adding 8J.). Both the chlorides and the oxychloride of phosphorus have been extensively used in the preparation of various organic substitution-products.)]. PHOSPHORUS.Na3 PS0 8 + sXaCl 4 3H 2 (Wurtz) [PSC1 3 4 6ONaH = PS(ONa) 3 + 3NaCl + 3OH 2 ]. a diiodide and a triiodide (Corenwinder. PBr3 [Sp. This compound may be obtained in a manner similar to the last. Boiling-pt. (473) IODIDES OF may on cooling the mixture artificially. yielding hydriodic acid and other products. if heated with a solution of caustic soda in excess. wt. Ann. A Tribromide.

I and 290). and these melt on cooling crystallize again in fine exposed to the air. whilst ammonia and nitrogen are disengaged but it is remarkable that dry chlorine and hydrochloric acid gases. and the vapour of sulphur. it is the phospham of Gerhardt. Soc. See also . tripotassic phosphate being formed. and if heated in a current of this gas. Soc. v. and between 248 and 266 a scarlet powder was deposited on the sides of the tube . The red mass may be distilled in closed tubes. 1866. colouring the phosphorus slightly red when heated by an oil bath to 212 (100 C. placed just phosphorus melted. the transformation of this iodide by heat into an allotropic : iodide . prisms. : : following first. next. even at a red heat and it is but very slowly attacked : . the new compound as it is Gladstone formed is slowly sublimed in the form of a white powder. Chem. and thirdly. Solutions of the alkalies exert scarcely any action upon it. at 284 (140 C. C.) the mass was quite solid. converts nearly the whole of the phos- When variety described by Schrotter. If phosphorous chloride be cooled by a freezing mixture. are without action upon it.. the colour became and 130 C. and probably its composition should be represented by the formula given above. and iodine was projected gradually into the phosphorus. 1864. it is decomposed with incandescence. it is to be introduced into a tube of Bohemian glass. and the cork which closed the tube was blown out by the vapour of phosphorus. It combines with sulphuretted hydrogen. ammonia is formed. I. (474) PHOSPHAM (HN2 PP). the decomposition of this new iodide into red phosphorus and a volatile iodide.PC1 8 ) is obtained. with formation of phosphoric anhydride . changes which occur in the process are supposed to be the phorus into the red . by concentrated nitric acid. but there can be no doubt that it contains hydrogen . 1865.).).). and saturated with ammoniacal gas. and when it is condensed in the cooler The portions of the tubes it is still in the red modification. When heated in hydrogen. red. the formation of diiodide of phosphorus . a sharp explosion took place tion of heat occurred. J. Chem. 289) finds that iodine. deliquesces rapidly when Brodie (Q. but when heated in the air it is slowly oxidized. nd heated to redness in a current of dry carbonic anhydride as long as any sal ammoniac is sublimed a yellowish-white bulky amorphous powder remains behind this substance is Rose's phosphide of nitrogen . a white saline mass (5H SN.PHOSPHAM. (120 deep red. which acts upon a further portion of the phosphorus . 269 are six-sided plates arid of the (50 iodide between 122 131 and 55 It formed . In closed vessels it sustains a red heat without fusion or volatilization.). and on raising the heat a sudden evoluto 392 (200 C. 225. (J". the iodine was dissolved. if projected into : : fused potassic hydrate. in a was and heated till it long tube. when heated with phosphorus in the proportion of i atom of iodine to 100 atoms of phosphorus. and thus the action is indefinitely continued.

c.270 OXIDES AND ACIDS OF PHOSPHORUS. dried is well of phosphorus placed in the dish. is that which unites with water to form phosphoric acid . PA = PA = tribasic. or other convenient means continuous as it current is of air through dried the of maintaining a the air apparatus : passing over pumice in the tube. which are respectively : proportion as the quantity of oxygen increases : these acids are the following Hypophosphorous acid (monobasic) Phosphorous acid (dibasic) Phosphoric acid (tribasic) . /. with contained moistened sulphuric acid.. (475) OXIDES AND pounds of phosphorus ACIDS OF PHOSPHORUS. which is closed at a with a cork . Only two comviz. is connected by the tube g. and fragment enters thoroughly by A kindled by touching it with a hot wire. in the centre is of sus- which pended a porcelain dish. and oxygen are known. 56.. with an aspirator. this acid is the of of sole the combustion hydride product rapid of phosphorus in dry oxygen or in atmospheric air. : In too parts. c.PHO8 [POHJOH)] [POH(OH) ] [PO(OH) 8 ]~ The most imconsiderable H P0 4 3 (476) PHOSPHORIC ANHYDRIDE: portant of the oxides of phosphorus P2 O. a large quantity of phosphoric E is a threeanhydride may be readily obtained in a few hours : necked globe. d. HPHA. By means of the apparatus shown in fig. it occurs native in The anquantity in the form of tricalcic diphosphate (Ca3 2PO 4 ). As the phosphorus .36 43-66 43'64 5 6 '34 Phosphorus forms three oxidized monobasic. Phosphorous anhydride Phosphoric anhydride . the bottle.= i42. and acids. this dish is attached 3 ff by means of platinum wire to the wide tube a b. H. dibasic. 330. in no 142 Phosphorus. Oxygen.

and the phosphoric anhydride alone remains in combination with The oxide and anhydride together will be the oxide of lead. 31 parts of phos: phorus therefore require 40 parts of oxygen for conversion into phosphoric anhydride. i'2O. phosphdrus the in a vessel until expelled by evaporating liquid platinum on cooling. The anhydride thus obtained generally contains traces of one of It forms a snow-white. intensely acid. it P 2 O + 3H 2 O = 2H 3 PO 4 5 . the excess of water and nitric acid having been distilled off. it surpasses in efficacy almost every The pure acid is generally procured (477) Phosphoric acid. of phosphorus are boiled in a glass The greater part of retort with pure dilute . in a hydrated state. ordinary dropped into water it vapour combines with it. acid. of 2'o when saturated. by a red heat the whole of the nitric acid is expelled. which is immediately closed with the cork after each addition. Owing to its powerful attraction for water. gr. which has a sp. which is decomposed with escape of nitric the phosphoric acid remains dissolved. and may be It does not emit sublimed by a heat approaching to whiteness. 271 burns away fresh pieces are introduced through the aperture a.PHOSPHORIC ANHYDRIDE. by boiling i part of phosphorus in 13 parts The phosphorus becomes oxidized of nitric acid of sp. and for this purpose substance. nitric acid. and extremely deliquescent. This glacial acid is extremely deliquescent. the greater part it is instantly dissolved. all has the excess of nitric acid is disappeared. dissipated is often used as a desiccating and dehydrating phosphoric anhydride known agent. the acid solidifies dense white fumes begin to arise to a transparent glassy mass. of oxide of lead. powder. but not caustic. When at temperatures. producing a It is solution. disappear. and the residue ignited .. found to weigh 42*1 grms. When the and oxide. The oxidation of phosphorus by nitric acid furnishes an easy means of ascertaining the composition of phosphoric anhydride. gr. the lower oxides of phosphorus. leaving a few gelatinous flocculi. . dissolved.nitric acid. in a weighed platinum dish the liquid is slowly evaporated. flocculent. showing an increase in weight upon the phosphorus and oxide of lead of 4*0 grms. After which slowly has once been cannot again be converted into the anhydride by the heat as the whole compound is then gradually of application in vapour. the acid solution is : added to 35 grms. which fuses at an elevated temperature. anhydrous. For this purpose 3*1 grms. frequently termed glacial phosphoric by the . emitting a hissing noise . non-crystalline.

a tribasic hydric disodic phosphate is obtained. until the solution becomes slightly alkaline. ordinary .272 P.. "which on evaporation crystallizes in large transparent rhombic If this solution be mixed with a prisms (Na 2 HPO 4. HP0 ) 3 [P02 (OH)] [ fl 3 J pQ 2 7 j PO (OH) 3] Pyrophosphoric acid . or with 4 equivalents of metals. There are three different forms of phosphoric acid. The precipitated calcic phosphate is separated by the liquid evaporated to dryness. -!- nitric acid having been liberated 8 3 . Although this solution was neutral or slightly alkaline before admixture with argentic nitrate.. Owing to the important influence which the study of these combinations has exercised upon the theory of saline combinations in general. right) or Tribasic PhosPO 4 If the liquid formed phoric Acid. neutral solution of argentic nitrate.. : Metaphosphoric acid Orthophosphpric phosphoric acid or . or the 'pyrophosphoric acid is employed. each of which possesses the properties of a distinct acid viz. . and sodic carbonate be then added. a canary-yellow precipitate of triargentic phosphate (Ag3PO4) is formed. it will be found afterwards to have a decidedly acid reaction upon litmus. according as the metaphosphoric. ignited. and form salts with i. with 3. and phosphoric acid (contaall minated with the soluble salts which the bones contained) remains behind. . by dissolving glacial (478) H . . Trihydric Phosphate . pure acid is procured by adding to a solution of superphosphate of lime (prepared from bones by the process already described as a preliminary step towards procuring phosphorus) tricalcic amtnonic sesquicarbonate till effervescence ceases .. and the residue Ammonia is expelled.'iOSPHORIC ACID..] Plumbic acetate (Pb2C 2 HO 3 may be used as a precipitant . Orthophosphoric (from vpOog. filtration.i2H 2 O). : = Ag3PO4 + 3 NaNO + HNO [PO(OH)(ONa) 2 + 3 N0 (OAg) =PO(OAg) 3 + 2NO 2 (ONa) + Na2 HP0 4 3 AgN0 3 2 NO 2) S (OH). triammonic is phosphate in precipitated. the orthophosphoric. 3 the acid in water be boiled for some time. HP 4 P L 2 3 (OH) 4 = f J PO(OH) 2-| (PO(OH) 2j teristics These different forms of the acid retain their peculiar characwhen dissolved in water.. it will be necessary to examine them somewhat in detail. leaving diphosphate less A solution.

. in the trisodic phosphate. . : which may be indi- . they are of the form of the sodic dihydric phosphate called NaH 2PO . briskly with 3 them . rendered alkaline precipitate by ammonia. this precipitate is freely soluble both in nitric acid and in ammonia. prismatic. which consists of Mg"H 4NPO i. as. The soluble orthophosphates are characterized by Tests. There are three varieties of these cated by general formulae as follows Trimetallic phosphates 2 Hydric dimetallic phosphates 1 . hydrate form the orthophosphates or salts. salts of this common tribasic phosphates. for example. transparent crystals. brittle. the 3 atoms of hydrogen in the acid have been displaced by 3 of a metal. as. formerly a strongly acid reaction. M PO M HPO MH PO 3 4 2 2 : 4 4 [PO(OM)J [PO(OH)(OM) ] [PO(OH) 2 (OM)j 2 consist It is not necessary that the 3 equivalents of basyl should two or even three of the same metal in these salts different basyls may coexist in the is same salt. ordinary . and exposed to the action of a current of sulphuretted hydrogen. whilst the black insoluble 3 4 sulphide formed. 4 4 2] 2 In the first class.i2H 2 O . 273 instead of argentic nitrate. and in this case a white triplumbic If this phosphate of lead be diphosphate (Pb 3 2PO 4) subsides. talline They is also yield a crys- precipitate this when a clear solution of magnesic stirred sul- phate.6H O T II. : OH basic hydrogen the have they are like displaced by 2 of a metal rhombic hydric disodic phosphate. and are often spoken of as the superphosphates. suspended in water. been Na 2 HPO 4 . these salts when soluble have a in the second class. phuric acid. the biphosphate of soda these salts have the form yellow triargentic phosphate which their neutral solutions with argentic nitrate. pure orthophosphoric acid is libe- rated and remains plumbic dissolved in is the liquid. well washed. salt which sodic ammonic hydric phosphate NaH 4NHP0 4 H [PO(ONa)(ONH 4 )(OH). . for example.H 4 2 O. .i2H 2 O the soluble salts of this class are neutral. Na3 PO4. Pb3 2PO 4 + 3H 2 S = 2H PO + 3PbS.TRIBASIC PHOSPHORIC ACID. fore it by evaporation in vacua over sulThe orthophosphoric is a tribasic acid . 3 Dihydric metallic phosphates . in microcosmic . filtration. and thereThe requires 3 atoms of a monad metal for saturation. The plumbic sulphide may be removed by and the acid obtained in deliquescent hard. 2 atoms of the strongly alkaline reaction . or have a feebly alkaline reaction : whilst the third class contains only i atom of metal with 2 of basic hydrogen . .

and the precipitate well washed with boiling water and carefully dried: 100 parts of bismuth phosphate (BiP0 4 ) With ferric salts phoscorrespond to 23-28 of phosphoric anhydride (P2 S ).274 PYROPHOSPHORIC ACID. the precipitate. then boiling. 2 molecules of the salt coalesce to form a . if neither the sulphuric nor hydrochloric acid be present. calcium. solution. becomes converted into dimagnesic pyrophosas a means of phate (Mg2 P 2 O 7 ). disodic (rhombic) phosphate (Na2 is 4 . it be heated to redness before redissolving. PbHP0 well washed and ignited. .' it is of the ignited residue represent acid solution of 15 of PZ rendered anhydrous 100 parts Chancel has shown that the 6 . it first melts in its water of crystallization. The quantity of phosphoric acid in a solution may be ascertained. TetrahydricPyrophosphate(H. saline mass which may be redissolved in water with all its former properties provided the temperature has not exceeded 302 (150 C. calcium. by means of plumbic acetate. requisite to remove any chlorine or sulphuric acid from the liquid. 4. When hydnc (479) Pyrophosphoric Acid . to a solution of a phosphate is added ammonic when molybdate acidulated with nitric acid. the deposition of this precipitate is favoured by boiling the liquid. whilst i molecule of water is expelled. the liquid must be boiled.) The dry mass consists of Na.* Neutral solutions of the orthophosphates give precibarium and calcium .2H 2 0). or silver. lized nitrate in 4 parts of nitric acid of sp. i'$6. by which means 24. which gradually evaporates leaving a hard. before this salt is added to it. [P 2 O 2 (O 2 Mg) 2 (ONH 4) 2 . should be neutralized by ammonia. which is prepared by dissolving I part of the crystalof separating phosphoric acid from (Bi'^NOJ furnishes an many metals. however.i2H 2 O) li HPO exposed to heat. In separating the bismuth phosphate by this reagent. barium. and adding 30 parts of water. the water and ammonia are free ammonia.i2OH 2] is insoluble in water containing when ignited. bismuth trinitrate and Care is aluminium. . but free : diphosphates in solutions of the nitrates of phosphoric acid gives no precipitate in or solution of ferric chloride. P z O 1 }. phoric acid forms an insoluble buff-coloured precipitate of ferric orthophosphate (FeP0 4 . and it them 100 parts of the ignited residue corresponding to 63-96 of P O-. similar to those furnished by the phosphates. which is also sometimes employed to estimate the quantity of filtering if necessary. which form phosphates soluble only in acidulated liquids. a characteristic yellow precipitate of ammonic molybdophosphate is formed. the tribaric and pitates with salts of are tricalcic readily soluble in acetic acid . such as admirable method iron. new salt. and should be then strongly acidulated with acetic acid. gr.jHPO 4 If. white. 2Na 2 HPO 4 magnesium * The arseniates give precipitates both with ammoniacal salts of and molybdic acid. phosphoric acid in a solution. before adding the solution of bismuth. a compound frequently employed contain which in solutions estimating the amount of phosphates expelled.

Pyrophosphoric acid appears to be tetra-basic and forms two classes of salts one with 4 atoms of a fixed P O 7 like the ordinary sodic pyrophosbasyl. or hydric disodic phosphate (478). salts of nickel and copper when mixed with a solution of sodic pyrophosphate yield double salts. composed of Na4 P2 O 7 . but on evaporation they become converted into tribasic phosphates by the assimilation of water acid.ioH 2 O) . with the formula 4 2 P O the other containing 2 atoms of hydrophate (Na 4 2 7 . (not by heat. Hydric Metaphosphate (HPO 3 ) M (480) Metaphosphoric in preparing the rhombic. remains neutral afterwards. and the corresponding salts of the No solid pyrophosphate (from irvp. the pyrophosphoric acid may then be obtained in' crystals by This tetra-sodic phosevaporation in vacuo over sulphuric acid. consisting of Ag4 P2 7 solution. and the solution instead of yielding a yellow precipitate with argentic nitrate. . 4 AgN0 3 + Na4P2 = 4 NaNO + Ag4P Or 3 2 "With a solution of plumbic acetate. it is is from the in which mode obtained. of salts of calcium and barium white precipitates of the pyrophosphates of these metals . pyrophosphates (Graham). two equal portions of phosphoric acid be taken. if neutral to litmus before. phate. and decomposed with sulphuretted hydrogen. containing 2 atoms of sodium to 3 of the other metal. Add. because no free acid 7 is liberated .intermixture with the silver O . P 7 The excess of sul4 2 must rid of be phuretted hydrogen got by exposure to the air H O . corresponding in gen : . 275 becoming or J Na 4P n (X + HO 2 [2PO(OH)(ONa) = OH + P O 2 2 3 (ONa) t fPO(ONa) l 2 .METAPHOSPHORTC ACID. it yields a solution of pyrophosphoric acid. 2Na4 P O 7 + 3 Cu"2NO 3 = Cu" Na 3 2 2P 2 O 7 + 6NaNO3 .JoH 2 0. usually termed the pyrophosphate of sodium. sodic pyrophosphate also occasions a white precipitate. the liquid no longer furnishes rhombic but acicular crystals. O on redissolving the residue in water and (PO(ONa) 2 _ evaporating the solution. fire). otherwise the acid assimilates water and converted into the tribasic acid H O + H P O =2H PO 2 4 2 7 3 becomes and 4 . these salts are stable while in solution. salt. of potassium or of ammonium can be obtained. In this case. the composition of which is repre- sented by the formula Pb 2 P 2 O 7 : and if the lead salt be suspended in water. and after neutralT 2 If. and of metal 2 a univalent (M 2 H 2 P 2 O 7 ). or disodic dihydric pyrophosphate Na 2 H 2 P 2 O 7 Neutral solutions of the pyrophosphates also give in solutions . M composition to the acid pyrophosphate of sodium. the now gives a white one.

the salt be heated to 302 (150 C. nitrate a gelatinous white precipitate (AgPO3 ) different in appearance and composition from either of the former phosphates of silver . but on igniting the residue. NaPO s will remain in the form of a transThis. the water having now changed its function in the salt. if dissolved in water. it does not lose weight. the glassy resi- due being converted almost entirely into metaphosphoric acid. or sodic metaphosphate.). for on again dissolving the salt it gives the usual re: actions of the metaphosphates. may give rise to substances change whose properties may be very different. and it is a striking and instructive illustration of the a in molecular facility with which chemical compounds. the two atoms of hydrogen will be expelled in the form of water. but becomes con- verted into the disodic dihydric pyrophosphate. "With plum: it is bic acetate a white precipitate also is formed (Pb2PO 3 ) fusible in boiling water. Sodic metaphosphate is capable of uniting with water of crystalthis water is lization. the acetic acid liberates metaphosphoric nitrate. the second quantity of acid be added to the neutralized solution.H^6 becomes Na 2 H 2 P 2 O 7 . 2NaPO 3 . ride It also gives white precipitates with baric chlo- Acetic acid does not coagulate albumin. soluble baric metaphosphate may be Sodic metaphosphate forms with salts of barium a white in- (Ba2PO3 which ) gradually dissolves when boiled. a tribasic sodic dihydric phosphate. which it retains if dried at 212 (100 C. as above directed. but if the two solutions be mixed. without any alteration in the proportions of its components. from its hydrogen having become basic (Graham) : Hydrated sodic metaphospbate. This change of properties in the salt. If. Tribasic phosphoric by prolonged heating to redness. it is soluble in excess of the sodium salt. -however. and argentic acid loses water and the albumin becomes coagulated. acid. and a fusible monobasic phosphate of sodium. Pyrophosphate of sodium and hydrogen. . and when decomposed with sulphuretted hydrogen it yields the corresponding acid (HPO 3 ). neither does a solution of sodic metaphosphate . thus admits of a satisfactory explanation . by constitution.) not basic.276 METAPHOSPHORIC ACID. and becoming con- . distinguished from the other hydrates by its power of coagulating the albumin of white of egg. gives with argentic parent glass. will be obtained on evaporating the liquid to dryness. assimilating 2 molecules of water. consisting of NaH 2 PO4 . izing one portion with sodic carbonate. although their percentage composition the same.

both these salts are very unstable. salts of silver and of magnesium corresponding to these compounds were classes of salts obtained. which consisted of 4Na 3 P0 4 . METAPHOSPHATES.. BaH 4 2PO v Metaphosphoric acid is monobasic and the solutions of its salt acid. MP 7 . consequently it cannot be concentrated by the application of heat. and pyrophosphates 2 OBTHOPHOSPHATES. M P0 M HP0 MH P0 3 4 ..toH 2 Pb"2 P2O7 and . as follows. Pharm.i2OH 2 ] [po(OH)ffHr Hjd dhodic (rbom bio) pho.. Chem. consisting of 2 Na 3 P0 4 .H 2 NaH 4 NHP04 4 H 2 . a.. 4 .. Sodic metaphosphate Plumbic Argentic III. ) Cun3 Na2 2F J A Argentic pyrophosphate Ag 4 P2 7 Fleitmann and Henneherg (Ann. Sodic pyrophosphate Plumbic Pyrophosphate sodium of copper Na 4 P 2 7 ... they obtained a salt.4QH Calcic phosphate (native) Ca" 3 2P04 Superphosphate of calcium Ammonic magnesic Ferric phosphate phosphate. NaH 2 P04 .] 2 (OH) 4 (0 2 Ca)"] Triplumbic phosphate Bismuthic Triargentic (yellow) . a definite sodium salt.P z 8 . Ixv. Fleitmann and Henneberg propose to represent these various classes of salts comparing quantities of each which contain equal amounts of metallic . 2 4.OH 2] [PO(OH)(ONa)(QNH 4 ). . .i2H 2 j [PO(ONa) 3 . in the proportion of I molecule of the pyrophosphate and 2 of the metaphosphate. b. [PO(OH) 2 (ONa).MODIFICATIONS OF THE PHOSPHATES. MP03 .oHJ 1 Sodic dihydric (acid) phosphate Microcosmic salt . and by fusing 8 molecules of the metaphosphate with i of the pyrophosphate.. The aqueous solution of metaphosphoric comes converted into the ordinary tribasic acid.6H2 Fe'"PO4 . metaphosphates. NajHpo< i2Hj() ^ . 324) have described two which are probably anhydro-phosphates.2H 2O Pb" 3 2P04 Bi'"P04 i [P2 [PAfaaCa)". Trisodic phosphate Na 3 P04 .. 277 verted into the tribasic baric tetrahydric diphosphate. : redden litmus feebly. NaP03 Pb" 2 P03 AgP03 [PO2 (ONa)] [P 2 4 (O2 Pb)"] [PO2 (OAg)] 4 2 PYBOPHOSPHATES. I. By melting sodic pyrophosphate and sodic metaphosphate together..P04 . Ca"H 4 2P04 Mg"H 4 N. and in solution Definite pass quickly into a mixture of pyrophosphate and metaphosphate. MM' 3 P 2 7 .. be- The following table furnishes a synoptic view of some of the : principal phosphates.. HPO 3 + H 2 O becoming H 3 PO 4 but the solution may be preserved for a short time at common temperatures without change. was obtained.3Pa 5 . when boiled. f Ag3 P04 II.

). would he compounds of the orthophosphates with different pro- Na3 P04 . P 2 O 3 may be procured by .2NaPO. but the subject needs further : investigation. burning phosphorus with a limited supply of dry air.NaP03 = Na4 P2 0. may be obtained from the salt by precipitation. Maddrell (Proc. Soc. (6NaP03 . but soluble in oil of vitriol. Chem. and this.2H 2 0. 1847. crystalline salt. A pyrophosphate. and phosphoric solution Phosphorous acid. ..9NaPO3 = Na P 10 31 1? thus : portions of a metaphosphate. or any metal isomor- phous with magnesium. forms an insoluble double metaphosphate the magnesium double salt is crystalline.3H 2 0) crystalline sodium salt has also been pre- pared. as well as the salts discovered by Fleitmann and Henneberg. These different varieties of metaphosphates are supposed to be due to the existence of several polymeric varieties of metaphosphoric acid.sodium. = H PH0 + 2 3 3 HC1 [PC1 8 + 3 OH 2 = POH(OH) 2 + 392 (200 3HC1]. so that each bubble of gas shall be completely absorbed by the phosphorus phosphorous chloride (PC1J is formed. but the bulk of the liquid is a solution of the crystalline which may be obtained on evaporation in oblique rhombic prisms salt. for example. the salt a being Na3 P04 .. is thus obtained. copper.5PA 6M 2 0. cona taste. whilst sisting of 6AgP03 . deliquescent. may be represented . If the acid liquid be concentrated by a heat not exceeding hydro- . A white.Orthophosphates Pyrophosphates Fleituiann and Henneberg.278 METAPHOSPHATES phosphoric PHOSPHOROUS ACID. when dissolved in a small quantity of hot water. The sodium salt. and is immediately decomposed by the water into hydrochloric and phosphorous acids PClj + aH. (481) PHOSPHOROUS ANHYDRIDE. inflammable powder. crystalline.Na 6 P 4O 13 and the salt b being Na8 P0 4 .. nickel. 4 PA 6M. They were formed by evaporating a solution of the sulphate or nitrate of the metal with an excess of phosphoric acid. Salts of potassium.2P 2 6 6M 2 0. . if prepared with phosphoric acid which contains magnesium. aluminium. 273) has described a series of monobasic metaphosphates which are anhydrous.0. If the ordinary or glassy sodic Modifications of Metaphosphoric Acid.6P2 5 M P2 7 2M 6 P4 O 13 M 12 P 10 31 4 i 2 MPOs which case the pyrophosphates. . Dihydric phosphite. is rapidly converted into the acid orthophosphate or sodic dihydric phosphate (NaH P0 4 ). and insoluble in water.i2H 3 0) the solution of this salt is neutral and has a cooling saline : The that of the ordinary or vitreous metaphosphate is insipid. 3 P 2 O5 a b or 4M 3P04 3 Metaphosphates in 6M 2 0. and heating until the sulphuric or other acid of the salt was expelled. forms a liquid which divides into two strata . p. volatile. by boiling.3NaP08 . destitute of crystalline structure. metaphosphate be fused and allowed to cool very slowly it furnishes a beautiful crystalline mass. Ditto ditto 6M 20. and others were thus obtained.). the quantity of series : anhydride each . the smaller of these contains unchanged tiodic metaphosphate . and consists of (3Mg2POg . phosphorus melted under water. which consists of the anhydride mixed with small quantities of oxide of phosphorus anhydride. successively increasing in basyl. A beautifully crystallized silver salt. . H 2 PH03 may he obtained in by passing a stream of chlorine very slowly through a deep layer of . . . and a similar lead (3Pb2P03 .

most others but sparingly so . even in the cold. the phosphites give a white precipitate of calomel. consists . phosphite.PHOSPHITES chloric acid HYPOPHOSPHOROUS ACID. and forms two classes of salts. it is also insoluble in acetic acid. A hypophosphite is produced when phosphorus is boiled with a solution of caustic potash or soda.H 3 P). 3 . and was termed phosphatic acid. dried at of baric dihydric diphosphite (BaH 2 2PH0 3). so far as to convert the whole into phosphoric acid . Another characteristic reaction of the phosphites is the reduction of sulphurous acid to sulphuretted hydrogen. the liquid therefore contains a mixture of phosphorous and phosphoric acids. unless heated with it . The acid phosphites when heated emit hydrogen gas. this The absorbing oxygen. a number of these tubes are then placed in a funnel. is expelled. by the slow exposed to the action may be safely effected both ends. and the acid is obtained in deliquescent rectangular It gradually absorbs oxygen from the air. 3 [POH(OH)(OM)J. of the formula Ba2PH 2 O 2 owing to the follow. the lower aperture of the tube being a little contracted so as to prevent the phosphorus from falling out . and first produced . normal phosphites of the alkali-metals are freely soluble. 2 [POH 2 (OH)]. and is decomposed by a temperature into phosphoric acid and phosphuretted hydrogen (4H 2 3 PH0 = It is also furnished in a less is pure form. a reaction which distinguishes it from hypophosphorous acid. and on evaporation a baric salt is obtained.5H 2 M PH0 M'HPH0 PH0 The acid phosphite of barium. this by placing sticks of phosphorus in tubes open at reception. consists of Na 2 when heated to 300 C. phos- phuretted hydrogen escapes. whilst a metaphosphate remains behind . the formation hastened by heating the liquid. 279 prisms. P 3 2 (0 2 Pb)" 3 5PbPH03 = Pb3 2P0 4 + Pb P2 O + H 3 P + H [5POH(02 Pb)" = + P O (0 Pb)" + PH 3 + HJ. acidulated with acetic of which is acid. the 5 molecules . It may thus be procured by Rose's method of boiling phosphorus with a solution of hydrate of baryta . for instance. for instance. the general formula of its normal salts being while that 2 3 [POH(OM) 2]. or with a hydrate of one of the alkaline earths. by gradually oxidation never proceeds Phosphorous acid is dibasic. of the acid phosphites is Normal sodic phosphite. HPH O 2 Hydric hypophosphite. With a solution of corrosive sublimate (HgCl 2 ). Free phosphorous acid does not 2 y 2 2 g 2 2 immediately reduce potassic permanganate. Phosphites. amongst them plumbic phosphite is the least soluble . which. for example. + H SOS 3 2 (482) HYPOPHOSPHOROUS ACID . This compound was formerly con- sidered to be an acid of phosphorus with a still smaller quantity of oxygen than the preceding. ing decomposition : . plumbic of water of crystallization are expelled. but its anhydride has never been obtained. which was at one time supposed to be a peculiar oxide of phosphorus. 3 H PHO. owing to the action of the sulphuretted hydrogen on the excess of sulphurous acid Z 2 : = 3 H P04 + H S. The rapidly discharges the colour of the permanganate in acid solutions. then.. BaH 2 2PHO g becomes Ba2PO + 2H The normal phosphites when $ 8 heated emit both hydrogen and phosphuretted hydrogen . and the dense acid liquid which is gradually formed drains into a vessel placed for its left combustion which occurs when phosphorus of the atmosphere at the ordinary temperature. with simultaneous precipitation of sulphur. In this process attracts being deliquescent phosphorous anhydride is moisture from the air. high 3 3H PO 4 4. 100 C. it forms phosphoric acid.

and of Wurtz have Hypophosphites. Like phosphorous acid. and iron. to the monobasic phosphates. and its solution gradually absorbs oxygen from the air. is When heated. phosphorus with a solution of baric sulphide. and by a stronger heat decomposed. they are gradually converted into phosphites by absorption of oxygen. of which the normal formula is Sodic hypophosphite. crystallizes in brilliant. consists of NaPH 2 .6H 2 0. The hypophosphites of the alkali-metals contain no water of crystallization : phosphite (Ca2PH 2 Calcic hypothey are deliquescent. and the liquid be warmed to about 131 (55 C. pure hypophosphorous acid is obtained in solution. Hypophosphorous acid forms an units crystallizable syrup. sometimes explodes spontaneously during the evaporation of its aqueous solution. sodium. hypophosphite. acid properties are but feebly marked. 2 2 Mg2PH Hypophosphorous acid is distinguished from phosphorous acid by a remarkable reaction with the salts of copper . also retain 6H 2 0. and a corresponding quantity of hydrogen is liberated. somewhat bitter taste . for example. aud is 2 ) requires Each molecule of the barium salt retains scirjely more soluble in boiling water. * . of Rose. which has a sour. but when their solutions are evaporated at a high temperature.). those of zinc and manganese retain but i molecule of water of Those of potassium.280 4 HYPOPHOSPHITES. crystallization. but if crystallized from a boiling solution is deposited in anhydrous tables. the lead salt may be represented as Pb2PH 2 O 2 They correspond. they reduce gold and silver from their salts. + 6OH 3 =3P 2 O 3 H 4 (0 8 Ba)'' + 2PH 3 ] . whilst phosphoric acid is formed . emitting phosphuretted hydrogen. which is now prepared largely for medicinal purposes. The hypophosphites are all soluble in water .* about 6 parts of cold water for solution. . many of them crystallize easily. shown that the hypophosphites are monobasic. Owing to the partial decomposition of the phosphuretted hydrogen. regular octohedra. a solid Sodic hypophosphite. the crystallized salts may be preserved unchanged. the last traces of baric sulphide are removed by the addition of a little plumbic sulphate. M'PH 2 O 2 [POH2 (OM)]. contain no water of crystallization. and strontium. 2HPH O 2 becoming H PO4 + H 3 3 P [2POH 2 (OH)=PO(OH) 3 + PH 3 ]. when free hydrogen escapes mixed with phosphuretted and sulphuretted hydrogen . and soluble in alcohol. therefore. Ba2PH Magnesic 2 2 . ammonium. it first loses water. if to an excess of free hypophosphorous acid a solution of cupric sulphate be added. cobalt. a little phosphorus is generally deposited at the same time. 2 . consequently the acid forms but a single class of salts. which are efflorescent. a molecule of water when crystallized at ordinary temperatures. The hypophosphites of nickel. which they lose at 302 (150 C. The researches of Dulong. whilst the barium is separated as Baric hypophosphite may also be prepared by heating sulphate. but 2 atoms of hydrogen have taken the place of I atom of oxygen in the radicle of the acid. by the spontaneous evaporation of their solutions .). on adding the requisite quantity of sulphuric acid. copper and lead.

which latter presents so and appearance of a metal. CHAPTER XV. HEXAD ELEMENTS. Cu 2 2 . always formed in small quantity when phosphorus is burned in air. and are exceedingly inflammable . together in all may be melted pounds exist proportions Sulphur and phosphorus several definite com: between them. tellurium. (483) OXIDE OF PHOSPHOBUS (P4 0). The combination of sulphur with phos- phorus should be gradually effected under warm water . as will be seen by com- paring the numbers in the different cases : . in order to avoid explosion. and the experiment requires to be conducted very carefully. It has neither smell nor taste. corresponding in composition with the oxides of phosphorus . this hydride is decomposed into hydrogen gas and metallic copper. and in addition to these. PS 6 . 281 insoluble hydride of copper. which possesses neither acid nor alkaline properties. A still lower degree of oxidation of It is phosphorus exists. to the boiling-point. The specific gravity and fusing-point of these elements increase as the atomic weight increases. may be obtained (Berzelius). and is one of the constituents of the yellow or red residue after the combustion has terminated. Elements.SULPHIDES OF PHOSPHORUS HEXAD ELEMENTS. All the sulphides of phosphorus are more fusible than either element separately. most of them can be obtained in crystals. of selenium are intermediate between those of sulphur and able it between and selenium and tellurium. They combine with the sulphides of the alkali-metals and form a series of definite salts. (484) SULPHIDES OP PHOSPHORUS. a compound of any importance. that it much is the external characters usually described with the metals. however. On raising the liquid which contains the precipitate. H and is quite insoluble in water. is precipitated. It is not. great heat is developed by their union. (485) Natural Relations of the Hexad Non-metallic Of this group the typical element sulphur has been already described. a marked analogy in chemical character is observ- They are all The properties characterized by a powerful attraction for oxygen. and is now generally regarded as amorphous phosphorus contaminated with a little phosphoric acid. a combination.

. Elements.282 HEXAD ELEMENTS.

.0~' . 283 'pounds which the elements of this group form with oxygen and hydrogen : Water.SELENIUM PROPERTIES. ' H.

the pulverulent selenium begins to soften at a temperature helow that of boiling water. gr. and is a very bad conductor of heat It is soluble in oil of vitriol. and gives off a deep yellow vapour. like sulphur. When solution which deposits unaltered selenium when diluted. of 6-37. from its solution in carbon c is variety disulphide. owing to If it be mainexisting. but is at a maximum at a place nearly coincide) t < crystalline selenium undergoes a very remarkable light. experiencing a molecular change. in minute rhomboidal pi-isms of sp. it forms a brittle solid. accordii 5 to Deville and Troost. so that the effect is n< t produced by the actinic rays. A bar of selenium who: e resistance in the dark was 330.).) culty.) i.peratnre suddenly rises till it reaches 320 (160 C. If these crystals be heated to about 334 (168 0. metallic lustre. and in the crystalline condition. is not acid.e. with a blue flame. gr. it appears that the resistance varii s with the nature of the light to which it is exposed. 7-67 at 1580 (860 C. at its boiling-point.) (Hittorf. emitting an odour resembling th. 212 (100 C.003 in the orange of the solar spectrum. gr. selenium only ignites with difficult. being nearly doubled when exposed to the full sunlight. If heate I however. insoluble in water.) it has a sp. which. of vitreous selenium. and to 220.284 SELENIUM PROPERTIES. that it is not due to the action of heat.) it melts smell.000 just on the outside edge of the red. sp. . or evt i to the light from a It has been conclusively show a paraffin lamp or gas-burner. in several distinct modifications. When collected the vitreous. is and of melted it is ductile. and dried. ins The statements power of -regarding point of fusion are discordant. dissolves about I per cent. in this black whtn consequence of which they are no longer soluble in carbonic disulphide mass is melted and quickly cooled. heated in the air. 4-5. C. varying glassy fracture. with the locus of the in maximum of the heat rays. and may be drawn out into its fine threads. same effect is produced to a less extent by exposure to diffused daylight. and deep brown colour. gr.). and increase in sp. forming a green electricity.000 ohms showed a resistance of only 277.000 in the re i. change under the influence f and from the determinations of Sale. is of sp. after which the selenium found to have become granular and crystalline. t of carbonic disulphide . it resumes its solubility in this menstruum. whi e at 2588 it has a of and has (1420 till. and at a few degrees above on cooling. . when heated to 1904 (1040 C. it expande I. It has neither taste nor in specific gravity from 4-3 to 4' 8. with . owing to its reconversion into the vitreous condition. a portion of it is at the same tirr e burning volatilized in red fumes. 5*68 a bulk occupies nearly equal o . Willoughby Smith has recently discovered that the electric conductivity of tl e . which.) as in the case of sulphur. which decreased to 255. this is probably due to the formation f a protoxide of selenium. The fusing-point of th s is 422 6 (217 It may also be obtained with some diffiC. < When in closed vessels. which. gr. below its melting-point the ten. they beconre almost black. to 4*7. selenium boils at a temperature below a r( I heat. The increase of conductivit f Tl e instantaneous. tained for some hours at 200 (93'3 C.

(488) CHLOEIDES OF SELENIUM. found that a bubble of the gas no larger than a pea deprived him of the sense of Seleniuretted hydrogen is obtained by acting on smell for several hours. leaving solved . except those of the metals of the alkalies. With the alkali-metals three are insoluble in water. Gr. white. soluble in water : those of cerium.) be obtained by burning selenium in a current of oxygen. the selenious anhydride as a white infusible mass. Most of the selenites. 5575. (487) SELENITJBETTED HYDBOGEN. SELENIOUS ANHYDRIDE (SeO 2 =iir5 Rel. reduces selenium from the acid. Hydroselenic acid. . but its odour is much more offensive. zinc. selenium vapour calculated on the supposition that it exactly corresponds with the volume of an atom of hydrogen is 55014. crystalline mass. and slowly decomposed by it . Observed. either of which. Theoretic. Se = 8i'5 Rel. which Berzelius resembles hydrosulphuric acid. of Vapour. Sjy. (489) OXIDES OF SELENIUM. Selenites. the first of these corresponds to sulphurous. which yield acids when united with the elements of water. Selenium forms two compounds with oxygen. . are flesh-coloured . Dihydric selenide . Se 2 Cl 2 heavier than water. Selenium unites directly with chlorine. of selenides. The vapour condenses in red flowers or in opaque metalliclooking drops.SELENIURETTED HYDROGEN. gas is soluble in water. with dilute hydrochloric or sulphuric acid. and precipitates many metals from their salts in the form H . The crystals are deliquescent. which volatilizes at a temperature below redness. 2-8199 Observed. and manganese. 2 2 795 Mol. if exposed to the air it The selenides of the alkali-metals are absorbs oxygen and deposits selenium. aqua regia. This substance is a colourless inflammable gas. occasions the deposition of selenium in the form of a reddishA solution of sulphurous acid also readily brown powder. wt. forming two compounds. with the general formula . Vol. forming a yellow vapour. Its solution has a feebly acid reaction . Theo: 3*8579 . '> - . the other a volatile. 4075 . one a brownish volatile liquid. the excess of nitric acid and condenses again in beautiful snow-white prismatic needles. that 285 The specific gravity of of an equivalent of oxygen. wt. 4*03 . \^ ^j. classes of salts may be formed : normal selenites. may it is but usually prepared by boiling selenium with nitric acid or retic Sp.. Gr. chloric acids. This selenide of potassium or iron. and the second to sulphuric acid. is in solution deoxidized SeO speedily by iron (H 2 3 ) [SeO(OH)J or by zinc. and their aqueous solution which is Selenious acid strongly acid. possesses a sour burning taste. hy which the selenium is is gradually oxidized and dis- then expelled by heat. SeCl 4 which is immediately decomposed by water into selenious and hydroA Bromide of selenium is also known. most of the others are black. but soluble in nitric acid. Mol. when digested in the liquid. F r~j. Vol.

Baric seleniate is similarly When heated decomposed. if boiled . M Se0 2 like disodic selenite. The acitl most conveniently prepared by deflagrating selenium or any selenite with nitre. a pungent liquid resembling the corresponding sulphur compound. The selenites are easily recognized by the peculiar odour emit when heated on charcoal in the reducing flame of of selenium which .. MH. acid selenites. selenk sulphurous acid will then : precipitate reduced selenium from the solution.SeO + ?. if heated beyond 554 C (290 C. is dibasic. chlorine and is selenious acid being liberated.286 SELENIC ACID. platinum is not attacked by it Sulphurous acid chloric acid without effect upon selenic acid. Carbonic Selenide . 4. Na Se0 2 3 . when plumbic sulphide is formed. H. and of the acid concentrated by evapo v athe solution filtration. when treated with sulphurous acid. but hydrodecomposes it by the aid of heat. Selenic acid Solutions of the seleniates give whit* precipitates with salts of barium. (491) CABBON BISELENIDE . CSe2 is formed by the Jt if action of the moist vapour of carbon tetrachloride on phosphorus selenide. MH and hyperacid the general formula selenites. dissolving the residue in water. of hydrogen Selenic acid dissolves iron and zinc with evolution it also attacks copper and even gold. and precipitating it with a solution of plumbic nitrate.) decomposed into selenious anhydride. itself is (490) SELENIC ACID. tion till it has a specific gravity of 2'6 it is . give a reddish-brown precipitate of reduced selenium.H 2 0) they a blowpipe.HCl SeO 3 + 2 O 44 2 C1 3 Selenic acid closely resembles sulphuric acid in its proper. 2SeO 3 like trihydric sodic selenite quadri-selenites. on charcoal in the reducing-flame of a blowpipe.S = H 2 SeO 4 + PbS. owing to the formation 01 seleniates of these metals. . water. and may thus be distinguished from baric sulphate.H 2 0. the insoluble plumbic seleniate thus obtained is suspended in water and decomposed by a current of sulphuretted hydrogen. These precipitates are insoluble in dilute nitru acid. =H H ties. and lead.Se03 like hydric sodic selenite (NaHSe03 . with the general formula 3 2(NaH s 2SeOs ). . upor. and selenic acid is set at liberty. the selenites in solution. with . and its salts are isomorphous with the sulphates. or = 145*5. PbSeO 4 -f The plumbic sulphide may be separated by H. strontium. these metals. and oxygen. the seleniates emit tht characteristic odour of selenium. Dihydric seleniate . which are oxidized at the expense of the acid. and is reduced to selenious acid boiled with hydrochloric acid. The anhydride of this acid is not H 2 SeO [SeO 2 (OH) 4 ! known. selenious acid being disengaged . Seleniates. When is the soluble seleniates are acid liberated.

TELLURIUM PROPERTIES. however. Pel. copper. a close analogy with amongst the metals. lead. tellurium. as in TeCl 4 2 : Q Q. vol. ii. Observed Sp. it is usually also accompanied by small Its most common ore is quantities of arsenicum and selenium. but but generally combined with various metals. when solidified after fusion. foliated tellurium ore of Nagyag. and named by him from tellus. fuses between and resembles bismuth in colour. and condenses in drops and flexible crystalline needles in the cooler parts of the apparatus. bismuth. Mol. the reader For additional particulars regarding the extraction of is referred to the Lehrbuch of Berzelius (German edition. heating the residue with nitric acid . the vapour of tellurium is thus mechani- forward. to remove the sulphides of lead and antimony. 9'oo. the earth.. Vol. sulphur and selenium. 1844. tellurium. (492) Mol. Dyad. as in H [Te0 2 (OH) 2 ]. and then after washing it.). however. 287 II. evaporated to dryness. of Vapour. Theoretic Sp. Gr. or lead . TELLURIUM: Te=i29. the solution of tellurous nitrate thus obtained is decanted. Sp. has a density of 9^00 at a temperature of 2534 (1390 C. 393- iv. 1 29 . and transmitting a current of dry hydrogen gas over cally it . 6-33 . . The distillation of tellurium is best conducted by heating it very strongly in a porcelain tube. mixed with sulphides of antimony and lead. p. such as gold. Te 2 258 . According to Mitscherlich. of tellurium in the form of tellurides of gold. the black. after which the tellurium is thrown down as a brown powder by the addition of sodic sulphite to the acid liquid. 8-9268 . Some specimens. and silver. of Vapour. silver. which contains about 13 per cent. although it possesses a high metallic lustre. It presents. ]] : . the finely-powdered ore in hydrochloric acid. Hexad as in H TeO 4 TELLURIUM first is a rare substance discovered by Miiller in investigated by Klaproth in 1798. 229) and Gmelin's Handbook. It is very brittle. wt. wt. Te Tetrad. Most English writers on chemistry class tellurium Properties. Atomic Vol. and at a high temperature isconverted into a yellow vapour which according to Deville and Troost. Gr. Gr. 1782. and treated with hydrochloric acid. It is found chiefly in the mines of Hungary and Transylvania. occasionally native and nearly pure.).). contain more than 90 per cent. at 2534 (1390 C. of the It may be extracted from this mineral by first digesting element. 800 and 900 (426 and 482 C. exhibits a carried . of Solid.

: dichloride of a violet colour . Vol. they are all solid crystalline substances . Telluretted hydrogen most of the metals from their in the form solutions. both of them are volatile . which hydrogen becomes brown by exposure to the air. of tellurous anhydride are produced. a gaseous body analogous to sulphuretted hydrogen. Tellurium is Acid.. but the iodides are decomposed by heat. 65'5is The most it compound of It is tel- lurium that which forms with hydrogen. Theoretic. . tellurium is soluble in cold concentrated sulphuric acid. Mol. ' | tip. water. (494) action 'of The tellurides of the alkali-metals are soluble in Two chlorides. burns with a blue flame edged with green. and is possessed of feebly acid properties. on dilution it is precipitated unchanged. Observed. H Te = 2 131. bulky of tellurous acid is Tellurous H = hydrate precipitated. to which it gives a fine purple-red colour . the bromides sublime unchanged. 4-489. when taken inimpart a persistent and intolerable odour of garlic to (493) TELLURETTED HYDROGEN: Dihydric Gr. burns with it a blue flame reddens and has an litmus. with water it forms a colourless solution. owing to the oxidation of the hydrogen and separation of tellurium. rhombohedral cleavage. 2 readily dissolved by nitric acid of sp. interesting Rel. TeO 3 [TeO(OH) 2] 179. which have a close analogy with the corresponding : sulphides. ternally. the air it takes fire. precipitates of tellurides. 4-5326. whilst thick white fumes Like sulphur and selenium. and with the alkaline bases . a circumstance which seems to indicate its Tellurium is a bad isomorphism with arsenicum and antimony. (495) Tellurium forms two oxides (TeO 2 . It may be obtained by decomposing the alloy of tellurium with The gas which by means of hydrochloric acid. TeCl 2 chlorine upon tellurium is and TeCl 4 have been . wt. 1-25. water. the vapour of the they are decomposed by a large quantity of Corresponding bromides and iodides of tellurium have been obtained . and emits a peculiar characteristic odour. obtained by the direci. a white. Minute quantities of tellurium. escapes odour which cannot be distinguished from that of sulphuretted zinc or tin. the breath. and if the solution be poured into water.288 TELLUKETTED HYDROGEN. these compounds are soluble. reddens litmus. telluride . contains its own volume of hydrogen. gr. is : It Tellurous acid has a bitter metallic taste its anhydride may be . {. combines slightly soluble in water. which correspond in composition to sulphurous and sulphuric anhydrides. When heated strongly in conductor of heat and of electricity. TeO 3 ).

or by boiling the nitric it is deposited in cystalline needles. is thrown down from its solutions in the reduced form by zinc or iron . . tellurates of the alkali-metals n. MHTe04 . then separated by sulphuric acid. like selenic forms three classes of salts formula. or one of its salts. of' The The telTe08 or quadritellurites. yielding red solutions. when . soluble only very slightly a Gr. M Te0 2 4 . If heated nearly to they furnish telluric anhydride. which is Sp. and are said to act powerfully as emetics. which have a nauseous These metallic taste . (496) Telluric Acid (H 2TeO 4 [TeO 2 (OH)J tellurous . MHTeO H the stronger acids the compounds which it thus furnishes have a metallic taste. which are in water. which dissolve in water. yield a black precipitate with sulphuretted hydrogen. . A and the barium is formed. easily. is heated to redness. redness are composed of H 2TeO 4 . oxygen is disengaged and the telluric is converted into tellurous anhydride. it well attraction for bases. like many of the metallic anhydrides. normal M TeO 2 g . crystals insoluble in water. reduced tellurium is precipitated under these circumstances. 289 obtained by gently heating the hydrate. if fused Tellurous anhydride possesses considerable volatility : with caustic potash. Telluric acid has but a feeble chemical acid. as as in alkaline solutions. but becomes white and crystalline on cooling. but. When telluric acidulated. The anhydride (TeO 2 =i6i . potassic tellurite Three varieties of tellurites exist is formed. Telluric acid crystallizes in striated hexagonal prisms. MHTe03 lurites so. and in nitric and hydrochloric acids. acid salts. acid. when yellow whilst hot. chloride in these cases by ferrous sulphate and by stannous the tellurium falls in brown flocculi. The when heated to redness in a tube with charcoal are reduced to tellurides. If 2 the alkali-metals are soluble. namely. fuses transparent glass. forming 5'93) acid solution.TELLUROUS AND TELLURIC ACIDS.195) is obtained by gently heating tellurium or potassic tellurate is acid with nitre. they exert but a feeble action on litmus. . whether in the form of a soluble tellurite or in that of a tellurate. With sulphuretted : hydrogen a black sulphide of tellurium is produced. Tellurium. Its salts with oxalic and tartaric acid are soluble. or the tellurate into a tellurite of the basyl.2H 2 0. salts. and then assume an This anhydride (TeO 3 =i77) is completely orange-yellow colour.H 2 Te0 4 Their solutions. All the soluble salts in which tellurium acts as a basyl are decomposed if mixed with hydrochloric acid and heated with sulphurous acid . those of the alkaline earths very sparingly anhydride also. which may be represented by the general and MHTe0 4 . neutral solutions of the salts of both its acids are also reduced . which is converted into a basic salt. combines with and hyperacid salts.

or extensibility under the hammer. in which some of these characters are strongly displayed. is obtained: the copy is then strongly heated. Iron. THE METALS. however. class. surface like the metals. are General Characters of the Metals. for instance. or fitness for drawing into wire. yet most of them in are devoid of it when in a minutely divided state. by employing finely-divided copper. and a little smaller than : the original. and Colour. Some of them are also endowed with the properties of ductility. which in all its chemical reladirectly opposed to the metals. yet possesses a strong . XVI. a high specific gravity. Opacity. SECOND DIVISION. silver. Although. all metals present the lustre termed metallic. and are good conductors both of heat and electricity.290 CHAPTER B. it is possible to make copies of medals or ancient coins. as a capable of receiving a high polish. and of malleability. (498) Lustre. These properties are not developed equally in all the metals . Many of separated from their compounds by electrolytic action. though reversed. an exact copy of the medal. I. If. This property admits of being applied arts. which is extremely distinct. with a beautifully polished is : surface. care being taken to exclude atmospheric air during the ignition the copy shrinks a little in all directions. or negative pole of the voltaic battery. platinum. gold. but a fac-simile is formed. tions is Bodies which are not metallic occasionally assume a brilliant Iodine. and even mercury. these metallic powders be subjected to pressure iinder the burnisher. copper. not metallic in their nature. may be readily obtained in this condition by processes to be mentioned hereafter. a sufficient approximation of their particles is to render them produced capable of reflecting light. they appear at the platinode. The metals. and are then characterized by a peculiar brilliancy termed the metallic lustre. and the in the fine metallic lustre reappears. which introduced with a medal into a mould by submitting it to pressure. : them have When some metals one or more of them may be wanting altogether and there are other substances. They (497) are possessed of a high degree of opacity. GENERAL PROPERTIES OF THE METALS. when polished.

tin. Great differences (499) Hardness. and bismuth. and copper is of a red colour. A red tint may thus be made evident in silver. at the ordinary temperature. evolves a powerful odour of garlic. and potassium may be spread when The taste of . Metals are among the most opaque bodies with which we are When reduced to acquainted: but their opacity is not perfect. have a bluish colour . lustre . Some. as in the alloy of tin and copper used for bells. Closely connected with the hardness are the brittleness and the tenacity of metals. popular carbon. gold. and palla- dium. such as lead and zinc. Zinc. a smell peculiar to themselves. or compounds of the metals with each other. like butter.291 is observable in a form of carbon. and volatilized. has or received known as its. other metals. gold is a bright yellow . is pre-eminently qualified for the construc- tion of the springs used in machinery. The brittleness require great force to effect their disintegration. pure gold. platinum. which. are nearly alike . arsenicum. and copper emit. graphite name of black-lead from its metallic appearance. iron. silver and copper. The metal. Many sonorous when struck of the harder metals are very elastic and but these properties are more strikingly . escapes from the vent-holes of the The native form of moulds during the process of casting iron. and in that combination of carbon with iron. are observable between the hardness of the different metals steel be rendered to hard scratch while lead will glass. others. with a shade peculiar to : each metal the tints of silver. like anti- mony. as iron. tin. known as steel. termed which kish. and a violet tinge in steel. and Tenacity. on of the metals possess a characteristic odour. plumbago. cadmium. of some of the metals is materially affected by temperature. or o oooi25 thick. by its high elasticity. displayed in some of the alloys. most of the soluble compounds of the metals is astringent or acrid. of not more than -TO ^. Brittleness. By repeated reflections from the same metal a distinct colour is often rendered obvious. a portion of the light is transmitted . allows a green light to pass. for -mm example. the same thing by the workman exceedingly fine leaves. though it is not seen upon looking at the polished surface. like iron and arsenicum. may enough take impressions from the finger-nail. while others. have a greyish hue . and of the peculiar kind termed metallic. is so brittle that it cannot be . Some arsenicum. may be pulverized without difficulty in a mortar.Wo inch. calcium and barium are pale yellow . which are very variable. colour of the reflected light varies with the nature of the In most cases it is nearly white. friction.

bent at a sharp angle without danger of destroying its cohesion. will be represented according to Wer- theim's experiments as follows: Lead . . but when cold it possesses considerable malleability. an alloy of copper and zinc. that be reduced brittle so becomes easily may again brittle at Brass. Taking the tenacity of lead=i. at 410 (210 C. the tenacity of the different metals. 8-9 . after annealing. on the contrary.) it to powder. while if heated to between 200 and 300 (or from about 95 to it 150 C. becomes temperatures approaching to redness.292 TENACITY OF THE METALS.) it may be wrought with facility.

. 293 Metal employed.TENACITY OF THE METALS.

The following metals are termed malleable metals. According to Wertheim all circumstances which increase the He finds the codensity. or by hammering : Gold . that of silver nearly as much. even the when the formation of alloy is attended with change of of a current of electricity. independently of the diminution caused by the rise of temperature which it a occasions.294 MALLEABILITY AND DUCTILITY OP THE METALS. metals which may be reduced to thin by lamination between rollers. means the tenacity of gold is reduced more than half. (500) Malleability leaves either i. and that of iron and copper about a fourth. that of platinum about one-third. as a rule increase the elasticity also.e. coefficients of the metals momentary diminution in the elasticity. i. and Ductility. produces transmission The volume. efficient of elasticity of an alloy to be sensibly the mean of the which enter into its composition.

MALLEABILITY AND DUCTILITY OF THE METALS. Gold . 295 the first five the property being possessed to a nearly equal extent by upon the list : i. tility.

. and silver.. The less fusible metals.. and pouring out the interior portions before the whole has had time to solidify. In the annexed table. Sp.. Copper. their powerful attraction for oxygen . is very hard and brittle. Gold Uranium Tungsten Mercury . in solvents by placing Some of the metals which fuse readily may be obtained in structure of a it The crystals without difficulty. its partiarrange themselves in a crystalline manner. . ciple.. . It may like iron. those which are least oxidizable possessing generally the highest specific gravity. such as copper.... metal is easily displayed in many cases.206 malleable cles STRUCTURE SPECIFIC GRAVITY OF THE METALS. but when the action is more rapid it is soft and tough. and it then becomes very brittle. and the metal then exhibits a indeed be stated. . antimony. tions are exhibited between the extremes of iridium and platinum. . and A large proportion of the copper occur native in crystals. . the most marked of which is platinum. on the which has on the one hand. the heaviest known forms other.Rose. while those which. gr. when deposited in crystals by slow voltaic action. silver.. for example.. Metal. 13*596 I2'i D'Elhuyart... Deville and Debray.. that bismuth.. iron. fibrous character. Many of them as. are the most brittle . G. . are often deposited in the crystalline form from their solutions by slow voltaic action.. have a fibrous structure.. of the melted metal to cool slowly. by allowing 2 or 3 kilos. . are possessed of a high degree of tenacity. ... Deville and Debray.. of matter. Platinum . In a few instances. but this ' is not usually the case. the walls of the cavity are Bisthen found to be lined with crystals on their inner surface.. muth is particularly well adapted for this experiment.. Osmium Iridium . the density may be somewhat increased by rolling and hammering. . . . more than half the The lighter metals are all characterized by density of water. ... 21-53 21-4 21-15 19-34 18-4 17*6 Wollaston. . .. Observer... however. . by repeated heatings and coolings. Peligot.. gold.... Eegnault. Rhodium . as a general printhe crystalline metals. Specific Gravity of the Metals. such as zinc. variathe specific gravity of the metals.... and arsenicum. Wide differences are observable in (501) Specific Gravity. metals crystallize in forms belonging to the regular system. the operation of which is very gradual. little and lithium.. Deville and Debray.

while platinum. 297 Thallium Palladium . Mercury. and cobalt a white heat . and a gold require bright cherry-red heat iron.. AND FUSIBILITY OF THE METALS.. copper. potassium and (502) Fusibility. ..) . Ruthenium Lead . cadmium. nickel. Silver.. Indium Tin Zinc . lead. for instance. rhodium. remains fluid as low as 37'9 ( 38'8 C. iridium. Glucinum Magnesium Calcium .. Rubidium Sodium Potassium Lithium The melting-points of the different metals not less widely than their densities.. Tin.. or even of the voltaic arc. Chromium Antimony Tellurium . thallium. .. antimony. .SPECIFIC GRAVITY Metal. above a red heat... gr. Sp. require the intense heat of the oxyhydrogen blowpipe. and aluminium. to effect their fusion... . .. and zinc melt below redness .. differ sodium melt below the heat of boiling water. Silver Bismuth Cobalt Copper Nickel Molybdenum Cadmium Manganese Iron . bismuth. Arsenicum Barium Aluminium Strontium . calcium. and several others.

transparent vapour. ... is not a conductor of electricity.. Lead . Daniell. and is reduced to a perfectly colourIt is imporless.. Palladium is also. E.. lithium and potassium afford the most striking instances of this. agglomerate but do not fuse in] the forge . Becquerel. platinum.. . above a red heat. ... 264 294 325 . . and of lithium.. at about 680 (360 C. of sodium. Manganese Molybdenum Tungsten .1 Ii36o-i38o C.. Observer.. (503) Volatility. Iron. . susceptible of it.. Rudberg.. .. .. Rhodium Iridium Vanadium Ruthenium Osmium Ii46o-i48o melting-points. Cadmium Bismuth Thallium 228 . Platinum C.... . undetermined. thallium.. specific gravity of potassium. before undergoing a soft intermediate stage. . Cast iron Cobalt . Crookes... power vapour. 773 1150 Daniell. Chromium Palladium .. pass through if two clean surfaces be presented to each other. .. when heated under ordinary atmospheric pressure. on the other. Many of the metals admit of being volatilized without difficulty. boils. E.. tant to observe that this vapour. Becquirel. 1037 i9i6 C.). show that there is nothing inconsistent with facts in the electric sparks supposition that hydrogen itself. . 1873 1996 2016 . Antimony Calcium . C. highest heat of forge. in which. . although the lightest known form of matter. although metallic. Wrought iron. E.. Becquerel. and though gaseous.. FUSIBILITY AND VOLATILITY OF THE METALS. they unite. Copper Gold . or weld together. and consequently an insu- . Aluminium Silver.. ... 44 2 507 561 617 > Stromeyer.. . and will allow the transmission of distinct as readily as atmospheric air. The insulating of mercurial on one and the small the hand.. Becquerel. E... Tellurium.... . . [ 412 about62i ! .298 Metal.. 2786 Nickel . . in a minor degree.. so as to form one continuous mass. Mercury.. Radberg. and strong their Some metals near pressure or hammering be employed. Arsenicum Zinc . complete fusion. .

have already been pointed out (132) . Even copper is not absolutely fixed in the fire. (504) Conducting Power for Heat differences of expansion exhibited and by The great Electricity. scintillation in the oxyhydrogen tilled in considerable quantities the oxyhydrogen flame. one-seventh of the lead escapes up the chimney. My friend Dr. and zinc a temperature of 1904 (1040 C. 299 its may possibly be a metal . should exhibit the properties of an alloy. the conducting power of each metal. lator of electricity. of which this is a fragment. and indeed. both for heat (149) and for electricity is also . Eight of the metals are sufficiently volatile to be distilled they are obtained. a gas at the ordinary temperature and condensable to a colourless transparent liquid exhibiting no metallic properties whatever. showed me a remarkable illustration of this fact : he has in his possession part of a beam which. the whole beam.CONDUCTING POWER FOR HEAT AND ELECTRICITY. Cadmium Potassium Magnesium Arsenicum is assumed the volatilized below redness. from the compounds from which Mercury Arsenicum Zinc Sodium Rubidium. On the other hand. this however. for many years. in the fire are likewise volatilizable to a certain extent. was suspended over a furnace in a copper smelting house in Norway. 1580 (860 C. Percy. contains minute beads of metallic copper studded through its texture the copper must have been raised in vapour and so deposited within its fibres. if hydrogen is a metal. Platinum may be the focus of an intensely powerful converted into vapour with jet. it approximates very closely to this class of bodies. and even before it has form cadmium requires a full red heat. Gold has been found similarly studding the beams of refineries . and rubidium require a still higher Those metals which are generally considered fixed temperature. In the liquid . and would be wasted unless means for collecting it were adopted. and it may be seen : to undergo volatilization in burning-glass. viz. different metals when exposed to equal degrees of temperature.) whilst potassium. and it may be stated generally that each metal possesses a specific expansion. in chemical properties.). : process of lead-smelting.. and silver has even been disby Stas by the heat produced in Fine wires of the most refractory metals may be dispersed in vapour by transmitting the discharge of a powerful Leyden battery through them. sodium. some years ago. its compound with arsenic substance is.

lead. and bismuth. the metals are insulators in the aeriform state. iu general it is found that the best conductors of heat are also the best conductors of electricity . zinc. but are employed for hardening other metals. Soc. impart to their alloys their physical properties in the proportion in which they themselves exist in the alloy . with each other. Arsenicum. tin. and platinum. silver. and which cadmium.300 ALLOYS. 276) . antimony. Comparatively few of the metals possess qualities such as render them suitable to be em(505) other. B. little Some altered of the physical properties of the metals are but by alloying. should be excepted. : 2. but although conductors in the solid and liquid conditions. mercury. tin. the combination or alloy being often adapted to purposes for which either metal separately would be unfit. gold. aluminium. Alloys formed by metals of the class with those of class B . alloys which Matthiessen has examined consist of two These he divides into three groups. 201). mean of that of their constituents . comprising lead. Chem. definite (239. He concludes that the metals considered under this aspect may be divided into two prina small one.. iron. viz. copper. and bismuth are too brittle to be used alone. many of which are most extensively used in the arts. antimony. and Alloys of metals of class A A 3.a little above or below that which is given by calculation. Matthiessen has made a special study of the effects produced upon the physical properties of metals by alloying them with one another (J. ployed alone by the manufacturer. . A. 1. like arsenic. zinc. and a more numerous class. Alloys of the metals of class B with each other. impart to their alloys their physical properties in the proportion in which they themselves exist in the alloy. the observed specific gravity is frequently . The specific gravity of the alloys of metals of class A is also the . 1867. Metals enter into combination with each and form compounds termed alloys. * Probably brittle metals. ALLOYS. Many of the physical properties of the metals are greatly altered by combination with others .* The metals. The specific heat of the alloys and their expansion by heat are always the mean of that of their components and they vary with the proportions of each component. the members of which do not cipal classes. but when metals of class A are alloyed with those of class B. constitute the entire number so used.

with 12 per cent. when melted alloy of bismuth. as is well known both the latter avails himto the glass-maker and to the metallurgist self of the fact to render his slags sufficiently fusible and liquid. In ably observed in the case of the silicates. or nearly in the atomic proportion (Bi^PbSn).) the easy C. or of lead. an These metals. emit a dead sound . 301 invariably below the The that of fusing-point of an alloy its is mean of an alloy agrees components. silver. in mixtures of the carbonates with each other it is also remarkthis respect. : by due admixture of various silicates. become nearly straightened when stretched by a moderate weight. but when a metal of class B is alloyed either with one of its own class or with one of class A. the conducting power for electricity exactly proportional to the quantity of each metal employed. yield a mass fusible in boiling water. of zinc. 2 of lead. when susincreased. struck. A striking and well-known illustration of this increased fusibility of alloys is seen in what is known as fusible metal. and tin. bars of tin-copper. its elasticity is much Bars of copper. the most fusible of the three metals.) higher. and for many applications in the still more easily arts are is of still greater importance. and that of lead is 396 fusibility of this alloy is always remarkable. but wires of equal . and struck. marked no change when the metals of class A are showing 20 per cent. is more than 198 (110 C. they emit a clear ringing sound. with other mixtures . and the same thing is true as regards the conducting power of these alloys for heat. or tin-lead. with emit very little sound when struck . In the metals of is class A. when alloyed with a small proportion of a Similar results are observed when weights are : such spirals. small proportion of one of class A. . alloyed together. or platinum. and proportions together j of tin. but when bars of a pended When a metal of class B alloyed with a copper-tin alloy (bell-metal) or of copper and zinc (brass) are On the other hand. if made suspended to spirals of hard-drawn wire of copper. or metal in class B. of copper. the chlorides when mixed with each other melt below the fusing-point of the mean. of tin. Alterations in hardness and elasticity are perceived . even if the propor- tions of its constituents be considerably varied. of lead. a sudden decrease in conducting power both for electricity and for heat takes place. (220 higher. and often below the The same thing is observed fusing-point of either constituent. lead. however. although the melting-point of tin.ALLOYS. of in the 4 parts of bismuth. gold.

. scarcely undergo any permanent change same weight. file tough..302 ALLOYS.. .metal. but moderately fusible compounds bell. copper) Silver .. and produces the white compound metal known under the name of German silver. 30 25 under 7 7 > . tin). and antimony. Copper.. through the same gauge (No. which can be cast.. and is hard enough to resist wear without cutting the paper or being inconveniently brittle... which expands at the moment of solidification so as to take the impression of the mould accurately. the qualities of which can be varied by varying the proportions of the two metals. lead. it is too tough to be conveniently wrought in the lathe and ings. . lead) . and which concompound.. The addition of nickel to brass destroys its yellow colour. 455 75 80 Advantage is taken in the arts of this variation in the hard- ness and elasticity of metals produced by alloying them together.. .. 23) : ib. the resulting body called an amalgam... breaking strain for double wire .... rolled.... platinum).. stitutes the different kinds of brass.. 7 Tin-copper (12 per cent.. dimension composed of copper-tin (12 platinum (30 per cent. Many ductile metals subjected to tension by the in elasticity by being belonging to class B are much increased alloyed with each other. or by the but when alloyed with zinc it forms a much harder . . platinum) .... ductility of metals is usually impaired by combination Alloys of two brittle metals are invariably The with one another. . . Copper and tin in various proportions yield the hard. Type-metal is a fusible alloy of tin. or turned. Tin Lead . ...... 2025 45~ 5 Platinum Silver-platinum (30 per cent... .. . silver- and gold-copper (8*4 per cent.. Tin-lead (20 per cent... Matthiessen gives the following approximative results upon the tenacity of certain metals and alloys for wires hard drawr. . per cent. in form when copper). tin) about 7 . known as bronze and When is the metals combine with mercury. .. . 80 7 90 75 Gold Gold-copper (8*4 per cent. copper) Copper-tin (12 per cent.. The qualities of copper are also modified in an important manner Copper alone is not fit for castby alloying it with other metals.

as when gold is added to melted tin. 3. Generally speaking. when alloyed with a minute muth. and zinc rz per cent. portion of lead. will dissolve In only i'6 per cent. The solid metal dissolves quickly with marked obtained . but the addition of one-tenth or one-twelfth of its weight of copper to either metal increases its hardness to the requisite extent. in order to produce energetic union between any two bodies.ALLOYS. Lead. each metal being dissolved only to a limited extent iu the other. ties . case with silver and mercury. or sodium mercury in these cases true chemical combination appears : certainly to occur. 'to The metal tin. brittle 303 bis- : such is the case with the compound of arsenicum and Alloys of a brittle -with a malleable metal are also brittle. of this a familiar instance is afforded by the standard coin of the realm : neither gold nor silver. as last case melted In the it on standing. or. and water to a certain extent by ether. however. which occur crystallized together in the proportion of an atom of each (AgHg). as when lead is added to melted tin. 3. Now. is sufficiently hard to resist attrition to the degree required for the currency. the alloys be mixed. of zinc. Hence it appears that . in the same manner as ether may to a certain extent be dissolved by water. for instance. do. and zinc may most alloys either are mixtures of definite compounds. with an excess of one or other metal. and some have been found Such is the combined in definite proportions in the native state. In most cases these compounds of metals with each other are united by weak stances perties. of zinc. of bismuth. The solid metal dissolves quickly without any marked rise of temperature. like manner bismuth will dissolve 8' 14 per cent. the compound is sometimes brittle . it may be observed that if a solid metal be added to a melted metal. gold. or they are solutions of the definite alloy in the excess of one of the metals 2*4 per cent. certainly exist. for example. On forming alloys consisting of two metals only. of lead. that the sub- when separate should exhibit great dissimilarity in pro- sometimes been questioned whether alloys are true chemical compounds definite compounds of the metals with each other. when unalloyed. for it appears to be necessary. one of three different results may be i. so that when copper is added the two metals separate partially would appear that a perfect alloy is not formed. the hardness of metals is increased by alloying them . dissolves slowly. so just as these two solutions may be mixed with each other. either It has : to evolution of heat. Even when two malleable metals are united. splits under the hammer.

When silver. forming in their calls a solidified solution. The more important alloys will. alloys from each other is what Matthiessen solid condition The separation of the components of sometimes easily effected by simple For instance. and in a similar manner. nearly freed from escapes through the pores of the leather. is readily dissolved by dilute sulphuric acid. be best considered separately when the individual metals which enter into their composition are described. in its modifica: . (506) Condition in which the Metals occur in Nature. acid which is without action upon one of its components German silver. mechanical means will sometimes suffice to effect the separation. but in many alloy of two oxidizable metals is much more alloy of readily oxidized than either of its constituents. from the conalloy of arsenicum and platinum. solid form. the amalgam formed is dissolved by an excess of mercury this excess. for example. i part of lead and 3 parts of tin. and are much more interesting and important than the alloys. while the superfluous mercury. for example. employed. used in the preparation of Sometimes an alloy is completely soluble in an enamels (581). forming compounds which resemble the alloys more than any other class of combinations the most remarkable instances of carbides and silicides are furnished by iron. by exposing brass to a high temperature. however. and are easily severed. but the compounds formed by the metal with the nonmetallic elements. The ties which unite the components of an alloy are feeble. however. which. burns when instances. the An much more easily than its components.304- CONDITION IN WHICH THE METALS OCCUR IN NATURE. : mass through chamois leather . which is a combination of copper with zinc and heated to dull redness : nickel. leaving the copper behind . is amalgamated with mercury. a heat sufficiently long Even mere tinued will expel almost the whole of the arsenicum. may be almost entirely removed by squeezing the means. although the acid will not attack metallic copper . and becomes converted into a white ash. and. The chemical properties of an alloy are generally such as might have been anticipated from those of its components. are for the most part held together by attractions of a very powerful order. although platinum itself com- pletely resists its action. an alloy of platinum with ten or twelve times its weight of silver is entirely dissolved by nitric acid. Carbon and silicon combine in small proportion with some of the metals without appearing to destroy their metallic character. the amalgam is retained in the silver. the zinc is volatilized. in a chemical point of view.

are the mineralizing These compounds. and more rarely chlorine. and many other metals combine with oxygen is very remarkable . alumina. the majority of the metals being in such as oxygen and combination with other elements. however. and power of conducting cast iron. or chlorides. arsenides. 305 combined with variable quantities compounds of the metals with sulphur have a metallic lustre. ores of the highest importance and utility constitute but a comparatively small portion of the components of the earth's crust . These earths are oxides of metallic bodies. sulphides. X . and antimony with arsenicum.METALLIC ORES tions of steel DISTRIBUTION OF THE METALS. mercury. which converts the metals into bodies apparently earthy. whilst chlorine and its allied group of elements form compounds which possess all the lime. which. more completely destroyed by oxygen. The energy with which iron. constitute what are termed the ores of the metals. and copper. as in the familiar cases of and zincic oxide. and the abundance in which they occur. alumina. It is not so scattered in abundance over the face of the globe. platinum. for instance. and the action of chlorine upon these metals at ordinary temperatures stronger. silver. Many are found alloyed with each other . in the habit of separating from and of employing in the metallic Most of the state for the various requirements of civilized society. qualities of true salts. Many of the : electricity are still The metallic character is extremely impaired. malleability. forms native alloys with palladium silver and with with mercury. silver. zinc. as galena and pyrites. is still The more common metals are very combined form. the attraction of which for oxygen is so intense that they are rarely isolated from it except for scientific purposes in the laboraIn their oxidized form they are everywhere tory of the chemist. yet they are destitute of the other physical properties by which metals are recognized ductility. are the bodies most frequently associated with the metals . at other times arsenicum. whether oxides. forms. magnesia. with those metals which their ores man is upon the large scale. Next to silica in its various (507) Distribution of the Metals. is and of these elements. gold. II. an exceptional circumstance. They are then said to occur in the native slate. are the compounds of lime. although some of the rarely less met with in the unabundant are found naturally in the metallic condition. such as gold. from their powerful chemical attractions. and magnesia. The occurrence of metals or natural alloys in nature is. sulphur. the most abundant components of the rocks and superficial portions of the globe. agents.

Occasionally it happens that a thin bed of metallic ore forms a part of the regular succession of the strata in Staffordshire. the deepest excavation not being greater. in proportion to the diameter of the earth. the the gault.306 STRATIFICATION MINERAL VEINS. successive strata in the each other series. or trachyte (which have been injected from below. granite. as may be distinctly seen in railway cuttings. but are collected into thin seams throughout or beds. however. These fissures vary in thickness from a few centimetres to a metre or two they are often filled with masses of basalt. as in Cornwall they are then found in fissures which traverse the ordinary strata of the district. of but bear marks. more or having under- gone igneous fusion. as they are commonly termed many these beds occasionally retain their original horizontal direction. The stratified or like granite. upon what upon way clay is termed the green. which and basalt. to The same great variations in thickness in different is found to occur in a uniform but each bed position in the parts. sedimentary rocks rest upon others. London the rests the the chalk chalk. and then constitute what the miner terms dykes.sand. whilst the materials were in the molten state under the effects of subterranean heat). but usually they have been forced into an inclined another : position so as to form an angle with the surface. and assume a direction which.. porphyry. or in the granite and clay-slate. is but this deficiency in their relative proportion pensated by the dispersed at more than comthey are not mode of their distribution. varying in thickness from 5 to 2oom (2 to 8 inches) are found lying between the beds of coal. which form mineral veins. than the thickness of an ordinary sheet of writing paper to a globe of two feet in diameter. such as in the mountain limestone of Cumberland and Derbyshire. still approaches it more or less. thin bands or : seams of the ore termed clay iron-stone. fication. Man has hitherto penetrated but a very small depth into the body of the earth. Usually. for random. following regular order. the metalliferous masses occur in still older formations . or diffused in minute quantity uniformly the mass of the earth. show no appearance of stratiless evident. for instance. but in other cases they are filled with * : : . is stratum liable In this the uppermost being those of most recent formation. that a great part of the superficial portions of the globe consists of a succession of beds one above or layers strata. though it never becomes quite vertical. and so green-sand upon on. over many square miles of country. Geological observations have shown.

the most : important mines occur upon the junction of the granite with the clay-slate or killas. is sub- ject to great variations . and its dip* or inclination to the horizon. and * The terms dip and strike have been illustrated by the roofs of a row of houses running east and west . in mining language. but they are occasionally intersected more east nearly or less obliquely by other lodes. direction to seek for This sudden break in a vein fault. at others it attains a considerable size. to which the term of caunter (contrary) lodes. for example. clay. the metalliferous veins run and west. the principal or original veins being traversed by the others. The veins which occur in the same spar. or else with earthy These veins extend from the of different impurities descriptions. Such cross courses as these frequently occasion the miner much trouble and perplexity. and which have been occasioned by differences in chemical composition of the two contiguous rocks in Cornwall. and form mineral veins or lodes.DIRECTION OF MINERAL VEINS. nearly at right angles to each other. as might be expected. for example. been ascertained. The most productive veins usually occur near the junction of two dissimilar kinds of rock the metallic ores having probably accumulated there in consequence of slow voltaic actions which have been going on through countless ages. and is its displacement is. since the subterranean force necessary to produce them filled is A often attended with great displacement of the original strata. at others mingled with quartz. are not always metalliferous . termed a It very rare for a mineral vein to occur alone>. and is sometimes lost altogether for want of knowing in what it. at one time it dwindles to a mere thread. they often appear to have been occasioned by the action of a force emanating from below. the ridge pole shows the direction of the strike x2 . or cross courses. surface downwards. which. 307 metallic ores. where so large a proportion of the mineral wealth of Great Britain is accumulated. often to a depth greater than can be followed even in the deepest mines. The ore sometimes occurs nearly pure . The existence of a vein having (508) Mining Operations. fluorcrystallized minerals. however. and various minerals. These cross courses. In Cornwall. district usually and various run in two directions. usually several are found together. produced the fissures which were subsequently with quartz. has been given. after bending and splitting the original strata. valuable vein of ore is from this cause frequently interrupted. The thickness of the same vein.

and c. or strike having been determined. as they are termed. FIG. 332. raising the ore to the surface If the produce be such as to encourage him through the shaft. these cross cuts are at right angles to the levels. In order When to be able to remove the ore from other parts of the lode above and below the point at which the first level is made. and into this the gallery or level is driven. horizontally into it. v v the vein or lode. whilst the slope of the slates shows the dip to the north and to the south. or cross cuts. at the distance of about 100 yards or 90 metres from the first. the cross cuts. or level. are made.308 general direction PLAN AND SECTION OF A MINE. FIG. to meet the lode at different points . 331. a second shaft is sunk in the course of the lode. so as to facilitate the ventilation of the mine and the extraction of the ore. the miner commences by sinking a vertical pit or shaft. he has reached the lode. at intervals of ten fathoms (about 18 metres). . to proceed. c. TIG. both above and below the first level. engine shaft. the shaft is continued downwards. and other galleries. right and left. in such a manner that he calculates upon cutting through the lode at some 30 or 40 fathoms (from about 50 to 70 metres) below the surface. 333of the strata east and west. Fig- 331 shows a E s represents the vertical cross section of the lode at the Callington Mine. he drives a gallery.

a level is driven east cannot be shown in this view but whenever a cross cut meets the and west. but their direction and position varies with that of the inclination and direction of the lode. and the hole is closed by ramming in clay or friable rock. supposing the figures to refer to the 332 the lode. under the portion of rock which is to be raised the powder is then introduced. they are shown at u. galleries and levels are so constructed that the water shall How from them into the principal shaft of the mine. or lowest part of this shaft. in which the direction of these galleries is exhibited levels represents a plan of the mine. or nearly 57 grammes. The shaded the portions of the lode which have been already worked away. Where side upon the A. The cross cuts cannot be shown in fig. u. 333. it will be seen. but when the workings extend below this point it becomes necessary to pump more or less constantly. L. the mine. down . somewhat obliquely. and through this the waters of the upper part of the mine readily escape . with the pickaxe and wedges. the object of which is to prevent the rubbish from failing in and overwhelming the parts in this figure indicate men while engaged in their work. usually about two ounces. copper wire runs from the . but after judicious clearing. Fig. The galleries in the mine are supported by strong timbering. E s represents the engine shaft. whilst the remainder is raised to the surface for the purpose of washing the ore. A surface and when the ramming or tamping is finished. The levels . so that by pumping from the sump. gunpowder properly The quantities of powder applied facilitates the progress greatly. the whole mine is freed from water. or winzes. it shown in : extremity of the plan. and are needed to facilitate the extraction of the ore from different parts of the lode. or parallel to each other.more nearly vertical at the right than at the left . being much . 309 lode. used for blasting in the mines are small. is carried from the shaft to the lowest accessible point of the surface . 332 shows the arrangement of the levels in the same mine . The greater part of the water is lifted The only to the adit level. and for this purpose powerful steam-engines are required. L. and L. w. 332. in the direction of the lode itself.MINING OPERATIONS. does not preserve the same dip at all points. is situated of a hill. a second smaller shaft. the wire is withdrawn. as the Cornish miners term them . as very often happens. fig. A. This is explained by fig. The different levels ate not immediately over. the different levels. an adit level. different points by short cuts. and the train is fired by means to the charge. these levels communicate at the depths of which in fathoms are indicated by the numbers attached to them . One tend with of the principal difficulties which the miner has to conis the continual oozing of water into the mine in all directions. The process of blasting consists in boring a hole to the depth of 18 inches or 2 feet (45 or 60 centimetres). or watercourse. shown at 332. Much of the excavation is done by hand. and its place supplied with a hollow rush charged with powder. in various parts.

of ore. MECHANICAL TREATMENT OF THE ORES. The same Baric sulphate has . they are held for a shorter time in suspension. for when they are accompanied by a loose friable clay. as the Cornish miners term them. The following is an outline of the mechanical operations pursued in dressing the ores of lead and tin . whilst that of ferrous carbonate and hydrated ferric oxide varies from 3'8 to 4/0. are set aside. but also by its market value an ore of tin. and are ready for smelting without further preparation . The ores of zinc and of iron are occasionally subjected to the which the metal itself is : operation of washing. The extraction of (509) Mechanical Treatment of the Ores. and that of calamine is about 4*2.310 of a fusee. particles of these materials of equal size expose a smaller surface in proportion to their weight to the action of water than the clay. be gun-cotton may advantageously The ore that is detached is raised to the surface of the mine in large wrought-iron buckets. principles apply to the more elaborate processes of Galena has a washing adopted with the ores of lead and tin. metals from their ores is effected by two classes of operations . and the same method is to a certain extent ores adopted with the may therefore be separated. tinstone of about 7. those of the first class are mechanical . 3'! . a density of 4-6. by : influenced not only The mechanical treatment is procured. but the bulk of the ore is broken . and are therefore carried by it to a smaller distance. of copper or of lead. and when agitated with water they subside more rapidly . by the nature and composition of the ore. or kibbles. consequently means. will be worth a more elaborate treatment than an ore of iron or of zinc. and in hard rocks substituted for gunpowder. if a lead or copper portions. the earthy portions specific gravity of 7-6 considerable extent. which are capable of copper wire and pithed reed filled containing about 3 cwt. is first sorted by hand : surface. the clay admits of being readily diffused in a finely divided state through the water. by their means the earthy parts contained in the matrix or vein-stone are to a certain extent separated the operations of the second class are chemical. or prills. A safety fusee is now commonly substituted for the with powder. and if subjected to the action of a current of water. from the higher price which the metal bears. to a ores of lead and tin copper : The ore having been brought to the the purest ore. fluor-spar of When and quartz of 2*65. from the by merely washing with water. reduced to particles tolerably uniform in size. and is easily removed by its The specific gravity of clay is not much more than 2*0.

The crushed ore now undergoes a of which is series of washings.DRESSING AND WASHING THE ORES. or schlich. from its friable character. each beam weighing about i\ cwt. By this means. the lower ends of which are shod with iron. taking care always to keep it beneath the surface of the water. which consists of a pair of horizontal cylinders placed parallel to each other at a little distance apart the cylinders may be either grooved or plain. the crushing mill. accumulates in the second. of ore. operation ofjigging. so that it slides down under them. is easily reduced to small fragments most of the galena. The ore is supplied to them : by a hopper from above. If it be a lead ore which is underlayers the going treatment. the crushed ore is sifted through coarse sieves the coarser parts are set aside for the stampers. These are placed in a wooden frame. alternately raising and lowering the sieve^ to which he also gives an alternate rotatory motion. The stamping mill consists of five or six upright wooden beams. which is turned by water or steam power. is deposited whilst the more finely divided portion. and passes at once to the stampers. . This consists in plunging the ore contained in a sieve into a pit. the object to separate the impurities from the valuable part of this is a the ore. in the one nearest the mill the purer and heavier part of the ore. when reduced to a sufficient of fineness. or crop. whilst the richer part is set aside for smelting. technically termed slime. galena. The ore is placed on an inclined plane behind the stampers. whilst what is left upon the sieve consists chiefly of the less friable fluorThis residue is mixed with the inferior qualities spar and quartz. are washed out through a grating in front. and the best The rougher portions go to pieces are again picked out by hand. and are alternately lifted up and allowed to fall back upon the ore by the action of arms projecting from a horizontal axle. passes : through the sieve and subsides to the bottom of the pit. wooden trough. After passing through the mill. the contents of the sieve are separated into of different quality. : Tin ore . 311 by hammers into lumps of about the size of a walnut. degree the action of a current of water which is constantly flowing by the mill the washed ore is carried into a channel in through which two pits are formed . and the finer portion is subjected to the . The crop is first subjected to washing in the buddle . through which water is constantly flowing the : workman keeps the ore in continual agitation. and is transferred to the stamping mill. and is crushed. The crushed particles. is usually disseminated through a compact hard matrix. therefore.

and is suspended is by chains from supports at the four corners . A is rough estimate of the value of any sample of dressed ore obtained by the process called vanning : small quantity of the ore is placed on a shovel. and ore added by a workman. the agitation struck smartly upon the side several times.312 fig. but they are all stopped the kieve is contents are allowed to the same in principle. This slime still retains some portion of ore is . nearly 2'5 metres long. 3 wide. the bed alter- . The water employed in the various washings is not allowed at once to run to waste. somewhat more inclined than the body of the buddle. ore to be washed is placed in small quantities at a time upon a board. which acts in a manner similar to the buddle. in which the slime and mud which have been carried away in the different operations may subside. the water carries it forward the it is : portions subside near the head of the trough. Various modifications of the washing process are resorted to. possible. The eye then at a glance roughly estimates the A quantity of each. it the bed of which is also inclined. and in order to recover this as far as again subjected to the action of a fine stream of water. above this are iron pyrites and blende . and o' '6 deep. and the lighter richer ones " the are carried further down. or tub. by giving it a dexterous lateral shake. or about 8 feet 334. THE BUDDLE WASHING OPERATIONS. but moveable. B. the upper half of the sediment is again passed through the buddle. long. a. a small stream of water enters. and agitated gently with a peculiar circular movement in water. who keeps the contents of the kieve in continual agitation by turning the paddle or agitator. at the bottom . and its subside . tributing board. and at the top are the fluor-spar and quartz. in the ground. either upon an inclined table. then. and 2 deep. the different constituents arrange themselves according to their density the galena. is is seen projecting at the When the vessel is nearly full. on which a number of small pieces of wood are fastened to break the stream. with one end somewhat elevated. and The spread out into a thin layer . 334. shown at c. and is reduced to a uniform thin sheet m by means of a dis- FIG. which is filled with water. The heads" are then tossed in Jcieve. i metre wide. fixed At the upper end. or it is washed upon a swinging table. or the tin-stone. the handle of which top. but is made to pass through a long shallow channel.

(510) Roasting. In roasting the ore in this furnace. which at proper intervals is allowed to fall upon the bed. d. or driven down upon the ore to be roasted. and then pass off through the flue^: when sufficiently roasted. H. or oxidation. and does not come into contact with the ore. are. mode of effecting it varies. a furnace however. care must be taken to prevent the heat from rising so high as to melt the mineral. of particular construc- termed a reverberatory is employed. one dependent on the addition. from which it is separated by the bridge. which is stirred at intervals to expose fresh surfaces to the action of the current of heated air of sulphurous anhydride. the In the most tion. the other on the removal of oxygen. reverberated. : from the burning mass. b the heated -. H. is first resorted to. the ore is allowed to fall gases. as they arise into the arched recess. common method. the sulphur burns off in the shape which escapes into the atmosphere. : . the heavier particles of the ore. d. which are kept closed by sliding plates till the roasting is complete. volatile ingredients. are charged with the ore. Fig. or Oxidation. whilst the lighter impurities are washed away. the process of In principle it is very roasting. are by this jarring movement of the table carried back to the upper part of it. divisible into The chemical operations are two main branches. from which the hoppers. If the mineral contain such as sulphur or arsenicum. c c the fuel is consumed upon a distinct hearth. 313 nately thrust forward 2 or 3 inches (about 6 or 8 centimetres) by the revolution of a cam. E. 335 shows a section of a reverberatory furnace. spread upon a board which overhangs the upper part of this table. from the construction of the arched roof. owing to the superior momentum which their density gives them. such as is employed for roasting copper ores. A.BOASTING. beneath the bed of the furnace through the openings. t is the platform. . OR OXIDATION. and is carried forward by a gentle stream of water . and is then allowed to fall back The ore is against solid wooden bearings with a sudden jar. in different cases. simple .wheel.

The furnaces employed in this operation are often of great size. whether natural or artificial. sinks. as is the case with zinc. OR SMELTING. whilst sulphurous anhydride escapes. certain fluxes. it may happen that the sulphide of the more oxidizable metal is completely converted into a metallic oxide. and subsequently purified. these melt and form a kind of glass. in roasting copper pyrites (the double sulphide of copper and iron). and vary in form with the nature of the metal in them the ore is heated intensely in contact with carbon. from its superior density. whilst the arsenicum forms latter arsenious anhydride . as it is : . and other earthy impurities of the ore. whence it In metallurgic is removed at intervals. and is collected on the sides of the chimney. or substances capable of forming fusible compounds with the earthy matters. while the melted glass or slag. it is not practicable to limit the degree of oxidation in this manner during the roasting the metal itself : passes into the state of oxide. it is copper is careful roastings (865). simultaneously with the elimination of the sulphur as sulphurous anhydride (685) . which removes the oxygen as carbonic oxide and carbonic It becomes necessary at this stage to get rid of the anhydride. which have not been comremoved pletely owing to the imperfection of the mechanical operations.314 REDUCTION. Where the metal possesses a high degree of oxidability. is applicable to most metallic oxides. and is thus completely defended from contact with the air the metal is drawn off at suitable intervals of time from the bottom of the furnace. most of the becomes condensed. For example. and that the sulphide of the less oxidizable metal is reduced to the metallic state. are added at the same time as the carbon. the iron is wholly converted into oxide. and which often form a large proportion of the ore. by a series of In the case of plumbic sulphide. also the practice so to regulate the supply of air in the furnace that the sulphur is wholly expelled in the oxidized condition. through which the reduced metal. : In order to effect this. The second chemical process (511) Reduction. whilst the greater part of the lead is extracted in the form of metal during a single roasting in the reverberatory (885). where the metal possesses but a moderate degree of oxidability. The object in this case is to remove the oxygen. or in chambers constructed for the purpose. metals of different of where degrees of sulphides operations oxidability are present. that of reduction. for the extraction of the metals. by heating the mineral with some substance which has a stronger attraction for oxygen than the metal itself possesses. whilst the extracted at once in the metallic state. or Smelting.

and the second and third volumes of the same work contain many excellent descriptions of processes in which metallic chemistry is applied to the purposes of industry and commerce. alkalies 3. For details upon metallurgic processes. Other modes of separating individual metals are employed. it is often necessary on this order. or the fourth volume of Dumas' valuable work. being greater than that of potassium. for example. for the : Much judgment purpose of increasing the fluidity of the slag. these are five in number Rubidium. 315 termed runs off at an aperture left in the side for the purpose. and bromine than iodine. that of potassium greater than that of sodium. Percy's Metallurgy. viz. . Potassium Lithium Caesium close 2.CLASSIFICATION OF THE METALS. sodium. the basic power of rubidium. into eight groups (page 13). which will be alluded to in their respective places. Sodium 4. Traite de Chimie appliquee aux Arts. With the basylous or electropositive elements.. and in deciding upon the proper proportion to be added frequently this object is economically effected by a j udicious mixture of different ores of the same : metal. I. The various modifications of these processes will be described in connexion with the different metals which require them. for example. being more active than bromine. The metals present a analogy in properties. . in the ordinary processes of analysis . may be consulted . chlo- rine. 1 The metals of the . Limestone is in some cases added to the ore with the view of fluor-spar or aiding the fusion of the siliceous impurities in other instances some other readily fusible material is added. it has been remarked that the electronegative character of those belonging to the same group is most strongly marked in those which have the lowest combining number . each of which aids the other by supplying some compound which was wanted to render the slag sufficiently fusible. The metals maybe divided (512) Classification of the Metals. Phillips's Metallurgy is a smaller and more compendious treatise on this subject. regard being principally had in this arrangement to the convenience of indicating the method of testing for them. is required in the selection of the flux. and that of sodium being superior to the basic power of lithium. account to depart from the strictly natural In treating of the groups of the non-metallic and electronegative elements. the reverse generally holds good.

* = weight of rubidium (85'4) is intermediate between that of caesium similar and potassium -1 3 3 +3 H = 86. formed by the metals of the alkaline The corresponding group are isomorphous only when they contain an equal numWith these metals ber of molecules of water of crystallization. the compound thus obtained cannot be rendered In these metals the basylous quality. and are isomorphous with them. will be described the salts of ammonium . The metals bonate. A salts remark is applicable to the intermediate members of some of the other groups. when exposed to the air. anhydrous by heat alone. displace They i atom of hydrogen from the acids. When the oxides have once combined with water. and possess such a powerful attraction for oxygen that they readily decompose water at the ordinary temperature with rapid disengagement of hydrogen they each form at least two oxides. both of which are freely soluble in water.. II.. The metals of the Barium | alkaline earths are three in 2. a normal carand an acid carbonate commonly known as the bicarbonate. and volatile at high temperatures they become tarnished alkalies are distinguished : The metals of the are monad : immediately that they are exposed to the air. from the Lithium. They decompose water at all . viz. or their capacity for saturating the acids. but only one of these. : that with the smallest proportion of oxygen. they present the closest analogy with the corresponding potassium compounds. i. easily fusible. . These metals are dyad. . is intermediate in properties between potassium and lithium. furnishes the link between this group connecting and the one which follows it. for 3 9 a+ 7 23. sparing solubility of its carbonate.316 which CLASSIFICATION OF THE METALS. yielding soluble hydrates of their aqueous solutions are power- fully caustic and alkaline. are soluble. : combine with water with great the general formula M'HO . avidity. With chlorine they form but a single chloride. is developed to the The hydrated alkalies. also. i atom usually displacing 2 atoms of hydrogen from its combinations. of the alkalies combine with sulphur in several proportions all of these compounds. characters by the following or and therefore univalent. absorb carbonic acid rapidly each alkali forms with this acid two salts. Strontium | 3. number Calcium. They are soft. forms salts the These basic oxides general formula of this basic oxide is M' 2 O. highest degree. possesses a combining number which is the arithmetic In like manner the atomic mean of the two. either in the solid form or in solution.

basylous. The hydrates of the formula M"H 3 O 2 are soluble to a certain extent in water. .. the * hydrates. several sulphides which are soluble in water. Metals of the earths : eight in number viz.CLASSIFICATION OF THE METALS. and are capable of forming salts by their action on acids . The corresponding salts of these metals are in many cases isomorphous. 317 temperatures with great rapidity. are decomposed by ignition. with the exception of that of barium. they each form two oxides which combine Avith water forming hydrates. the protosulphides being less so than those which contain Their carbonates are insoluble in higher proportions of sulphur. Aluminium Glucinum Yttrium 3. They form insoluble phosphates and oxalates. They form pure water. i. III. 2. which assumes The metals of this group are also powerfully the form of M"C1 2 . They each furnish but one chloride. but are soluble to a small extent in water charged with carbonic acid.

not as sesquisulphide.318 tures. and become converted into oxides. Corresponding salts furnished by the protoxides of this group are isomorphous. in a current of aqueous vapour decompose it. chloride.Fe 2 O 3 Several of the metals of this group viz. The chromic salts. Chromium and manganese also exhibit an isomor- . which are very soluble in water. reacts with acids and forms cor- responding they also form oxides of the formula MO. the sparing the solubility of its sulsolubility of its oxide and its sulphide. when transmitted through the solutions of these metals acidulated with sulphuric acid. . as well as but a single class of salts with they all the radicles of the acids. Nickel Chromium Manganese. six in number : Cobalt Iron 2. These protoxides. and furnish powerful metallic acids. whilst hydrogen escapes they also evolve or in in hydrochloric when dissolved dilute sulphuric hydrogen : this class are powerful formula M"O. it stands in closer relation to and several other particulars. and sulphide. and each of these metals forms but a single oxide. phate. and the salts formed by the sesquioxides with the same acid are likewise isomorphous with each other. iron. when heated to dull redness are hexad in a third. V.M O 3 corresponding with the magnetic oxide of iron. burn with flame when heated in air to a sufficiently high temperature. 5. chromium. Magnesium. are dissolved more or less freely by ammonia. isomorphism of its salts with those of zinc. except in the case of cobalt and nickel. and cadmium are dyads . the CLASSIFICATION OF THE METALS. Hydrated sulphides of these metals are produced by the addition of a solution of sulphide of potassium or ammonium is to a solution of their salts . Metals more or 1.. less analogous to iron 4. with the exception acid. does not precipitate them. however. zinc. are precipitated as hydrated chromic sesquioxide. manganese form trioxides or even higher oxides. which. the precipitate so occasioned insoluble in excess of the alkaline sulphide. 6. Uranium They all act in combination as dyads in one series of their com- pounds. Sulphuretted hydrogen gas. or as tetrad or pseudo-triad in another series. 3. The protoxides of the metals of they bases : have the general M . and salts : . zinc and cadmium. FeO. of the metals of this group forms a sesquioxide. and some These metals. of that of uranium. usually of the form water readily when heated. They yield // H 2 O 2 which part with their hydrates. Each especially if ammonic chloride be present in the solution.

4. form a volatile and pentachloride. 319 phous relation to the sulphur group. and vanadium. is the fourth a dyad . whilst niobium. which is more allied in character to phosphorus than is a powerful base . but often hexads. since it only produces one oxide. Niobium Tantalum n. and tungsten. and tantalum. the next two are sometimes tetrads. Stannous oxide nearly wanting The metals included in this group decompose water when its vapour is passed over them at a red heat (with the exception of arsenicum. 6. according to the recent researches of Roscoe. as in pentachloride of antimony. with the halogens is exhibited in the isomorphism of the permanganates with the corresponding perchlorates and periodates. or equivalent to six atoms of hydrogen . and manganates have the same crysIn the case of manganese a singular connexion talline form. but they do not evolve hydrogen when treated to the metals) with dilute sulphuric acid. the three which follow are pentad . of these there are twelve.. have likewise strong analogies with Molybdenum 2 atoms of the metal each other. 7. Antimony 12. furnishing a silicon : volatile tetra-chloride and a dioxide . 10. which does not exhibit the close analogy with zirconia that it was formerly supposed to possess. but basic qualities are in the oxides of the other metals in this group. A nium. inasmuch as the corresponding sulphates. 8. pentad or quinquivalent. they exhibit considerable analogy with zirconium is similarly related to silicon. Metals which yield acids when their higher oxides are combined with water . are occasionally. : * This metal would be more properly placed in another group. although usually tetrad or quadrivalent . Molybdenum Tungsten 9.CLASSIFICATION OF THE METALS. each yields a liquid volatile tetrachloride. 3. . Tin Titanium Zirconium 5. 2. VI. as follows : viz. rutile close parallelism in properties exists between tin corresponding compounds such as tinstone and tita- (SnO 2 ) and (TiO 2 ) being isomorphous . chromates. 1. Vanadium Arsenicum Bismuth. whilst the last three. though usually triads.* Thorinum first The certain three of these metals are bivalent or dyads under circumstances. owing to their want of basylous power. according to Marignac. yield definite compounds with fluorine. all furnish an anhydride with and 5 atoms of oxygen. as well as in their powerful attraction for fluorine. ThO. and in this particular.

VII. they are precipitated from acid solutions by sulphuretted hydrogen. | Lead 3. Rhodium 9. They have but a feeble attraction for oxygen. such as potash. but in the case of thallium the Copper forms salts which are precipitation is incomplete. Mercury Silver 4. all form powerfully basic oxides. found as minerals in the form of sulphides. Copper 2. occasionally triad. in cuprous chloride. They are not related to each other . as well as to cobalt and nickel . Many are.. but in chemical properties it is more allied to mercury and silver. The persulphides of with the exception of arsenic acid. decompose water with evolution of hydrogen in the presence of a powerful The metallic acids formed by these metals base. and in the compounds which it forms with carbonic acid. Gold 6. Copper and lead exhibit a considerable tendency to the formation of basic salts : they are not dissolved either by dilute sulphuric or by . but the other metals of this group usually occur in the . Ruthenium 8. owing to this tendency to form acids. Platinum Palladium 7. and lead in some of its compounds is isomorphous with those of the alkaline earths.. The next group contains four metals i. Indium. copper as is occa- sionally pseudo-monad. and in many cases form crystallizable compounds with them. by any strong chemical resem- blances copper and lead exert no decomposing action upon water. jority of cases it is dyad in function like lead. all of them Mercury and silver are often yield more than one series of salts. 5. nearly insoluble in water. but in the ma- VIII. the oxides of the first five being decomposed into oxygen and the metal by simply heating them to a temperature below visible redness. of which there are nine 1. Osmium Iridium. These metals are unable to decompose water at any temperature. and their sulphides do not combine with the sulphides of the alkali-metals. 3. Thallium | 4. even at a full red heat . this group of metals are soluble in the sul- phides of the alkali-metals. viz.320 CLASSIFICATION OF THE METALS. The last group consists of the noble metals. : viz. 2.. and in many cases simple exposure to a strong light produces a similar decomposition . hydrochloric acid isomorphous with those derived from the protoxides of the metals in the iron group. displays a close resemblance to magnesium and zinc. whilst in some organo-metallic compounds it has tetrad powers. Thallium is usually monad. of them.

Their attraction for sulphur and for chlorine is much stronger than for oxygen. called Dichlorides . A gas is evolved. type of the M^Cl^. iron. ~i . (513) five only The first two arsenicum. GENERAL. . Chlorides of the type. MCI. : rnvrn Chlorides of the type 'M'^ ]^ C1-M-M-C1 . such as zinc and under peculiar circumstances to undergo partial potassium. They may be considered as derived from one or more molecules of hydrochloric acid. The simplest bodies produced by the combination of metals with the non-metallic elements are those obtained by the union of the metallic elements with the monad (514) negative element chlorine. Hg2 Cl2 . Chlorides KC1.. : HYDRIDES. A few metals. is supplied by a metal. appear volatilization along with the hydrogen at the moment that this arsenicum is also said to exist. there are metals which form combinations with hydrogen viz. the chlorides of the noble metals have a form double chlorides with the chlorides of Silver exhibits considerable analogy with lead it is poweris somewhat allied to fully basylous . and some three or even four to : strong tendency the metals of the alkalies. antimony. M'"C1 3 . of these compounds are gaseous. As far as is at present known. frequently called Subchlorides as Calomel (Mercurous chloride) 2nd. and are decomposed by a solid hydride of red heat into the metal and hydrogen. several of them being frequently associated together. All of them form two chlorides. o Y . as . in which the place of the hydrogen The ist. such as Calcic chloride 4th. CHLORIDES. principal groups of chlorides are the following. called Trichlorides. such Potassic chloride 3rd. such as Antimonious chloride II. : II. palladium copper. 321 native state. Chlorides of the type CaCl 2 .HYDRIDES CHLORIDES. SbCL. PROPERTIES OF THE COMPOUNDS OF THE METALS WITH THE NON-METALLIC ELEMENTS. copper. and potassium. called Monochlorides .

They are conductors of the voltaic current when The chlorides M"C1 2 or Dichlorides.. such as Molyhdic chloride . SbCl 5 . 3. they may all be melted without undergoing decomposition. Aurous and argentic chlorides are insoluble in water . The chlohighly basylous metals.. Platinic chloride 7th. when anhydrous... of the type called Hexachlorides . and those of silver and thallium. such as A1 2 C16 . Monochlorides. .. They present characters which are similar to those of the foregoing group.. except those of copper. called Tetrachlorides .. but when heated in vessels from which air is excluded. to which. cuprous chloride and calomel. all that are of interest they are insoluble in water. may slowly readily decomposition. 1. platinum. a heat but the other chlorides fuse below redness.. including the chlorides of the alkalimetals. as well as aurous chloride. having been usually described as : protochlorides Amongst the rides of the less this group are the chlorides of many such as barium and calcium... The chlorides 'M' 2 C1 2 or Subchlorides. M iv . Chlorides of the type such as .. MoCl6 . and palladium. Chlorides .. are few in number^ and of small importance. com-/ prising 2. are All strongly opposed to these basylous chlorides in properties.. fused.322 VARIETIES OF METALLIC CHLORIDES. are solid at common temperatures .. Chlorides of the type MC1 .. Cupric chloride loses half its chlorine and becomes converted into cuprous . . Chlorides .. form an important group. 3 | 'M"' 2 C1 6 5 th.. decomposed by and volatilized without when even be heated. The chlorides MCI. such as Antimonic chloride 8th. The compounds con- tained in this group are formed by the union of i atom of a metallic dyad with 2 atoms of chlorine. Aurous chloride is thallous chloride is but sparingly soluble. indeed. of the type called Pentachlorides . Cl 4 . the chlorides of this group. they bear the closest resemblance they were till quite recently considered to form part of it. frequently termed Sesquichlorides Aluminic chloride 6th. members of electropositive dyads. or Protochlorides. PtCl 4 . M C1 V 5. like that of mercury. MTlg.

: hence their formulae should be doubled... 'Each of these compounds contains i atom of the metallic element united with 3 atoms of chlorine. perature without chlorides of is = 2 vols. . . whilst platinous chloride.. such as those of zino and mermetal... .. and the result is remarkable. 5. is quite insoluble.. Antimonious chloride Bismuth trichloride . ShCl a BiCI s AuCl s . . of which the most important are aluminic chloride.. + oxychlorides 2 3 + 'M'" 2 C1 6 formerly called Sesquichlorides. as decomposition ... . but now considered as M tetra chlorides viz .. Auric chloride ... and furnish soft and sectile masses. . constitute a remarkable group... .. elevation of temperature... 1V C1 4 . Auric chloride is decomposed into aurous chloride by a moderate the other heat.. and a considerable portion of oxide of the metal is formed. since if also = 2 vols. .. the other members of the group are freely soluble in water.. A1 2C1 6 ment. Several cury. . hydrochloric acid escapes. .. . comprises or terchlorides.... ferric chloride.. and 323 . T2 . . AsCl3 + 3 H 2 . is may be distilled without decomposition.. . The next group M'"C1 3 . O = 3HC1+ H 3 AsO 3 [AsCl3 + 3OH 2 = 3 HCl + and bismuth furnish = H O SbOCl SbCl sHCl. PtCl 2 decomposed into free chlorine...... The chlorides. Next we have a group of chlorides... and palladious chloride a residue of the pure are of the chlorides remain semi-transparent after fusion. . of which the following are the most important : Arsenious chloride' ... in one of its modifications. chloride. . but sparingly soluble those known as trichlorides 4. the vapour density of the aluminium and iron has been ascertained by experi- HH follows : Aluminic chloride Ferric chloride ... They are decomposed by the addition of water . .. somewhat horny in aspect. arsenious chloride into arsenious acid and hydrochloric acid. and at a higher temperature loses all its chlorine three chlorides may be volatilized unchanged by a moderate ..... . described by chemists as the bichlorides.. Plumbic chloride platinous chloride...VARIETIES OF METALLIC CHLORIDES.. . and is volatile at a high tem- As(OH) 3 ] whilst the chlorides of antimony . . formerly 6.. Al 2Cl a FeiA> I * \lf P Chromic chloride (judging by analogy) The aqueous solutions of these chlorides undergo partial decomposition when evaporated.. . Many of these chlorides... and chromic chloride..

SiCl 4 Tungstous cliloride . titanium. 8.. Fed. Parallel in properties with these volatile pentachlorides are the chlorides of the type M vi Cl a. does not take place. and may be distilled unaltered. and are analogous to them in composition . the corresponding chlorides and oxides compound. .. but if a metallic chloride be heated in a current of oxygen or of atmothe chlorine is and an oxide of the metal air. . .. BuCl 4 The first three . and gold are the following : groups. WCl g .... . .. With the exception of the tetrachlorides of platinum. WC1 4 PtCl 4 Titanic chloride .. Molybdic chloride ..compounds are liquid at ordinary temperatures. the hexachlorides of two other acidifiable metals Perchloride of : molybdenum tungsten. SnO Sn0 2 AuCl Au 2 AuCL. which corresponds with pentachloride of phosphorus.. PdCl 4 IrCl 4 .. emit dense fumes when exposed to the air... The tetrachlorides of tin. palladium. .. 2 Fe Cl : FeO Fe.. the chlorides generally correspond in number with the oxides.. The chlorides MC1 5 or Pentachlorides are represented by pentachloride of antimony. 7.. These chlorides are volatile and are decomposed by water.. . . . but yielding hydrated metantimonic acid.. and the noble metals... . two atoms of chlorine occupying the position of one atom of oxygen in the For instance. . . and may be sublimed unaltered in vessels from which air is excluded. is The only instances in which this decomposition produced. the remaining compounds are fusible volatile solids.. if the quantity of water be large. At ordinary temperatures the action of chlorine upon the metals is generally stronger than that of oxygen .. PROPERTIES OF METALLIC CHLORIDES.324 Silicic chloride ... and ruthenium. of iron.. . MoCl4 Paithenic chloride . AuO. occur in the case of the chlorides of the noble metals and in those belonging to the first and second In the case of the metals which have but slight attraction for oxygen. SnCl 2 Sn01 4 . with separation of all its chlorine as hydrochloric acid.. tin. which by a high temperature are decomposed into metal and free chlorine. .. .O... iridium. . form crystallizable double salts with the chlorides of the alkali-metals. TiCl 4 Platinic chloride Stannic chloride Zirconic chloride SnCl4 ZrCl 4 Palladio chloride Iridic chloride . MoCl g .. spheric expelled. .. is decomposed by water... Tt is fujning and volatile. forming an oxychloride if the proportion of water is small..

with charcoal. . we have a double chloride of platinum and potassium (2KCl. and has been regarded by some chemists as a soluble oxychloride. frequent occurrence that a chloride of one of the alkali metals combines with a chloride of one of those metals which have a feebler attraction for oxygen. in the case of the compounds of iron. oxygen is expelled and a.Fe 2 Cl 6 + 6KHO =6KC1 + Fe 2 H 6 O 6 . 4. Indeed.. however. : . In cases where the except in the course of an analysis. glucinum.PtClJ and a double chloride of gold and sodium (NaCl. the compound produced when the oxide is soluble in water is remarkable for its bleaching properties. Fe 2 Cl 6 + 3BaH 2 O 3 = ^BaCl 2 + Fe 2 H 6 O 6 .PREPARATION OF METALLIC CHLORIDES. In many cases chlorine unites with the oxides of the metals.2H 2 O). and forms a powerful base. is seldom employed chloride. Sometimes the chloride of a metal combines with its oxide and forms an insoluble oxychloride. formed by heating the metal in a current of dry chlorine in this way the perchlorides of antimony and iron are prepared. example. chloride of the metal remains but this process is never adopted for procuring the chlorides. If the basic oxides be heated to redness in a current of dry chlorine.HgCl 2 ). is volatile. i. Many of the metallic chlorides may be Preparation. and the same thing holds true in very many cases with the corresponding bromides and iodides. chloride the oxide of the metal aluminium. or titanium. of oxides frequently exceeds that of the chlorides. the number. 325 Yet it is easy to prepare the oxides by heating the hydrates obtained from solutions of the chlorides by precipitation for . forming oxy chlorides . and a current of dry chlorine passed over the mixture the charcoal removes the oxygen in the form of carbonic oxide. and the chlorine. and the oxides of which Thus partake rather of the character of acids than of bases. metallic metal combine with the gas producing chloride of sulphur and a This process. both the sulphur and the 3. as is the case with the It is a still more oxychloride of mercury (3HgO. like that of may be mixed .AuCl 3 . the higher chlorides of the noble metals generally form double salts of this nature . owing to the strong attraction of chlorine for sulphur . 2. The sulphides are generally more readily decomposed by a current of gaseous chlorine than the oxides. the following reactions may be observed : FeCl 2 + 2 KHO = 2KC1 +FeH O. When the metal exhibits a strong attraction for oxygen.

and concentrating the solution by evaporation until it crystallizes. Sometimes this process is employed for the purpose of isolating those .326 DECOMPOSITIONS OF METALLIC CHLORIDES. In this way sodium is employed to decompose aluminic or magfor the purpose of procuring the aluminium or an uncombined form . particularly in the class to which the earths belong . such as argentic. 7. 5. Iron. in hydrochloric acid. and in a similar mannei potassium is employed to obtain uranium from uranous chloride. decomposing any excess of nitric acid by evaporation to dryness In and and with an excess of hydrochloric acid . fails in many cases. forms a chloride which volatilizes and In becomes condensed in the cool part of the apparatus. its it is applicable. MgCl 2 + 2HCl. 6. The chlorides of cobalt. for example. the attraction of hydrogen for oxygen and for sulphur greatly facilitating the progress of the decomposition. for be obtained in fine cubic crystals by reducing ferrous chloride in this manner. such as those of gold H O = MgO + platinum. This process. may process is occasionally resorted to as a means certain metals in a state of purity. however. The insoluble chlorides. to maintain a current of hydrogen of sufficient rapidity to carry . It is necessary. uniting with the metal. nesic chloride magnesium in or a soluble chloride. may be formed by the addition of hydrochloric acid. a pure chloride of the metal may be obtained on re-dissolving the residue in water. are reduced when heated in a current of hydrogen. however. 2 cases chlorides of the metals. and calcium may be thus obtained. effected. and mer9curous chloride. many cases the chloride may be obtained by transmitting dry hydrochloric acid gas over the oxide or the sulphide of the metal heated to low redness.^ All the metallic chlorides. consists in dissolving carbonate. Stannic 8. excepting those of the metals of the alkalies and earths. plumbic. metals whose oxides resist decomposition by the usual means. An easier method. are obtained by dissolving the metal in aqua regia. chlorides of magnesium and aluminium. if it be attempted to render the chloride anhydrous. in Cases where chlorides are oxide. nickel. lose their chlorine as hydrochloric acid solutions when their some are evaporated. In many cases the reduction is easily and this of procuring example. of the chlorides of the less electro-positive metals are decomposed when heated with the more basylous metals. or its when the hydrated the metal itself. to a solution of the salts of these metals. Decompositions. Many chloride (SnClJ may thus be obtained by heating metallic tin with an excess of corrosive sublimate and trichlorides of antimony and bismuth can be prepared in a similar manner. particularly required.

by which the decomposition of the bromate is more easily effected. however. The bromide is removed from the excess of charcoal by solution in water. present.METALLIC BROMIDES. when heated with sul(Kuuheim). in the absence of chlorine. almost always estimated in the form of argentic chloride The (AgCl). by a pure solution of potash. except in boiling a given weight of the compound with the case of argentic chloride. phuric acid and black oxide of manganese. either in a dry state or in the presence of water.. it and. 327 away the hydrochloric acid from the reduced metal. and may be arranged in corresponding. The other bromides may be : procured by acting upon the inetals with bromine. and acidulated with nitric acid. by argentic which occasions a white precipitate of argentic bromide. and gently warmed If iodine or bromine be before adding the argentic nitrate. They are also easily formed by dissolving the oxides or the carbonates in hydrobromic acid. a bromide and a may bromate of the metal are thus formed. are decomposed when heated in a current of steam. generally leaving corresponding oxides. (516) The BROMIDES (428. chloride of bismuth. The composition of an insoluble chloride or of a basic chloride may be ascertained. as otherwise the chloride would. be reproduced by the decomposition of the acid. in most cases. except those of the alkali-metals. nitrate. be precipitated with the chlorine. it will determined separately. and then determining the quantity of chlorine in the before adding the alkaline solution by means of argentic nitrate : solution of silver. All the chlorides. and of barium and mercury. solution should be acidulated with nitric acid. Bromine may be precipitated from its solutions. and by evaporation ta dryness and gentle ignition of the residue the bromate is decoma small quantity of charcoal may posed. . 338)* is Chlorine (515) Estimation of Chlorine in Metallic Chlorides. leaves an oxychloride All the soluble chlorides. 100 parts of which represent 24:74 of chlorine. and must be the corresponding weight of argentic iodide or bromide being deducted. leaving a pure bromide be previously added. groups earths : the bromides of the metals of the alkalies and alkaline be prepared by digesting a solution of the alkali or of the earth with bromine in slight excess. 430) closely resemble the chlorides in chemical characters. can be estimated by this means. evolve chlorine gas. the alkaline liquid must be filtered from the undissolved metallic oxide. Other particulars relating to the chlorides have been already mentioned (335.

then if x represent the proportion of chloride. and s = 108 . chlorine be present the precipitate will consist of a mixture of it must be collected and the bromide and chloride of silver and a drop or two of zinc metallic with then weighed. position. and consequently y. From be the weight of the reduced silver .$ 143-5 108 + - 188 y . iodides also form double with the oxides and chlorides compounds : for example. a portion of the precipitate has escaped decom. by mixing it with a solution of the : metallic salt. x. dried. the iodine per cent. and weighed. or the argentic bromide in the mixture. the precipitate must be allowed to subside and ten or twelve during hours. and a combination of stannic chloride with the stannous iodide (SnI . If ioo parts of the bromide corresponding to 42*55 of bromine. iodides exhibit a strong tendency to form double salts. digested have reduced the will zinc the a two in or acid . of iodine. may be obtained in orange-coloured . it will be found that s and chloride of silver may be calculated the mixed bromide and chloride. such as those of mercury. since if it be not. when collected and dried. (517) The IODIDES (435) may be formed by processes analogous to those employed for the bromides the insoluble iodides. and lead.SnCl ) 2 4 crystals (Kane). may then be collected on a (70 C. =5-6134 3-2247 in. may be obtained from a solution of potassic iodide.328 THE IODIDES. and y that of bromide of silver. there are several compounds of the iodide with the oxide of lead . silver. the iodides of the strongly basylous metals combining readily to form crystallizable double iodides with those of the less electro- The The positive metals. =m x s . sulphuric day : bromide and chloride to metallic silver this must be well washed. mercury. must be precipitated by means of palladious nitrate . The quantity of iodine in a solution which contains iodides. may be estimated by the addition of argentic nitrate slightly acidulated with nitric acid: the resulting buffcoloured argentic iodide. contains 54-04 If chlorine or bromine be present. such as those of silver. It should be wholly soluble in nitric acid. and lead. or the argentic chloride in the mixture.) : filter and dried exceeding 158 this precipitate at a temperature not is insoluble in cold . and let : the above data the relative proportions of the bromide let be the weight of m m= x + y. if chlorides be absent.

the ordinary ore of The metallic oxides may be subdivided according to their chemical functions into 3 classes viz. The general properties of these compounds (518) FLUORIDES. however. lowing process slightly : mixed with pounded glass. it does if is the the modified substance. dilute nitric 3*29 It or hydrochloric acid. Estimation of Fluorine. the silicic fluoride comes over. forms of haematite. by a mixture of ferrous sulphate and cupric sulphate (873). i.METALLIC FLUORIDES. feebly When the atom of a dyad enters into combination with powers equivalent .* of the type HO 2 . The most important compounds of the metals with the non-metallic bodies are those which they form with oxygen. G.. whilst the ammonic fluoride may be dissolved out with a little water. the (519) . such as JVIgO ['M' 2 O]. . of iodine. Many of the most abundant and valuable metallic ores are oxides such as specular and magnetic iron ores. and tinstone. is : : evolved produces the usual corrosive action of hydrofluoric acid on glass (443) the proportion of silica in the insoluble residue : to the fluorine. but soluble in ammonia. and distilled into a flask containing a solution of ammonia. the silica is rendered insoluble. different tin. and can be collected and weighed. A simple method of detecting and of approximatively estimating fluorine. has been proposed by Dr. metallic metallic acids. Wilson. have been already given (443). which when form the hydrated The atomic proportions in which the constituents of the prinor indifferent oxides 3. basic. * Suboxides. basic oxides . The fluorides are usually preof the direct action pared by hydrofluoric acid either upon the metal or more usually upon the oxide of the metal. the mixture is next heated. but less perfectly. from bromine and chlorine. is not very uniform. Those which are insoluble salt may be procured by mixing a solution of the metallic with one of potassic or sodic fluoride. and the presence of fluorine shown by mixing it with oil of vitriol the vapour which is not already contain silica. and made into a thin cream with oil of vitriol. saline : anhydrides. when present even in very The folsmall quantities. and is immediately decomposed on evaporating the liquid in the flask to dryness on a water-bath. 2. Iodine may also be separated contains 70*457 per cent. THE OXIDES. and cipal varieties of metallic oxides are united are exhibited in the following table: i. placed in a retort.

KKO. H }0 Ba" H }0 . we have an analogous oxide . A1. potassic hydrate . The dioxides correspond in composition to a group containing 2 molecules of water. In the sesquioxides and trioxides the molecular type is a group consisting of three molecules of water. . Sesquioxides. such as 2. the f oxides to a group containing 4 molecules of water. of two molecules of water. Argentic oxide. the oxides of the triad metals and of the tetrad metals in the pseudotriad condition .330 THE OXIDES. such as potassium . Ag' 2 O[OAg2] Lime. such as Alumina. neutral. as for instance : K TT ) [ 0. thus M. HHO. but if only one atom of hydrogen be displaced by the metallic monad we have a If the metallic dyad displaces half the hydrogen hydrate of the metallic oxide.H. or if both atoms of hydrogen be displaced by a single atom of a metallic dyad. such as fact. Uranic sesquioxide. | of the type HO 2 . Cuprous oxide //Cu 3 O ['Cu' 2 O] . Cobaltic sesquioxide. as indicated in the table. and so on. in barium. ~O only to those of the atom of a monad.O. or by placing one dash to the right of the symbol indicating that one attraction of each atom is satisfied by the oxygen. Ca"O. 3. the fact may be indicated as in the text. and one to the left showing that the two atoms of the metal are united together by one attraction of each. * These oxides may. anhydrous baryta .. it' each atom of hydrogen in the molecule is displaced by an atom of a metallic monad. we have a hydrate of the oxide of the metallic dyad. feebly basic. Monoxides* M' 2 O strongly basic. or even acid. anhydrous potash. M V be regarded as compounds formed upon the type of a single molecule of water. 'Al'" 8 O 8 Al'" a O 8 f' = UO 2 3 2 Co / " O3 ['Co'" 2 O 3] Arsenious sesquioxide. alumina being (Al'") O and its normal hydrate . baric hydrate. by placing two dashes at the bottom and to the left of the symbol . each atom of the metal representing 3 or 6 atoms of hydrogen in the combination . M /// 2 O3 and 'M"' 3 O 3 . Ba"0. for example : HHO. water. of the type HO 6 3. As"' 2 O 3 As | /// 2 O3 = AsO . [OMJ or WO. ~! |.

metallic anhydrides. Pb2O. .H 2 O. Antimonic anhydride. for instance. Although these 2 oxides usually give rise to an unstable series of salts. ironstone. of the type trioxide. instead of CuHO <Ju(OH) Ba * Possibly o-o / \ . Trioxides. Anhydrides. metal .Fe"' 2 O3 Chrome 5. M vi O3 . few of the dyad type 2 metals. A. of the type W*Oy H O 10 5 Arsenic anhydride. MgO^ of the H O4 8 : saline oxides. normal hydrates of these oxides appear the mercurous and plumbous oxide being anhydrous. classifying them in the order just indicated. of the type Dioxides. or Fe"O. Cu 2 O mercurous oxide. becomes for the time equivalent only to a single atom of hydrogen. Sb 2 O 5 The oxides that it will constitute so important a series of compounds.. particularly to the acids. being metallic copper and the black oxide j Cu 2 O with hydrochloric acid the reaction is as follows converted .THE OXIDES. i. 4.Cr'" 2 O 3 . such as copper. 6. or red oxide of copper. which usually is equivalent to two atoms M A of hydrogen. plumbous oxide. they frequently become decomposed into the normal oxide and free : Hg O . be necessary to consider their relations. Fe"Fe"' 2 O 4 .s 2 O. such as iv M H/X. to exist. to water and somewhat more in detail. O 2 2 Baric dioxide. For example. we have the cuprous oxide. O 2 . Fe"O. such as Molybdic Mo O 3 VI Tungstic trioxide. 7. into = Cu + CuO but Cu O+ 2HC1 = : 2 HjO + Ci^Cl.. Stannic dioxide. lead. HO 6 3 . 331 type Three-fourths oxides. but Platinic dioxide. BaO * SnIV O 2 . of the O ['M' 2 O]. M V 2 O 5. cuprous oxide. and mercury. Suboxides. generally neutral or acid. Pt iv rarely basic. and No the yellow hydrated cuprous oxide being 4Cu 2 O. or black oxide of and mercury. such as Magnetic oxide of iron. form oxides in which one atom of the metal.

and cadmium.2H 2 O and the hydrated oxides of lead and tin consist of 2PbO. it is only very slightly soluble. nickel. lead.332 2. and very energetic. iron. The hydrates of the alkalies cannot be again decomposed by exposure are slowly volatilized without decomposition -by a prolonged exposure to an elevated temperature. zinc. . : This class of the most powerful bases they are formed by the union either of 2 atoms of a metallic monad with i atom of oxides includes oxygen. didymium. Magnesia combines It is very sparingly soluble . manganese. mercury. although that of lime is but sparingly so. cobalt. magnesium. thorinum. Among the members of the second subdivision are included the alkaline earths. but the hydrates of baryta and strontia fuse at an elevated temperawater and the .H 2 O. The other anhydrous oxides just mentioned do not combine with water when mixed with it. the formula CuO. or by the union of i atom of a metallic dyad and i of oxygen.g. however. Hydrated cupric oxide has. Hydrated argentic oxide is very unstable .. or all M"O. Most acids. a single molecule of the hydrate being in each case formed by the combination of single molecules of is also CaH 2 2 earth: as. for instance. The following equations may be taken as exemplifying some of the ordinary cases of the action of acids upon these oxides and their hydrates : . tin. and palladium. and 2SnO. The first subdivision includes the five alkalies and the oxides of thallium and silver. Monoxides. The lime action of water upon anhydrous baryta. copper. one molecule of water and one of alkali yielding two molecules of the to heat. of the type M'.H 2 O. uranium. plumbic very slowly with water. even by These hydrates are soluble in water. the oxides of lanthanum. CaO 2 Calcic hydrate requires a full red heat for its decomposition. strontia. which dissolves them rapidly and in large quantity . VARIETIES OF THE METALLIC OXIDES. The anhydrous oxides of the alkali-metals become converted into hydrates with development of intense heat on the addition of water. chromium. form of the monoxides.. and the protoxides of cerium. but hydrate: e.O. ignition. Their monohydrates can usually be obtained by precipitating a solution of one of their salts by the addition of a solution of one of the alkalies in slight excess. + H O= O ture. and mercuric oxide are each somewhat more soluble. by their reaction with the ordinary salts which are neutral in their action upon test- paper. prolonged and baric hydrate does not part with water. KKO + HHO = 2KHO.

Magnetic oxide . These oxides do not form salts with acids. two-thirds of the oxygen remaining apparently in a state of intimate combination with the metal . alumina. 333 Ag T1 2 2 + 2HN0 3 = H HC1 + 2HI 3 2 2 2 + 2AgN0 3 KC1 2T1I KHO + CaO 3.VARIETIES OP THE METALLIC OXIDES. nish salts when acted upon by acids.Au 3 O 3 or . for instance : form Sesquioxides of cobalt and nickel exhibit no tendency to salts by the action either of acids or of bases. of the type MO 3 4 or M"O. They furmanganese. uranium. the Sesquioxides. they are resolved into the corresponding compounds by the action of acids . being probably compounds of a protoxide with a sesquioxide . and bismuth. 4. and the sesquioxides of cerium. Cr 2 3 + 6HC1 3 *V>. the sesquioxide of gold is insoluble in water. The basic sesquioxides have but a feeble attraction for water . although they are only feebly marked. as for instance: Fe 3 O 4 + 8HCl=FeCl 2 + Fe 2 Cl 6 + 4H 2 O. when lose precipitated by alkaline solutions from the solutions of their salts. Three-fourths Oxides. of the type M"' 2 3 and 'M'" 2 3 oxides of this class are feeble bases. among O . however. Most of them are included iron. as. + H S04 2 = 3H O + = 3 ap + 2 Cr3 Cl 6 Fe 23 S04 . These oxides of iron. and aluminium. but its hydrate (H 2O. + H 3 S0 4 =H O + =H + =H O + O CaSO 4 . being feebly but decidedly acid when dissolved in water. antimony. which water during drying. occasionally. AuHO 2) presents the properties of an acid. no chloride corresponding to these sesquioxides being known : Co 2 O 3 4-6HCl=2CoCl 2 Sesquioxide of arsenicum possesses no basic properties. but all these salts redden litmus usually 3 molecules of water are separated by the : reaction of the base upon the acid . When heated with hydrochloric acid. antimony. for instance. chromium.M'" 2 O 3 . they furnish very bulky gelatinous precipitates. form salts with the elimination of one molecule of water only. they evolve chlorine and furnish a lower chloride . and uranic oxide invariably.

is such represented by the peroxides of sodium (Na.6H 2 O. and silver do not become hydrated. exhibits known 2 as plumbates. bases.O 2 ) and (Ag2 2 ). of iron. . of the type 3 This class includes the metallic anhydrides in 4 atoms of 6. is the best representative of this and includes corresponding class. uranium. of which the platinic oxide (PtO 2 ) and palladic oxide (PdO 2 ) are the most important . . 2. as for example: 1. are decomposed with evolution of oxygen when thrown into water . These oxides form either no strontium. and those of barium (BaO 2 ). The second variety silver O corresponding salts or only very unstable ones they retain the When heated with oil of second atom of oxygen but feebly. for example. Of baric dioxide forms the hydrate BaO 2 . aKHO + PbO = 2 K Pb0 + H 0. and cobalt. MgO.. and when fused with the hydrated alkalies furnishes compounds dioxide.VARIETIES Op THE METALLIC OXIDES. which is rather numerous. manganese. such. vi Trioxides. they are feeble as PtO 2 . the three oxides last mentioned conduct the voltaic current : plumbic some properties of a metallic anhydride. For each of these dioxides a corresponding chloride. PbO. BaO 2 + 2HCl=BaCl +H O 2 . as property is most strongly developed . and with water form hydrates. indeed. j O MO M O . whilst water is eliminated 3 2 . = or liberate chlorine and form water. lead. spinelle. nickel. may be obtained. manganese. M O .2H 3 O. whilst the peroxides of manganese. and lead.Al 2 O 3 gahnite. and form a sulphate corresponding to 2MnSO 4 + O 2 + 2H 2 O. When the protoxide . which the acid example. as the distinctly marked . ZnO. besides the double oxides. as those of potassium and sodium.Cr2 O g . 2MnO 2 + aH 2 SO4 treated with hydrochloric acid they either furnish hydric peroxide. Fe 3 O 4 or FeO. but yield hydrates possessed of feebly marked acid characters when precipitated from their combinations. : ought stannic and the titanic anhydrides. FeO.Al 2 3 iv or of the type 2 2 2 5. chrome ironstone. anhydrides In the third variety of dioxides the character of the metallic is such. The first comprises the basic oxides. for . calcium. containing chlorine. with which silica and zirconia also to be classed these oxides do not unite directly with water. oxides of chromium. : vitriol they give off oxygen. + 4 HCl=PbCl 2 + 2H 2 O + Cl 2 these dioxides some.Fe 2 O g . Dioxides Of these there are three distinct varieties.

335 chromic molybdic. such as the peroxides of silver. As 2 O 5 . directly or indirectly. The oxides when found crystallized in the native state. and present protoxides. on the contrary.VARIETIES OF THE METALLIC OXIDES. the former being electronegative.Mn 2 O 3 while the two higher oxides. ruthenic anhydrides are insoluble in water.O 5 are the representatives of this : water when mixed with it. basic oxides in general are devoid of all metallic appearpar excellence the characters of earthy matters. allow it to pass with facility. their The molybdic. . the less is it disposed to form salts by reaction with the acids . is (MnO. when united with the elements of water form the manganic and permanganic acids (H 2 and 4 MnO . will be referred to hereafter. are all insulators of the voltaic curbut some of the higher oxides. 2 of oxygen which an oxide contains. It is singular lead. Arsenic anhydride is deliquescent and freely soluble . when the bodies themselves are described. Although the ferric and manganic anhydrides have not been isolated. and ruthenic anhydrides. frequently present chemical qualities of opposite kinds. and the extremes. whilst the lower oxides are electropositive. H Mn O a general rule. group of oxides when combined with water they furnish well-marked metallic acids. tungstic. and the same maybe said of the black oxide (MnO 3 ) . of the type 2 Arsenic. and possessing acid properties. O5 Anhydrides. The compounds of the same metal with oxygen are often numerous . rent when solid. the antimonic compound Sb. and manganese. the weaker base . . trioxides. An excellent example of this is afforded by the manganese sesquioxide : protoxide O (Mu 2 3 ) is a ) the (MnO) much oxides of powerful base . are . the red oxide is a a saline or indifferent oxide. and then to form salts. its hydrate As frequently possesses acid properties. vanadic anhydride is does not combine with slightly soluble . or the oxide with the maximum of oxygen. it reacts upon bases The The ance. and peroxides The upon water. and the oxide with the minimum of oxygen. the greater the number of atoms g). tungstic. and antimonic anhydrides. that all these conducting peroxides may be formed in solutions of salts of their respective metals by the action of the current itself. and place is obviously in this group. properties of the metallic acids or hydrated compounds obtained by the action of these dioxides. M . and shows little disto furnish corresponding salts by reaction either upon acids position or alkalies. vanadic.V 2 O 5 and T 7. or basic in their nature.

perature as the protoxides of potassium. and tungstic. solution 2 2KHO = K SO 4 + ZnH O 2 precipitated 2 . are decomposed at a temperature below bases. sodium. even after the application of this intense heat. require and alumina fusion. manganic. bination with water. but even those acids. lime. their effect to Baryta.. strontia. are only very sparingly soluble. it is advisable to separate the metals in the form of sulphides . which are less powerful bases. the five alkalies. and The insolubility of the baryta. : oxide of bismuth require the heat of the oxyhydrogen jet . and thallous oxide. . and black oxide of iron. however. usually redden litmus-paper. tures . and the sesquibut cupric oxide. others. molybdic. among these are arsenious and antimonious sesquioxide and oxide. which. although their anhydrides have no such effect. such as hydrated cupric oxide. is in general far from being so complete as that of the corresponding sulphides. Most of the oxides may be obtained in comPreparation. such as lime and yttria. with potassic ZnSO4 -f The metals which form powerful and alkaline earths. retain the water with while great obstinacy . like the alkalies that of boiling water. oxides. exhibit no appearance of fusion. the oxides of lead. except in particular cases. may be obtained in several ways : They may often be formed directly. chromic sesquiless fusible and volatile. and mercury in particular. The anhydrous oxides i. so that in analytical operations. are perceptibly soluble in pure water. while some oxides. and generally less than that of the metals specific gravity considerably much have a tures themselves. water to any considerable extent viz. and lead. the addition of oxygen to a metal renders Ferrous oxide. and are generally prepared by the decomposition of a solution of one of their salts by an alkaline hydrate : in this its manner is zincic sulphate yields hydrated zincic oxide when hydrate. such. Those hydrated compounds of oxygen with the metals which such as the chromic. strontia.336 GENERAL PROPERTIES AND PREPARATION OF THE OXIDES. for example. As it much a general rule. molybdic trioxide. and molybdic Nine only of the basic oxides are soluble in osmic tetroxide. silver. and possess acid characters arsenic acids are often freely soluble in water . many of All the metallic oxides are solid at ordinary temperathem are fusible at a red heat. like the tantalic. harder than the metals that furnish them. trioxide. by burning the metal in . chromic a much higher temsesquioxide. are the only oxides which melt at a of the metal from which they are prothat below temperature A few of the oxides are volatile at moderate temperaduced.

like iron or lead fast as it is like zinc or . absorb an additional Litharge. arsenicum. sodium. This process is best adapted to metals which. 6. is thus conquantity of oxygen. are volatile. and baric dioxide. 2PbO. may in this way be obtained from caustic baryta. Sometimes is first oxide 4. as of some other metals. 337 or in oxygen. hydrated impure in the and then rendered mentioned. arsenic and chromic arsenious anhydrides are thus converted respectively into The higher oxides of iron and anhydride and chromic oxide. bismuth.PbO 2 . and barium. grating the metal or its sulphide with nitre . however. preOccasionally the for the ignition of a sulphate is resorted to. cobalt. oxides. titanium. rubidium. pletely return to the state of protoxide . reduced . It may be stated as a general rule. may At a red heat many of the oxides lose their oxygen. Fe3 O 4. lithic carbonate. platinum. . if roasted at a low red heat in a current of air or of oxygen. Anhydrous potash and soda are obtained by this method . and uranic oxides. this process is often employed 5. with the exception of those of caesium. and it is resorted to on the large scale in the preparation of arsenious anhydride. silver. Several of the metallic protoxides. the tendency of the metallic acid to form a salt by reaction with the alkali favours the oxidation of the metal : manganese. i. as in preparing alumina and All the acid oxides may be obtained by deflaferric oxide. air. 2. and palladium may thus be comthe peroxides of lead. and of the oxides of zinc and lead. BaO 2 . barium. way already precipitated copper. is only partially decomposed in this from which is au limestone. prepared commonly way the carbonate. the higher oxides of osmium. or protoxide of lead. In some 3. mercury. and fresh surfaces of the metal are continually exposed to the action of the gas. potassium. nickel.PREPARATION OF THE METALLIC OXIDES. Another method consists in the decomposition of a nitrate of the metal by means of heat. either partially or entirely. : lime is anhydrous by heat paration of ferric . and barium. The oxides of gold. Decompositions. and the metallic anhydrides lose a portion of their oxygen . carbonates. or which produce fusible in such cases the oxide is removed as formed. manganese furnish the magnetic oxide. for example. that the attraction Z II. are decomposed at a red heat . verted into red lead:. and the red oxide Mn O 3 4 . and chromium. and strontium cases it is found advantageous the oxides of mercury. are prepared. which expels the elements of the nitric anhydride and leaves the oxide : in this way to prepare the oxide by the All the decomposition of the carbonate of the metal by heat. as well be obtained in this way.

oxides of many of the metals which decompose water at a red heat may nevertheless be deprived of their oxygen in a rapid current of hydrogen . a large number of them are reduced to the metallic state. which is sufficient to enable them to be distilled from the carbonaceous mixture. able metals. carbonic anhydride is obtained. such as potassium and sodium. with smallest tendency to combine oxygen . for example. which are the densest metals. and are also those which show the gold. but not with those of chromium or manganese. and cadmium. decompose carbonic anhydride at a high temperature. expelling their oxygen into chlorides. zinc. resist its action ing magnesia : . with the oxides of iron. even without the oxides. hydrogen. exceptand the earths in the third group. this rule. zinc. and potassium and sodium are obtainstill able from their from the compounds by its agency. protoxides by formation of water. being the most readily oxidized. Lithium and the metals of the earths are not sufficiently volatile to pass over in vapour. specific gravity. The alkalies and the earths are not reducible by The reducing action of carbon at a high temperature is more important . 3. with simultaneous most readily when the current of hydrogen is brisk. they cannot be obtained from their oxides by the action of carbon. this is the case. such as potassium. all the metals which yield their oxygen to hydrogen do so to carbon.338 DECOMPOSITIONS OP THE METALLIC OXIDES. of and converting them application heat. so that carbonic oxide only is formed when they are reduced . whether the gas that is formed during the reduction be carbonic oxide or carbonic The more readily oxidizanhydride. so that the The vapour of water is carried away as fast as it is formed. At an elevated temperature few of them. It depends upon the nature of the metal. This arises in part volatility of these two metals. The oxides temperature. is liable to exception. of a metal for oxygen increases in the inverse proportion of its the lightest metals. 4- Dry chlorine sometimes decomposes the basic metallic such as argentic and mercuric oxide. whilst at a full red heat. and iron. 2. and although their attraction for oxygen is less intense than that of potassium or of sodium. however. indium. while if the reduction takes place readily. especially in the case of the acidifiable metals. as is the case with copper and lead. and upon the temperature employed. This reduction goes on are not affected by hydrogen gas at the ordinary All the higher oxides of the metals are reduced to hydrogen at a low red heat. while platinum.

the alkalies and alkaline with sulphur pletely earths are converted into a mixture of sulphate arid sulphide. as in the case of oxide. are unaltered. MnH 4 4 . oxide be capable of being decomposed by hydrogen its composition may be ascertained. but chlorides of the metals cases. whilst the . ganese. but : Most of the when heated oxides are decomposed more or com- magnesia. The protoxide of manunder these circumstances. and either collecting and weighing the water produced.ESTIMATION OF OXYGEN IN THE METALLIC OXIDES. the metals of the first two groups yield bleaching compounds. previously If the metallic (520) Estimation of 0-xygen in Metallic Oxides. or by converting it into a nitrate. The potassic hydrate in this case parts with its hydroxyl. 3CoH O + C1 =. in the presence of a large quantity of potash. chromic oxide. determined synthetically. The sesquioxides of cobalt and nickel are usually prepared in this manner for : example. as well as the earths proper. become converted into the metallic acid. and afterwards expelling z2 . and the sesquioxide may. The oxides of the third group. which reacts upon a portion of the excess of alkali and forms a ferric salt. experience no particular change. a given weight of the metal being converted into oxide. stannic. but those in the ferric group are converted into a mixture of chloride and hydrated sesquioxide. the whole of the metal may be converted into hydrated sesquioxide. by heating it in a current of the gas. the action of is quite different . the process of oxidation may even proceed farther. and by heat are converted into chlorates and chlorides. either by heating the metal in a current of air. are more readily decomposed by sulphur if they be mixed with carbon. or determining the amount of reduced metal which a given weight of the oxide In other cases the composition of the oxide is has yielded. 2CoH 2 O 2 + 2KHO + Cl 2 Co 2 6 O 6 4-2KCl. in the manner already explained (351). when potassic ferrate is produced. Most of the other oxides The oxides are converted into sulphides. the oxides of gold 339 and platinum metallic state. 2 2 6 6 2 If the liquid be strongly alkaline. the earths proper. with escape of sulphurous anhydride. yields the hydrated peroxide. which is transferred to the cobalt. If the metal be capable of forming an acid with 3 atoms of oxygen. CoCl 2 2 + Co H O = H chlorine combines with the potassium. Fe 2 H 6 O 6 -f less 5. and titanic anhydrides. are simply reduced to the are formed in other chlorine If the hydrated oxides be suspended in water.

are only sparingly soluble. A shown by the sulphides of and antimony. and two only of barium are known. or orpiment (As 2 S 3 ). indeed. the sulphides. large number of the native sulphides forming important ores. the sulphides are more numerous than the oxides for instance. but many of the higher sulphides. and recondensed to say. and it usually happens that for each oxide a corresponding sulphide may be formed . are insoluble in water : calcic and magnesic sulphides. they combine with it. they may be converted in the solid form . indeed.] . off' the second atom of sulphur. Arsenious sulphide. for example : 2 + 20H 2 =Mg(OH) 2 +2SH 2 . and give and mercuric sulphide. Sulphur frequently combines with the same metal in several proportions. copper. Most of them may be fused at a heat a little above redness. weighing the quantity of oxide which The combinations of sulphur with the (521) SULPHIDES. and if the air be excluded. may be sublimed if that is vapour. These have been termed sulph-hydrates. for 2 example K S + H S = 2KHS. with the exception of those of the alkali-metals and of strontium and barium. If solutions of the sulphides of the metals of the alkalies and alkaline earths be subjected to a current of sulphuretted hydrogen. or Those of calcium and magnesium are decomhydric sulphides. CaS + H 2 S = CaH 2 S 2 . as in the present a close analogy with the oxides. but there are not fewer than five sulphides of each of : these metals. three oxides of potassium and sodium. or cinnabar (HgS). Sometimes. exhibit a high metallic lustre. excluded from the air into . these sulphides are usually purified by this operation. The sulphides of all the metals. hydro-sulphides. and is left. as is iron. are decomposed. the protosulphides undergo no change in composition . metals are numerous. and form soluble compounds corresponding to the hydrates 2 . and in many instances are of great value. All the metallic sulphides are solid at ordinary temperatures. however.3iO PROPERTIES OF THE METALLIC SULPHIDES. the elements of nitric anhydride by the application of heat. lead. into posed hydrates by boiling with water . such as the ferric sulphide and stannic sulphide (SnS 2 ). case of the metals of the alkalies and alkaline earths. whilst a lower sulphide of the metal is left.

.As 3 S-. which crystallizes in beautiful transparent tetrahedra.9OH 2].. . VS WS 2 M^ 3 3 MoS 4 SnS SnS 2 .. . 341 Several of the sulph-hydrates may be obtained in crystals.. like the oxides.Sb S 5 -f-6HCl becomes 6NaCl + !) [2 SbS(SNa) 3 + 6 HC1 =6NaCl 4. or Na3 SbS 4 . of the alkali-metals afford illustrations of basic sul- sulphides phides.. .. A large number of similar compounds may be formed with the sulphides of other metals.. Au 2 S PtS. + 3 SH 2] . form acids with Arsenic sulphide.. the sulphides of which are soluble in solutions of the sulphides of the alkaliThe following sulphides metals.. Ehodic sulphide Arsenious sulphide Arsenic sulphide Bo2 S As 2 Ss As 2 S S Sb 2 S s Sb2 S 5 . . may be subdivided into basic number and acid sulphides.Sb 2 S 5 . .. such as sulphuric or hydrochloric. Antimonious sulphide Antimonic sulphide Vanadic teti'asulphide Stannic sulphide . disodic sulphide..ACID AND BASIC SULPHIDES. if the solutions be evaporated out of contact with the air. as the oxides The protoare upon the type of one or more molecules of water. like antimony and arsenicum. dissolved may be by a solution of ammonic sulphide. forming a mixture of a sulpho-salt with an oxy- . Sb 2 S 5 + 3 H 3 S 3Na 2 S.. for example.. sulphuretted hydrogen being evolved. compounds are ..j Platinic sulphide .. and the sulphide of the electronegative metal precipitated. The sulphides. .. one or more molecules of sulphuretted hydrogen.. and by a : solution of dipotassic sulphide Auric sulphide .9H 2 O [SbS(SNa) 3 . These electronegative sulphides are often soluble in solutions of the alkalies. in this way combines with oxygen. V34 S The sulphides of iridium.. ... Vanadic persnlphide Tungstic trisulphide Molybdic trisulphide Molybdic tetrasulphide Stannous sulphide . from others which are insoluble. and these for the most part soluble in water.i5H 2O . and forms a soluble crystalline compound 3Na S. and they enter into combination with the higher sulphides of metals which... .. according to the nature of the metal and the of atoms of sulphur with which each atom of metal is These may be supposed to be formed on the type of combined...Sb 2 S. in like manner antimonic sulphide Sb^. As 2 S.. The sulphides of tellurium.. In consequence of the tendency to the formation of these double sulphur salts.i8H 3 O.. The double salts thus obtained are decomposed by the addition of an acid. ... many of the sulphides which are insoluble in water are dissolved freely by solutions of sulphide of potassium this circumstance is frequently taken or sulphide of ammonium in the of advantage laboratory during the progress of an analysis. for the purpose of separating certain metals.. forms a compound with disodic sulphide 3Na S.

. and manganese. when diluted. while the pure metal remains behind . are dissolved A by dilute when heated and hydrochloric acid in the cold. in the case of silver. The sulphides of the noble metals. and still more readily a chloride of the metal being formed and hydro- Others. generally becoming converted into sulphates. The sulphides are all decomposed when heated in a current of chlorine gas. and passes off as sulphurous anhydride (SO 3 ). 2CaS + CO 2 + 20 8 =CaS 8 8 + CaC0 3 large number of the sulphides. in most cases. or of sulphides and arsenides of the metals. Many of the hydrated sulphides are oxidized by exposure to the air. 3 8 caustic 3 sulphide. though less readily than hydrochloric acid. a portion of argentic sulphate is commonly formed. remains in combination with oxygen* The sulphides of the metals of the alkalies and of the alkaline earths become converted into sulphates of the metal. it is in lead. such as iron. Aqua regia attacks . lose their sulphur. they are all decomposed . furnishes hydrated sesquioxide of the metal. chloride of sulphur and chloride of the metal This property is sometimes made use of in the being formed. when roasted in a current of air. and copper are partially converted into sulphates. while sulphur is liberated and the sulphides of the metals of the alkalies and alkaline earths become converted : into thiosulphates (hyposulphites) . Sb 2 S 3 + 6HCl becoming 2SbCl -f 3 3H 2 S. cobalt. for instance. and the oxide of the metal only is left. the sulphides of iron. whilst the metal. DECOMPOSITIONS OF THE SULPHIDES. lead. for instance. however. acts in a similar manner upon the sulphides of the more oxidizable metals.312 salt. analysis of ores consisting chiefly of sulphides. which burns off in the form of sulphurous anhydride. and the same thing occurs less completely with many of the metals which have a strong attraction for oxygen . especially those of the more oxidizable metals. such as those of nickel. Sulphuric acid. however. but by a stronger heat these sulphates afterwards lose their acid. The hydrated sulphide of iron. when dissolved in gives the following result: Sb 3 S 3 2 K SbO + KgSbS + 3H O [Sb access to S 3 + 6OKH ~ Sb(OK) 8 + + 6KHO = Sb(SK) 3 + If free oxygen or atmospheric air be allowed Decompositions. Antimonious potash. the sulphur becomes oxidized. the heated sulphides. require boiling with the concentrated acid this way that acid acts aiitimonious hydrochloric upon sulphide : : sulphuric acid evolved. zinc. the volatile metallic chlorides are n this way separated from the more fixed ones.

and form sulphides . are obtained. The sulphides can be prepared by various : methods. but the sulphates of the other metals frequently lose a portion of their sulphur. if the heat be continued. forming subsulphides. dissolved out from the excess of charcoal . required. When the sulphides are fused with the alkaline carbonates or with the hydrated" alkalies. of which sulphur. but the compounds thus obtained often contain sulphur dissolved in. Ferrous sulphide is usually prepared in this manner. Many of the metals combine directly with sulphur. sulphur. the mass. Sulphur may be heated with the metallic oxides. globules. Vermilion and realgar are also frequently prepared by the direct union of their constituents. Hydrogen is sometimes employed 2 for preparing the sulphides from the sulphates. which are placed In this manner in a tube and ignited in a current of the gas. they are also decomposed by nitric acid. and decomposes the sulphides as readily as gaseous chlorine and a mixture of hydrochloric acid and potassic chlorate is equally effectual in decomposing them. although itself combustible. With the exception of mercuric sulphide. K SO 4 + 4C = K by water and S 2 -f filtered the protosulphides of the alkali-metals are easily obtained. but when definite and pure sulphides are The lowest sul2. it decomposes with the alkalies and alkaline many earths. which burn vividly when heated in its vapour. or disseminated through. 4. collect into yellow can be oxidized only by prolonged digestion in the acid. forming . and which. 343 . charcoal. Indeed. sulphuric acid and nitrate of the metal being formed. Preparation. other means should be adopted. a sulphate. either when heated in a glass tube open at both ends. Some other particulars relating to the sulphides have been already mentioned (399). during this operation part of the sulphur is often separated in the form of tough elastic masses. 5. of the metals of the alkalies and alkaline earths may be phides procured by decomposing their sulphates by igniting them in closed vessels with charcoal oxygen is removed by the carbon carbonic whilst the sulphide remaining may be oxide. and the mass contains a variable mixture of sulphide with oxide of the and different oxysalts of sulphur. or when roasted upon alkali-metal. In other . as well as all their oxygen. 3. and a sulphide with variable proportions of i.DECOMPOSITION AND PREPARATION OP THE SULPHIDES. supports the combustion of many metallic bodies. Before the blowpipe the sulphides are easily recognized by the odour of sulphurous anhydride which they emit. they are partially decomposed. if heated with it. 4CO.

copper. solution with a salt of barium. 7. that of man: those of cadmium and arsenicum are yellow. TiO 2 4-CS 2 = the metals of the groups may also be procured as insoluble precipitates. to precipitate the sulphuric acid. each with its peculiar shade . may be formed by heating the metal in a current of sulphuretted hydrogen. lead. iridium. as . bismuth. when mixed in slightly acid regia sulphur.MnS. 100 parts of baric sulphate representing 34*34 of sulphuric If a salt of silver be present. after it has been well washed with boiling water and ignited.K 2 S = K 2 SO 4 + ^H 2 O. and nickel are not thrown down by manganese. furnishes data for the calculation of the sulphur . cases the sulphides in procuring titanic sulphide from titanic TiS 2 + CO 2 last three .sulphides of molybdenum. platinum. ganese flesh-red also is . cobalt. nickel. or in the vapour of carbonic This latter method is the plan commonly adopted disulphide. MnSO 4 + a7H 2 O. or 13-73 of sulphur. rhodium. 6. but can be prepared by double decomposition. stannic sulphide and hydrated stannous sulphide is chocolate brown. baric nitrate must be employed yellow upon ore appears to be complete. by passing a stream of sulphuretted hydrogen through neutral or The hydrated sulphides of zinc. its amount must be added to that which has been converted into . uranium. vanadium. In many cases the acid solutions of their salts. gold.344 PREPARATION AND ESTIMATION OF METALLIC SULPHIDES. mercury. and weighed. is more or less pure. If during the solution of a sulphide in aqua regia. and palladium sulphides are of a black. : colours of these hydrated sulphides are characteristic of the metal for example. iron. the precipitated silver. it is not necessary to wait till the whole of the sulphur is dissolved the undissolved portion may be collected on a small counterpoised filter. by mixing a neutral solution of the salts of any of these metals with that of a sulphide of one of the alkali-metals thus manganous sulphate if mixed with dipotassic sulphide yields potassic sulphate and manganous sulphide. and osmium are brown. the sulphur have collected into clear the balls. yield the insoluble baric sulphate. the hydrated sulphide of zinc is white . The . sulphuretted hydrogen in acidulated solutions. . (522) Estimation of Sulphur in Metallic Sulphides. cobalt. Hydrated sulphides of anhydride . the amount of which. and . and the action anhydride. Sulphur always estimated in the form either of a sulphate or of free The sulphur in a sulphide is easily converted into a sulphate by the agency either of gaseous chlorine or of aqua and the soluble sulphates. whilst in a large number of instances including the sulphides of iron.

in a solution of ammonia. (534) NITRIDES. and passing the vapour of phosphorus over it in this case it is mixed with a large proportion of calcic phosphate. that a slight alteration of circumstances often suffices to restore it sudNitride of copper is formed by passdenly to the gaseous state. The only carbides of importance are those (526) of iron. in which case water is formed at the expense of the hydrogen of the ammonia and the oxygen of the oxide. molybdenum. the phosphide is formed by heating the oxide strongly. as for example in that of calcic phosphide. rapidly at a red heat Titanium. current of phosphuretted hydrogen through a solution of the corresponding salt . Nitrides of mercury and iron ferric may be passing ammonia over mercuric and prepared by oxide in a similar manner. and part of the nitrogen escapes. the proportion of which is to he ascertained by means of a barium salt in the manner above described. and vanadium absorb nitrogen and crystalline nitrides of chromium and . on account of the readiness with which they explode. The presence of selenium in a com- pound is readily ascertained by the peculiar odour which when heated in the reducing flame of the blowpipe. phosphides are converted into phosphates. may owe their but the compoexplosive character to the formation of a nitride sition of these bodies has been only imperfectly investigated. (525) The PHOSPHIDES of the metals are of comparatively small importance they are never met with in the native state. hydrogen is disengaged. ammonia over ing dry cupric oxide. phosphides of copper and mercury may be thus obtained. So weak is the : chemical attraction of nitrogen for most metallic bodies. The insoluble phosphides may often be obtained by passing a . In some cases. it emits It is not improbable that the fulminating obtained compounds.NITRIDES METALLIC PHOSPHIDES. at a temperature not exceed- ing 482 (250 C. thus. CARBIDES. of and of silver.). The phosphides of the metals of the alkalies and alkaline earths decompose water when thrown into it self-lighting phosphuretted : . magnesium have also been obtained. liberated and phosphoric anhydride is formed. When heated in is air. platinum. which will be considered in detail when treating of that or the metal . by digesting the hydrated oxides of gold. and a hypophosphite of the metal remains in the solution. 6CuO + 4H 3 Cu 6 2 + N= N 6H 2 O + N 2 . 345 sulphuric acid. (523) THE SELENIDES and TELLURIDES are closely analogous to the sulphides in general characters. but they are too rare to need particular description.

and entering into combination with the alkalies. and boracic acids. are powerful bases. however. for example.346 metal. acids were discovered into the composition of which hydrogen entered. and yet these bodies were found in other respects to correspond perfectly with Lavoisier's definition. to which latter class of compounds the term is restricted by many later writers. into the nature both of bases and acids. and to which it is Lavoisier considered an acid to be an applied in this work. A base. but they contain no metallic substance. and to possess . hydrobromic acids example. whilst a salt and water are formed. HYPOTHESIS ON THE CONSTITUTION OF SALTS. and the distinctive characters of the acid are neutralized more or less completely. It has already been stated (6) that is produced by the action of an acid upon a substance which any It is. these carbides are more fusible than the metals themselves. sulphurous. most frequently an oxide of a metal. however. the distinctive properties of which it neutralized. as hydrochloric. which is capable of effecting a double decomposition with an acid. however. of oxygen to one of the constituents of the atmosphere. magnesium. combine with carbon . and a few other metals. but they are . The term acid was indifferently phosphoric. acids then By degrees. capable of reddening vegetable blues. and copper.generally of small importance. oxidized body more or less soluble in water. hydriodic. with a sour taste. such as sulphuric. and Bases. carbonic. palladium. Manganese. iridium. is not of the necessarily a metallic oxide . and into that minutely (527) Acids ' compounds formed by their action upon one another. generally speaking. nitric. iron. quinine. and this view was rendered highly probable from a consideration of the composition of the principal known. is meant a body always of a compound nature. aluminium. also THEORY OF SALTS. Amongst the most interesting of the silicides are those of calcium. he supposed that the presence of that energetic body was essential to the existence of an acid . By the word base. name When Lavoisier gave the (528) Oxyacids and Hydracids. but in which no oxygen could be detected : such. necessary to examine more base is termed a salt. and morphine. III. for . applied to the anhydrides and to the compounds produced by the union of the anhydrides with water. the hydrates of ammonia. SILICON and BORON form analogous compounds with the metals.

with an oxide such as potash . and the old notation). it was proposed to subdivide salts into two classes. a true double decomposi: tion occurs. the second class was formed by the hydracids. indeed. in which it was supposed that the acid properties depended on the presence of oxygen essential . is still recognized by many chemical writers. the theory was modified. salts of the oxyacids of which sulphate of potash. To meet this objection. In consequence of this supposed difference in constitution. When. metallic copper. being composed upon the same plan or type as This diswere termed haloid salts (from aAc. in the case of (NaCl) NaO. the salts of the hydracids. nitric. might present the equivalents sulphate. such as the nitric. : the other class being produced by the combination of a metal with the characteristic element in a hydrogen acid. while a hydracid.HO) yield common Thus.HO + HCl= NaCl + lEO.SOy which supposes the union of i equivalent of the anhydride with i equivalent of a metallic oxide . if made to act upon a base yields a body. KO. the first. has no action upon. for example. in which hydrogen was an was noticed. like nitrate of potash. forming a blue solution of cupric : applying heat so as to render the salt anhydrous.SOS . therefore. The salts of the second sea-salt. the radicle of the acid being salt left in combination with the metal itself: thus hydrochloric acid (HCl) and caustic soda : (NaO. the acids do not unite directly with the metals without evolution of gas . a hydracid acts upon a base. S= 16.N0 5 being formed by the union of an oxyacld. or anhydride as we now term it. The supposition that a salt consists of an anhydride united to a base still affords the simplest explanation of many chemical decompo- tinction . that when bodies belonging to either of these classes combine with metallic compounds. and form neutral combinations. and the acids "were divided into two great classes. sea-salt). such as sul- phuric. on the hydrochloric and component. KO. and others of analogous composition. contrary. combination appears to take place directly dilute sulphuric acid. may be taken as the type (employing for the 8. the first of which comprised the oxyacids. 347 all the characters of powerful acids. class. it will be observed that the oxygen of the oxide is precisely sufficient to convert the hydrogen of the acid into water this union. with their oxides.OXYACIDS AND HYDRACIDS. which when dry contains neither hydrogen nor oxygen. it On was found that the = be represented under the form MO. actually takes place. such as hydriodic It acids. these were termed oxysalts . and the water so formed is expelled on the application of heat. but it quickly dissolves its oxide.

g.318 sitions . Carbonic anhydride is also without on litmus. nitric. does not redden dry litmus . by a slight modification of the old formula . and boracic anhydrides. when heated in contact with a base or a metallic oxide. passed into the hydrated form. which forms the radicle of the salt. and which are indicated by names. e. been shown that the anhydrides of those oxyacids which can be obtained in an isolated form. One analogous equivalent of oil of precisely to the vitriol treated hydracids with i equivalent of oxide of lead would thus produce an equivalent of sulphate of lead and an of water. which be termed the oxion of the salt may of the united with 4(consisting anhydride oxygen) hydrogen. The separation of salts into two classes. it corrodes all organized substances with great activity. hypothesis was advanced by Davy and by Dulong. BINARY HYPOTHESIS OF SALTS. The other salts of the acid would be formed from these hydrogen compounds by the displacement of the hydrogen by an equivalent amount of each of the different metals which enter into the their respective composition of the various salts. Sulphuric anhydride. The foregoing obser(529) Binary Hypothesis of Salts. of the oxyacids.N0 6 . phosphoric. indispensable. is however.SO^ + PbO equivalent becoming P^SO^ + HO. When such compounds have entered into combination with water they may be represented as hydracids. for instance. H. we have . which reduces all salts to one type. it may be moulded in the fingers without injury but when once it has united with the elements of water and . A According to this view frequently termed the binary theory of salts all the hydrated acids are regarded as salts containing hydrogen in the place of a metal. for example. such.. and the other of those of the hydracids.N0 5 may be expressed as H. do not possess the properties generally admitted to constitute the true acid character. nitric acid HO.Cl: each equivalent of these bodies. In accordance with this view. in a manner already examined. one consisting of the salts not. as sulphuric. corresponding to hydrochloric acid H. vations seem to prove that there is a marked difference between the composition of the oxyacid and the hydracid series of salts. Most chemists indeed now regard the compounds which were previously considered as hydrated acids as salts composed of a compound radicle. so that hydrogen acts the part of a feeble basyl towards a group of elements. and it is difficult to represent many of the complex sili- cates satisfactorily by any other plan. or a single It has already element. carbonic. gives off i equivalent action of water.

upon this view. : j . A belong to an entirely distinct group of compounds Hydracids. 2HC1 + Zn = ZnCl 2 + H 2 . analogous to that of the same metal . comparison of a few of the so-called hydracids with some of the liydrated oxyacids will show the analogy between them whilst the corresponding anhydrides will be at once seen to . H upon hydrochloric acid . and the reaction is. and displacing so that (resuming the notation which regards the hydrogen O = i6 and water H 2 O) H 2 SO4 + Zn become ZnSO 4 + 2 . the zinc merely entering into combination with sulphion. 349 already given a simple explanation of the liberation of hydrogen when dilute sulphuric acid is acted upon by zinc .BINARY THEORY OF SALTS.

maintained in its existing condition by the mutual .. where the acid contains oxygen. exhibits no tendency to further oxidashould become K 2 . by the union of ammonia. SO 4 . radicles or oxions. ammonic NH NH a powerful affinity to unite with the ammonia which has no : appreciable attraction for hydrogen. hydrochloric 3 for which it has such acid should the chlorine leave hydrochloric tion of chloride. so in the same salt there are directions in which it yields to. by using in the latter case the termination the the sulphites being sulphosion. like carbonic anhydride. nor powerful nate for example. directions in As in a crystal there are certain which the mass admits of cleavage with greater facility than in others. to the Binary Hypothesis. of oxion the osion . and as two or three different directions of cleavage may be found in the same crystal by varying the direction in which the force is applied.NO 3 . it that a salt. or else a compound like ammonium (H 4N). as the oxion in cases . and according as that chemical force is applied in one way or in another. must be regarded as a whole viz. acid. have ever been obtained in an tion. and the advantages which it oifers in the explanation of certain modes of decomposi- open to many serious objections and indeed it cannot be regarded as a correct representation of the composition of a In fact. the nature of which will vary according to the mode which has been selected for effecting its decomposition. SO3 . It also appears to be highly improbable that a body of such chemical attractions as potash should. termed the bast/I of It is easy to distinguish the oxions of acids in ic from the salt.CO 2 is it likely that they will be. can no longer be looked upon as consisting of two distinct parts. part with its oxygen to a substance which. for instance). pounds (286). none of the compound salt under all circumstances. Attention has and so the oxion of nitrites. isolated form. it is . so that 2 O. Na. the compound splits up into simpler substances.CO 3 or in the production. equivalent to a metal. Notwithstanding (53 O ) Objections the ingenuity of the foregoing hypothesis. nitrosion. actions of all the elements which compose it. that the hydrogen of the and HC1. already been directed to the bearing of the electrolysis of saline com- those of acids in ous NO . 2 on. These different elements are not all united with each other in every direction with an equal amount of force.CO 3 . is either a metal (sodium. the application of chemical force more readily than in others . The conclusion which is most probable is this when once formed. 4 C1. in potassic carbo- K . upon this theory of their constitution.350 OBJECTIONS TO THE BINARY HYPOTHESIS. but as a new substance. . the other.

that neither the old nor the new absolutely correct. a numerous tion of which oxygen enters. are of subordinate Generally speaking. . it may often be consaline compounds.CO 2 . may sometimes be CaO. 3 probability therefore is. results.salts being replaced atom by an atom of sulphur in the corresponding compound the sulphur the series. series of compounds parallel to these oxy-compounds. carbonic anhydride is liberated. which gas and carbonic anhydride is K = as instantly resolved into oxygen . although the empirical formula CaCO 3 will So. CO 3 + 2C K 2 + 3CO. and which aim at explaining the functions of the different atoms of which they are composed. venient to represent certain salts as compounds of the anhydride and the base written : calcic carbonate. generally be preferred.SDLPHO-SALTS. again. however. sulphur-salts the to of them are decomoxy-compounds. and into carbion. . for instance. many importance in posed by water. Anhydrous magnesic sulphate may. be poured upon potassic carbonate. if the solution of a powerful acid. but that each may in turn be employed to represent the salt when subjected to the influence of particular circumstances. and they have been the subject of much less study and research than the oxy-salts. . for example. 2K 2 + 4H 2 O The view is give aK 2 CO 3 becoming 2K 2 + 2CO 3 and whilst aCO becomes 2CO 2 + O 2 2H + 4KHO 2 . Many chemists regard these compounds as salts in which the electropositive sulphides. . In certain cases therefore it is evident that the binary theory may elucidate the decompositions observed. almost exclusively with reference to those salts into the composiThere is. notwithstanding the difficulties which prevent its adoption as a correct statical representation of the molecular arrangement of On the other hand. if a solution of 2 be subjected to electrolysis by the aid of the carbonate potassic voltaic battery. the salt splits up into potassium (which is immediately oxidized by the water in the midst of which it is liberated). K 2 CO 3 + 2HNO 3 = 2KNO 3 + CO 2 -h H 3 O but if another portion of the same potassic carbonate be mixed with charcoal. in which sulphur enters into combination with the metal. metallic potassium and carbonic oxide are the . such as nitric acid. be often written MgO. 351 For example. and potassic nitrate is produced. and heated in an iron retort to whiteness. as employed to indicate the composition of salts. The preceding remarks have been made (531) Sulpho-Salts.SO 3 although we generally adopt the form MgSO^ which Constitutional formulae involves no theory of its constitution. CO^. each of oxygen in the series of the oxy. in the case of the sulphates. Again. have been already described (332).

But chemists in are in the habit of regarding many salts as neutral composition which are not neutral in their action upon tests. sodium. for nitrate be made to act upon and water will be formed. or Normal Salts.352 COLOURED TESTS VARIETIES OF SALTS. or silver displaces the hydrogen in i molecule of the acid or in which i atom of a dyad such as lead or copper 3. plumbic solved in water it reddens litmus. are HO 2HNO 3 regarded as neutral in composition. which. it be mixed if The yellow blue acid becomes to brown when is mixed with an turmeric colour of changed if the alkali is restored be caused to the combine but alkali. A salt which affects neither is the blue of litmus nor the yellow of turmeric said to have a neutral reaction. molecular constitution is analogous to that of the oxy-salts. with an alkali. its reactions upon coloured tests. Salts are usually spoken of as neutral. (533) Neutral. or basic .. Pb // O + 2HNO 3 = H 2 O + Pb"2NO3 and the salt is neutral in composition. PbO instance. though if dis. displaces the hydrogen of 2 molecules of nitric acid . in the case of cupric nitrate (Cu"2NO 3 ). it is neutralized as according by equivalent quantities of a weak base or of a strong one. and has an acid reaction : the same thing is true. No doubt their phides of arsenic and antimony. for example. upon certain litmus. is changed to red by the colour of litmus reddened by an an whilst the action of acid. 223 parts of plumbic 126 parts of nitric acid. vary considerably intensity. there is considerable ambiguity in the manner in which they are applied. The idea of neutrality im- plies that the peculiar characters both of the acid and of the result of chemical combination. and alkali have disappeared as a this which neutralization is judged of. act the part of and the electronegative sulphides. 62 parts of nitrion in combination with 39 parts of potassium furnish io of potassic nitrate in when dissolved does not affect the water. Salts of nitric acid in It is therefore which T atom of a monad like potas- sium. will differ considerably in their action coloured The upon coloured tests for example. such as the higher sul. act as acids. but though these terms are in general use. bases such as the protosulphides of potassium. . basic properties of different metallic oxides in Equal quantities of the same acid. one of the usual means by consists in observing the effect which is produced vegetable colours by a solution of the salt. (53 2 ) Varieties of Salts. &c. : neutral in colour either of blue or of reddened litmus-paper. whatever may be their action upon vegetable oxide colours. (KNO 3 ). If. yellow The blue colour of with an acid. also. acid.

and sets free the litmus acid. if a salt with a strong oxion and a comparatively feeble basyl be mixed with the blue litmus. combination of the metals of one of the alkalies or earths with the oxion of a feeble vegetable acid which is naturally of a red which becomes blue when it is neutralized by an alkali. upon the yellow colour of renders powerfully brown. and it immeaction and in this sense these terms will be used hereafter. guity in the use of the word neutral.upon litmus. according as the basyl of the neutral salt has given up more or less of its oxion. but it turmeric paper. one of which is dissolved and mixed with a solution of potassic hydrate until the liquid becomes neutral in its reaction . If a quantity of oxalic (534) Polybasic Acids acid be divided into two equal portions. " salt as " radical. is mixed with this blue colouring matter. such as nitric or sulphuric. 353 Thermo-chemical experiments seem to indicate that this acid reaction of the aqueous solutions of certain salts is due to partial decomposition. but of the litmus salt of the alkali-metal. defines a normal is all of the acid or of a positive compound Frankland one in which the displaceable hydrogen exchanged for an equivalent amount of a metal. experiences. even from a salt of neutral composition. formed by the explained. potassic carbonate (K 2 appears to be basic in CO 3 ) its is neutral in composition. Acid Salts. The change in the tint of the coloured test is therefore not to be regarded as an absolute proof of neutrality or acidity in the The change of colour which the litmus composition of a salt. which it This ambidiately restores the blue tinge to reddened litmus.NEUTRAL. may. For analogous reasons is it sometimes happens that a salt which neutral in composition may exhibit characters in which the Common or dibasyl preponderates to a greater or less extent. Again. and liberates the litmus acid. he entirely obviated by describing as normal salts the salts above-mentioned as neutral in composition . "When a powerful acid. which appears of a more or less intense red. . is readily Blue litmus is itself a species of salt. however. the strong oxion seizes upon a part of the basyl which is in combination with the litmus. which appears of its natural red hue. but on the addition of an alkali the blue is restored by the reaction of the newly added base upon the litmus acid and the formation colour. a salt is II. A A in water. OR NORMAL SALTS POLYBASIC SALTS. employing the term neutral solely with reference to the action of the body upon coloured tests . the oxion of the strong acid seizes upon the basyl which the litmus contains.

will crystallize out as the liquid cools. atoms of hydrogen. and the hydric potassic sulphate. as occurs. in the acid sulphate and the acid oxalate of potassium. are simply salts of hydrogen . formed which. Hydrochloric acid HC1. the molecule of the acid contains 2 2 HC H O 3. one of which is neutral and the other acid. for. 2 K H 2 SO 4 =2KHSO 4 . forming two classes of salts. com- monly known as the binoxalate. . consisting of the normal or dipotassic If this salt be redissolved in water. a certain quantity of hydrogen. and. of potassium Again. to redden litmus powerfully. it is apparent that there are certain acids in which their hydrogen admits of displacement by a metallic basyl in one proportion only. commonly called the bi sulphate or acid SO 4 + sulphate of potassium (KHSO 4 ) will be formed. salt by dissolving potassic for the nitre will nitrate in nitric acid. (K C 2 4 . fail. when this monad is presented to it in the form of a hydrate. it must be remembered. If. in addition to the oxion and basyl. Acids in the molecule of which but a atom of hydrogen single admits of displacement by an atom of a metallic monad.354 POLYBASIC SALTS. HKO and acetic acid. : because the acid is only partly neutralized by the metal. and strongly acid salt. the experiment will be found to crystallize out unchanged. and on evaporation to yield a new salt. and the second portion of oxalic acid be added to it. from the experiments just described. susceptible of displacement by two atoms of a monad . fusible. and the acid character predominates in such salts. chemical union of the two bodies will occur the liquid so obtained will be found to have a sour taste. for basic instance. nitric acid. on evaporation. This hydrogen is not to be regarded as present in the form of water of crystallization for it it discharges a more important function. O containing exactly half as much potassium in proportion to the acid as the first salt . Such acid salts consequently contain. takes the place of one of the atoms of the metal on these occasions . oxalate. are examples of this class. or acid oxalate. The bodies now distinguished as acids.H 2 O). whilst there are other acids in which the hydrogen admits of displacement by a metal in two proportions. may be obtained crystallized in six-sided prisms. are said to be monobasic. this is the hydric potassic oxalate. which crystallizes in rhomboidal prisms. if the normal or dipotassic sulphate (K 2 SO 4) be dissolved in hot sulphuric acid. potassium which is attempt be made to form a similar acid This salt contains only half the amount of If an present in the normal sulphate. 3 2 however. tabular plates of a new.

H PO 4 3 . however. such an acid is Again. or by one atom of a said to be dibasic. Many of the organic acids belong to this class. the molecule of the acid contains 3 atoms of hydrogen of susceptible displacement by 3 atoms of a monad like potassium or silver.SALTS FORMED FROM SESQUIOXIDES. 3. For instance. is H SO4 2 oxalic. qui oxides act upon the acids just as are formed by the In certain cases the ses- sulphate by the action of the two bodies in the proportions indicated in the following equations yield a : + H 2 S0 4 = (U 2 2 )" S0 4 + H 2 H 2 S0 4 = (Sb3 2)" S0 4 + H 2 3 + Bi 3 + H S0 4 = (Bi )"S0 4 +H 2 Fe 2 3 + H 2 S0 4 = (Fe 2 rS0 4 + H 2 A1 2 3 + H 2 S0 4 = (A1 2 2 )"S0 4 +H 2 U 2 3 Sb 2 2 2 2 These sulphates. the oxide of uranium (U 2 O 3 }". or 4 atoms) are said to be polybasic. where two atoms of hydrogen in the acid are replaced by i atom of the dyad calcium. . When a dibasic acid acts upon the oxide or hydrate. if said to be tribasic. Ordinary nitre affords an instance of a normal salt formed by the action of the hydrate of a metallic monad upon a monobasic acid. as Peligot has A A 2 . uranyl. a salt is produced similar to that obtained by the reaction of sulphuric acid upon calcic hydrate. or by one atom of a triad like bismuth. a dibasic acid. are all insoluble . and aluminium. with the exception of the first. H C 2 O 4 and 2 H 2 C 4 H 4O & acids. . But numerous salts are known which the protoxides do. in certain circumstances action of sesquioxides upon the acids. 355 the acid . + normal PVO and potassic sulphate affords an of a normal salt by the reaction of the example of the formation 3 2 2HNO = H O + Pb"2NO K 2 SO 4 3 . like sulphuric. hydrate of a monad metal with . tartaric. like potassium. + These three varieties include the most 2KHO H SO = 2 4 common prot- forms of normal salt. zinc. dyad like . Orthophosphoric acid. the sesquioxides of antimony and uranium. is a good citric. Pb"2NO 3 illustrates the case of a obtained by the reaction of the protoxide of a dyad metal upon a monobasic acid. of a metallic dyad. as well as those of bismuth. plumbic nitrate. Ca"H 2 O 2 + 2 SO 4 s=2H 2 O-i- H Ca"S0 4 . iron. KHO + HNO =H 3 2 O-f-KNO 3 salt . Acids which allow the substitution of more than one atom of hydrogen by a corresponding number of atoms of a metallic monad (whether 2. instance of this kind and among the organic acids the H 3 C 6 H 5 O 7 may be mentioned.

whilst in the sesquioxides and the salts corresponding to them the metals are trivalent. by trebling in the following manner . three molecules of the dibasic acid are required to form a normal soluble salt. in certain cases are bivalent. these ferric salts... Other metals besides iron behave in the same manner chromium and cerium. in particular cases may be : bivalent. however. in which case the metal becomes trivalent. these metals are bivalent .2Pe2 A1 2 3S0 4 2A1 2 .356 METALS WITH VARIABLE EQUIVALENTS. again. as in the ferrous salts. platinum.2Sb2 Fe2 3S0 4 .. has been isolated indeed. Cr'" a Cl 6 Ce'" 2 Cl g . for example. (Fe'") 2 O 3 + 3H SO 4 2 yield 3H O + (Fe 2 /// ) 2 3SO4 . and two atoms of the metal are therefore equivalent to 6 atoms of For example. Tin. Many of them are O 3 . Tn the majority of instances. instead of being bivalent... for instance. 3SO 4 and under these particular circumstances iron itself. retain water not indicated in these formulae : M Basic antimonious sulphate Sb 23S0 4 . opening chapter of the third volume of this work. it was for some years mistaken for metallic uranium. represented they may. becomes trivalent in . .. or 2 conveniently represented by the general formula be formulae the given above. thus affording an example of the remarkable fact of a metal possessing two different values in its compounds.SO 3 . termed it. they are bivalent in chloride and sulphate . they often.. Cr'" z 3S0 4 .. . Cr"S04 Ce"S0 4 and trivalent in Chromic chloride and sulphate Ceric chloride and sulphate . Cr"Cla . until Peligot proved that it contained Bismuthyl (Bi 2 O 2 )" has also been prepared. . Ce'" 2 3SO4 In the protoxides and salts corresponding to them. (A1'") 3 O 8 + 3H 2 SO 4 yield 3H 2 O + (Al'") 2 hydrogen. derived from the sesquioxides.. when a dibasic acid.2Bi 2 O 3 3 3 aluminic sulphuric. such as the acts upon a sesquioxide. and palladium. Cerous chloride and sulphate Ce"Cl 4 . 3 bismuth ferric Bi 2 3SO 4 . . Chromous . other oxides of the formulae corresponding to uranyl have not as The foregoing salts are generally regarded yet been isolated. such as alumina or ferric oxide. . as basic salts. in others This subject will be further considered in the quadrivalent.. but the oxygen. whilst in other cases they are undoubtedly trivalent metals .

may be obtained. be decomposed. It is not necessary that the which the sist salts of two or the three atoms of basyl the dibasic or tribasic acids contain should con- of the same metal.POLYBASIC ACIDS. and normal or dipotassic tartrate is produced. as it will expelled with effervescence. but in this case a different salt. we have a tribasic sodic ammonic hydric phosphate. An equivalent quantity of potassic carbonate may be substituted for caustic potash with equal effect. bitartrate of potash. which conand the acid tains no hydrogen. Now it frequently happens that hydrogen is one of the basyls present in the salt. . the sodic potassic tartrate. Cream of another tartar. . . that several basyls may coexist in the same salt. Indeed. 4 4 6 . formed like cream of tartar. of acid salts is formed. bisulphate of potassium already adverted to (p. either of litmus or of turmeric paper. when dissolved in water. the salt. known as will Rochelle salt. 354). KNaC H O . K 2 C 4 4 O & a salt which no longer affects the colour H . in the case of the various phosphates. or. In disodic dihydric pyrophosphate.PO 4 4H 2 O).H 4N. while the place of the second atom of metal has been supplied by an atom of hydrogen but they are not always so produced an acid sulphate of potassium. This is well seen in the nomal ferric and aluminic sulphates. K 2 SO 4 . usually has a sour taste. be formed as represented in the following equation NaHCO KHC H 4 4 6 =H 3 + 2 4- C0 + KNaC 4 H 4 O 6 2 . and redden litmus powerfully. offers good illustration of this kind of salt. as it is often called. : the hydrogen is displaced by the second atom of potassium. and when such is the case. where each of the three atoms of basyl differs from the others. KHC H . 3". . and another molecule of caustic potash be added. such as the so-called binoxalate and the 2 (Na2 H 2 P2 O 7 ). and the carbonic anhydride Sodic carbonate may be substituted for potassic carbonate. all the acid taste disappears.4H 2 O. always occurs Acid salts are generally dibasic acid . from a which has reacted with one molecule only of a powerful monad base. of sodium and in. of an agreeable acidulous taste it consists of 4 4 in fact. Cream of tartar is a sparingly soluble crystallizable compound.SO S chromate or bichromate of potassium. for example atoms of hydrogen supply the place of a atoms the microcosmic salt (Na.H.7 The normal salts derived from these different sesquioxides by the action of acids upon them have usually an acid taste. it has already been shown. K^CrO^CrOg. a dibasic potassic hydric tartrate if now it be dissolved in hot water. and reddens litmusIt is in this way that the most common variety paper strongly. O 6 and is. : .

such as sodium and potassium. It is not possible to form double salts ad libitum. as potassic (MgSO 4 . The so-called bicarboriates. the acid in salts question is dibasic. The formation of another remarkable series of double salts. of metals isomorphous with magnesium are capable of forming double salts of this nature with some anhydrous sulphate not isomorphous sulphate. This. An excellent illustration of such a method of the formation of double salts is afforded in the case of a certain class of the All the sulphates sulphates. does not always happen all the water of thus be expelled with crystallization may the exception of a which a much higher molecule. in composition but one-half of their . particularly investigated by Graham. basic acids has presented us with certain cases in which double salts are formed. Chemists assume that when two different metallic monads. When 1 00 C. single requires heat for its expulsion .H 2 O 6H 2 O) is heated to out of the seven molecules of water are expelled. Some other con- siderations relating to the basicity of acids and to the polybasic acids will be more conveniently deferred until the nature of the organic acids has been discussed. with this class such. binoxalates. under these circumstances it was found that this last molecule of water might readily be replaced by a molecule of certain anhydrous salts. mode in which water attaches In most cases the water of crystallization by exposing it itself to certain may be expelled from a times salt to a temperature not exceeding that of : someboiling water. by bringing 2 in 'with of acid contact i equivalents equivalent each of any any two bases. combine with the same oxion in the proportion of r atom of each metal to form a double salt (like There are several varieties of double salts. DOUBLE SALTS. basylous constituents consists of hydrogen. or salts containing an anhydride. and many other similar compounds are true double salts of this class. appears to be directly con- nected with the salts. most common two dissimilar metals with the same acid radicle or oxion..358 in a similar form. nary acid salts Such salts have been distinguished from ordiby the term anhydro-salts. The foregoing description of the poly(535) Double Salts. analogous to normal or neutral salts. for instance. but the seventh molecule is retained until the temperature is raised magnesic sulphate . six . however. the being those which are produced by the union of Rochelle salt). The larger number of double which have been produced are thus formed by the combination of different metals with polybasic oxions.

Bonsdorff proposed to consider these compounds in the light of salts in which the chloride or iodide of the electronegative metal (platinum. There are a few instances of two different oxions or acid radicles being united to one basyl. In this way sulphates formed from sesquioxides often. but it contains only 6 molecules of water of . gold. having the same crystalline form as magnesic sulphate. the constituent chlorides themselves are salts. There is another well-known variety of double salts. and allowed to crystallize. Instances are common > in which two different haloid salts unite with each other usual between the cortipounds of this description are most chlorides. fusion with each other. a new double salt (MgSO 4 . never resolved by electric action into their constituent chlorides. Sodic chloride. in which it is not necessary that the component salts should be formed from oxides of the same class. potassic sulphate. although they cannot be procured by the usual method of crystallization from a solution containing equivalent quantities of the Many double salts may be formed by two salts. 359 considerably.HgI 2 ) are good instances of such compounds. they are more frequently met with among natural than artificial com: binations.) the electropositive but this view . chloride is (chloride of not tenable. K SO 4 6H 2 O) is crystallization. unite with the sulphates formed from protoxides to produce well-characterized double salts a striking example of this kind is afforded in the important class of alums. &c. but they are neither sufficiently numerous nor important to merit lengthened notice . deposited. constitutional. The seventh molecule has been displaced by the and this portion of water has been termed by Graham.magnesic sulphate and potassic sulphate be separately dissolved in water in molecular proportions. or saline water. &c. for example. Such salts are potassium. Common alum consists of a combination of potassic with aluminic sulphate and water of crystallization (K^Al^SC^^HgO): numerous other salts. or even contain a similar number of equivalents of the radicle of the acid.) acted the part of an acid towards sodium. and bromides of the less oxidizable metals and those of the metals contained in the alkalies and earths : the potassic platinic chloride (2KCl. in fact. mixed while hot. are known.PtCl 4 ) and the potassic mercuric iodide (2KI.DOUBLE SALTS. iodides. and of similar composition. If. and the acid reaction of the higher chlorides is not neutralized or modified by combination with the chlorides of the alkali-metals .however. having the same crystalline form. may be melted with an .

we give.PbB^Oj u2NO|3 . oxides of the dyads.point than either of its form .6H 2 2(Cu2C 2 H 3O2 ).4CuO. J As examples Malachite of basic carbonates.H 2 O Pb2C 2 H 3 2 . the acids. the molecules of base in excess being assumed to be attached to the normal salt in a tion compounds is In many cases subsalts may be com- manner analogous is to that by which the water of is crystalliza- retained in ordinary instances. which has a much lower component chlorides in a separate decomposed when it is dissolved in water..2Hg2 H 2 O2 : . The following are instances of basic acetates Verdigris Tribasic eupric acetate Tribasic plumbic acetate Cu 2 C 2 H 3 2 . are the following : Brochantite Tribasic eupric sulphate CuS04> 3CuH 2 CuS04 . lead. such as the sesquioxides of antimony and bismuth. for example. that they do not form basic salts . such as the alkalies.. have a still greater pro- No general rule can be laid down for pensity to form basic salts. they are usually designated (536) basic salts. salt is obtained. very different series of saline compounds still remains for consideration. or is baric chloride . A The theory of the formation of these very imperfect. pared to salts which contain water of crystallization. . or subsalts. but among the common acids.. when basic. and zinc. and in these the proportion of base predominates over that of the acid . such as the oxides of copper. and the oxides of silver and thallium.. 2 2 Tufpeth mineral . nitric. CuC03 . amount of calcic. and Among basie sulphates.2HgO. indeed one of the peculiarities of the monad bases. have a strong tendency to do so. strontic.PbH 2 8 .CuH 2 0. HgS04 .CuO.5i bO..360 equivalent SUBSALTS. carbonic.2<JuH 2 . white the oxides of the triads.H{r2 H 2 2 3(Hg3 2N0 3 ). Dibasic plumbic nitrate Tetrabasic eupric nitrate iPbaNQj.CuH 2 2 Blue carbonate of copper White lead 2CuCO3 .2l'bO.3CuH 2 O2 Mercurous subnitrate De Marignac's do 5(Hgs 2N03 ). and in each case a compound salt fusing. but the double Subsalts..H s O.3H 2 Hexabasic plumbic acetate Pb2C 2 H 3 O2 . . The tendency to the formation of subsalts It is limited to certain acids and bases. those which most frequently form basic salts are the acetic acids. Among basic nitrates are.j 2PbC0 3 .. sulphuric. mercury.

for example. of the salts of copper exhibit a Many instance are the : 2 molecules of argentic chloride similar power (603). Just as 361 acids. METALS OF THE ALKALIES. A class of compounds which resemble (537) Oxychlorides. we have polybasic basyls. Such combinations usually occur between oxides and chlorides or iodides of metals same metal. . are the chlorides. the pure chlorides or iodides of which never form any but anhydrous crystals. which require more This than one atom of a monobasic oxiou for their saturation. fyc. oxyiodides.METALS OF THE ALKALIES. or of the cyanide of a metal is united with one or more molecules of the oxide of the Turner's yellow. the subsalts more than any others. has been scarcely examined. of the iodide. that is the case. with the metals of the alkaline earths . and form compounds which are in many respects anomalous . bodies termed oxyIn these compounds. is a well-known commercial article belonging to this class. so are there polyacid basyls as the such is. CHAPTER GROUP I. such for compounds of ammonia with many dry salts will in this manner absorb 3 molecules of ammonia. which they form. Some salts enter into combination with other bodies. dyads or triads. but as yet the class of double salts. one molecule of the chloride. which is an oxychloride of lead (PbCl^yPbO). and oxycyanides. XVII.

when they replace each other. [' = 39-1] (62 Sp. formulae employed above for felspar and mica require explanation. and chromium are also these compounds frequently replace isomorphous with alumina a portion of the alumina in its combinations.A1 24 SO 4 . Gr. Biaxalmica K . Alum Felspar .362 NOTATION OF MIXTURES OF ISOMORPHOUS COMPOUNDS. and the true function of silica in lated them at present so ill-defined.. Mica.24H 2 O.3 (M"' 2 O 3 . but the sesquioxides of iron.. I.) Native Compounds which contain Potassium.Al O 3 . . . . will crystallize together in any conceivable proportion. the general formula for mica may then Mica = M' 2 O.' stand for the metallic base of the protoxide. . . manganese. 144'5 5 C. may be regarded as a compound of i molecule of a silicate of a protoxide of a metal with 3 molecules of a Let different silicate of a sesquioxide of a different metal. The same fact can also be represented by stating that they may vary indefinitely in * The formulae of the combination is silicates are so complex. or even without altering its general chemical formula. M'" for the metallic base of the sesquioxide be expressed thus : M .SiO 2 ) . in different specimens of mica the relative proportions of iron and aluminium are fact liable to great variations silicate . The (538) Formulas of Mixtures of Isomorphous Compounds.* It often in the happens that isomorphous bases displace each other same mineral without altering its form or mineralogical characters. .3SiO 2 . for example. without altering the form of the mineral.3[(AlFe)"' 8Os]. is this that the replacement may occur in any proportion . the potash being the metallic protoxide and the alumiiia being the metallic sesquioxide . this arises silicate that the ferric and aluminic from the which are isomorphous. as the principle of notation adopted in these cases will be applied hereafter to the formulae of a large number of minerals.6SiO 2 K 3 O. (KNa)' 2 O. and this is The peculiarity especially the case with the sesquioxide of iron. : of isomorphous metals. that I have throughout formuas containing silica in combination with the bases. . for example. POTASSIUM (Kalium) Fusing-pt. Now potash and the components of potash-mica are principally silicate of silicate' of alumina..6SiO 3 . 0*865 .

and lastly the quantity of oxygen in the protoxides. is 3. In like manner. and consequently saturate the same pro- portion of required. in the Davy. for instance. the ratio of the oxygen in both sets of bases to the In felspar. that the two proportionals of metal required for combination with the 3 proportionals of oxygen in the sesquioxide. . or a have smaller or larger. that i molecule of potash alone would have This frequent partial displacement of one isomorphous metal another in native crystallized minerals. in the case of the potassium in felspar. the place of part of the potassium may be supplied by sodium . that is to say. provided that the united amount of all the metals so bracketed be exactly sufficient to form a true sesquioxide with the three proportions of oxygen. that in the sesquioxide of aluminium of potassium or sodium is i . thus. if the proportion of oxygen in the silica be taken as 12. but up to that period they had resisted all attempts to decompose them. renders much caution by The diffinecessary in interpreting the results of an analysis. but the proportions of the two taken together require exactly the same amount of oxygen.POTASSIUM. but indefinite proportion of the aluminium its place supplied by an equivalent quantity of iron. especially that these difficulties are experienced. to ascertain the proportion of oxygen in the silica. year 1807. increases with of the a mineral of course formula of fixing culty the complexity of its composition. then the proportion of oxygen when contained in the sesquioxides. (AlFeMu)'" 2 O 3 . The alkalies and the earths had long been suspected to be compound bodies. may for- Now mulae is the method of notation adopted in the preceding to indicate precisely this that the proportions employed of the two or more metals. and it is with the silicates It is usual. silica. and that in the protoxide This remarkable metal was discovered by (539) POTASSIUM. because. the analytical operations are completed. oxygen in the silica remains uniform. however much the proportions of the different metals may vary in different specimens of the same mineral. the symbols of which are bracketed together. 363 amount. and its isolation marks an important era in the progress of philosophical chemistry. are liable to vary within any conceivable limits. may either consist wholly of aluminium. provided only that the quantity of the two metals taken together in any one specimen furnishes such a proportion of a metallic sesquioxide as will saturate the silica in that portion of the mineral .

the decomposition of the other alkalies and earths followed as a more correct ideas upon fundamental necessary consequence points of chemical theory were introduced. They burn vividly in the air. but a (Phil. a curved gun -barrel. trace of moisture confers ppon it a sufficient degree of con- ducting power . and improved by Brunner. The dry hydrate is an insulator. Chirnie. 6 inches (15 centim. became an important addition to the reagents of the laboratory.PREPARATION OF POTASSIUM. new methods of research were placed within reach of the analytical chemist. leaving an intensely alkaline residue. and ignited till it ceases to emit combustible A porous vapours. 2. when decomposed by heat in a vessel from which air is excluded. Davy originally obtained potassium (540) Preparation. material which salt is best adapted to its preparation is the potassium of some vegetable acid.) square. which The process by which potassium is now obtained consists 3in decomposing its carbonate by charcoal. in 1808.-stance is placed in a capacious iron crucible furnished with a cover. This method of procuring the metal however is difficult and expensive. 3 kilos. and only furnishes it in very small quantity. setting free the potassium and the hydrogen. the former of was condensed in a well-cooled copper receiver. leaves a large quantity of carbon. When once potassium. invented a method by which potassium may be obtained by purely chemical means in Iron turnings were heated to whiteness in greater abundance. and : potassium itself. attention to a number of minute The precautions is requisite. and potash had been proved to be an oxide of this metal. For this purpose hydric potassic tartrate About (crude tartar) i preferred. by decomposing a fragment of caustic potash (which had become slightly moistened upon its surface by exposure to the air for a few minutes) by the current of a Wollaston's voltaic battery of 200 or 250 pairs of plates. i. which. a plan originally invented by Curaudau. This operation has been carefully studied Mareska and Donne (Ann. from its powerful attraction for oxygen. Gay-Lussac and Thenard. or 7 Ib. however. of this sub. [3] xxxv. under such circumstances globules of metallic potassium are separated at the negative wire. de by In order to ensure a successful result. decomposition ensued. 4). which was covered with a clay lute. 1808. and may be preserved under naphtha. to preserve it from the action of the air at a high temperature. . Trans. and melted caustic potash was allowed to pass slowly over the ignited iron . the iron combined with the oxygen. had been separated from its compounds. 147).

and forms a coating which The heat is then urged until it becomes very protects the metal from oxidation. c. and are confined in their places by only a quarter of an inch (6 IDmcm< thick. A mixture of coke and charcoal forms a fuel well adapted to this purand care should be taken that the temperature of the furnace should be as uniform as possible in every part. a. and preserved under exterior. from the furnace.iron tube. d. ) clamp screws: the iron plate should be ^ in. lest the tube should become obstructed by Should any obstruction occur. the socket The object of preparing the receiver of fitting upon the neck of the iron retort. is naphtha. rapidly cooled . this apparatus is sufficiently cold. When the operation is complete. which fit closely to each other. pose. (3O ) long. 4^ inches (or n centi- FIG. a. the receiver containing the potassium removed. metres) long. d. 337. and instantly plunged into a vessel of rectified Persian naphtha. and quickly introduced into a wrought iron retort. is broken up into lumps of about the size of a hazel-nut. When a full reddish-white heat is attained. the fire is whole process. upon supports of fire-brick. the borax melts. removed by thrusting in an iron rod if this fails. FIG. when cold.EXTRACTION OF POTASSIUM. intense. fig. the potassium is detached. the fire should be immediately withdrawn this is readily effected by removing the fire bars. of the furnace. It consists of two pieces of wrought-iron. e. ff. vapours of potassium begin to appear. . which it is found most advantageous to construct of the form shown on an enlarged scale in fig. which is this is usually made of one of the iron bottles in which mercury is imported introduced into a furnace. 337. proThe vessel is kept cool by immersion in water. mass of potassic carbonate. . and so to withdraw it from the action of the carbonic oxide which is disengaged during the Before this receiver is connected with the tube. and burn with a brilliant flame the receiver is now adjusted to the iron neck of the retort. with the exception of two which support the retort the fuel thus falls into the The receiver is kept cool by the application of a wet cloth upon its ashpit. intimately is 365 mixed with very finely divide! carbon. the receiver is open at both ends. (4 and 5 inches (or 1 2 om> ) wide . When vided with a cover. 12 in. a wrought. . 336. 336. as shown at b. so as to form a shallow box ) deep. mm- form is to ensure the rapid cooling of the potassium. b. which is not allowed to mm iron plate which forms ') through the project more than a quarter of an inch (6 part of the front wall. this particular slowly raised until the retort attains a dull red heat powdered vitrified borax is then sprinkled over its exterior. : . . is by moistening the exterior of the crucible with cold water the charred mass. g. and placed horizontally thus obtained: this . serves to convey the vapours of potassium produced during the distillation into a receiver. it must be the accumulation of solid potassium.

each atom of potassium displaces one half the hydrogen in a molecule of water. If exposed to the air. A third distillation may be necessary. the melted metal swims about rapidly upon the surface of the water. having a specific gravity of only o'865. charge bonic oxide and potassium . even for a few minutes. The potassium ject is it so obtained is to a second distillation in . Upon the application of heat the mixture is wholly converted into carCO 3 + C 2 The. (62'5 C. Potassium is light enough to float in water. and burns with great violence. at temis peratures a little above this it soft. the latter is immediately decomposed. Donne found this loss to amount to about one-third of the entire quantity of the metal contained in the charge. which (541) Properties. if it be neglected. in to almost remains the tube attached always impure potassium A the retort . essential is if little the potassium be required in a state of perfect purity. The powerful attraction which potassium has for oxygen is well shown by its action on water on throwing a piece of the metal on to water. it becomes covered with a film of oxide. : malleable it .) it is becomes pasty. not pure . and at I44'5 Whilst in the soft condition. 2 + 3CO. finally disap.) it is completely liquid. 2H 2 O-f K 2 =2KHO + H 2 while the escaping hydrogen becomes ignited by the intense heat developed by the reaction. a black detonating compound formed by exposure to the atmosphere. it is best to tube as soon as it is cold. Potassium is a bluish-white metal. In order to obtain the maximum produce of potassium. and is even speedily produced spontaneously. forming potassic : hydrate. although the metal be kept under naphtha. Mareska and some loss during the process being inevitable. and has a crystalline fracture at 32 (o C. and to immerse it in water. This precaution for.366 POTASSIUM ITS PROPERTIES. 2 K =K usually yields about one-fourth of its weight of crude potassium. . and when heated to its point of volatilization it bursts into flame. and burns with a beautiful rose-red flame . and it yields a beaulike iron tiful green vapour. it is necessary to suban iron retort. is brittle. the carbonate of i molecule should contain or 138 parts of the carbonate by weight to 24 of carbon. quantity operated on.) . this substance explodes violently upon the slightest The purified metal amounts to about two-thirds of the friction. two clean surfaces of the metal admit of being welded together at a red heat it may be distilled. tion of the detonating detach this and in order to prevent the possibility of the formacompound already mentioned. as the temperature rises at 59 (15 C. it is carbonate and carbon necessary that the mixture of potassic to 2 atoms of carhon.

wise absorbs carbonic oxide with facility when heated moderately in it. where it is immediately above a bed of rock-salt ico feet or 30 metres in thickness. A native compound of chloride of potassium and magnesium has recently been discovered in a bed of clay in the neighbourhood of Stassfurt. selenium. and at a high temperature it will remove oxygen from almost all compounds which contain that element. 367 pearing Avith an explosive burst of melted potassic hydrate which of is steam. or when the vapour of potassium is allowed to condense a dark red compound. KC1 Cl. attended with great It is remarkable that this salt depression of temperature. which takes up about a third of its weight. and evaporating. a blue subchloride of potassium also exists. but at a higher temperaPotassium enters directly ture the hydrogen is again expelled. or Chloride of potassium. Comp.CrO 3 ). poses nearly in contact with them. or under the surface of some liquid. and occasions considerable waste in the ordinary method of : preparing potassium. forming a hard translucent mass (KC1. and potassic salt quantity from kelp. It becomes necessary therefore to preserve the metal either in exhausted hermetically sealed glass tubes. = This salt is ashes of burnt sea. 52*41 . It crystallizes in cubes. when the globule formed becomes sufficiently Potassium decomcool to come into contact with the water. which is instantly decomposed by water. which does not contain oxygen. K. which is also decomposed by water it is obtained in needles when a solution of potassic : dichromate in hydrochloric acid is allowed to crystallize. extracted in considerable is prepared pure by directly neutralizing either the acid or the normal potassic carbonate with hydrochloric acid. and is very readily soluble in cold water.weed. slowly in an atmosphere of the gas K C O is thus formed from which the metal cannot be : . 47'5974'6 . Gr. With chromic acid it forms a corresponding compound (KCl. contain if it be heated which all gases oxygen. into combination with the halogens and with sulphur. i'994 . According to Bunsen. the used largely as a source of the It may be required in the manufacture of alum. At a heat short of redness potassium absorbs hydrogen and becomes converted into a greyish mass (HK 4 ?). It likeand tellurium. in 100 parts . near Magdeburg. This is . possesses the property of absorbing the vapours of sulphuric anhydride.POTASSIC CHLORIDE. like naphtha. (542) POTASSIC CHLORIDE. Sp.SO 3 ). recovered it furnishes potassic rhodizonate when treated with water. burning vividly when heated with them.

or Iodide of potassium . Br. whereby a mixture of ferrous and ferric iodides is produced. K. Iodide and iodate of potassium are formed. amounting to nearly one-fourth of its weight.MgCl 2 . By gentle ignition of the residue obtained on 6KHO = evaporation. and the salts of magnesium and potassium afterwards. This bed of and chlorides of contains the sulphates potassium. 76 46 . decomposes the bromate by a current of to expel the excess of the till sulphuretted hydrogen. I. in 100 parts. Comp. which it would occupy. Comp. which crystallizes in cubes. and the remaining iodide must not be strongly heated. It mav be obtained by adding bromine to a solution of caustic potash until the liquid permanently acquires a slight yellow colour potassic bromide and bromate are formed. resembling rock-salt in appearance. and evaporates the . Gr.368 BROMIDE AND IODIDE OF POTASSIUM. Lowig dissolves the : mixed salts in water. KI = i66'i IODIDE. which are sometimes elongated into prisms or flattened into plates. solution crystallizes (544) POTASSIC 2KBrO 3 + 6H 3 S = aKBr + 6H 2 O + 383. The liquid is then boiled. 67*17.6H 2 O). is a very soluble salt. simple method consists in adding iodine to a solution of caustic potash A gently warmed. KBr= 1 19*1 . and extremely deliquescent. The i salt is decomposed. which has received the name of carnallite. until the solution begins to assume a brown tint. K. sulphur. under these volatilizes at a red heat. gas. 32*83. stoppered vessel. and a solution of potassic car- . from its pink colour. clay and of magnesium. supposing the formed by the gradual drying up of an inland sea. where the common salt would crystallize out first. 3!. the iron being purposely added in excess . (543) Potassic bromide. A iodine and circumstances ferrous iodide is formed by the direct union of the metal with the iodine the solution is decanted. and a quantity of iodine equal to one-third of that which it already contains is : added.. the iodate fuses. and the upper part of the deposit consists chiefly of a hydrated double chloride of magnesium and potassium. Gr. derable quantities of potassic chloride are also obtained from bittern. with 10 parts of water.. This Sp. 3-056 . It is now extensively worked for the sake of the potassic chloride it precisely the position deposit to have been Consicontains. or Bromide ofpotassium . of sodium. but with a more pearly lustre. filters warms gently from the* deposited . as potassic iodide better plan is to digest 2 parts of of in a part iron. the mother liquor from the evaporation of sea-water (563). (KCl. This Sp.+ 5KI + KIO 3 + 3H 2 O. in 100 parts. 23-54. 2-672. valuable medicine may be procured in several ways.

o. Dipotassic oxide Deutoxide of Potassium Peroxide of Potassium II. neither should it turn brown .. . obstinately retains a portion of the potassic iodide. 2KI + O + 2NO 2 I 2 of iodine occurs. defined compounds with oxygen potash. bitterish taste. Sp. K = K (X = K = 2 2 2 4 94/2 or 83'oi 1699 29^04 no'2 \\i. developed iodide be mixed with strong nitric acid an immediate separation it. solution of potassic fluoride in hydrofluoric acid it is a convenient source for obtaining anhydrous hydrofluoric acid. moistened with hydrochloric acid (carbonate would be indicated by effervescence). (KHF 2 =78'i) POTASSIC HYDBIC FLUOBIDE. as a transparent gelatinous to a salt of potassium . B B . Fe 2 T 6 + FeI 2 + 4K 2 CO 3 and produced the solution is next dense O the Fe filtered from 44 -f 4CO 2 8 magnetic oxide of iron.. it dries (547) OXIDES OF POTASSIUM. .. . A K O = 58'i. completely soluble in six times its it should not effervesce when gr. with which it forms Pure potassic iodide weight of alcohol (sp. Potassic iodide crystallizes in anhydrous cubes. Cr2 7 + 7H a S 2 4HNO = 2KN0 +2H + . suboxide also appears to be formed upon the surface of the metal A during its gradual oxidation in dry . corrodes glass. 0*83) is . air. which are It is very soluble in water. K. 2KF. and furnishes the salts a basic oxide. of the alkali . Potassium forms three wellwhich constitutes and two other blue oxides which do not form corresponding salts with acids.. 3 3 2 mixture of potassic dichromate and sulphuric acid gives a similar result.'2 70^96 54'99 -(-p- 45'oi = = = 100 100 100. if potassic iodate were mixed with colour free iodine would be shown by the brown If the solution of the on adding the acid. a smaller extent in alcohol. not deliquescent in dry air. solution has the property of dissolving iodine. or Fluoride of potassium and hydrogen crystallizes in cubes or rectangular four-sided tables from a ..SiF 4 = 22O'2.. however. . (545) POTASSIC FLTTOEIDE. potassic iodide . -|- Potash. and to Its it has a cooling. the oxide of iron. 2*454) is a very deliquescent salt obtained by neutralizing hydrofluoric acid Its solution has an alkaline reaction and with a solution of caustic potash. a deep brown liquid. This salt is- one of the most insoluble compounds of potassium to a white earthy-looking powder. 369 bonate added in small quantities so long as effervescence is SKI a precipitate occurs. or Fluoride of potassium (KF Gr.OXIDES OF POTASSIUM. it falls whenever hydrofluosilicic acid is added Advantage is occasionally taken of its insolubility to separate potassium from some of its salts : in this way chloric acid is sometimes prepared from potassic chlorate. (546) POTASSIC SILICOFLCOEIDE precipitate . and on evaporation it yields crystals of is .

or still better the by deflagration ot a mixture of the nitrate with iron. expelled and It is white.2H 2 O). liquid is evaporated rapidly in at a heat approaching redness. terial. but below that temperature it furnishes a powder of a chromeIt absorbs moisture rapidly when exposed to the air. pure potash is formed. A much purer product may be obtained by decomposing pure a red heat by metallic copper. POTASSIC HYDRATE. POTASH. 2*2. and after it has thus become hydrated. KHO = 56'i. 2 very deliquescent. is Sp. potash is therefore generally procured in the state of hydrate. or Caustic Potash. it is is (KHO. Gr. it in which form may be obtained without difficulty. made into a thin paste with water. Peroxide of potassium. adding to the boiling solution a quantity of caustic lime equal in weight to half the potassic carbonate used . decomposed by water with evolution of oxygen and formation of a solution of the oxide K 2 2 (548) DIPOTASSIC pound OXIDE. 2 4 =I42'2 This substance is formed when potassium is heated Q. : and potassic hydrate remains in solution . (Harcourt. i6'O4) prepared by dissolving potassic carbonate.370 CAUSTIC POTASH. H 2 O.). 267). the . the operation must be completed in a current of 0-ently in a current oxygen gas: if formed at a temperature of 536 (280 C. like then either cast into cylinders in a metallic mould. J. Comp. oil : it a clean iron or silver basin. K 2 O = 94'2. from a hot concentrated aqueous solution. and added arid in small portions at a time. and is . potash may also be obtained crystallized in acute rhombohedrons. of dry air. K yellow colour. K 2 CO 3 4. in 10 or 12 times its weight of water. of which the pearlash of commerce is an impure variety. till flows without ebullition. Chem. Soc. 2KHO + K = 2KKO + H 3 when hydrogen is . and caustic. when moistened with water the two substances combine with incandescence. or Caustic poured upon a cold stone slab.CaH 2 O 2 giving 2KHO + CaCO 3 After decantation from the precipitate. %y<)6. so that the liquid may be maintained at the boiling point a crystalline calcic carbonate is precipitated. Dipotassic tctroxide. and allowed to solidify. or by heating potassium with an equivalent quantity of the hydrate. in 100 parts K 2 O. Caustic potash is one of the most indispensable reagents to . it slowly cakes dry together. Anhydrous potash fuses at a red heat. and is volatilized at a high For most purposes the presence of water is immatemperature. the lime should be slaked. xiv. subsequently dissolving out the potash with water and evaporating the potassic nitrate at solution. can be prepared by allowing thin slices This of com- metallic potassium to become oxidized in air perfectly free from moisture and carbonic anhydride . no degree of heat is sufficient to expel the water.

glass bottles into the composition of which no oxide of lead enters. : it in alcohol. and when cold it is broken up and off placed in a well-closed bottle. crystallized hydric potassic carbonate : (commonly known as bicarbonate. the chemist. with 4 baryta or with potassic sulphate.white subabsorbs both moisture and carbonic anhydride rapidly from the air . : sulphates. it is soluble in about half its weight of water. ultimately goes igneous fusion is . as the solution gradually dissolves this oxide out of glass. the impurities above mentioned reCommon potash is therefore often purified maining undissolved. and is likewise very soluble Caustic potash has a peculiar nauseous odour. It is therefore 371 necessary that he should be able readily to ascertain its purity. If pure. sulphates. with Potassic hydrate. showing the showing the absence of calcic salts. after fusion. potassic hydrate is perfectly soluble in water without effervescence a 'dilute solution should give no precipitate with baryta-water. K SO 4 + BaH O = 2 2 BaSO +2KHO. cautery. the development of considerable heat. Caustic potash. and if needful prepare it for himself when required pure. is absence of chlorine. iron. by dissolving it in alcohol and evaporating the solution in a silver vessel. for this reason its solution cannot be filtered except through pounded glass or sand. and an acrid taste it is a powerful . by means of lime obtained from The impurities which occur most frequently in black marble. it yield any precipitate with ammonic no neutralizing it precipitate. caustic potash are peroxide of potassium and the carbonordinary in the ates. chlorides. may be decomposed manner above described. and silicates of calcium. stance is a hard. and quickly destroys both animal and vegetable matters . raising the temperature until it underthe alcohol is thus expelled. when pure. and then The solution should be preserved in decanting the clear liquid. showing the absence of carbonates and and lead. and is always best clarified by allowing the impurities to subside. On with nitric acid. aluminium. KHCO 3 ). entirely soluble in alcohol. A dilute solution of pure potash may be readily obtained by a hot solution of baric adding hydrate to a solution of potassic until the liquid gives no further precipitate either sulphate. the melted poured hydrate upon a silver plate from the black crust which forms over its surface. B B 2 It . argentic nitrate gives Freedom from iron or metallic impurities is shown by the absence of any precipitate on the addition of hydric ammonic sulphide (H 4NHS).OR POTASSIC HYDRATE. greyish. neither should oxalate.

table gives approximatively the proportion of in 100 parts by weight of solutions of contained anhydrous potash the alkali of various densities The following : Strength of Solutions of Potash (Daltori). s . attacks vessels even of green glass and of porcelain when heated in them.372 also APPLICATIONS OF POTASH.

Much potash accumulates as an organic salt in the fleece of the sheep and is wasted. M. in which mineral it exists in the proportion of from 10 to 12 per cent. The proportion . all fertile soils. dried brushwood is incinerated." by simply washing. contains the potassium in the form of carbonate this salt is then extracted by water from the insoluble portions. which is called " A suint. numekinds of mica. or 9lb. water. of which they consider nearly 6oz. The chalk during the ignition evolves carbonic anhydride. Compounds of potassium derived from the disintegration of felspar. Ward and Wynants a few years ago contrived a method of extracting potash from felspar in the form of carbonated or of caustic alkali. of it. land cultivated for beet-root is now recoverable by suitable treatment of the waste after the sugar has been extracted. the mixture not being allowed actually to melt. : rous other silicates contain a small proportion of potash. is A good deal of the potash which is carried off the recoverable.. but the process does not seem to have The felspar is first ground to a been commercially successful. especially in the leaves. fine powder. and the remaining ash. these rocks become gradually disintegrated by the action of the carbonic acid in rain and among the soluble products of their decomposition potassic carbonate is assimilated by plants . circumstance large and succulent parts in the of acids. it is then fritted in a furnace. Maumene and Rogelet collected this peculiar potassic salt. Merle now obtains considerable quantities of potassic chloride from the : mother-liquors of sea-water by a modification of the method of Balard (563). and mixed with a suitable quantity of chalk. of the dry wood. which seldom constitutes more than i per cent. and facilitates the extraction of the soluble products. form of potassic facility : salts. and rendered caustic by the addition of slaked lime. and they form a necessary constituent in antiscorbutic remedies. which contain 2 or 3 per cent. at a temperature somewhere about the softening point of silver.NATURAL SOURCES OP POTASH.. 373 scurvy . fleece weighing 4 kilos. and certain besides these. which mechanically preserves the porosity of the mass. which yield 5 or 6 per cent. organic Owing to this usually of be obtained with quantities potash may young shoots. Messrs. The mass obtained is then lixiviated. they accumulate it. are present in small proportion in the grand reservoirs of this alkali-metal being the different varieties of clay.. contains about 7 ounces (200 grammes) of pure potash. and evaporating the wash water. and fluorspar . By exposure to the air and atmospheric vicissitudes. slaked lime.

or to mix the sulphate intimately with finely it powdered charcoal. The residue obtained is deliquescent. represented by the formula 5H 2 O: at 302 (150 !) they lose water and leave the hydrate obtained. supposing the materials to be employed in a pure state (K 2 O. and acquires a yellow colour. K The usual dry directions are to heat potassic sulphate in a current of hydrogen. the reactions which occur when sulphur is heated with caustic or carbonated potash are somewhat complicated but they are now well understood. of lime required is indicated by the following formulae. . four-sided prisms are obtained having a composition 2 S. : without difficulty. finds that the result usually represented by the equation. . and acts power- When a current of sulphuretted upon is transmitted a solution of caustic potash it is hydrogen through and if the be allowed to pass till the liquid rapidly absorbed. If a solution of potash be divided into two equal portions and one be converted into the hydric potassic sulphide (KHS). On the addition of a strong acid to the solution. DIPOTASSIC SULPHIDE. no sulphur being 4 . It combines with this element in not less than 4 and possibly in Owing 5 different proportions.H 2 O are obtained which give off their water of crystallization at about 392 (200 C. K 2 S 2 K 2 S 3 K 2 S 4 and K 2 S 5 to this circumstance. (Hofmanns Jury Report. : hedrons of hydrated potassic hydric sulphide 2KHS.) 3SiO 2 H-7CaO-t-CaF2 Potassium takes fire readily (549) SULPHIDES OF POTASSIUM. and may be traced . 3 2 on evaporating vacuum deliquescent K K Sj2H 2 2 O. is sulphuretted hydrogen deposited . Gaz.Al 2 O 3 : . 468). p. . howis not that 2 =K S+4H O. 1862.K 2 SO 4 4-4H 2 2 that a mixture of free alkali and a variable Bauer. given 2 off" K S 2 -J- H SO 4 = H S + K SO 2 2 abundantly. ever (Chem. compound KHS will be formed on this solution in colourless transparent rhombovacuo evaporating the skin as a caustic.374 SULPHIDES OF POTASSIUM. The solution of this sulphide is colourless when first prepared. or Protosulphide of potassium . 2 Some doubt exists as to the possibility of forming this compound. 1858. and burns with brilliancy when heated in the vapour of sulphur. . fully is it amount of one of the the result. this solution KHS + KHO in a becoming K S + H O. a solution of pure dipotassic sulphide will be 2 = 2K owing to the formation of the sulphide K 3 S2 . . gas is the completely saturated.) and melt at a dull red heat to a mobile yellow liquid. S. K 2 S ?.but higher sulphides of potassium has a reddish-yellow colour. and ignite in covered vessels. 4KHS + O 2 S 2 + 2H 2 O. 51. but if exposed to the air it quickly absorbs oxygen. and be then mixed with the other half of the solution of potash.3SiO 2 .

SULPHIDES AND SULPHATE OF POTASSIUM.S. as shown in the annexed equation 4K2 COS + 5 S 2 = K2 S04 + 3K. and forms a deep yellow solution in water. a decomposition ensues similar to that which occurs when potassic hydrate and sulphur are fused together . which remains in a finely-divided state mixed with the excess of charcoal. When a solution of caustic potash is boiled with sulphur.jSS 3 ) corresponding to the sulphite (K 3 SO $ ) was supposed to be formed by reducing potassic sulphate by the vapour of carbonic disulphide. or Dipotassic disulphide.4 CO 2 A dipotassic tetrasulphide (K 2 S 4 or K. by the precipitation of white. the higher sulphides to air.C02 In the old process of : . about i'i.brown colour . the sulphate is reduced leaving an impure sulphide. or compound which takes fire spontaneously in the air. and the excess of sulphur is separated. excess of sulphur till saturated : or by fusing any of the dry sulphides with an excess of sulphur . S O3 + 6S persulphide of potassium . in the case of all sulphide. they become colourless. of sulphur. ing the vapour of carbonic disulphide over ignited potassic carbonate as long as any gas makes its escape carbonic anhydride and carbonic oxide are produced. 2 S 2. The Sesquisulphide (tersulphide formerly). but from Schone's experiments it would appear to be a mixture approximating in composition to B^S^. by this means thin orange-red hygroscopic laminae are obtained containing K2 S 4 . 2 5 + 3H 2 2 2 . By exposing solutions of divided sulphur. it may. gr. K SO4 2 . and one of the higher sul- phides of the metal 6 molecules of caustic potash and 1 2 atoms of sulphur would thus furnish i molecule of thiosulphate and 2 of S O. is obtained pure by pass2Sg K KHS K . and yields a pyrophorus. On the addition of a stronger acid they are decomposed with but the lowest evolution of sulphuretted hydrogen. be prepared in the wet way by dissolving the proper quantity of sulphur in an aqueous solution of the monosulphide and evaporating the solution in vacua . The Disulphide. finely On adding the persulphide to an excess of hydrochloric acid of sp. potassic thiosulphate is formed. 69 parts of dry pearlash are fused with 40 parts of sulphur. sulphides with All these sulphides have an alkaline reaction to test-paper.2H 2 0. and forms sulphuric acid. a deep reddish-yellow liquid is formed. Dipotassic pentasulphide. and is of an orange colour. 6KHO =K +2K (55) POTASSIC SULPHATE. which contains the thiosulphate. as follows: 2K2 C03 + 3CS 2 = 2K2 S g + 4CO 4. the excess of sulphur separates and floats above the sulphide. 375 black. owing to the heat emitted by its rapid absorption of oxygen. It fuses easily. which has a dark liver. the resulting yellowish-brown mass consists of 3 molecules of sesquisulphide and i molecule of potassic sulphate part of the carbonate in this case yields oxygen to one portion of the sulphur. however. may be formed by exto the air till it begins to become turbid. or Sulphate of potassium. and an odour of sulphuretted hydrogen more or less distinct. it is deliquescent. the persulphide of hydrogen (400) is separated as an oily liquid. or persulphide (K 2 S 5 or K Z SS 4) corresponding to the sulphate (K 2 S0 4 ) is formed by boiling a solution of any of the preceding making liver : : . whilst the remainder is converted into the sulphide. attended. -:. posing an alcoholic solution of and evaporating to dryness in vacua. If potassic sulphate be mixed in fine powder with half its weight of lampand heated in a covered crucible.

the normal sulphate crystallizes first. Comp. Comp. 2*475. and afterwards. and it always contains it is and valuable salts of potassium. 54/07. 2*070. and allowing the solution to crystallize. or Bisulphate of Potassium: (KHSO 4 =i36'i) . in six-sided pyramids.376 ACID SULPHATE. owing to the oxidation of nitrogen contained in nitrites or nitrates are more or less of organic . phate is the liquid has become strongly acid.K SOV formed on a large scale as a residuary product in the preparation of nitric acid from potassic nitrate. 2 O. is = 174*2. they are very soluble in water and have a sour bitterish taste. 2 2 O. AND NITRATE OF POTASSIUM. 3 . This sa^ * 8 3 2 HNO . Acid sulphate. H PO . whilst a salt consisting of An analogous combe formed with may pound. . Gr. It appears to be formed in the moist portions of the soil. It crystallizes from a strongly acid solution in rhomboidal tables. which fuse at a heat below redness. or Nitre as this salt is frequently termed. (551) POTASSIC NITRATE. The nitre is obtained by lixiviatThe earth ing the soil. sa ^ crystallizes either in anhydrous six-sided prisms. when cases where the action of an acid is required at a high temperature upon salts or metallic oxides with which it may be fused. at other times disseminated through the superficial stratum itself. the bisulThis salt is sometimes used as a flux in deposited. towards which raised by capillary action.) for its solution. If redissolved in water. 2'66 . at some little distance below the surface. sulphate Jacquelain finds that if be dissolved in nitric acid. Gr. in 100 parts. In temperate climates. which furnishes it consists principally of loose porous calcic carbonate. a little nitre normal potassic and hydric potassic sulphate (KHSO 4) are formed. phosphoric acid.K SO 4 crystallizes in oblique prisms. or Nitrate of potassium . either almost always found in the shallow wellwaters of towns. crystals decrepitate strongly when Potassic sulphate forms a series of double salts with the The sulphates of the metals isomorphous with magnesium. K KNO = NO S. 53'4i Saltpetre. Gr. requires about 12 parts of water at 32 C. where it upon the soil. Sp. Sp. and by prolonged ignition lose half their acid . Sp. 46*59. mixed with decomposing felspar. and another class of salts (the alums) with the sulphates of the metals isomor- phous with aluminium. 4 3 2 HVDRIC POTASSIC SULPHATE. 4593- ^n terminating (o S0 3 . in 100 parts. heated. or in four-sided oblique it K rhombic prisms. occasionally crystallizes The bisulphate in K 2 S0 4 S03 ion anhydrous needles. derived from various districts in occurs sometimes as an efflorescence is matters. is one of the most important The principal supply of nitre the East Indies.

These heaps are watered from time to time with urine or stable runnings. mingled with. it may possibly. although the nitrates usually appear to be produced by the oxidation of ammonia. The artificial formation of been practised with considerable success in various countries of Europe. the heap being kept damp. is : and the nitre bed as any precipitate occurs. about 4 kilos. the animal debris during their infiltration through the withstanding the numerous investigations of which soil. the quantity required being proportioned to the value of the estate. and the insoluble calcic carbonate separated The clear liquor is then evapo+ Ca2NO3 = CaCO 3 + 2KNO 3 rated and crystallized. It is found by the saltpetre-boiler that . but not wet . to pay a certain tax in raw nitre. the slow combination of atmospheric nitrogen and oxygen. and indeed it is due to not improbable that nitrification is. in the process of putrefaction. By .NITRE PLANTATIONS. in favourable cases. In Sweden this supply of nitre is considered of such importance that each landed proprietor is obliged nitre has. Ozone appears to have the power of combining directly with nitrogen. Davy. Three years usually elapse before the washed after this interval a cubic foot of the debris should yield between 4 and 5 ounces of nitre. As there is always a considerable quantity of calcic and magnesic nitrates present. in loosely aggregated heaps. furnishing annually a large amount of the salt. Where animal matters are present in abundance. or of some basic substance which can combine with the acid at the moment of its generation. . potassic carbonate. however. is K 3 CO 3 decomposed. including in later times those of J.)- Nitre Plantations. of Schonbein. the formation of nitric acid is chiefly due to the gradual oxidation of ammonia developed access of air . this means the calcic nitrate . as Schonbein conjectures. of Kuhlothers. or a cubic metre. be concerned in the natural production of nitric acid. The process of nitrification becomes arrested if the temperature be allowed to fall much below 59 (15 C. in the shape of wood ashes. at suitable intervals the earth is lixiviated. exposed to the air. ashes and lime rubbish. the process of nitrification is very imperfectly understood. The free and the presence of a certain amount of moisture is the oxidation is also materially favoured by an excess necessary of an alkaline or earthy carbonate. which will not crystallize. and still the subject. but sheltered from rain. it 377 Not- has been mann. The method adopted for the artificial pro- duction of nitre consists in placing animal matters. is added so long salt crystallized.

a white. steadily smoulders away is consumed. mixed with oxygen escapes. isomorphous with those of sodic nitrate its weight of water at 64 (18 C. but it is a dimorphous salt. and frequently used in the labo- . is returned systematically to the other side of the heap. mixed with a fresh portion of animal matter. translucent. where. this salt occurs also in solution in plants. and a mixture of potassic nitrogen oxide and peroxide remains. The heaps are so constructed as to form a terrace of steps. and when cast into moulds. fibrous. it forms the well known until touch-paper. of nitre just the sap of certain plant. Owing is to the facility with which nitre parts with oxygen. of nitre. known as sal prunelle.378 PROPERTIES OF NITRE. while the evaporation proceeds with rapidity upon the exposed side. from capillary action. Nitre fuses easily without decomposition at a is temperature of solidifies to 6^'4 (358 C. thus facilitated. shall rest upon an impervious flooring of clay. Besides the natural and artificial sources described. 3^ times it is soluble in bohedra. &c. In Prussia. as they are termed. expelled. radiated mass. and this account fireworks. it when on ignited. exposing the back in the form of an upright wall to the prevailing wind the watering is . a cubic metre of the earth yields about 30 kilos. it is insoluble in alcohol If paper be dipped in a solution cooling and saline. so that the liquid which drains away from them may be collected and preserved. is it a powerful oxidizing agent. the earth in which nitre has once been formed furnishes fresh nitre more readily than on the first occasion. so as to avoid using a larger quantity of water than is actually needed to dissolve the saltpetre. and a deliquescent mass of impure potassic nitrite is By a still stronger heat the nitrite is decomposed. Care is taken that the nitre plantations. the tobacco may be enumerated. and in about a : its taste is third of its weight of boiling water . largely employed in firing trains of powder. and the washed earth. : of nitre and dried.). The washing of the earth charged with saltpetre is conducted in a systematic manner (570). When heated to redness. Nitre and com- usually crystallizes in long six-sided terminated by dihedral summits .). part of its oxygen is formed. mon borage among which the sunflower. striated prisms. which. by a more methodical treatment. the nitre from time to time a layer of earth is chiefly accumulates : removed from this wall for lixiviation. and is occasionally obtained by spontaneous evaporation of small drops of its solution in microscopic rhomProperties.

and also forms a compound with the potassium. as soon as nitre equal to about 5 times the weight of the water has been added. a quantity of nitre has been added equal to three times the weight of the water employed . In the refining of nitre. argentic nitrate. for the purpose of estimating the proportion of sulphur which they contain. in the following manner loo gallons of water is placed. when the water has attained the boiling-point.* when the liquid has been rendered salt * The quantity of : sodic chloride in grough or crude East Indian nitre is ' generally small . 600 litres. and with a portion of its potassium. may solution of cupric sulphate. and calcic and magnesic nitrates after it has heen fused. and its solution gives no precipitate with solutions of powdered baric chloride. Advantage is frequently taken of the oxidizing action of nitre. after which. If nitre be intimately mixed with any metallic sulphide in fine powder. or about operation. or rapid combustion. It was formerly the practice to purify the salt by three successive crystallizations . is removed by means of perforated ladles . advantage is taken of the circumstance that whilst the solubility of nitre increases rapidly as the temperature rises. in order to convert into sulphuric acid the small quantities of sulphur existing in certain substances of organic origin. the oxide produced possesses acid characters. at the expense of the oxygen of the nitre. (55 2 ) Refining of Saltpetre. the solution is diluted with two-thirds the quantity of water at first employed. the coin will be melted. Baume's quick flux conof a mixture of 3 parts of nitre. when pure. into a red-hot crucible. and to a large amount the sodic chloride. becomes of a bright green be quickly deprived of chlorine by moistening the finely- with pure nitric acid and gently heating it. but the same object is now effected by a single In a deep copper boiler. until. such as antimonious sulphide. until a portion of it. when dissolved in water. when moistened with Nitre salt colour. : The impurities of most frequent occurrence in nitre are potassic and sodic sulphates and chlorides. and i of its combustion is so great. unless the heat has been cautiously regulated. i that if a small silver coin be put into a mass of the mixture which will go into a walnut-shell. gives no precipitate with argentic nitrate. sawdust. whilst the metal at the and thrown. the heat given out during sists part of sulphur. : 379 when thrown upon glowing coals it produces a ratory as such brisk scintillation. a large proportion of which remains undissolved. is not deliquescent. I kilo- . but in the artificial nitre obtained from the beds' it often rises in such a case the liquid is skimmed from time to time. at a time. The quantity of sulphuric acid thus produced is precipitated and weighed as baric sulphate. forms potassic sulphate. and it be kindled. In the case of antimony. a little potassic nitrite is liable to be formed in the latter case a fragment of the : salt. and fresh nitre is added. and twice its weight of crude nitre is added this : : gradually becomes dissolved.REFINING OF SALTPETRE. in small quantities same time becomes oxidized to the maximum. if the liquid be strongly coloured. that of sodic chloride is scarcely affected by it. or potassic carbonate. Nitre. the sulphur burns with a brisk deflagration.

this becomes charged with nitre containing traces of chlorides.. 74-8 i 32 1*9 36 270 I3'3 lOO'O The proportions used vary a little : in different countries. .. the bottom of which is In this vessel the formed by two inclined planes which meet in the middle. and 3 atoms of charcoal Nitre .. in order to prevent the formation of large such crystals would mechanically retain the mother-liquor. The crystallization is effected in a shallow vessel.. whilst the saltpetre : (553) Gunpowder. and upon them is poured a solution of saltpetre saturated in the cold . pure nitre undissolved.. The principal consumption of nitre is in the manufacture of gunpowder. as will be seen from the following table Composition of Gunpowder in 100 parts. sulphur. from which crystals they could not be subsequently freed without recrystallization. and is fit for use.. olution is kept in continual agitation. in proportions approaching to i atom of sulphur. and the tanks are then filled up with pure water . 2 molecules of nitre. whilst the undissolved salt is almost chemically pure the solution of nitre thus obtained serves to wash a fresh portion of the crystals . 202 . remains almost entirely in the : is deposited in extremely small crystals. the liquid is drawn off. this liquid dissolves the chlorides. these are allowed to drain. the tanks are mother-liquor with which they are saturated. being nearly as soluble in cold water as in hot. The sodic chloride... Nitre ..380 clear GUNPOWDER. which consists of an intimate mechanical mixture of nitre. and are then removed to tanks provided with false perforated bottoms. and allowed to run into the crystallizing pan... Sulphur Charcoal . and charcoal. : 2KN03 S Sulphur Charcoal . by a few minutes' ebullition. . .... where they are deprived of the For this purpose. solution. 30 = = = In 100 parts. the refined saltpetre is then dried. completely filled with the crystals. technically termed saltpetre flour . it is strained through bag filters. but leaves the In the course of a few hours.

mixed with the nitrogen and carbonic anhydride. : is fired. are powder in the proper proportions. of the explosion.* Much of gunpowder. alder. which becomes speedily converted into Nitre of the purest quality is alone emsulphuric acid and attracts moisture. and of carburetted hydrogen. 381 excess of sulphur is carefully avoided. would occupy a space equal to about 300 times the bulk of the moment but from the intense heat developed at the . or in dogwood charcoal being employed only dogwood is preferred making rifle powder. sulphur is never used in the state of flowers of sulphur . are different from those Karolyi. it pose he enclosed a charge of powder in an iron cylinder of such strength that This charged just burst when the powder was fired by means of the electric spark. and ground for mixed in * In burning gunpowder in a copper tube with the view of collecting the small proportion of nitric oxide. at the ordinary temperature of the air. ployed. consisting chiefly of nitrogen and carbonic anhydride. The flowers of sulphur always contain sulphurous acid. on account of its The great explosive injurious action upon the metal of the gun. which. and are intimately blended in a revolving drum . care is requisite in the selection of the materials for the manufacture The charcoal must be burned thoroughly. whilst potassic sulphate and carbonate are found in abundance they become volatilized by the heat of the exploand the white smoke observed when gunpowder constitute sion. obtained somewhat different. but not at too high a : temperature that from the willow. Chevreul found a bonic oxide. reduced to a fine meal by grinding. ment works at Waltham Abbey. however (Phil. instead of consisting of chiefly potassic disulphide. with a little sulphuretted hydrogen. results has succeeded in analysing the gases of gunpowder which had been fired in conFor this purditions closely resembling those which occur in artillery practice. and 3 atoms of carbon. for the purpose. however. is to the sudden of due gunpowder development of a large power An volume of gaseous bodies. Bunsen. is always used for gunpowder. cylinder was suspended in a hollow spherical bomb. cannot readily be represented by any simple formula. they are then made into a stiff paste with water. in this condition it is preferred for fireworks . Supposing the powder used mixture to be made in the proportion of i atom of sulphur. of cargases over mercury. from which the air was . 2 molecules of nitre. and the solid residue. Mag. The charcoal In the Governalways contains a notable proportion of hydrogen and oxygen. and consequently also the results of the combustion procured by this regulated action. but distilled sulphur. the reaction is often approximatively represented thus : The actual results. the dilatation amounts to at least 1500 times the volume of the gunpowder employed. attending the firing of ordnance.GUNPOWDER. but the temperature. Oct. and Linck. contains but a small quantity of this substance. 1863). These three materials having been separately ground and sifted.

Ordnance Nitre Sulphur 1 . ^Ash .. Composition oftJie Powder power.... Charcoal ... the gases and firing. the slightly coherent mass thus procured is broken up.. Potassic sulphate carbonate ^Ammonic 2-68 Solid thiosulphate 19-40 2-85 O'll 2-57 - 69-25 sulphide Charcoal v Sulphur 4-69 0-17 lOO'OO .... The results obtained were the following exhausted before : I.. it is then subjected to the action of a hydraulic After the explosion had been produced.. powder....... and spread. (Carbon 7378 12-80 ip- 77-I5 8-6 3 ..382 GUNPOWDER PRODUCTS OF ITS COMBUSTION..... used.. Gaseous /Nitrogen .. some hours under edge-stones in the incorporating-mill ... the solid residue of the powder were submitted to analysis.. 1 0-38 1-82 J 3'39 11-78 0-42 1-79 0-28 0-31 100-05 2... hydrogen ^ 7'39 2*64 O'll 0*27 0*40 30-58 Marsh gas sesquicarb. in layers of about an inch in thickness.. Small-arms.. Products of Combustion by weight.. Hydrogen Oxygen .. .. between plates of gun-metal . Carbonic anhydride J Carbonic oxide 977 J io-o6\ Hydrogen Sulph..

when introduced into a mortar power. as in blasting for mining operations. or even upon a board.. press which exerts a force of 70 tons upon the square termed press cake. Baric nitrate. are barrels caused to revolve about glazed. the quick and and 15 of charcoal. is thus obtained . gunpowder with combustibles in various proportions. mercury effects would be produced like those due to fulminating where a prolonged heaving force is required. is to favour the rapidity of inflammation. The which The ignition of the whole charge does npt take place simultaneously throughout. independently of the diminution of its tendency to absorb moisture. baric sulphate. it is The heavier the powder the greater is its explosive considered unfit for use. are bnoken into small fragments.) object of granulating the powder. The residue is digested in water. leaving little residue. finally. and . by submitting them to the action of toothed The grains are next sorted rollers in a machine constructed for the purpose. when added to a solution of of baric sulphate these salts. when added to the liquid filtered from the . too rapid an action would be expended upon the barrel of the gun itself. for examination are dried over sulphuric acid in indicates the amount of moisture. by leaving interstices through the flame is enabled to penetrate and envelope each grain. It has been found that a powerful concussion of powder between pieces of iron will frequently kindle it. otherwise sufficient full time would not be given to allow the ball to receive the advantage of the expansive force of the gas generated . while still damp. foot of good English cannon powder weighs about 58 Ib. will yield the sulphuric acid in the form and argentic nitrate. two which it takes fire is about 482 (250 C. or granulated. the loss . the action of the powder is still further retarded by mixing it with sawdust . Mining powder is often glazed . by adding powdered graphite in the polishing barrels this operation retards the rate of ignition. . and weighed. 20 of sulphur. or polished by placing them in 39 times in a minute. furnishes the amount of nitre and other salts. In the formation of the fusee. these masses. acidulated with nitric acid. shot from 260 to 280 feet. on level ground. and.GUNPOWDER NITRITE AND CHLORATE OF POTASSIUM. the powder employed for this purpose usually contains 65 parts of nitre. the data for ascertaining the amount of chlorine from The charcoal and sulphur are contained in . set at an angle of 45. Good gunpowder burns rapidly in the open air. of 8 inches diameter. nor is it desirable that it should do so. will give the precipitated argentic chloride. The analysis of is mingled gunpowder is easily effected: 100 grains of the powder vacua. not blackening or kindling paper upon which it is fired. by means of sieves into different sizes. and diminishes the hygroscopic character of the powder. after which they are thoroughly dried in closets heated by steam. should throw a 68 lb. Two ounces of the best English powder. it may be exploded by The temperature at the blow of a leaden bullet fired at it. and certain kinds of fireworks. : 383 foot a hard sonorous mass. slow match. if below 55 A cubic lb. and washed the solution. and if the powder be placed upon lead. when evaporated in a counterpoised capsule.

It may be anhydrous. as the chlorate potassic requires 16 parts of cold water for solution. which when heated on an iron shovel until fusion takes place. K 2 O. which may be obtained by evaporating the solution to dryness. which after The two it from boiling water form anhydrous 6-sided plates . It forms numerous double salts with other metallic nitrites (392). In the process now generally chlorine employed for preparing the salt on a large scale. salts are easily separated by crystallization. and i part of sulphur. explodes suddenly with a very loud report. 2*326 . chloride are formed (Ca2C10 water dissolves and potassic chlorate and calcic 2KCl=2KClO 3 + CaCl 2 ) boiling 3 + both the potassic chlorate and the calcic chloride. whilst the charcoal mixture of 3 parts of nitre. evaporation. From this mixture the chlorate is deposited in 6-sided prisms. to a concentrated solution of the mixed salts. . Comp. . recrystallization has a cooling : a somewhat higher temperature is decomposed. is a white 2 (554) POTASSIC NITRITE. (555) . prepared by decomposing nitre by fusion at a red heat. = 122*6 C1 2 O 5 . chloride decompose each other. . potassic chloride is then added in the proportion of 74*5 parts of the chloride to 168 parts of the caustic lime originally employed. A KN0 water. in 100 parts. furnishing oxygen gas of great purity. and 39*15 of oxygen are evolved. produces a substance known as pulvis fulminans. dissolving the residue in . 2 of potassic carbonate. POTASSIC CHLORATE. KC1O 3 Sp. which may be obtained in crystals. and . 100 parts of the salt leave behind. or Nitrite of potassium. The 60*85 P arts of potassic chloride.384 GUNPOWDER. the portion which does not dissolve in water they may be separated by means of carbonic disulphide or by the use of benzol at a boiling temperature. deliquescent salt. and leaving potassic chloride as a fixed residue When heated to redness. 430 C. and leaves it in the crystalline form by spontaneous is left undissolved and may be weighed. One mode of preparing this salt has already 61*58. and allowing the nitre to crystallize out of the deliquescent nitrite. . Gr. or Chlorate of potassium . excess of is passed into a mixture of 300 parts of lime and 154 of potassic chloride with a comparatively small quantity of water. which dissolves out the sulphur. 38*42. somewhat analogous to that of nitre of water heated dissolve "When to of the salt. the operation being performed in close leaden tanks provided with The calcic chlorate and potassic agitators and heated by steam. chlorate is a more powerful oxidizing agent than nitre . parts boiling 61-5 between 698 and 806 (370 and salt and the at melts.whilst the calcic chloride is excessively soluble.). been explained (353) It may be more economically obtained by converting milk of lime into a mixture of calcic chlorate and chloride by passing through it an excess of chlorine . 100 taste.

leaving 53-82 of potassic = I38'